Disclosure of Invention
The acrylic ester copolymer can enable the pressure-sensitive adhesive tape to have higher shearing resistance and easy stripping property after illumination, and meanwhile, enable the pressure-sensitive adhesive tape to have hydrophobicity and high chemical corrosion resistance, further improve the performance and service life of the pressure-sensitive adhesive tape, and meet the use requirements of the pressure-sensitive adhesive tape in chemical mechanical polishing.
In order to achieve the above object, a first aspect of the present disclosure provides an acrylate copolymer comprising an azobenzene acrylate monomer repeating unit having a structure as shown below,
,
Wherein R1 is H or methyl, R2 is C2~12 alkyl, R3 is C2~16 fluoroalkyl, and n is any integer from 1 to 3.
Optionally, R2 is a C2~10 linear alkyl group, preferably one or more of n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-heptyl and n-decyl, and/or,
R3 is a perfluoroalkyl group of C2~12, preferably R3 is a perfluoroalkyl group of C2、C4、C6、C8、C10 or C12.
Optionally, the acrylate copolymer further comprises acrylate soft monomer repeat units, acrylate hard monomer repeat units, carboxy acrylic acid monomer repeat units, and hydroxy acrylate monomer repeat units;
The acrylate hard monomer comprises, by weight, 5-60 parts of acrylate hard monomer repeating units, 1-20 parts of carboxyl acrylic acid monomer repeating units, 1-30 parts of hydroxyl acrylate monomer repeating units and 5-50 parts of azobenzene acrylate monomer repeating units, relative to 100 parts of acrylate soft monomer repeating units.
Optionally, the content of the acrylate hard monomer repeating unit is 10-40 parts by weight, the content of the carboxyl acrylic acid monomer repeating unit is 1-10 parts by weight, the content of the hydroxy acrylic acid monomer repeating unit is 3-15 parts by weight, and the content of the azobenzene acrylic acid ester monomer repeating unit is 15-30 parts by weight relative to 100 parts by weight of the acrylate soft monomer repeating unit.
Optionally, the acrylate soft monomer repeat units are derived from an acrylate soft monomer selected from one or more of ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isooctyl acrylate, and lauryl methacrylate;
the acrylate hard monomer repeating unit is derived from an acrylate hard monomer, and the acrylate hard monomer is selected from one or more of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate;
The hydroxy acrylate monomer repeating unit is derived from a hydroxy acrylate monomer, the hydroxy acrylate monomer is a hydroxy acrylate monomer with hydroxyl functionality of 1, preferably, the hydroxy acrylate monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
The carboxylic acrylate monomer repeat units are derived from a carboxylic acrylate monomer which is a carboxylic acrylate monomer having a carboxyl functionality of 1, preferably the carboxylic acrylic monomer is selected from acrylic acid and/or methacrylic acid.
Alternatively, the acrylate copolymer has a glass transition temperature of-45 to-20 ℃.
A second aspect of the present disclosure provides a method of preparing a pressure-sensitive adhesive tape, the method comprising:
The acrylic copolymer, the tackifying resin, the curing agent and the fourth organic solvent are mixed to obtain a sizing material, and the sizing material is coated on a substrate and then is cured.
Optionally, the method further comprises the step of compounding the cured adhesive layer with release paper;
Optionally, the thickness of the release paper is 0.10-0.18 mm;
the curing treatment conditions comprise that the temperature of the curing treatment is 50-100 ℃ and the time of the curing treatment is 1-5h.
Optionally, the content of the tackifying resin is 5-30 parts by weight, the content of the curing agent is 0.5-3 parts by weight, and the content of the fourth organic solvent is 20-100 parts by weight relative to 100 parts by weight of the acrylic copolymer, wherein the method satisfies one of the following conditions:
(a) The fourth organic solvent is selected from ethyl acetate and/or toluene;
(b) The tackifying resin is selected from one or more of rosin resin, rosin resin derivative, terpene resin, terpene phenolic resin, styrene terpene resin, C5 petroleum resin and C9 petroleum resin;
(c) The curing agent is isocyanate curing agent with isocyanate functionality of more than 2, and is selected from one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate and isophorone diisocyanate;
(d) The solid content of the sizing material is 20-50wt%, and the viscosity of the sizing material at 25 ℃ is 500-4000 cP;
(e) The base material comprises polyethylene terephthalate and/or polypropylene, preferably polyethylene terephthalate, and the thickness of the base material is 0.01-0.1 mm.
A third aspect of the present disclosure provides a pressure-sensitive adhesive tape prepared by the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides a use of the pressure-sensitive adhesive tape of the third aspect of the present disclosure in chemical mechanical polishing.
Through the technical scheme, the acrylic ester copolymer disclosed by the invention comprises the repeated units of the azobenzene acrylic ester monomer, the azobenzene acrylic ester monomer comprises the acrylic ester group which is easy to polymerize and the flexible alkyl, and when the polymer is formed, the azobenzene group is more easy to generate isomerization conversion on the side chain of the polymer, and when the polymer is used for preparing the pressure-sensitive adhesive tape, the pressure-sensitive adhesive tape can have higher shearing resistance and easy stripping property after illumination. In addition, the tail group of the azo-benzene acrylate monomer repeating unit of the acrylate copolymer disclosed by the invention comprises a fluorine-containing alkyl chain, and the pressure-sensitive adhesive tape prepared by using the copolymer has hydrophobicity and high chemical corrosion resistance, so that the performance and the service life of the pressure-sensitive adhesive tape can be further improved, and the use requirement of the pressure-sensitive adhesive tape in a chemical mechanical polishing pad can be met.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides an acrylate copolymer comprising azo-benzene acrylate monomer repeat units having the structure shown below,
,
Wherein R1 is H or methyl, R2 is C2~12 alkyl, R3 is C2~16 fluoroalkyl, and n is any integer from 1 to 3.
The acrylic ester copolymer disclosed by the disclosure comprises an azobenzene acrylic ester monomer repeating unit, the azobenzene acrylic ester monomer comprises an acrylic ester group which is easy to polymerize and a flexible alkyl group, and when the polymer is formed, the azobenzene group is more easy to generate isomerization conversion on a side chain of the polymer, and when the polymer is used for preparing a pressure-sensitive adhesive tape, the pressure-sensitive adhesive tape can have higher shearing resistance and easy stripping property after illumination. In addition, the tail group of the azo-benzene acrylate monomer repeating unit of the acrylate copolymer disclosed by the invention comprises a fluorine-containing alkyl chain, and the pressure-sensitive adhesive tape prepared by using the copolymer has hydrophobicity and high chemical corrosion resistance, so that the performance and the service life of the pressure-sensitive adhesive tape can be further improved, and the use requirement of the pressure-sensitive adhesive tape in a chemical mechanical polishing pad can be met.
In the context of the present disclosure,Representing a chemical bond.
The inventors of the present application found that there are two isomers of azobenzene groups in an azobenzene acrylate monomer, namely, a trans isomer in a rod shape and a cis isomer in a crutch shape. The trans isomer is planar, while the benzene ring of the cis isomer is perpendicular to the C-n=n plane, making the whole molecule a crutch-like structure. The ground state energy level of the trans isomer is 50 kJ/mol lower than that of the cis isomer, and is a thermodynamically stable conformation, so that the trans isomer is more stable than the cis isomer. Aggregates can be formed due to pi-pi stacking effect of azobenzene in trans isomer, and the type of aggregates depends on the transition dipole of coplanar groups and the angle (θ) of the axis direction of the interconnection. H-aggregates can be formed when θ >54.7 ° (critical angle θc), and J-aggregates can be formed when θ <54.7 °. The pressure-sensitive adhesive tape can have stronger shearing resistance by utilizing the strong supermolecular interaction between trans-isomer azobenzene aggregates.
Furthermore, an azobenzene group is an optically active group capable of undergoing trans-cis or cis-trans isomerisation under the action of light or heat. Trans-azobenzene can be converted to the cis-isomer upon light irradiation at a wavelength of about 365 and nm, and the cis-isomer can be converted back to the trans-isomer upon light irradiation at a wavelength of about 530 and nm. The cis-azobenzene cannot form aggregates due to the non-coplanar structure, the intermolecular interaction is weakened, the viscosity of the pressure-sensitive adhesive system is reduced, and the pressure-sensitive adhesive tape can be easily peeled off after ultraviolet irradiation by utilizing the characteristic.
In addition, fluorine atoms have high electronegativity and small atomic radius, and mutual repulsion between adjacent fluorine atoms leads to spiral distribution of fluorine atoms along a carbon chain, so that the fluorine atoms tightly wrap the carbon chain, and other atoms are difficult to embed. Thus, the fluorinated alkyl chain does not react with most of the known strong chemical agents, strong acids and strong bases, and has good chemical resistance. Meanwhile, due to the high electronegativity and small atomic radius of fluorine atoms, the surface energy of the fluorine-containing material is very low, and excellent hydrophobic performance is shown. The inventor of the present application makes the tail group of the azobenzene acrylate monomer be a fluorinated alkyl chain, so that the pressure-sensitive adhesive tape has hydrophobic and chemical corrosion resistant properties.
According to one embodiment of the present disclosure, the R2 is a C2~10 linear alkyl group, preferably one or more of n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-heptyl and n-decyl. According to the embodiment, after the azobenzene acrylate monomer is polymerized, the azobenzene acrylate monomer is easy to generate cis-trans isomer conversion on the side chain of the acrylate copolymer, and the acceptor chain is less constrained, so that the pressure-sensitive adhesive tape has good stripping property.
According to one embodiment of the present disclosure, R3 is a perfluoroalkyl group of C2~12, preferably R3 is a perfluoroalkyl group of C2、C4、C6、C8、C10 or C12. The above embodiments are advantageous for imparting hydrophobic and chemical resistance properties to pressure-sensitive adhesive tapes.
In one embodiment, a method of preparing an azobenzene acrylate monomer includes:
S1, performing a first esterification reaction on fluoroalkyl alcohol and dicarboxylazobenzene to obtain a first fluoro product;
S2, carrying out a second esterification reaction on the first fluoro product and the alkyl glycol to obtain a second product;
s3, carrying out substitution reaction on the second product and acyl chloride;
Wherein the fluoroalkyl alcohol has a structure shown in formula (1), the alkyl glycol has a structure shown in formula (2), the acyl chloride has a structure shown in formula (3), and the dicarboxylazobenzene has a structure shown in formula (4);
,
,
Wherein R1 is H or CH3 alkyl, R2 is C2~12 alkyl, R3 is C2~16 fluoroalkyl, and n is any integer from 1 to 3.
According to one embodiment of the present disclosure, R2 is a straight chain alkyl of C2~10, preferably one or more of n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-heptyl and n-decyl, R3 is a perfluoroalkyl chain of C2~12, preferably R3 is a perfluoroalkyl chain of C2、C4、C6、C8、C10 or C12.
According to one embodiment of the present disclosure, step S1 is performed in a first organic solvent in the presence of a first dehydrating agent and a first catalyst, which may be of a variety well known to those skilled in the art, for example, the first dehydrating agent may be selected from N, N '-dicyclohexylcarbodiimide, the first catalyst may be selected from 6-dimethylaminopurine, and the molar ratio of the dicarboxylazobenzene, the fluoroalkyl alcohol, the N, N' -dicyclohexylcarbodiimide to the 6-dimethylaminopurine is (2 to 15): (1 to 3), and the first organic solvent may include one or more of dichloromethane, acetone, butanone, and N, N-dimethylformamide.
According to one embodiment of the disclosure, the first esterification reaction conditions include a reaction temperature of 20-40 ℃ and a reaction time of 8-24 hours. The embodiment is beneficial to preparing the azobenzene acrylate monomer.
According to one embodiment of the present disclosure, the step S2 is performed in a second organic solvent in the presence of a second dehydrating agent and a second catalyst, which may be of a variety well known to those skilled in the art, for example, the second dehydrating agent may be selected from N, N '-dicyclohexylcarbodiimide, the second catalyst may be selected from 6-dimethylaminopurine, and the molar ratio of the alkyl glycol, the first fluoro product, the N, N' -dicyclohexylcarbodiimide and the 6-dimethylaminopurine is (2 to 15): (1 to 3), and the second organic solvent includes one or more of dichloromethane, acetone, butanone and N, N-dimethylformamide. The embodiment is beneficial to preparing the azobenzene acrylate monomer.
According to one embodiment of the disclosure, the second esterification reaction conditions comprise a reaction temperature of 20-40 ℃ and a reaction time of 8-24 hours. The embodiment is beneficial to preparing the azobenzene acrylate monomer.
According to one embodiment of the disclosure, in the step S3, the molar ratio of the second product to the acyl chloride is 1 (3-5), and the condition of the substitution reaction can comprise that the reaction temperature is 20-40 ℃ and the reaction time is 8-24 h. The substitution reaction of the present disclosure is a conventional art in the art, and the present disclosure is not particularly limited, and includes, for example, contacting the second product with triethylamine in an anhydrous organic solvent, adding acid chloride under ice water bath conditions to perform the substitution reaction, wherein the water content of the anhydrous organic solvent is 100ppm or less, and the temperature of the ice water bath is 0 ℃ or less. The embodiment is beneficial to preparing the azobenzene acrylate monomer.
According to one embodiment of the present disclosure, the acrylate copolymer further comprises one or more of acrylate soft monomer repeat units, acrylate hard monomer repeat units, carboxy acrylic acid monomer repeat units, and hydroxy acrylate monomer repeat units.
According to one embodiment of the disclosure, the acrylate copolymer further comprises an acrylate soft monomer repeating unit, an acrylate hard monomer repeating unit, a carboxyl acrylic acid monomer repeating unit and a hydroxyl acrylate monomer repeating unit, wherein the content of the acrylate hard monomer repeating unit is 5-60 parts by weight, the content of the carboxyl acrylic acid monomer repeating unit is 1-20 parts by weight, the content of the hydroxyl acrylate monomer repeating unit is 1-30 parts by weight, and the content of the azobenzene acrylate monomer repeating unit is 5-50 parts by weight relative to 100 parts by weight of the acrylate soft monomer repeating unit. The embodiment is beneficial to the fact that the prepared acrylic ester copolymer is high in shearing resistance, easy to peel, hydrophobic and chemical corrosion resistance when being used for pressure-sensitive adhesive tapes.
According to one embodiment of the disclosure, the content of the acrylate hard monomer repeating unit is 10-40 parts by weight, the content of the carboxyl acrylic acid monomer repeating unit is 1-10 parts by weight, the content of the hydroxyacrylate monomer repeating unit is 3-15 parts by weight, and the content of the azobenzene acrylate monomer repeating unit is 15-30 parts by weight, relative to 100 parts by weight of the acrylate soft monomer repeating unit. The embodiment is beneficial to the fact that the prepared acrylic ester copolymer is high in shearing resistance, easy to peel, hydrophobic and chemical corrosion resistance when being used for pressure-sensitive adhesive tapes.
According to an embodiment of the present disclosure, the acrylate soft monomer repeating unit is derived from an acrylate soft monomer, which is a conventional type in the art, and the present disclosure is not particularly limited, and for example, may be an acrylate soft monomer having a homopolymer glass transition temperature of 0 ℃ or less, and may be selected from one or more of ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isooctyl acrylate, and lauryl methacrylate. In the present disclosure, when the acrylate soft monomer repeating unit includes a plurality of monomer repeating units, the ratio of each monomer repeating unit is not particularly limited, and one skilled in the art may make the glass transition temperature of the acrylate copolymer within a desired target temperature range according to conventional technical means.
According to one embodiment of the present disclosure, the acrylate hard monomer repeating unit is derived from an acrylate hard monomer, which is a conventional type in the art, and the present disclosure is not particularly limited, and may be, for example, an acrylate hard monomer having a homopolymer glass transition temperature of 25 ℃ or more, and may be selected from one or more of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. In the present disclosure, when the acrylate hard monomer repeating unit includes a plurality of monomer repeating units, the ratio of each monomer repeating unit is not particularly limited, and one skilled in the art may adjust the glass transition temperature of the acrylate copolymer within a desired target temperature range according to conventional technical means.
According to one embodiment of the present disclosure, the hydroxyacrylate monomer repeat unit is derived from a hydroxyacrylate monomer, which may be a hydroxyl-containing acrylate monomer having a hydroxyl functionality of 1, such as may be selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
According to one embodiment of the present disclosure, the carboxylic acrylate monomer repeat units are derived from a carboxylic acrylate monomer, which can be a carboxylic acrylate monomer having a carboxyl functionality of 1, which can be selected from acrylic acid and/or methacrylic acid, for example.
In one embodiment, a method of preparing the acrylate copolymer of the first aspect of the present disclosure comprises polymerizing an acrylate soft monomer, an acrylate hard monomer, a carboxy acrylic acid monomer, a hydroxy acrylate monomer, and an azo-acrylate monomer.
According to one embodiment of the disclosure, the polymerization reaction is performed in a third organic solvent, and the polymerization reaction conditions comprise that the solid content of a polymerization reaction system is 20-50wt% in the presence of an initiator, the polymerization reaction temperature is 50-100 ℃, and the polymerization reaction time is 4-12h. The above embodiment is advantageous in obtaining the acrylic acid ester copolymer.
According to one embodiment of the present disclosure, the content of the initiator is 0.5 to 1 part by weight with respect to 100 parts by weight of the acrylate soft monomer. The initiator may be a radical initiator conventional in the art, and may be one selected from azobisisobutyronitrile, benzoyl peroxide and cumene hydroperoxide. The third organic solvent is a good solvent of various acrylic esters, and can be selected from ethyl acetate and/or toluene.
According to one embodiment of the present disclosure, the acrylate copolymer has a glass transition temperature of-45 to-20 ℃. In the above embodiment, the primary adhesion of the pressure-sensitive adhesive tape can be improved.
A second aspect of the present disclosure provides a method of preparing a pressure-sensitive adhesive tape, the method comprising:
The acrylic copolymer, the tackifying resin, the curing agent and the fourth organic solvent are mixed to obtain a sizing material, and the sizing material is coated on a substrate and then is cured.
According to one embodiment of the present disclosure, the content of the tackifying resin is 5 to 30 parts by weight, the content of the curing agent is 0.5 to 3 parts by weight, and the content of the fourth organic solvent is 20 to 100 parts by weight, relative to 100 parts by weight of the acrylate copolymer, and the fourth organic solvent is selected from ethyl acetate and/or toluene. The embodiment is beneficial to preparing the pressure-sensitive adhesive tape with stronger shearing resistance, easy stripping property, hydrophobicity, oleophobicity and chemical corrosion resistance.
According to one embodiment of the present disclosure, the conditions of the curing process include a temperature of 50-100 ℃ and a time of 1-5 hours. The embodiment is beneficial to preparing the pressure-sensitive adhesive tape with stronger shearing resistance, easy stripping property, hydrophobicity, oleophobicity and chemical corrosion resistance.
According to one embodiment of the present disclosure, the tackifying resin may be selected from one or more of rosin resins, rosin resin derivatives, terpene resins, terpene phenolic resins, styrene terpene resins, C5 petroleum resins, and C9 petroleum resins.
According to an embodiment of the present disclosure, the curing agent may be an isocyanate curing agent having an isocyanate functionality of 2 or more, and may be one or more selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, isophorone diisocyanate.
According to one embodiment of the present disclosure, the solids content of the compound is 20 to 50wt%, and the viscosity of the compound is 500 to 4000cp at 25 ℃.
According to one embodiment of the disclosure, the substrate comprises polyethylene terephthalate and/or polypropylene, preferably polyethylene terephthalate, and the thickness of the substrate is 0.01-0.1 mm.
According to one embodiment of the present disclosure, the method further comprises compounding the cured glue layer with a release paper.
According to one embodiment of the disclosure, the release paper can be selected from one of coated release paper, double-adhesive release paper, yellow silicon paper, white card release paper, embossed silicone paper, kraft silicone paper, writing paper release paper, glassine release paper and CCK release paper, and the thickness of the release paper can be 0.10-0.18 mm.
A third aspect of the present disclosure provides a pressure-sensitive adhesive tape prepared by the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides a use of the pressure-sensitive adhesive tape of the third aspect of the present disclosure in a chemical mechanical polishing pad.
The present disclosure is described in detail below with reference to specific embodiments. The following examples will assist those skilled in the art in further understanding the present disclosure, but are not intended to limit the disclosure in any way.
Unless otherwise indicated, all reagents used in the present disclosure are commercially available. In the examples of the present disclosure, the viscosity of the compounds was tested by a textile Ji Laibo instrument model TR-100 EU-C. The glass transition temperature of the acrylate copolymer was measured by a Differential Scanning Calorimeter (DSC) model Mettler Toledo DSC.
Preparation example 1
S1, respectively weighing fluorinated alkyl alcohol, N '-Dicyclohexylcarbodiimide (DCC) and 6-Dimethylaminopurine (DMAP), dissolving in a dry first organic solvent, adding dicarboxylazobenzene under the condition of ice salt bath, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, adding dichloromethane into filtrate to dilute a reaction system, adding deionized water for washing, and drying an organic phase to obtain a first fluoro product, wherein the mole ratio of dihydroxyazobenzene, fluorinated alkyl alcohol, N' -dicyclohexylcarbodiimide and 6-dimethylaminopurine is 5:1:1, and the first organic solvent is dichloromethane;
S2, respectively weighing alkyl glycol, N '-Dicyclohexylcarbodiimide (DCC) and 6-Dimethylaminopurine (DMAP), dissolving in a dry second organic solvent, adding a first fluoro product under the condition of ice salt bath, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, adding dichloromethane into filtrate to dilute a reaction system, adding deionized water for washing, and drying an organic phase to obtain a second product, wherein the molar ratio of the alkyl glycol to the second product to the N, N' -dicyclohexylcarbodiimide to the 6-dimethylaminopurine is 5:1:1;
S3, dissolving the second product and triethylamine in anhydrous dichloromethane, dropwise adding acyl chloride under the condition of ice water bath, reacting for 24 hours at 25 ℃ after the dropwise adding, collecting an organic phase, drying, and purifying by using silica gel column chromatography to obtain the azobenzene acrylate monomer. The water content of the anhydrous organic solvent is less than 100ppm. The ice water bath condition is that the temperature is below 0 ℃, wherein the molar ratio of the second product to the acyl chloride is 1:2.
In this preparation example, the fluoroalkyl alcohol has a structure as shown in formula (1), R3 is a perfluoroalkyl group of C6, n is 2, the alkyl glycol has a structure as shown in formula (2), R2 is a linear alkyl group of C10, the acyl chloride has a structure as shown in formula (3), R1 is methyl, and the dicarboxylazobenzene has a structure as shown in formula (4);
,
;
The prepared azobenzene acrylate monomer has the structure shown as follows.
,
Wherein R1 is methyl, R2 is C10 linear alkyl, R3 is C6 perfluoroalkyl, and n is 2.
Comparative preparation example 1
S1, respectively weighing straight-chain alkyl alcohol, N '-Dicyclohexylcarbodiimide (DCC) and 6-Dimethylaminopurine (DMAP), dissolving in a dry first organic solvent, adding dicarboxylazobenzene under the condition of ice salt bath, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, adding dichloromethane into filtrate to dilute a reaction system, adding deionized water for washing, and drying an organic phase to obtain a first fluoro product, wherein the mole ratio of dihydroxyazobenzene, straight-chain alkyl alcohol, N' -dicyclohexylcarbodiimide and 6-dimethylaminopurine is 5:1:1;
S2, respectively weighing alkyl glycol, N '-Dicyclohexylcarbodiimide (DCC) and 6-Dimethylaminopurine (DMAP), dissolving in a dry second organic solvent, adding a first fluoro product under the condition of ice salt bath, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, adding dichloromethane into filtrate to dilute a reaction system, adding deionized water for washing, and drying an organic phase to obtain a second product, wherein the molar ratio of the second product to the alkyl glycol to the N, N' -dicyclohexylcarbodiimide to the 6-dimethylaminopurine is 1:5:1;
S3, dissolving the second product and triethylamine in anhydrous dichloromethane, dropwise adding acyl chloride under the condition of ice water bath, reacting for 24 hours at 25 ℃ after the dropwise adding, collecting an organic phase, drying, and purifying by using silica gel column chromatography to obtain the azobenzene acrylate monomer. The water content of the anhydrous organic solvent is less than 100ppm. The ice water bath condition is that the temperature is below 0 ℃, wherein the molar ratio of the second product to the acyl chloride is 1:2.
In this preparation example, the linear alkyl alcohol has a structure as shown in formula (1), R3' is a linear alkyl group of C8, n is 2, the alkyl glycol has a structure as shown in formula (2), R2 is n-decyl, the acyl chloride has a structure as shown in formula (3), R1 is methyl, and the dicarboxylazobenzene has a structure as shown in formula (4);
,
;
The prepared azobenzene acrylic ester monomer has the structure shown in the specification,
,
Wherein R1 is methyl, R2 is n-decyl, R3' is C8 straight chain alkyl, and n is 2.
Example 1
The acrylic ester copolymer of the embodiment 1 is obtained by copolymerizing an azobenzene acrylic ester monomer, an acrylic ester soft monomer, an acrylic ester hard monomer, a hydroxyl acrylic ester monomer and a carboxyl acrylic ester monomer, wherein the azobenzene acrylic ester monomer is the azobenzene acrylic ester monomer obtained in the preparation example 1, the acrylic ester soft monomer is selected from isooctyl acrylate and n-butyl acrylate, the acrylic ester hard monomer is selected from methyl methacrylate, the hydroxyl acrylic ester monomer is selected from hydroxyethyl acrylate, and the carboxyl acrylic ester monomer is selected from acrylic acid;
The acrylic acid soft monomer comprises 80 parts by weight of isooctyl acrylate and 20 parts by weight of n-butyl acrylate, wherein the content of methyl methacrylate is 20 parts by weight, the content of azobenzene acrylic acid ester monomer is 25 parts by weight, the content of acrylic acid is 8 parts by weight and the content of hydroxyethyl acrylate is 10 parts by weight relative to 100 parts by weight of acrylic acid soft monomer.
Preparing an acrylic ester copolymer, namely weighing monomers of the components according to a proportion, adding 1 part by weight of initiator azodiisobutyronitrile and 430 parts by weight of ethyl acetate, heating and stirring at 60 ℃ under the protection of nitrogen to perform polymerization reaction for 8 hours;
Characterized in that the acrylate copolymer comprises the structure shown below,
,
R1 is methyl, R2 is C10 linear alkyl, R3 is C6 perfluoroalkyl, n is 2, and the glass transition temperature of the acrylate copolymer is-38 ℃.
The pressure-sensitive adhesive tape is prepared by mixing the prepared acrylic ester copolymer, tackifying resin rosin resin, curing agent diphenylmethane diisocyanate (MDI-50) and fourth organic solvent ethyl acetate to obtain a sizing material, wherein the solid content of the sizing material is 30wt%, the viscosity at 25 ℃ is 2500cP, the sizing material is coated on a PET substrate with the thickness of 50 mu m, the PET substrate is placed at 65 ℃ for curing for 2 hours, the cured sizing layer is compounded with release paper, the release paper is yellow silicone paper, and the curing agent content is 0.5 part by weight, the tackifying resin content is 30 parts by weight, and the fourth organic solvent content is 70 parts by weight relative to 100 parts by weight of acrylic ester copolymer.
Example 2
The acrylic ester copolymer of the embodiment 2 is obtained by copolymerizing an azobenzene acrylic ester monomer, an acrylic ester soft monomer, an acrylic ester hard monomer, a hydroxyl acrylic ester monomer and a carboxyl acrylic ester monomer, wherein the azobenzene acrylic ester monomer is the azobenzene acrylic ester monomer obtained in the preparation example 1, the acrylic ester soft monomer is selected from isooctyl acrylate and n-butyl acrylate, the acrylic ester hard monomer is selected from methyl methacrylate, the hydroxyl acrylic ester monomer is selected from hydroxyethyl acrylate, and the carboxyl acrylic ester monomer is selected from acrylic acid;
The acrylic acid soft monomer comprises 80 parts by weight of isooctyl acrylate and 20 parts by weight of n-butyl acrylate, wherein the content of methyl methacrylate is 30 parts by weight, the content of azobenzene acrylic acid ester monomer is 15 parts by weight, the content of acrylic acid is 8 parts by weight and the content of hydroxyethyl acrylate is 10 parts by weight relative to 100 parts by weight of acrylic acid soft monomer.
The preparation of the acrylic ester copolymer comprises the steps of weighing monomers of the components according to the proportion, adding 1 part by weight of benzoyl peroxide serving as an initiator and 310 parts by weight of ethyl acetate, heating and stirring at 70 ℃ under the protection of nitrogen, and carrying out polymerization reaction for 7h. The glass transition temperature of the acrylate copolymer was-32 ℃.
The pressure-sensitive adhesive tape is prepared by mixing the prepared acrylic ester copolymer, tackifying resin rosin resin, curing agent diphenylmethane diisocyanate (MDI-50) and fourth organic solvent ethyl acetate to obtain a sizing material, wherein the solid content of the sizing material is 35wt%, the viscosity at 25 ℃ is 3200cP, coating the sizing material on a PET base material with the thickness of 55 mu m, curing for 2 hours at 65 ℃, compounding the cured sizing layer with release paper, and the release paper is yellow silicon paper, wherein the content of the curing agent is 0.5 weight part, the content of the tackifying resin is 30 weight parts, and the content of the fourth organic solvent is 60 weight parts relative to 100 weight parts of the acrylic ester copolymer.
Example 3
The acrylic ester copolymer of the embodiment 3 is obtained by copolymerizing an azobenzene acrylic ester monomer, an acrylic ester soft monomer, an acrylic ester hard monomer, a hydroxyl acrylic ester monomer and a carboxyl acrylic ester monomer, wherein the azobenzene acrylic ester monomer is the azobenzene acrylic ester monomer obtained in the preparation example 1;
The acrylic acid soft monomer comprises 75 parts by weight of isooctyl acrylate and 25 parts by weight of n-butyl acrylate, wherein the content of methyl methacrylate is 30 parts by weight, the content of azobenzene acrylic acid ester monomer is 25 parts by weight, the content of acrylic acid is 5 parts by weight and the content of hydroxyethyl acrylate is 10 parts by weight relative to 100 parts by weight of acrylic acid soft monomer.
The preparation of the acrylic ester copolymer comprises the steps of weighing monomers of the components according to a proportion, adding 0.5 part by weight of initiator azodiisobutyronitrile and 380 parts by weight of ethyl acetate, heating and stirring at 55 ℃ under the protection of nitrogen to perform polymerization reaction for 10 hours, wherein the glass transition temperature of the acrylic ester copolymer is-27 ℃.
The pressure-sensitive adhesive tape is prepared by mixing the prepared acrylic ester copolymer, tackifying resin rosin resin, curing agent diphenylmethane diisocyanate (MDI-50) and fourth organic solvent ethyl acetate to obtain a sizing material, wherein the solid content of the sizing material is 31wt%, the viscosity at 25 ℃ is 2700cP, coating the sizing material on a PET base material with the thickness of 50 mu m, curing for 2.5 hours at 65 ℃, and compositing the cured sizing layer with release paper, wherein the release paper is yellow silicon paper, the content of the curing agent is 1 part by weight, the content of the tackifying resin is 20 parts by weight and the content of the fourth organic solvent is 45 parts by weight relative to 100 parts by weight of the acrylic ester copolymer.
Example 4
The acrylic ester copolymer of the embodiment 4 is obtained by copolymerizing an azobenzene acrylic ester monomer, an acrylic ester soft monomer, an acrylic ester hard monomer, a hydroxyl acrylic ester monomer and a carboxyl acrylic ester monomer, wherein the azobenzene acrylic ester monomer is the azobenzene acrylic ester monomer obtained in the preparation example 1;
The acrylic acid soft monomer comprises 50 parts by weight of isooctyl acrylate, 30 parts by weight of lauryl methacrylate and 20 parts by weight of n-butyl acrylate, wherein the content of isobornyl methacrylate is 30 parts by weight, the content of azobenzene acrylic acid ester monomer is 20 parts by weight, the content of acrylic acid is 5 parts by weight and the content of hydroxyethyl acrylate is 8 parts by weight relative to 100 parts by weight of acrylic acid soft monomer.
The preparation of the acrylic ester copolymer comprises the steps of weighing monomers of the components according to the proportion, adding 1 part by weight of initiator azodiisobutyronitrile and 490 parts by weight of ethyl acetate, heating and stirring at 60 ℃ under the protection of nitrogen, and carrying out polymerization reaction for 10 hours. The glass transition temperature of the acrylate copolymer was-25 ℃.
The pressure-sensitive adhesive tape is prepared by mixing the prepared acrylic ester copolymer, tackifying resin rosin resin, curing agent diphenylmethane diisocyanate (MDI-50) and fourth organic solvent ethyl acetate to obtain a sizing material, wherein the solid content of the sizing material is 25wt%, the viscosity at 25 ℃ is 1500cP, coating the sizing material on a PET base material with the thickness of 55 mu m, curing for 2.5 hours at 65 ℃, and compounding the cured sizing layer with release paper, wherein the release paper is yellow silicon paper, the content of the curing agent is 0.7 part by weight, the content of the tackifying resin is 10 parts by weight, and the content of the fourth organic solvent is 30 parts by weight relative to 100 parts by weight of the acrylic ester copolymer.
Example 5
This example 5 is identical to example 1 except that the azobenzene acrylate monomer content is 10 parts by weight. The glass transition temperature of the acrylate copolymer was-40 ℃.
Example 6
This example 6 is identical to example 1 except that the content of acrylic acid is 12 parts by weight and the content of hydroxyethyl acrylate is 16 parts by weight. The glass transition temperature of the acrylate copolymer was-30 ℃.
Example 7
This example 7 is identical to example 1 except that the azobenzene acrylate monomer content is 35 parts by weight. The glass transition temperature of the acrylate copolymer was-28 ℃.
Comparative example 1
The acrylic ester copolymer of the comparative example 1 is obtained by copolymerizing an acrylic ester soft monomer, an acrylic ester hard monomer, a hydroxyl acrylic ester monomer and a carboxyl acrylic ester monomer, wherein the acrylic ester soft monomer is selected from isooctyl acrylate and n-butyl acrylate, the acrylic ester hard monomer is selected from methyl methacrylate, the hydroxyl acrylic ester monomer is selected from hydroxyethyl acrylate, and the carboxyl acrylic ester monomer is selected from acrylic acid;
the acrylic acid soft monomer comprises 80 parts by weight of isooctyl acrylate and 20 parts by weight of n-butyl acrylate, wherein the acrylic acid soft monomer comprises 35 parts by weight of methyl methacrylate, 8 parts by weight of acrylic acid and 10 parts by weight of hydroxyethyl acrylate.
The preparation of the acrylic ester copolymer comprises the steps of weighing monomers of the components according to the proportion, adding 1 part by weight of initiator azodiisobutyronitrile and 460 parts by weight of ethyl acetate, heating and stirring at 60 ℃ under the protection of nitrogen, and carrying out polymerization reaction for 8 hours.
The pressure-sensitive adhesive tape is prepared by mixing the prepared acrylic ester copolymer, tackifying resin rosin resin, curing agent diphenylmethane diisocyanate (MDI-50) and fourth organic solvent ethyl acetate to obtain a sizing material, wherein the solid content of the sizing material is 25wt%, the viscosity at 25 ℃ is 2500cP, coating the sizing material on a PET base material with the thickness of 50 mu m, curing for 2 hours at 65 ℃, compounding the cured sizing layer with release paper, and the release paper is yellow silicon paper, wherein the content of the curing agent is 0.5 weight part, the content of the tackifying resin is 30 weight parts, and the content of the fourth organic solvent is 90 weight parts relative to 100 weight parts of the acrylic ester copolymer.
Comparative example 2
This comparative example 2 is identical to example 1 except that the azobenzene acrylate monomer is the monomer prepared in comparative preparation example 1.
Test case
The pressure-sensitive adhesive tapes prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to test of peel strength, shear strength, water contact angle, chemical resistance, polishing life and failure mode analysis, and the results are shown in tables 1 to 2.
The test method is as follows:
peel strength test GB/T2792-2014 was used to test peel strength before and after UV irradiation.
Tensile shear Strength test GB/T7124-2008 is adopted to test tensile shear strength before ultraviolet irradiation and after ultraviolet irradiation.
Contact Angle test contact angle of pressure sensitive adhesive layers were tested using ASTM D7334-08.
Testing of the rate of change of chemical resistance:
Pouring the polishing solution into a glass container, placing a sample to be tested, ensuring that the polishing solution can completely submerge the sample, closing a container cover to be completely sealed, soaking for 40 hours, washing the polishing solution remained on the surface of the sample with water, and wiping. The test pieces were tested for peel strength and tensile shear strength by the above-described methods, and the chemical resistance change rate was calculated using the following formula, Δδ= (δ0-δ)/δ0 x100%,
Wherein delta is the chemical resistance change rate (%) of the pressure-sensitive adhesive,
Δ0 —is the average of the initial peel strength or tensile shear strength,
Delta-is the average value of the peel strength or tensile shear strength after immersion in the polishing solution.
Polishing life and failure analysis:
The polishing pad and polishing table were bonded using a pressure sensitive adhesive tape, run-on verification was performed, and the life and failure mode of the polishing pad were tested.
Ultraviolet irradiation, namely irradiation is carried out by adopting a 365nm ultraviolet lamp, the light intensity is 200mW/cm2, and the irradiation time is 5min.
TABLE 1
TABLE 2
From the data in tables 1 and 2, the easy-to-peel and hydrophobic properties of the pressure-sensitive adhesive tapes of the present disclosure can demonstrate that the prepared acrylate copolymers contain azo-benzene acrylate monomer repeat units containing an azo-benzene group and a fluorotail group. The azobenzene acrylic ester monomer has a specific structure, is used for preparing the pressure-sensitive adhesive tape, can enable the pressure-sensitive adhesive tape to have strong shearing resistance, is easy to peel off after illumination and has high chemical corrosion resistance, and the pressure-sensitive adhesive tape has hydrophobic property, so that the service life of the pressure-sensitive adhesive tape is prolonged. The pressure-sensitive adhesive tape of the present application has a better chemical resistance of the adhesive layer, which fails after the failure of the polishing layer, whereas the pressure-sensitive adhesive tape of the comparative example has a poor chemical resistance of the adhesive layer, which fails by degumming before the failure of the polishing layer.
Compared with examples 5 and 7, the content of the azobenzene acrylate monomer repeating unit of example 1 is within the preferred range of the present disclosure, the prepared pressure-sensitive adhesive tape has better shear resistance, easy peeling and chemical resistance, and the pressure-sensitive adhesive tape has hydrophobic property, and the service life of the pressure-sensitive adhesive tape is longer.
Compared with example 6, the contents of the carboxylic acrylic monomer repeating unit and the hydroxy acrylic monomer repeating unit in example 1 are within the preferred content ranges of the present disclosure, the prepared pressure-sensitive adhesive tape is superior in shear resistance, easy peeling and chemical resistance, and the pressure-sensitive adhesive tape has a hydrophobic property, and the service life of the pressure-sensitive adhesive tape is longer.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.