This application claims priority to U.S. provisional application 61/532,275 filed on 8/9/2011, which is incorporated herein by reference in its entirety.
Summary of The Invention
In accordance with the present invention, there is provided a polymerizable composition comprising (a) at least one first (meth) acrylate functional monomer represented by the following formula (I),
reference is made to the formula (I), L1Selected from at least one of: (i) optionally substituted polyvalent hydrocarbyl optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof, and (ii) a divalent linking group represented by the following formula (A),
referring to formula (A), Y is O or S. With further reference to formula (I): l is2N is, for each subscript, independently, an optionally substituted divalent hydrocarbon group optionally interrupted by at least one of-O-and-S-; r1N is independently selected for each subscript from the group consisting of hydrogen and methyl; and subscript n is 2 to 6. The polymerizable composition according to the present invention may optionally comprise (b) a polymerization moderator, in addition to the (meth) acrylate functional monomer represented by formula (I).
Further in accordance with the present invention, there is provided a polymerizable composition comprising (a) at least one thio (meth) acrylate functional monomer represented by the following formula (II).
Reference formula (II): l is3Is optionally substituted polyvalent hydrocarbyl optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof; r8Independently for each t is selected from hydrogen and methyl; and t is 2 to 6. In addition to comprising at least one thio (meth) acrylate monomer represented by formula (II), the polymerizable composition further comprises (b) at least one (meth) acrylate functional monomer represented by the following formula (III).
Reference to formula (III): l is4Is optionally substituted polyvalent hydrocarbyl optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof; l is5Independently for each u is an optionally substituted divalent hydrocarbon group; r9And R10Independently for each u is selected from hydrogen and methyl; and u is 2 to 6. For some embodiments, the polymerizable composition according to the present invention may optionally further comprise (c) a polymerization moderator, in addition to comprising (a) the thio (meth) acrylate functional monomer represented by formula (II) and (b) the (meth) acrylate functional monomer represented by formula (III).
According to a further embodiment of the present invention, there is provided a polymerizable composition comprising: (a) at least one (meth) acrylate functional monomer represented by the following formula (IV),
reference formula (IV): l is6Selected from optionally substituted polyvalent hydrocarbyl groups; l is7Each v is independently an optionally substituted divalent hydrocarbon group optionally interrupted by at least one of-O-and-S-,
R11for each v is independently selected from hydrogen and methyl,
v is 2 to 6; and R12And for each w is independently an optionally substituted divalent hydrocarbon group. With further reference to formula (IV), w is 0 to 10, and Z is selected from hydrogen or a group represented by the following formula (V),
reference formula (V), R13Is hydrogen or methyl. In addition to the (meth) acrylate functional monomer represented by formula (IV), for some embodiments, the polymerizable combination according to the present inventionThe compound (a) may optionally further comprise (b) a polymerization moderator.
Detailed Description
Molecular weight values, e.g., weight average molecular weight (Mw) and number average molecular weight (Mn), of the polymers used herein are determined by gel permeation chromatography using appropriate standards, e.g., polystyrene standards.
As used herein, polydispersity index (PDI) values represent the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of a polymer (i.e., Mw/Mn).
The term "polymer" as used herein refers to homopolymers (e.g., prepared from a single monomeric species), and copolymers (e.g., prepared from at least two monomeric species).
As used herein, the term "(meth) acrylate" and similar terms, such as (meth) acryloyl and (meth) acrylate, refer to both methacrylate and acrylate.
As used herein, the term "thio (meth) acrylate" and similar terms, such as thio (meth) acryloyl and thio (meth) acrylate, refer to thiomethacrylate and thioacrylate.
As used herein, reference to a "linear or branched" group, such as a linear or branched alkyl group, is understood to include: methylene or methyl; is straight-chain, e.g. straight-chain C2-C25A group of alkyl groups; and suitably branched, e.g. branched C3-C25A group of alkyl groups.
The term "halo" and similar terms, such as halo, halogen group, halide, and halide group, as used herein, refer to F, Cl, Br, and/or I, such as fluoro, chloro, bromo, and/or iodo.
Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any sub-range or sub-ratio subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all subranges (including the endpoints) between the minimum value of 1 and the maximum value of 10; that is, all subranges or sub-ratios beginning with a minimum number of 1 or more and ending with a maximum number of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.
Unless otherwise indicated, a left-to-right representation of a linking group, such as a divalent linking group, as used herein includes other suitable orientations, such as, but not limited to, a right-to-left orientation. For non-limiting illustrative purposes, divalent linking groupsOr equivalent-C (O) O-from left to right representation includes representation thereof from right to leftOr the equivalent-O (O) C-or-OC (O) -.
The articles "a", "an", and "the" as used herein include plural referents unless otherwise specified, and are expressly limited to one referent.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about".
Monomers of the compositions of the present invention include groups such as, but not limited to, multivalent and/or divalent L1，L2，L3，L4，L5，L6，L7And L8They may in each case be independently selected from optionally substituted hydrocarbon radicals. The term "hydrocarbyl" and similar terms, such as "hydrocarbyl substituent", as used herein, refers to: straight or branched C1-C25Alkyl (e.g. straight or branched C)1-C10Alkyl groups); straight or branched C2-C25Alkenyl (e.g. straight or branched C)2-C10Alkenyl); straight or branched C2-C25Alkynyl (e.g., straight or branched C)2-C10Alkynyl groups); c3-C18Cycloalkyl, including polycyclic cycloalkyl, and polycycloalkyl (e.g., C)3-C10Cycloalkyl groups); c5-C18Aryl radicals, including polycyclic or polycyclic aryl radicals (e.g. C)5-C10Aryl groups); and C6-C24Aralkyl (e.g., C)6-C10Aralkyl).
The term "hydrocarbyl" as used herein includes "heterohydrocarbyl", which is a hydrocarbyl group in which at least one carbon, but less than all of the carbons, is replaced with a heteroatom, such as, but not limited to, O, N, S, and combinations thereof. Examples of heterohydrocarbyl groups from hydrocarbyl groups may be selected from the group including, but not limited to: c3-C18Heterocycloalkyl (having at least one heteroatom in the ring), including poly-fused-ring heterocycloalkyl, and polycyclic heteroalkyl; and C5-C18Heteroaryl (having at least one heteroatom in an aromatic ring), including polycyclic or polycyclic fused ring heteroaryl.
Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and structural isomers thereof. Representative alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and structural isomers thereof, related to those containing two or more ethylenically unsaturated groups. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative multi-fused cyclic cycloalkyl groups include, but are not limited to, decalinyl, tetradecahydroanthracenyl, and tetradecahydrophenanthrenyl. Representative polycycloalkyl groups include, but are not limited to, bicyclo [2.2.1] heptyl (norbornyl), and bicyclo [2.2.2] octyl. Representative heterocycloalkyl groups include, but are not limited to, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl, including, but not limited to piperidin-4-yl. Representative polycyclic heterocycloalkyl groups include, but are not limited to, 7-thiabicyclo [2.2.1] heptyl, 7-oxabicyclo [2.2.1] heptyl, and 7-azabicyclo [2.2.1] heptyl. Representative aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, and triptycenyl. Representative heteroaryl groups include, but are not limited to, furyl, pyranyl, and pyridyl. Representative aralkyl groups include, but are not limited to, benzyl, and phenethyl.
The term "optionally substituted" as used herein with respect to groups including, but not limited to, hydrocarbyl, alkyl groups, cycloalkyl groups, and aryl groups, wherein at least one hydrogen thereof is replaced or substituted with a group other than hydrogen, such as, but not limited to, halo groups (e.g., F, Cl, I, and Br), hydroxyl groups, ether groups, thiol groups, thioether groups, carboxylic acid groups, carboxylate groups, phosphate groups, sulfonic acid groups, sulfonate groups, nitro groups, cyano groups, hydrocarbyl groups (including, but not limited to, alkyl, alkenyl, alkynyl, cycloalkyl groups including multi-fused ring cycloalkyl and polycycloalkyl groups, heterocycloalkyl groups, aryl groups including hydroxy-substituted aryl groups, such as phenol, and include a fused ring aryl; heteroaryl, including poly-fused ring heteroaryl; and aralkyl groups), and amine groups, e.g., -N (R)11’)(R12’) Wherein R is11’And R12’Each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl.
For non-limiting illustrative purposes, the hydrocarbyl group of the substituted hydrocarbyl group may be selected from one or more hydrocarbyl groups previously described herein, e.g., straight or branched C1-C25Alkyl groups, which may be substituted by one or more of the substituent groups described hereinbefore, e.g. one or more C3-C12Cycloalkyl radical and/or one or more C5-C18Aryl groups, for example, ethyl substituted with cyclohexyl and/or phenyl.
Optionally substituted groups, including, but not limited to, optionally substituted hydrocarbyl, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, and optionally substituted aryl groups, each of the various groups described herein may be independently selected from the groups described above, such as, but not limited to, a multivalent and/or divalent linking group L1，L2，L3，L4，L5，L6，L7And L8May be independently and optionally interrupted at each occurrence by at least one of-C (O) -, -S-, -O-, and combinations thereof, or possibly interrupted by at least one of-O-and-S-. Interrupted by at least one of-c (O) -, -S-, and-O-, or interrupted by at least one of-O-and-S-, as used herein, means that at least one carbon, but less than all carbons, of the optionally substituted group (e.g., optionally substituted hydrocarbyl group, optionally substituted alkyl group, optionally substituted cycloalkyl group, and optionally substituted aryl group) is independently replaced by one of the divalent non-carbon linking groups described. Optionally substituted groups (e.g., optionally substituted hydrocarbyl groups, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, and optionally substituted aryl groups) can be separated by two or more of the above linking groups, which can be adjacent to each other or separated by one or more carbons. For non-limiting illustrative purposes, the combination of adjacent-C (O) -and-O-can provide a divalent carboxylate linking or spacing group-C (O) -O-. For purposes of further non-limiting illustration, the combination of adjacent-C (O) -and-S-can provide a divalent thiocarboxylate linking or spacer group-C (O) -S-. For purposes of non-limiting illustration, the combination of adjacent-O-, -C (O) -and-O-can provide a divalent carbonate linking or spacing group-O-C (O) -O-.
Additionally or alternatively, interrupted by at least one of-C (O) -, -S-, and-O-, or interrupted by at least one of-O-and-S-, as used herein, means that the various groups may be separated or interrupted by at least one of-C (O) -, -S-, and-O-, or possibly separated or interrupted by at least one of-O-and-S-, e.g., multivalent, as used hereinAnd/or a divalent linking group L1，L2，L3，L4，L5，L6，L7And L8Can be independently selected from the various groups at each occurrence. For non-limiting illustrative purposes, when L1Selected from two or more radicals, e.g. optionally substituted polyvalent, straight-chain or branched C1-C25Alkyl and optionally substituted polyvalent C3-C12Cycloalkyl, or consisting of said two or more groups, said polyvalent groups may be interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. For purposes of further non-limiting illustration, a linking group, such as L1May be selected for some embodiments from divalent ethyl groups (e.g., ethyl-1, 2-diyl, -CH)2-CH2-) and divalent cyclohexyl groups (e.g., cyclohexyl-1, 4-diyl,they may be interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. For purposes of non-limiting illustration, a divalent ethyl group interrupted by-S- (e.g., ethan-1, 2-diyl, -CH)2-CH2-) and divalent cyclohexyl groups (e.g., cyclohexyl-1, 4-diyl,may be represented by the following formula (E).
As used herein, the term "multivalent," with respect to a multivalent linking group, refers to a group that is used to link the linking group to at least two covalent bonds of two or more substituents or moieties of a compound or monomer. As used herein, the term "divalent" with respect to a divalent linking group refers to a group that is used to link the linking group to two covalent bonds of two substituents or moieties of a compound or monomer.
The monomers of the polymerizable compositions of the invention described herein include monomers represented by formula (I), formula (II), formula (III), formula (IV) and related monomers, optionally in each case further including one or more by-products including one or more free-radically polymerizable ethylenically unsaturated groups, such as, but not limited to, oligomers including one or more free-radically polymerizable ethylenically unsaturated groups, resulting from the synthesis of such monomers. Byproducts, such as oligomeric byproducts, may optionally also be present in the polymerizable compositions of the present invention.
The polymerizable composition of the present invention, including its monomers, for example, represented by formula (I), and its various groups will be described in more detail below.
Reference is made to formula (I), and for some embodiments, L1May be selected from optionally substituted polyvalent linear or branched C1-C25Alkyl, optionally substituted polyvalent C3-C12Cycloalkyl, optionally substituted polyvalent aryl, and combinations thereof, said groups optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. Can be selected as L1Each group of (a) may itself be optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. Additionally or alternatively, and as previously discussed herein, when L is1Selected from two or more radicals, e.g. optionally substituted polyvalent, straight-chain or branched C1-C25Alkyl and optionally substituted polyvalent C3-C12Cycloalkyl, or when composed of two or more such groups, the multivalent groups may be interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof.
For some embodiments, the divalent group L of formula (I)2May be selected from optionally substituted divalent straight or branched C1-C25Alkyl, optionally substituted divalent C3-C12Cycloalkyl, optionally substituted divalent aryl, and combinations thereof, the foregoing groups optionally interrupted by at least one of-O-and-S-.
According to some embodiments, L of formula (I)1Selected from polyvalent linear or branched C optionally interrupted by at least one of-C (O) -, -S-and-O-1-C10An alkyl group. According to some further embodiments, L of formula (I)2Independently for each n is chosen from divalent linear or branched C optionally interrupted by at least one-O-)1-C10An alkyl group. L is1And L2Examples of multivalent and divalent alkyl groups that may each be independently selected include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, including structural isomers thereof.
For some embodiments, the polyvalent L of the first (meth) acrylate functional monomer represented by formula (I)1The linking group being chosen from polyvalent linear or branched C interrupted by at least one-S-group1-C10Alkyl, and n of formula (I) is 2 or 3. L is1May be selected from polyvalent straight or branched C1-C10Alkyl groups include, but are not limited to, those previously described herein.
For some embodiments, the multivalent L of formula (I)1The linking group is a divalent linking group, n is 2, and L1Represented by the following formula (B),
-(R2-S)p-R3-
formula (B)
Reference formula (B), R2Independently for each p is selected from optionally substituted divalent straight or branched C1-C10Alkyl, and/or optionally substituted divalent C3-C12A cycloalkyl group. With further reference to formula (B), R3Selected from optionally substituted divalent straight or branched C1-C10Alkyl, and/or optionally substituted divalent C3-C12Cycloalkyl, and p is 0 to 10. R2And R3Divalent alkyl groups that may each be independently selected include, but are not limited to, those previously described herein for L1Those described.
R for various p2And R3Non-limiting examples of optionally substituted divalent linear or branched alkyl groups that may each be independently selected include, but are not limited to: -CH2-；-CH2CH2-；-CH(Ph)CH2-, wherein Ph represents an optionally substituted phenyl group (-C)6H5)；-(CH2)3-；-CH(CH3)CH2-；-(CH2)4-；-CH(CH3)CH2CH2-；-CH2CH(CH3)CH2-；-C(CH3)2CH2-；-(CH2)5-；-CH(CH3)CH2CH2CH2-；-CH2CH(CH3)CH2CH2-；-C(CH3)2CH2CH2-; and-CH2C(CH3)2CH2-。
R for various p2And R3Non-limiting examples of optionally substituted divalent cycloalkyl groups that may each be independently selected include, but are not limited to: cyclopropyl-1, 1-diyl; cyclopropyl-1, 2-diyl; cyclobutyl-1, 1-diyl; cyclobutyl-1, 2-diyl; cyclobutyl-1, 3-diyl; cyclopentyl-1, 1-diyl; cyclopent-1, 2-diyl; cyclopent-1, 3-diyl; cyclohex-1, 1-diyl; cyclohex-1, 2-diyl; cyclohex-1, 3-diyl; and cyclohex-1, 4-diyl.
For the aforementioned R for various p2And R3Non-limiting examples of optionally substituted divalent linear or branched alkyl groups and optionally substituted divalent cycloalkyl groups, each of which may be independently selected, wherein one or more hydrogens may each be optionally and independently substituted or replaced with groups other than hydrogen, including, but not limited to, those groups described previously herein for the term "optionally substituted".
According to some embodiments, the divalent group L of formula (I)2Can be represented by the following formula (C),
-(R4-O)q-R5-
formula (C)
Reference formula (C): r4Independently for each q is selected from optionally substituted straight or branched C1-C10Alkyl, and optionally substituted C3-C12A cycloalkyl group;
R5selected from optionally substituted straight or branched C1-C10Alkyl, and optionally substituted C3-C12A cycloalkyl group; and q is 0 to 10.
For each q R4And R5Non-limiting examples of optionally substituted divalent linear or branched alkyl groups that may each be independently selected include, but are not limited to, those previously described herein for R2And R3Those described, wherein one or more hydrogens may each be optionally and independently replaced or replaced with a group other than hydrogen, including, but not limited to, those groups described herein before for the term "optionally substituted". R4For each q and R5Non-limiting examples of optionally substituted divalent cycloalkyl groups that may each be independently selected include, but are not limited to, those previously described herein for R2And R3Those described, wherein one or more hydrogens may each optionally and independently be replaced with a group other than hydrogen, including, but not limited to, those groups described herein before for the term "optionally substituted".
According to some embodiments, n of formula (I) is 2, L1Represented by the formula (B) and L2Represented by formula (C), in which case the first (meth) acrylate functional monomer may be represented by the following formula (Ia):
with reference to formula (Ia), R1，R2，R3，R4，R5P and q are each independently as previously described hereinDescribed herein. The first (meth) acrylate functional monomer represented by formula (Ia) includes at least two thioether linkages (-S-).
With further reference to formula (Ia), and for some embodiments of the invention: p is 1; each q is independently 0 to 10, provided that at least one q is at least 1; r2，R3，R4And R5Each is a divalent ethyl group, such as ethyl-1, 2-diyl; and each R1Independently hydrogen or methyl.
With additional reference to formula (Ia), and according to some embodiments: p is 1; each q is 1; and R2，R3And R5Each selected from divalent ethyl groups, such as ethyl-1, 2-diyl, in which case the first (meth) acrylate functional monomer may be represented by the following formula (Ib):
with reference to formula (Ib), each R1Independently selected from hydrogen and methyl, as described herein before.
For some embodiments, L of formula (I)1Selected from the following formula L1(a) The trivalent radical as shown in (a) is,
reference formula L1(a) And for some embodiments, R11And R12Each independently selected from: divalent straight-chain or branched alkyl radicals, e.g. divalent straight-chain or branched C1-C25Alkyl, or divalent straight or branched C1-C10Alkyl, or divalent straight or branched C1-C4Alkyl, or divalent C1-C2An alkyl group; divalent cycloalkyl radicals, e.g. divalent C5-C8A cycloalkyl group; divalent phenyl radicals, including straight-chain or branched C1-C9An alkyl-substituted divalent phenyl group. When L is1Selected from the group consisting of formula L1(a) The trivalent radical is represented by formula (I) wherein n is 3.
When L is1Selected from the group consisting of formula L1(a) The first (meth) acrylate functional monomer represented by formula (I) may be represented by the following formula (Ic):
with reference to formula (Ic), each R1And each L2Each independently as previously described herein.
The first (meth) acrylate functional monomer of the polymerizable composition of the present invention, for example, as represented by formula (I), may be prepared by methods well known in the art. For some embodiments, and for non-limiting purposes, the first (meth) acrylate functional monomer represented by formula (I) may be prepared by reacting one mole of a polythiol having n thiol groups (-SH) with at least n moles of one or more oxirane-functional materials (and/or one or more cyclic ethers) to form a hydroxy-functional intermediate having n hydroxy groups, where n in each case is as described with reference to formula (I). Examples of oxirane-functional materials include, but are not limited to, alkylene oxides, such as ethylene oxide and propylene oxide. Alternatively, the polythiol may be reacted with a 2-halo-1-hydroxy-alkane, such as 2-chloroethanol, according to methods well known in the art. Alternatively still, the polythiol may be reacted with a1, 2-alkylene carbonate, such as ethylene carbonate, according to methods well known in the art. The reaction of a polythiol with an oxirane-functional material, or a 2-halo-1-hydroxy-alkane, or a1, 2-alkylene carbonate, results in the formation of a hydroxy-functional intermediate.
The hydroxyl functional intermediate may then be reacted with a (meth) acrylate with simultaneous removal of the alcohol to form a first (meth) acrylate functional monomer represented by formula (I). Alternatively, the hydroxy-functional intermediate may be reacted with a (meth) acryloyl halide, such as (meth) acryloyl chloride, and subjected to subsequent processing steps to remove the resulting hydrogen halide and/or salt thereof. Alternatively still, the hydroxy-functional intermediate may be reacted with (meth) acrylic anhydride according to methods well known in the art. The hydroxyl functional intermediate may also be reacted with (meth) acrylic acid with the concomitant removal of water to form a first (meth) acrylate functional monomer represented by formula (I).
When L is1When represented by formula (a), and for non-limiting illustrative purposes, the first (meth) acrylate functional monomer represented by formula (I) can be prepared by the reaction of a carbonyl dihalide (when Y of formula a is O) or a thiocarbonyl dihalide (when Y of formula a is S) with two moles of a thiol functional material represented by the following formula (F):
reference formula (F), L2And R1Each as described herein before for formula (I).
Or, when L is1When represented by formula (a), and for further non-limiting illustrative purposes, the first (meth) acrylate functional monomer represented by formula (I) can be prepared by the reaction of N, N-carbonyldiimidazole (when Y of formula a is O) or N, N-thiocarbonyldiimidazole (when Y of formula a is S) with two moles of thiol functional material represented by formula (F).
With reference to formula (I), and according to some embodiments, n is 2, L1Selected from divalent linking groups represented by the formula (A), and L2Represented by the following formula (B),
-(R2-S)p-R3-
formula (B)
Reference formula (B), R2For each of p, and R3Each independently as described herein before, and p is 0 to 10.
When n is2，L1Represented by the formula (A) and L2When represented by formula (B), and for non-limiting purposes, the first (meth) acrylate functional monomer represented by formula (I) may be prepared by reacting a carbonyl dihalide (when Y of formula a is O) or thiocarbonyl dihalide (when Y of formula a is S) with a dithiol, such as dimercaptodiethylsulfide (which may also be equivalently referred to as bis (2-mercaptoethyl) sulfide), to form an intermediate dithiol having-c (O) -or-c (S) -linkages in its backbone. The intermediate dithiol is then reacted with two moles of an oxirane-functional material, such as ethylene oxide, to form a dihydroxy-functional intermediate. The dihydroxy functional intermediate may then be reacted with two moles of (meth) acrylate ester with the simultaneous removal of 2 moles of alcohol to form a first (meth) acrylate functional monomer. In the general synthesis procedure described above, the carbonyl dihalide may be replaced by N, N-carbonyl diimidazole (when Y of formula a is O) and/or the thiocarbonyl dihalide may be replaced by N, N-thiocarbonyl diimidazole (when Y of formula a is S). With further reference to the general synthetic procedure described above, the (meth) acrylate reactant may be replaced by a (meth) acryloyl halide, such as (meth) acryloyl chloride.
With reference to formula (I), and for some embodiments n is 2, and L1Selected from divalent linking groups represented by the following formula (D),
-C(R6)(R7)-
formula (D)
Reference formula (D), R6And R7Each independently selected from hydrogen, optionally substituted straight or branched C1-C10Alkyl, optionally substituted C3-C12Cycloalkyl, and optionally substituted aryl. Or, R6And R7Together form C4-C12Optionally substituted cycloalkyl.
With further reference to formula (I), for some embodiments when n is 2 and L1When represented by formula (D), L2Represented by the following formula (B),
-(R2-S)p-R3-
formula (B)
Reference formula (B), R2For various p and R3Each independently as described herein before, and p is 0 to 10.
For some embodiments, when L1Represented by the formula (D), L2For some embodiments represented by formula (B), and where n is 2, the first (meth) acrylate functional monomer represented by formula (I) may be represented by formula (Id),
reference formula (Id), R1，R2，R3，R6，R7And each p is independently as previously described herein. With further reference to formula (Id), and for some embodiments of the invention, each R1Independently selected from hydrogen and methyl, R6And R7Each independently selected from hydrogen and methyl, R2And R3In each case ethyl-1, 2-diyl, and each p is independently 1 or 2.
With reference to formula (I), when L1Represented by the formula (D), L2When represented by formula (B), and n is 2, the first (meth) acrylate monomer of the polymerizable composition of the present invention can be prepared by methods well known in the art. For non-limiting illustrative purposes, the first (meth) acrylate functional monomer represented by formula (Id) may be prepared according to the following representative scheme- (a).
Scheme- (A)
Reference scheme- (A), R1，R6And R7Each as described herein before with reference to, for example, formula (Id)And R' is a monovalent hydrocarbon radical, e.g. straight or branched C1-C25Alkyl, or C3-C12A cycloalkyl group. With further reference to scheme- (a), 1 mole of aldehyde or ketone (a) is reacted with 2 moles of a dithiol, such as dimercaptodiethylsulfide (b) (which may also be equivalently referred to as bis (2-mercaptoethyl) sulfide), to form a thiol-functional adduct (c). The thiol-functional adduct (c) is reacted with 2 moles of an oxirane-functional material, such as oxirane (d), to form a hydroxy-functional intermediate (e). The hydroxyl functional intermediate (e) is reacted with 2 moles of (meth) acrylate (f) with the concurrent removal of 2 moles of alcohol (g) to form a first (meth) acrylate functional monomer (h) which can be used in the polymerizable composition of the present invention.
With further reference to scheme- (a), the formation of the thiol-functional adduct (c) may be accompanied by the concomitant formation of by-products, such as oligomeric by-products. The formation of oligomer by-products can be minimized by adjusting the relative molar amounts of aldehyde/ketone (a) and dithiol (b). For non-limiting illustrative purposes, at least 4: the molar ratio of dithiol (b) to aldehyde/ketone (a) of 1 is such that oligomer by-product formation is typically minimized.
Referring additionally to scheme- (a), the (meth) acrylate (f) may be replaced with a (meth) acryloyl halide, such as (meth) acryloyl chloride, in which case 2 moles of hydrogen halide, such as hydrogen chloride, would be produced instead of 2 moles of alcohol (g). The first (meth) acrylate monomer (h) will be separated from the hydrogen halide according to processing methods known in the art.
With further additional reference to scheme- (A), the aldehyde or ketone (a) may be replaced with an acetal or ketal represented by the following formula (a-1).
Reference formula (a-1), R6And R7Each as described herein before, and Ra and RbEach independently selected from optionally substituted straight or branched C1-C25An alkyl group, a carboxyl group,optionally substituted C3-C12-cycloalkyl, and optionally substituted aryl. For some embodiments, the aldehyde or ketone (a) of scheme- (a) may be replaced with an equimolar amount of an acetal/ketal represented by formula (a-1). For non-limiting illustrative purposes, for some embodiments, the acetal/ketal represented by formula (a-1) is acetonyldimethyl ketal.
With further reference to formula (I) and according to some embodiments, n is 2, and L1Is a divalent linking group represented by formula (G-1), as described in further detail below. For some embodiments, a divalent linking group L of formula (G-1)8Is a residue of a hydrocarbyl group having two non-conjugated carbon-carbon double bonds. For some embodiments, L of formula (G-1)8Is a residue of vinyl-cyclohexene, and L8Is represented by formula (G-2), as described in further detail below, and L of formula (I)1Represented by formula (G-3), as described in further detail below.
The polymerizable composition of the present invention may further comprise at least one thio (meth) acrylate functional monomer represented by the following formula (II) in addition to the first (meth) acrylate functional monomer represented by the formula (I),
with reference to formula (II), and as previously discussed herein, L3Is an optionally substituted polyvalent hydrocarbyl group optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. Each R of the formula (II)8The groups are independently selected for each t from hydrogen and methyl, and t is from 2 to 6.
L of a thio (meth) acrylate functional monomer of formula (II)3Groups that may be selected include, but are not limited to, groups previously described herein for L1Those described for formula (I). For some embodiments of the invention, the polyvalent L of formula (II)3The radicals being selected from optionally substituted polyvalent linear or branched C1-C25Alkyl, optionally substituted polyvalent C3-C12Cycloalkyl, optionally substituted polyvalent aryl, and combinations thereof, the foregoing groups optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof.
For some embodiments, t is 2, and L of formula (II)3Represented by formula (B), as previously described herein, and the thio (meth) acrylate monomer may be represented by the following formula (IIa).
Reference is made to the formulae (IIa), R2，R3，R8And p are each independently as previously described herein.
For some embodiments of the invention, and with further reference to formula (IIa), p is 1, and R2And R3Each is a divalent ethyl group, such as ethyl-1, 2-diyl, in which case the thio (meth) acrylate functional monomer represented by formula (IIa) may be represented by formula (IIb) below.
Reference formula (IIb), each R8Independently selected from hydrogen and methyl, as described herein before.
The thio (meth) acrylate monomer represented by formula (II) may be prepared by methods well known in the art. For non-limiting purposes, a polythiol, such as dimercaptodiethylsulfide, or a salt of a polythiol, such as dimercaptodiethylsulfide disodium salt, may be reacted with a (meth) acryloyl halide, such as (meth) acryloyl chloride, to form a thio (meth) acrylate functional monomer represented by formula (II) or, for example, formula (IIa).
With further reference to formula (II) and for some embodimentsT is 2, and L3Represented by the following formula (G-1).
Reference formula (G-1), R2，R3And p is independently at each occurrence as described herein before for formula (B). With further reference to formula (G-1), L8Is an optionally substituted divalent hydrocarbon group. For some embodiments, L8Selected from optionally substituted divalent straight or branched C1-C25Alkyl, optionally substituted divalent C3-C12Cycloalkyl groups, optionally substituted divalent aryl groups, and combinations thereof.
A divalent group L of the formula (G-1)8For some embodiments are the following residues: optionally substituted hydrocarbon radicals having two non-conjugated carbon-carbon double bonds, e.g. optionally substituted straight-chain or branched C having two non-conjugated double bonds1-C25Alkyl, and/or optionally substituted C with two non-conjugated double bonds3-C12A cycloalkyl group. For some embodiments, L of formula (G-1)8The method comprises the following steps: vinyl-cyclohexene, for example the residue of 4-vinyl-1-cyclohexene or 3-vinyl-1-cyclohexene. According to some non-limiting embodiments, L of formula (G-1)8Is a residue of vinyl-cyclohexene, and is represented by the following (G-2).
According to some embodiments, and with reference to formula (II), t is 2, and L3Represented by the formula (G-1), wherein L8Is a residue of vinyl-cyclohexene and is represented by the formula (G-2), in which case L3More specifically, it is represented by the following formula (G-3).
With reference to formula (G-3), and according to some embodiments, the two groups bonded to the cyclohexane ring are ortho, meta, or para with respect to each other, and are not bonded to the same carbon of the cyclohexane ring. With further reference to formula (G-3), R2，R3And p is independently in each instance as described herein before for formula (B).
Further, when t is 2 and L3When the two groups represented by formula (G-3) and bonded to the cyclohexane ring are para with respect to each other, the thio (meth) acrylate monomer represented by formula (II) may be more specifically represented by the following formula (IIc).
According to some embodiments, when t is 2 and L3The thio (meth) acrylate monomer represented by the formula (II) is more specifically represented by the following formula (IId) when the two groups bonded to the cyclohexane ring are meta with respect to each other and represented by the formula (G-3).
With reference to formulae (IIc) and (IId), each R1Independently selected from hydrogen and methyl, and R2，R3And p are each independently as described herein before for formula (B).
With additional reference to formulae (IIc) and (IId), and for some embodiments, R2And R3Each is an ethyl-1, 2-diyl group, and each p is 1, in which case the thio (meth) acrylate monomers represented by the following formulae (IIc) and (IId) may be represented by the following formulae (IIe) and (IIf), respectively.
Thio (meth) acrylate functional monomers similar to those represented by formulas (IIc) and (IId) can be prepared by methods well known in the art. For non-limiting illustration purposes, 2 moles of a dithiol, such as dimercaptodiethylsulfide, are reacted with one mole of a vinyl-cyclohexene, such as 4-vinyl-1-cyclohexene, under thiol-ene reaction conditions well known in the art to provide a thiol-functional intermediate. The thiol-functional intermediate is then reacted with 2 moles of a (meth) acryloyl halide, such as (meth) acryloyl chloride, to form a thio (meth) acrylate functional monomer represented by formula (IIe) or formula (IIf), or mixtures thereof.
For non-limiting illustrative purposes, thiol-ene reactions generally involve the reaction of a material having one or more thiol groups, such as a dithiol, with a material having one or more carbon-carbon double bonds, such as a vinyl compound, (meth) acrylate, and/or allyl compound. For some embodiments, materials having one or carbon-carbon triple bonds are used, as described in further detail herein for the synthesis of monomers represented by formula (IV). For free radical initiated thiol-ene reactions, the reaction of a material having one or more thiol groups with a material having one or more carbon-carbon double bonds is typically carried out in the presence of a free radical initiator, for example a peroxide-type and/or azo-type free radical initiator. Examples of peroxide free radical initiators include, but are not limited to: peroxy monocarbonates, such as t-butylperoxy 2-ethylhexyl carbonate and t-butylperoxyisopropyl carbonate; peroxy ketals, such as 1, 1-di- (tert-butylperoxy) -3,3, 5-trimethylcyclohexane; peroxy dicarbonates, such as di (2-ethylhexyl) peroxy dicarbonate, di (sec-butyl) peroxy dicarbonate and diisopropyl peroxy dicarbonate; diacyl peroxides, such as 2, 4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide; peroxy esters, such as tert-butyl peroxypivalate, tert-butyl peroxyoctoate, and tert-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, and acetyl cyclohexane sulfonyl peroxide. Examples of suitable azo-type free radical initiators include, but are not limited to, azobis (organonitrile) compounds, such as azobis (isobutyronitrile) and azobis (2, 4-dimethylvaleronitrile). Additional non-limiting examples of azo-type free radical initiators are described in further detail herein for the synthesis of the monomer represented by formula (IV). The free radical initiator is typically present in an amount at least sufficient to initiate a reaction between the thiol compound and the compound containing one or more carbon-carbon double bonds. For some embodiments, the free radical initiator is present in an amount of 0.01 wt% to 5 wt%, based on the weight of the reactants. The thiol-ene reaction can be carried out at any suitable temperature, such as room temperature (e.g., about 25 ℃) to 100 ℃. The reaction temperature typically depends at least in part on the temperature or temperature range at which the free radical initiator is thermally activated.
When the reactants are multifunctional, such as polythiols having two or more thiol groups and materials having two or more carbon-carbon double bonds, the thiol-ene reaction can result in the formation of some oligomeric species. For some embodiments, the formation of oligomeric species may be minimized by adjusting the molar ratio of the reactants. For non-limiting illustrative purposes, for the reaction between a dithiol and a material having two carbon-carbon double bonds (reactive with thiol groups), the dithiol may be present in an excess amount relative to the material having two carbon-carbon double bonds, for example greater than or equal to 2: 1, or greater than or equal to 3: 1, or greater than or equal to 4: 1 is present.
It is to be understood that for the purposes of the present invention, the "base-catalyzed thiol-ene reaction" conditions are the preferred conditions for the thiol-ene reaction of a thiol compound with a material having (meth) acrylate groups. Base catalysts that may be used for these purposes include those well known to those skilled in the art; tertiary amines including, but not limited to, triethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, and 1, 4-diazabicyclo [2.2.2] octane; and tertiary phosphines, including but not limited to trioctylphosphine, tributylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.
The polymerizable composition according to some embodiments of the present invention may optionally include, in addition to the first (meth) acrylate functional monomer represented by formula (I), at least one second (meth) acrylate functional monomer represented by formula (III) below.
With reference to formula (III) and as described herein before, L4Is an optionally substituted polyvalent hydrocarbyl group optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. With further reference to formula (III), L5Independently for each u is an optionally substituted divalent hydrocarbon group. R of the formula (III)9And R10The groups are independently selected for each u from hydrogen and methyl, and u is from 2 to 6.
A polyvalent linking group L of the formula (III)4May be selected from the group consisting of the previously referenced L1Those classes and examples of described multivalent linking groups of formula (I). A divalent linking group L of the formula (III)5May be selected from the group consisting of the previously referenced L2Those classes and examples of described divalent linking groups of formula (I).
For some embodiments, the multivalent linking group L of formula (III)4May be selected from optionally substituted polyvalent linear or branched C1-C25Alkyl, optionally substituted polyvalent C3-C12Cycloalkyl, optionally substituted polyvalent aryl, and combinations thereof, the foregoing groups optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. For some embodiments, u of formula (III) is 2, and a multivalent linking group L4Is a divalent linking group, which may be represented by formula (B), as previously described herein for formula (I).
For oneFor some embodiments, a divalent linking group L of formula (III)5May each independently be selected for each u from: optionally substituted divalent straight or branched C1-C25Alkyl, or optionally substituted divalent straight or branched C1-C10Alkyl, or optionally substituted divalent straight or branched C1-C4Alkyl, or optionally substituted divalent C1-C2An alkyl group; optionally substituted divalent C3-C12Cycloalkyl, e.g. optionally substituted divalent C5-C8A cycloalkyl group; optionally substituted divalent aromatic radicals, e.g. divalent phenyl radicals, including straight-chain or branched C1-C9An alkyl-substituted divalent phenyl group; and combinations thereof. For some embodiments, the divalent linking group L of formula (III)5May be represented by formula (C), as described herein before for formula (I).
The second (meth) acrylate functional monomer represented by formula (III) may be prepared by methods well known in the art. For non-limiting illustration purposes, when u is 2, a polythiol, such as dimercaptodiethylsulfide, is reacted with a bis (meth) acrylate, such as an alkylene glycol bis (meth) acrylate including, but not limited to, ethylene glycol bis (meth) acrylate or a polyalkylene glycol bis (meth) acrylate including, but not limited to, diethylene glycol bis (meth) acrylate, under base-catalyzed thiol-ene reaction conditions to form a (meth) acrylate functional monomer represented by the second formula (III). The synthesis of the (meth) acrylate functional monomer represented by the second formula (III) may result in the formation of by-products, such as oligomeric by-products, which may optionally be present in the polymerizable composition of the present invention.
According to some embodiments, and with reference to formula (III), u is 2, and L4Represented by formula (G-1), and more specifically by formula (G-3), as previously described herein. When u is 2 and L4L of formula (III) when represented by formula (G-1) or more specifically by formula (G-3)5Represented for some embodiments by formula (C),as described herein before for formula (I). Such type (meth) acrylate monomers of formula (III) may be prepared by methods well known in the art. For non-limiting illustration purposes, 2 moles of a dithiol, such as dimercaptodiethylsulfide, are reacted with one mole of a vinyl-cyclohexene, such as 4-vinyl-1-cyclohexene or 3-vinyl-1-cyclohexene, under free radical thiol-ene reaction conditions to provide a thiol-functional intermediate. The thiol-functional intermediate is then reacted with a bis (meth) acrylate, such as an alkylene glycol bis (meth) acrylate, or a polyalkylene glycol bis (meth) acrylate, under base-catalyzed thiol-ene reaction conditions to form a second (meth) acrylate functional monomer represented by formula (III), wherein L is4Represented by formula (G-1) or more specifically represented by formula (G-3), and L5Represented by formula (C).
For some embodiments, the polymerizable composition of the present invention includes a (meth) acrylate monomer represented by formula (I), and at least one of a thio (meth) acrylate monomer represented by formula (II) and/or a (meth) acrylate monomer represented by formula (III). When composed of a (meth) acrylate monomer represented by formula (I) and at least one additional monomer represented by formula (II) and/or (III), for some embodiments, the (meth) acrylate monomer represented by formula (I) is present in an amount of 1 to 99 weight percent, alternatively 20 to 90 weight percent, alternatively 40 to 80 weight percent, and the additional monomers represented by formula (II) and/or formula (III) are present in total in an amount of 1 to 99 weight percent, alternatively 10 to 75 weight percent, alternatively 20 to 60 weight percent, the weight percentages being based in each case on the total weight of the recited monomers.
According to some embodiments, and as previously described herein, the polymerizable composition comprises at least one thio (meth) acrylate functional monomer represented by formula (II) and at least one meth (acrylate) functional monomer represented by formula (III). The monomers represented by formulas (II) and (III) are each independently as previously described herein. For some embodiments, the polymerizable composition comprising monomers represented by formulas (II) and (III) is free of (meth) acrylate functional monomers represented by formula (I). The relative amounts of the monomers represented by formula (II) and formula (III) may vary. According to some embodiments, the thio (meth) acrylate functional monomer represented by formula (II) is present in an amount of 20 to 99 weight percent, alternatively 35 to 90 weight percent, alternatively 50 to 80 weight percent, and the (meth) acrylate functional monomer represented by formula (III) is present in an amount of 1 to 80 weight percent, alternatively 10 to 65 weight percent, alternatively 20 to 50 weight percent, the weight percentages being based in each case on the total weight of the recited monomers. As previously mentioned, any of the polymerizable compositions of the present invention described above may further comprise a polymerization moderator as described herein below.
For some embodiments, the polymerizable composition of the present invention may include at least one ethylenically unsaturated monomer selected from the group consisting of 1, 2-divinylbenzene, 1, 3-divinylbenzene, 1, 4-divinylbenzene, bisphenol A ethoxylate diacrylate (CAS #64401-02-1), bisphenol A ethoxylate dimethacrylate (CAS #41637-38-1), bisphenol A propoxylate diacrylate (CAS #67952-50-5), bisphenol A propoxylate dimethacrylate, bisphenol A glyceride diacrylate (CAS #4687-94-9), bisphenol A glyceride dimethacrylate (CAS #1565-94-2), bisphenol F ethoxylate diacrylate (CAS #120750-67-6), bisphenol F ethoxylate dimethacrylate, bisphenol F propoxylate diacrylate, bisphenol F propoxylate dimethacrylate, bisphenol S ethoxylate diacrylate, bisphenol S ethoxylate dimethacrylate, bisphenol S propoxylate diacrylate, bisphenol S propoxylate dimethacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (meth) acrylic anhydride, or mixtures thereof. The concentration of the foregoing comonomers, alone or in combination, ranges from 0.5% to 60% based on the total monomer weight of the polymerizable composition. The effect of the starting materials on the refractive index and other properties of the final polymer takes into account the amounts used, either alone or in combination.
Further, the polymerizable composition of the present invention may further comprise at least one polyethylenically unsaturated monomer selected from trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di (pentaerythritol hexa (meth) acrylate, tris (2-hydroxyethyl) tri (meth) acrylate, 2,4, 6-triallyloxy-1, 3, 5-triazine (CAS #101-37-1), 1,3, 5-triallyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione (CAS #1025-15-6), or mixtures thereof. The concentration of the foregoing comonomers, alone or in combination, ranges from 0.1% to 20%, based on the total monomer weight of the polymerizable composition. The effect of the starting materials on the refractive index and other properties of the final polymer takes into account the amounts used, either alone or in combination.
For some embodiments, the polymerizable composition of the present invention comprises at least one (meth) acrylate functional monomer represented by formula (IV), as previously described herein. Polyvalent L of formula (IV)6And divalent L7The groups may be selected from L as herein before for formula (I), respectively1And L2Those groups described. For some embodiments of the invention, the multivalent L of formula (IV)6The radicals being selected from optionally substituted polyvalent linear or branched C1-C25Alkyl, optionally substituted polyvalent C3-C12Cycloalkyl, optionally substituted polyvalent aryl, and combinations thereof, the foregoing groups optionally interrupted by at least one of-C (O) -, -S-, -O-, and combinations thereof. According to a further embodiment, the divalent L of formula (IV)7The groups are independently selected for each v from optionally substituted divalent straight or branched C1-C25Alkyl, optionally substituted divalent C3-C12Cycloalkyl, optionally substituted divalent aryl, and combinations thereof, the foregoing groups optionally interrupted by at least one of-O-and-S-.
With further reference to formula (IV), for some embodiments of the invention, divalent R12The groups may be selected for each w, selectedly from R as herein before for formula (C)4Those groups described. For some embodiments, R of each formula (IV)12Independently selected for each w from the group consisting ofDivalent straight-chain or branched C of generations1-C10Alkyl, and optionally substituted divalent C3-C12A cycloalkyl group.
With further reference to formula (IV), according to some embodiments, v is 2, and L6Is a trivalent residue of a hydroxy-functional compound having a single carbon-carbon triple bond. Examples of hydroxy-functional compounds having a single carbon-carbon triple bond that can be used to prepare the (meth) acrylate functional monomer represented by formula (IV) include, but are not limited to, propargyl alcohol, but-2-yne-1, 4-diol, but-3-yne-2-ol, hex-3-yne-2, 5-diol, and mixtures of two or more thereof. A portion of the hydroxyl functional groups on a hydroxyl functional compound having a single carbon-carbon triple bond may be esterified. For example, a portion of a hydroxy-functional compound having a single carbon-carbon triple bond may include C1-C12Alkyne-functional esters of carboxylic acids, such as propargyl acetate, propargyl propionate, propargyl benzoate and the like.
When v is 2 and L6Is a trivalent residue of a hydroxy-functional compound having a single carbon-carbon triple bond, the (meth) acrylate monomer represented by formula (IV) can be prepared according to the general description below with propargyl alcohol as the hydroxy-functional compound having a single carbon-carbon triple bond. Typically, a thiol-functional intermediate is first formed by reacting 1 mole of propargyl alcohol with about 2 moles of a dithiol, such as dimercaptodiethylsulfide, under free radical thiol-ene reaction conditions well known in the art. The dithiol groups may each form a covalent bond with one carbon of a C-C triple bond group, or with two carbons of a C-C triple bond group. While not intending to be bound by any theory, it is believed that one dithiol group forms a covalent bond with each individual carbon of the C-C triple bond. The resulting thiol-functional intermediate is reacted with at least 2 moles, for example 2 to 3 moles, of an oxirane-functional material, for example ethylene oxide, or a cyclic ether to form a hydroxy-functional intermediate. Alternatively, the thiol-functional intermediate may be reacted with at least 2 moles, for example 2 to 3 moles, of a 2-halo-1-hydroxy-alkane, for example 2-chloroethanol, according to methods well known in the art, thereby forming a hydroxy-functional intermediate. Similarly, thiol functional intermediates may be reacted withAt least 2 moles, for example 2 to 3 moles, of a1, 2-alkylene carbonate, for example ethylene carbonate, are reacted according to methods well known in the art, thereby forming a hydroxy-functional intermediate. The hydroxy-functional intermediate is then reacted with at least 2 moles, for example 2 to 6 moles, of a (meth) acrylate ester with concomitant removal of the alcohol to form a (meth) acrylate functional monomer represented by formula (IV). Alternatively, the hydroxy-functional intermediate may be reacted with at least 2 moles, for example 2 to 3 moles, of a (meth) acryloyl halide, for example (meth) acryloyl chloride, such that a (meth) acrylate functional monomer represented by formula (IV) is formed, and the desired product is separated from the resulting hydrogen halide after work-up procedures well known in the art. The formation of the thiol-functional intermediate may result in the simultaneous formation of oligomeric species, which may optionally be present in combination with the (meth) acrylate-functional monomer represented by formula (IV).
During the formation of some (meth) acrylate functional monomers represented by formula (IV), the formation of thiol functional intermediates as previously described herein can be carried out in the presence of a free radical initiator. The free radical initiator may be selected from compounds well known in the art. Non-limiting examples of free radical initiators include, but are not limited to, azo or peroxide type free radical initiators, such as azobisalkane nitriles. The free radical initiator may be selected from azobisalkane nitriles, which may be available from DuPont under the tradename VAZO. Examples of VAZO initiators that may be used include, but are not limited to, VAZO-52, VAZO-64, VAZO-67, VAZO-88 initiators, and mixtures thereof. The preparation of thiol-functional intermediates is described in further detail in U.S. Pat. No.7,888,436B2, column 8, lines 3-53, the disclosure of which is incorporated herein by reference.
For some embodiments of the present invention, the polymerizable composition comprising at least one (meth) acrylate functional monomer represented by formula (IV) may further comprise at least one monomer selected from the group consisting of monomers represented by formula (I), formula (II), formula (III), and combinations of two or more thereof. For some embodiments, when the polymerizable composition consists of (meth) acrylate monomers represented by formula (IV) and at least one additional monomer represented by formula (I), (II), and/or (III), the (meth) acrylate monomers represented by formula (IV) are present in an amount of 1 to 99 weight percent, alternatively 25 to 95 weight percent, alternatively 50 to 90 weight percent, and the total amount of further monomers represented by formula (I), (II), and/or (III) is present in an amount of 1 to 99 weight percent, alternatively 5 to 75 weight percent, alternatively 10 to 50 weight percent, the weight percentages being based in each case on the total weight of the recited monomers.
According to some non-limiting embodiments, the polymerizable composition of the present invention comprises a (meth) acrylate monomer represented by formula (IV) and a (meth) acrylate monomer represented by formula (I), wherein L of the (meth) acrylate monomer represented by formula (I)1Free of substitution with a group represented by the following formula (M):
reference formula (M), Z, R12And w are each as previously described herein for formula (IV).
In a particular embodiment, the present invention relates to a polymerizable composition comprising:
(a) at least one thio (meth) acrylate functional monomer of the formula (IIg),
wherein the content of the first and second substances,
L8is a divalent linking group selected from the group consisting of,
(i) a divalent linking group represented by the following formula (D),
-C(R6)(R7)-
(D)
wherein R is6And R7Each independently selected from hydrogen, optionally substituted straight or branched C1-C10Alkyl, optionally substituted C3-C12Cycloalkyl, and optionally substituted aryl, or R6And R7Together form C4-C12Optionally substituted cycloalkyl, and
(ii) a divalent linking group represented by the following formula (A),
wherein Y is O or S, and
R2independently for each p is selected from optionally substituted divalent straight or branched C1-C10Alkyl, and/or optionally substituted divalent C3-C12A cycloalkyl group,
each R is3Independently selected from optionally substituted divalent linear or branched C1-C10Alkyl, and/or optionally substituted divalent C3-C12Cycloalkyl radicals, each p being from 0 to 10,
each R is8Independently selected from hydrogen and methyl; and
(b) optionally a polymerization moderator.
The monomers of the compositions of the present invention, for example, the monomers represented by formulas (I), (II), (III) and (IV), can be prepared from polythiols having two or more thiol groups as described previously herein. Examples of polythiols that can be used to prepare the polymerizable compositions of the present invention include, but are not limited to, monomers and related monomers represented by formula (I), formula (II), formula (III), formula (IV), including, but not limited to, 1, 2-ethanedithiol, 2,2' -thiodiethanethiol, 2, 5-dimercaptomethyl-1, 4-dithiane, 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), tetrakis (7-mercapto-2, 5-dithiaheptyl) methane, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), 4-mercaptomethyl-3, 6-dithia-1, 8-octane dithiol, 4-tert-butyl-1, 2-benzenedithiol, 4,4' -thiodithiol, benzenedithiol, ethylene glycol di (2-mercaptoacetate), ethylene glycol di (3-mercaptopropionate), poly (ethylene glycol) di (2-mercaptoacetate), poly (ethylene glycol) di (3-mercaptopropionate), polythiol monomers represented by the following formula (K),
reference formula (K), R11And R12Each independently as herein before referred to formula L1(a) Described herein. Polythiols represented by formula (K) are suspected to be prepared by esterification or transesterification reactions well known in the art, for example, between 3-mercapto-1, 2-propanediol (CAS registry number 96-27-5) and a thiol-functional carboxylic acid or thiol-functional carboxylate in the presence of a strong acid catalyst, such as methanesulfonic acid, while removing water or alcohol from the reaction mixture. The polythiol represented by formula (K) optionally further comprises by-products, such as oligomers that can optionally include disulfide (-S-S-) linkages, resulting from the synthesis of the polythiol.
A non-limiting example of another dithiol that may be used to prepare the monomers of the compositions of the present invention is represented by the following formula (N-1).
Reference formula (N-1), R2、R3And p are each independently as described herein before for formula (B). With further reference to the formula (N-1), L8As described herein before for formulae (G-1), (G-2) and (G-3).
For some embodiments, and as described herein before for formulas (G-1), (G-2), and (G-3), L8Is the residue of an optionally substituted hydrocarbyl group having two non-conjugated carbon-carbon double bonds, such as vinyl-cyclohexene. For some embodiments, of the polymerizable compositions of the present inventionThe monomer can be prepared using a dithiol represented by the following formula (N-2).
Reference formula (N-1), R2、R3And p are each independently as described herein before with reference to formula (B). For some embodiments, the two groups of formula (N-2) that are bonded to the cyclohexane ring are ortho, meta, or para with respect to each other and are not bonded to the same carbon of the cyclohexane ring.
In some particular embodiments of the invention, L of formula (I)2L of the formula (IV)7R of formula (Id)3R of formula (1a)4/R5And L of the formula (Ic)2Each being a divalent hydrocarbon radical containing one carbon atom, e.g. CH2-, -CH (R) -, or C (R)1)(R2) -, each of which R, R1And R2Independently represents an optionally substituted hydrocarbon group. For example, wherein L of formula (I)2Is CH2The monomers of (a) can be prepared by reacting 1 molar equivalent of a thiol with 1 molar equivalent of formaldehyde (e.g., paraformaldehyde) to give an intermediate containing a terminal thio hemiacetal group. The OH-terminated molecule can then be esterified with (meth) acrylic acid by reaction with (meth) acryloyl chloride or (meth) acrylic anhydride; direct esterification with (meth) acrylic acid; or by transesterification with an alkyl (meth) acrylate, such as methyl (meth) acrylate. Alternatively, the thiol may be treated with a substituted aldehyde (HC (= O) R) instead of formaldehyde. For example, when a thiol is reacted with benzaldehyde, L2Will represent CH (R) -, wherein R is phenyl.
In a further embodiment of the invention, L of the formula (I)2L of the formula (IV)7And R of formula (Id)3Each of which may be an optionally substituted divalent hydrocarbyl group, wherein the optional substitution is an aryl group, for example a phenyl group. For example, L of the formula (I)2May be CH2CH (R) -or CH (R) -CH2-, wherein R represents a phenyl groupAnd (4) clustering. The reaction product may be derived from the reaction of 1 molar equivalent of a thiol with 1 molar equivalent of styrene oxide (by ring opening of the epoxide ring) to form a polyhydroxy-terminated sulfur-containing material having an aromatic ring, followed by reaction of the terminal OH groups with (meth) acryloyl chloride or (meth) acrylic anhydride, by direct esterification of (meth) acrylic acid, or by transesterification with alkyl (meth) acrylates to form (meth) acrylate end groups.
Any of the polymerizable compositions of the present invention optionally can include one or more monomers having a single ethylenically unsaturated free-radically polymerizable group. Examples of monomers having a single ethylenically unsaturated free radically polymerizable group that may optionally be present in the polymerizable compositions of the present invention include, but are not limited to: acrylic acid; methacrylic acid; esters of acrylic acid such as methyl or ethyl acrylate, and 2-hydroxyethyl acrylate; esters of methacrylic acid, such as methyl or ethyl methacrylate, phenoxyethyl methacrylate, norbornyl methacrylate, cyclohexyl methacrylate and 2-hydroxyethyl methacrylate; allyl esters, for example, allyl benzoate; allyl carbonates, for example, phenylallyl carbonate; vinyl esters such as vinyl acetate; styrene; and vinyl chloride; ethylenically unsaturated carboxylic acid anhydrides, such as maleic anhydride, citraconic anhydride, and itaconic anhydride. More specifically, for example, the monoethylenically unsaturated monomers may include methyl methacrylate, methacrylic acid, maleic anhydride, phenoxyethyl methacrylate, styrene, and mixtures thereof. The monoethylenically unsaturated monomers, when used, are typically present in an amount of from 0.1% to 60% by weight, based on the total monomer weight of the polymerizable composition, for example from 1% to 55% by weight, or from 3% to 45% by weight, based on the total monomer weight of the polymerizable composition. The effect of the starting materials on the refractive index and other properties of the final polymer takes into account the amounts used, either alone or in combination.
For some embodiments, the polymerizable compositions of the present invention may further comprise a polymerization moderator. The presence of a polymerization moderator can minimize the formation of any distortion or defects, e.g., striations and/or cracks/crazes, in the polymerization product obtainable from the polymerizable composition of the present invention. Examples of polymerization moderators that may be included in the polymerizable compositions of the present invention include, but are not limited to, dilauryl thiodipropionate, 1-isopropyl-4-methyl-1, 4-cyclohexadiene (γ -terpinene); 1-isopropyl-4-methyl-1, 3-cyclohexadiene (α -terpinene); 1-methyl-4- (prop-2-ylidene) cyclohex-1-ene (terpinolene); and α -methylstyrene dimer, 1, 1-diphenylethylene, cis-1, 2-diphenylethylene, 3,7, 7-trimethylbicyclo [4.1.0] hept-3-ene (3-carene), 4-isopropenyl-1-methylcyclohexene (dipentene), (S) - (-) -4-isopropenyl-1-methylcyclohexene ((S) -limonene), 2, 6-dimethyl-2, 4, 6-octatriene, 4-tert-butylcatechol, triphenylmethane, and mixtures of two or more thereof.
For some embodiments, the polymerization moderator is selected from 1-isopropyl-4-methyl-1, 4-cyclohexadiene; 1-isopropyl-4-methyl-1, 3-cyclohexadiene; 1-methyl-4- (prop-2-ylidene) cyclohex-1-ene; 2, 6-dimethyl-2, 4, 6-octatriene, and α -methylstyrene dimer.
The term "alpha-methylstyrene dimer" as used herein refers to a polymerization moderator comprising at least one of 2, 4-diphenyl-4-methyl-1-pentene, and optionally 2, 4-diphenyl-4-methyl-2-pentene and/or 2-phenyl-1-propene (also referred to as alpha-methylstyrene). For some embodiments, the alpha-methylstyrene dimer polymerization moderator comprises from 90 to 93 weight percent 2, 4-diphenyl-4-methyl-1-pentene, from 6 to 8 weight percent 2, 4-diphenyl-4-methyl-2-pentene, and from 0.25 to 0.75 weight percent 2-phenyl-1-propene, the weight percentages being based in each case on the total weight of the alpha-methylstyrene dimer.
The polymerization moderator may be present in the polymerizable composition of the present invention in a wide range of amounts. In some embodiments, the polymerization moderator is present in the polymerizable composition of the present invention in an amount of from 0.01 weight percent to 15 weight percent, alternatively from 0.1 weight percent to 8 weight percent, alternatively from 0.3 weight percent to 5 weight percent, based on the total weight of the monomers and the polymerization moderator.
For some embodiments, the polymerizable composition of the present invention may further comprise an initiator that is capable of initiating free radical polymerization of ethylenically unsaturated groups of the monomers therein. For some embodiments, the polymerizable compositions of the present invention include a free radical initiator that is thermally activated. By "thermally activated" is meant that the free radical initiator is activated at elevated temperatures, e.g., above ambient room temperature, e.g., above 25 ℃, as will be described in further detail herein.
For some embodiments, the thermally activated free radical initiator may be selected from the group consisting of organic peroxy compounds, azobis (organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations of two or more thereof.
For some embodiments, the thermally activated free radical initiator is selected from one or more organic peroxy compounds. Examples of organic peroxy compounds that can be used as thermal polymerization initiators include, but are not limited to: peroxy monocarbonates, such as tert-butyl peroxy-2-ethylhexyl carbonate and tert-butyl peroxy-isopropyl carbonate; peroxy ketals, such as 1, 1-di- (tert-butylperoxy) -3,3, 5-trimethylcyclohexane; peroxy dicarbonates, such as di (2-ethylhexyl) peroxy dicarbonate, di (sec-butyl) peroxy dicarbonate and diisopropyl peroxy dicarbonate; diacyl peroxides, such as 2, 4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauryl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide; peroxy esters, such as tert-butyl peroxypivalate, tert-butyl peroxyoctoate, and tert-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, and acetyl cyclohexane sulfonyl peroxide.
For some embodiments, further examples of peroxy compounds from which the free radical initiator may be selected include, but are not limited to, 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxy) hexane, and/or 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane.
Examples of azobis (organonitrile) compounds that may be used as thermal polymerization initiators in the polymerizable compositions of the present invention include, but are not limited to, azobis (isobutyronitrile), 2,2' -azobis (2-methyl-butyronitrile), and/or azobis (2, 4-dimethylvaleronitrile).
For some further embodiments of the present invention, the thermally activated free radical initiator is selected from 1-acetoxy-2, 2,6, 6-tetramethylpiperidine, and/or 1, 3-dicyclohexyl-O- (N-cyclohexylideneamino) -isourea.
The amount of thermal polymerization initiator used to initiate and polymerize the polymerizable composition of the present invention can vary, and can depend at least in part on the particular initiator or initiators used. For some embodiments, only the amount of initiation and maintenance of the polymerization reaction is required, which may also be referred to as the initiation amount. For some embodiments, the thermally activated free radical initiator is present in an amount of from 0.01 to 7 parts initiator, alternatively from 0.1 to 3.5 parts initiator, alternatively from 0.5 to 2.5 parts initiator, in each case parts initiator per 100 parts monomer (phm) present in the polymerizable composition.
For some embodiments, the thermal cure cycle for curing the polymerizable composition of the present invention comprises heating the polymerizable composition in the presence of an initiator from room temperature to at most 50 ℃ to 150 ℃ for 2 hours to 48 hours, or from 30 ℃ to at most 90 ℃ or 100 ℃ for 12 to 24 hours, or from 65 ℃ to at most 115 ℃ or 125 ℃ for 12 to 24 hours.
The polymerization of the polymerizable composition of the present invention results in the formation of a polymeric product, which may be in the form of a shaped article. The polymerization product obtained from the polymerization of the polymerizable composition of the present invention is a solid and, for some embodiments, transparent. The clear polymeric products prepared from the polymerizable compositions of the present invention may be used in optical or ophthalmic applications.
For some embodiments, the polymerizable compositions of the present inventionThe composition produces a polymerization product having a refractive index of at least 1.57, alternatively at least 1.58, alternatively at least 1.59; an ABBE value of at least 30, alternatively at least 33, alternatively at least 35; and a Fischer microhardness value of at least 50N/mm2Or at least 70N/mm2Or at least 90N/mm2. For some embodiments, the initial (zero second) Barcol hardness of the polymerization product prepared from the polymerizable composition of the invention is at least 1, alternatively at least 10, alternatively at least 20. The refractive index, ABBE value, and fischer hardness value can be determined according to methods well known in the art. For some embodiments: refractive index value (n)e20) And ABBE values were determined using Metricon2010 prism coupler, film thickness/refractive index measurement system according to manufacturer's service guidelines; the fischer hardness values were determined according to ISO14577 using a fischer technologies h100C micro hardness measurement system.
The polymerization products prepared from the polymerizable compositions of the present invention can be used to form solid articles, such as optical elements or devices. The term "optical" as used herein refers to reference to or association with light and/or vision. For example, optical components or devices may include ophthalmic components and devices, display components and devices, windows, mirrors, and/or active and passive liquid crystal cell components and devices. The term "ophthalmic" as used herein means relating to or relating to the eye and vision. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including mono-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses) and other elements for correcting, protecting, or enhancing (cosmetically or otherwise) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles. The term "display" as used herein refers to a visual or machine-readable rendition of information in words, numbers, symbols, designs, or views. Non-limiting examples of display elements and devices include screens, monitors, and security elements, such as security markers. The term "window" as used herein means an opening adapted to allow radiation to pass therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, grids, and optical switches. The term "mirror" as used herein means a surface that specularly reflects a substantial portion of incident light.
The aforementioned optical element or device may further comprise a polarizer, for example, a linear polarizer, a circular polarizer, or an elliptical polarizer. Suitable polarizers are known in the art. For example, the polarizer may be linearly polarizing, and may be in the form of a coating, film, or wafer. The polarizing coating may comprise dichroic materials (including photochromic-dichroic materials) as described herein below, and may be oriented in one or more directions as described below. Further, the polarizer may be in the form of a film comprising a polymer component and a dichroic material that is oriented in the direction in which the film is oriented. Polarizing discs typically have a polarizer (in the form of a polymer film or coating) sandwiched by two layers of transparent optical polymer material.
For example, the polarizer may comprise a polymeric component comprising poly (vinyl alcohol), poly (vinyl butyral), polyethylene terephthalate, cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, polyurethane, polyether, polyester, polyamide, polyalkyl (meth) acrylate, mixtures thereof, and/or copolymers thereof.
In addition, the polarizer may comprise a linear polarizing film, including optical films, comprising a dispersed phase of polymer particles disposed within a continuous birefringent matrix, which may be oriented in one or more directions. The size and shape of the disperse phase particles, the volume fraction of the disperse phase, the film thickness, and the amount of orientation are selected to achieve a desired degree of diffuse reflection and total transmission of radiation of a desired wavelength in the film. Such membranes and their preparation are described in U.S.5,867,316 at column 6, line 47-column 20, line 51, the cited portions of which are incorporated herein by reference. The polarizer, when linearly polarizing, may also comprise a birefringent multilayer optical film, which is described in U.S.5,882,774 column 2, line 63-column 18, line 31, the cited section of which is incorporated herein by reference. In addition, the polarizer may also comprise a bi-component polarizer (i.e., dichroic and reflective polarizing components), such as described in U.S.6,096,375 column 3, line 7-column 19, line 46, the cited portions of which are incorporated herein by reference.
Further, the polarizer may be linearly polarized, and may include the following alignment films: polyvinyl alcohol, vinyl butyral, polyethylene terephthalate, polyalkyl (meth) acrylates, polyamides, poly (amide-ether) block copolymers, poly (ester-ether) block copolymers, poly (ether-urethane) block copolymers, poly (ester-urethane) block copolymers, and/or poly (ether-urea) block copolymers. The term "oriented film" as used with respect to a linear polarizer means that the film has at least a first general direction (oriented) such that one or more other structures or components comprising the sheet are positioned or suitably arranged along the same general direction. For example, the orientation or ordering of the dichroic compound along the long axis of the dichroic compound is at least parallel to at least the first general direction of the film or layer. As used herein with respect to the order or orientation of materials or structures, the term "general direction" refers to the predominant arrangement or orientation of materials, compounds, or structures. Further, those skilled in the art will appreciate that even though there may be some variation in the arrangement of materials, compounds or structures, the materials, compounds or structures may have a general orientation, provided that the materials, compounds or structures have at least one primary arrangement.
Suitable polarizers may also include "K-type" polarizers in which the dichroic material is prepared by, for example, dehydration of poly (vinyl alcohol). Such polarizers are often referred to as natural polarizers because the light absorbing chromophores are due to conjugation in the polymer backbone and not from dichroic materials (e.g., dichroic dyes) that incorporate a polymer component. Such K-type polarizers may comprise an oriented film of poly (vinyl alcohol) having light polarizing (dichroic) molecules comprising conjugated blocks, such as poly (vinylidene) blocks (i.e., - [ CH = CH-]n) By heating in the presence of a dehydration catalyst, e.g. steam of aqueous hydrochloric acidOriented poly (vinyl alcohol) film. The K-type polarizer may also be formed by: attaching an acid donor layer comprising a photoacid generator to the oriented poly (vinyl alcohol) film, and exposing to radiant energy at a temperature sufficient to effect partial dehydration of the vinyl alcohol polymer to the vinyl alcohol/poly (vinylidene) copolymer. See, for example, U.S.6,808,657.
As previously mentioned, the polarizer may comprise a dichroic material. Non-limiting examples of suitable dichroic materials may include, but are not limited to, compounds such as azomethine, indigoids, thioindigoids, merocyanines, indanes, quinophthalone dyes, perylenes, phthalimidines, triphenodioxazines, indoloquinoxalines, imidazo-triazines, tetrazines, azo and (poly) azo dyes, benzoquinones, naphthoquinones, anthraquinones and (poly) anthraquinones, anthrapyrimidinones, iodine and iodates. The term "compound" as used herein refers to a substance formed by combining two or more elements, components, ingredients, or parts, including but not limited to molecules and macromolecules (e.g., polymers and oligomers) formed by combining two or more elements, components, ingredients, or parts.
The dichroic material may also include a polymerizable dichroic compound. That is, the dichroic material may include at least one polymerizable group (i.e., "polymerizable group"). For example, although not limited thereto, in one non-limiting embodiment, the dichroic compound can have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent terminating with at least one polymerizable group.
The dichroic material may also comprise a photochromic-dichroic compound. The term "photochromic-dichroic" refers to a material that exhibits photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least detectable by an instrument. Thus, a "photochromic-dichroic compound" is a compound that exhibits photochromic and dichroic (i.e., linearly polarizing) properties under certain conditions, which properties are at least detectable by an instrument. Thus, a photochromic-dichroic compound has an absorption spectrum for at least visible radiation that changes in response to at least actinic radiation, and is capable of absorbing one of at least two orthogonal plane-polarizing components of transmitted radiation more strongly than the other (i.e., is capable of exhibiting dichroism). Further, the photochromic-dichroic compounds disclosed herein can be thermally reversible with respect to conventional photochromic compounds discussed herein below. That is, the photochromic-dichroic compound can switch from a first state to a second state in response to actinic radiation and convert back to the first state in response to thermal energy.
For example, according to various non-limiting embodiments disclosed herein, the photochromic-dichroic compound can have a first state (which has a first absorption spectrum), a second state (which has a second absorption spectrum different from the first absorption spectrum), and can be adapted to switch from the first state to the second state in response to at least actinic radiation and to revert back to the first state in response to thermal energy. Further, the photochromic-dichroic compound can be dichroic (i.e., linearly polarizing) in one or both of the first and second states. For example, although not required, the photochromic-dichroic compound can be linearly polarizing in the activated state and unpolarized in the bleached or bleached (i.e., unactivated) state. As used herein, the term "activated state" refers to the photochromic-dichroic compound causing at least a portion of the photochromic-dichroic compound to switch from a first state to a second state when exposed to sufficient actinic radiation. Further, although not required, the photochromic-dichroic compound can be dichroic in both the first and second states. Although not limited thereto, for example, the photochromic-dichroic compound can linearly polarize visible light in both the activated state and the bleached state. Further, the photochromic-dichroic compound can linearly polarize visible light in an activated state, and can linearly polarize UV radiation in a bleached state.
Examples of photochromic-dichroic compounds suitable for use in the present invention can include, but are not limited to, those described in detail in U.S. patent application publication No.2005/0012998a1, paragraphs [0089] - [0339], the disclosure of which is incorporated herein by reference.
As previously described, the polarizer may comprise an oriented polymer film. The polymer components and dichroic materials (including the dichroic-photochromic materials described above), as well as any other components that may be included, used to prepare the polymer film may be blended together and then subjected to any of a variety of processing techniques known in the art to form a film. The techniques may include, for example, extrusion, solvent casting, calendering, blow molding, or a combination of these techniques. Alternatively, the compositions used to prepare the polymer components can be blended together and then subjected to any of a variety of processing techniques known in the art to form a film. Once the film is formed, a solution comprising the dichroic material may be added to the film, for example by suction methods well known in the art, and the sucked film may then be oriented to orient the dichroic material.
The film may be secured in an oriented configuration in any of a variety of securing means known in the art. For example, a film oriented by stretching may be secured in an oriented configuration by mechanical securing means (e.g., by using a clamp) to prevent the sheet from returning to the pre-stretched configuration. Other means may include heat fixing or heat tempering, i.e. fixing the oriented film by heating. When the film is prepared from reactive (e.g., crosslinkable) polymer components, the film may be formed, for example, by extrusion or solvent casting, such that the components do not react. Once formed, the film can be oriented and then fixed in the oriented configuration by reacting (e.g., crosslinking, including self-crosslinking) the polymer components. For example, such crosslinking may be carried out by subjecting the oriented film to conditions that promote reaction of functional groups of any of the polymer components, e.g., subjecting the oriented sheet to heat or radiation, including actinic (ultraviolet) and/or ionizing (electron beam) radiation.
Additionally or alternatively, the polymerization products prepared from the polymerizable compositions of the present invention can be used to prepare photochromic articles, including, but not limited to, photochromic lenses. When used to prepare photochromic articles, such as photochromic lenses, the polymerized product should be transparent to the portion of the electromagnetic spectrum that activates the photochromic substance incorporated in the matrix. More specifically, the polymerization product should be transparent to the wavelength of Ultraviolet (UV) light that produces the colored or open form of the photochromic substance and to the portion of the visible spectrum that includes the wavelength of maximum absorption of the photochromic substance in its UV activated form (or open form). Photochromic substances that can be used in the polymeric products of the present invention include, but are not limited to, organic photochromic compounds or substances containing compounds that can: (a) incorporation (e.g., dissolution, dispersion, or diffusion) into the polymerization product; or (b) adding the polymerizable composition prior to polymerization.
The present invention also relates to a photochromic article comprising: (a) the polymerization product of one or more of the polymerizable compositions of the present invention; and (b) a photochromic amount of an organic photochromic material.
Examples of classes of organic photochromic materials that may be included in the photochromic articles of the present invention include, but are not limited to, spiro (indoline) naphthoxazines, spiro (indoline) benzoxazines, benzopyrans, naphthopyrans, chromenes, organometallic bis-thionates (dithizonates), fulgides and fulgimides and mixtures or combinations of two or more thereof.
A first class of organic photochromic substances contemplated for use in forming the photochromic articles of the present invention are those having a maximum activated absorbance in the visible range of greater than 590 nanometers, for example, greater than 590 to 700 nanometers. These materials typically exhibit a blue, blue-green, or blue-violet color when exposed to ultraviolet light in a suitable solvent or matrix. Examples of such materials useful in the present invention include, but are not limited to, spiro (indoline) naphthooxazines and spiro (indoline) benzoxazines. These and other classes of such photochromic substances are described in the open literature. See, for example, U.S. patents: 3,562,172, respectively; 3,578,602, respectively; 4,215,010, respectively; 4,342,668, respectively; 5,405,958, respectively; 4,637,698, respectively; 4,931,219, respectively; 4,816,584, respectively; 4,880,667, respectively; 4,818,096. See also, for example: japanese patent publication 62/195383; and textbooks technical quesienchemistry, volume iii, "photochromym," Chapter3, glenn h.brown, Editor, john wileyandsons, inc., new york, 1971.
A second class of organic photochromic substances contemplated for use in forming the photochromic articles of the present invention are those having at least one and preferably two absorbance maximums in the visible range of 400 to less than 500 nanometers. These materials typically exhibit an orange-yellow color when exposed to ultraviolet light in a suitable solvent or matrix. Such compounds include certain chromenes, such as benzopyrans and naphthopyrans. Examples of such chromenes are described in the following non-limiting list of U.S. patents: 3,567,605, respectively; 4,826,977, respectively; 5,066,818, respectively; 4,826,977, respectively; 5,066,818, respectively; 5,466,398, respectively; 5,384,077, respectively; 5,238,931, respectively; and 5,274,132.
A third class of organic photochromic substances contemplated for use in forming the photochromic articles of the present invention are those having a maximum absorbance in the visible range of 400-500 nanometers and another maximum absorbance in the visible range of 500-700 nanometers. These materials typically exhibit a yellow/brown to violet/gray color when exposed to ultraviolet light in a suitable solvent or matrix. Examples of such materials include, but are not limited to, certain benzopyran compounds, which have a substituent at the 2-position of the pyran ring, and substituted or unsubstituted heterocycles, such as a benzothiophene or benzofuran ring fused to the benzene portion of the benzopyran. Such materials are described in U.S. Pat. No.5,429,774.
Other photochromic substances that are contemplated are photochromic organometallic bis-thionates, such as (arylazo) -thioformic arylhydrazide salts, including, for example, mercury bis-thionates, which are described, for example, in U.S. Pat. No.3,361,706. Fulgides and fulgimides, such as 3-furyl and 3-thienyl fulgides and fulgimides, are described in U.S. Pat. No.4,931,220 at column 20, line 5 through column 21, line 38.
The disclosures in the above patents relating to such photochromic substances are hereby incorporated by reference in their entirety in each case. The photochromic articles of the present invention can contain one photochromic substance or a mixture of two or more photochromic substances as desired. Mixtures of photochromic substances can be used to achieve certain activated colors, such as, but not limited to, near neutral gray or brown.
The various photochromic substances described herein can be used in amounts and proportions (when mixtures are used) such that the polymerization product to which the compound mixture is applied or incorporated exhibits a desired resulting color, e.g., a substantially neutral color, such as a gray or brown shade, when activated with unfiltered sunlight. For some embodiments, the color of the activated photochromic substance may be used to obtain a near neutral color or a neutral color. The relative amounts of the aforementioned photochromic substances used can vary and depend in part on the relative color intensities of the activating substances of the compounds and the desired final color.
The photochromic compounds or materials described herein can be applied to or incorporated into the polymerizate by various methods described in the prior art. The method includes, but is not limited to, dissolving or dispersing the material within the polymerization product, such as: sucking the photochromic substance into the polymerized product by soaking the polymerized product in a hot solution of the photochromic substance or by heat transfer; providing a photochromic substance as a separate layer between adjacent layers of a polymeric product (e.g., a polymeric film or a portion of a polymeric layer); and applying the photochromic substance as a coating or polymer layer disposed on the surface of the polymerized product. The term "suction" or "sucking" refers to penetration of the photochromic substance or substances into the polymerization product only, solvent assisted transfer absorption of the photochromic substance to the porous polymer, vapor phase transfer, and other such transfer mechanisms.
The amount of photochromic substance or combination containing photochromic substance applied to or incorporated into the polymerization product is not critical, provided that a sufficient amount is used to produce a photochromic effect that is discernible to the naked eye after activation. Generally, such an amount may be described as a photochromic amount. The particular amount used will generally depend on the desired color intensity after irradiation thereof and after the method used to add or apply the photochromic substance. Typically, the more photochromic substance applied or added, the higher the color intensity. For some embodiments, the total amount of photochromic substance added or applied to the photochromic optical polymerizate can range from 0.15 to 0.35 milligrams per square centimeter of surface to which the photochromic substance is added or applied.
It is also to be appreciated that photochromic substances can be incorporated into the polymerizable compositions of the present invention prior to curing. However, when so doing, it is preferred that the photochromic substance be resistant to potentially adverse interactions with initiators that may be present and/or thioether linkages within the monomers forming the polymerization product. Such adverse interactions can lead to deactivation of the photochromic substances, for example by putting them into an open or closed form. Organic photochromic substances that are sufficiently encapsulated within the matrix of the organic polymeric product as described in U.S. Pat. No.4,931,220 can also be incorporated into the polymerizable compositions of the present invention prior to curing.