R wherein²And R³Be halogen atom or C1～C8 alkyl independently of one another, wherein halogen atom can be F, Cl, Br or I, and C1～C8 alkyl can be methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, cyclohexyl, heptyl or octyl group;

Z be singly-bound, C1～C8 alkylidene group (alkylene group), C2～C8 alkylidene (alkylidengroup), C5～C15 ring alkylidene group (cycloalkylene group), C5～C15 ring alkylidene (cycloalkyliden group) ,-S-,-SO-,-SO₂-,-O-,-compound shown in the CO-, formula 3 or the compound shown in the formula 4, wherein C1～C8 alkylidene group or C2～C8 alkylidene can be methylene radical, ethylidene (ethylene group), propylidene, butylidene, pentylidene, hexylidene, ethidine (ethylidenegroup), isopropylidene (isopropylidene group) etc.; C5～C15 ring alkylidene group or C5～C15 ring alkylidene can be ring pentylidene, cyclohexylene, cyclopentylidene base (cyclopentylidene group) or cyclohexylidene base (cyclohexylidene group);

A and b are 0 to 4 integer independently of one another:

[formula 3]

[formula 4]

Aromatic dihydroxy compound shown in the formula 2 can be two (hydroxyaryl) alkane as two (4-hydroxyphenyl) methane,

Two (3-first how-4-hydroxyphenyl) methane, two (3-chloro-4-hydroxyphenyl) methane,

Two (3,5-two bromo-4-hydroxyphenyl) methane, 1,1-two (4-hydroxyphenyl) ethane,

1,1-two (2-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) ethane,

2,2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane),

2,2-two (3-methyl-4-hydroxyphenyl) propane,

2,2-two (2-methyl-4-hydroxyphenyl) propane,

2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane,

1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propane,

2,2-two (3-chloro-4-hydroxyphenyl) propane,

2,2-two (3-fluoro-4-hydroxyphenyl) propane,

2,2-two (3-bromo-4-hydroxyphenyl) propane,

2,2-two (3,5-two fluoro-4-hydroxyphenyl) propane,

2,2-two (3,5-two chloro-4-hydroxyphenyl) propane,

2,2-two (3,5-two bromo-4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) butane,

2,2-two (4-hydroxyphenyl) octane, 2,2-two (4-hydroxyphenyl) toluene,

2,2-two (4-hydroxyl-1-aminomethyl phenyl) propane, 1,1-two (4-hydroxyl-tert-butyl-phenyl) propane,

2,2-two (4-hydroxyl-3-bromophenyl) propane,

2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane,

2,2-two (4-hydroxyl-3-chloro-phenyl-) propane,

2,2-two (4-hydroxyl-3,5-dichlorophenyl) propane,

2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane,

2,2-two (3-bromo-4-hydroxyl-5-chloro-phenyl-) propane,

2,2-two (3-phenyl-4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) butane,

2,2-two (3-methyl-4-hydroxyphenyl) butane,

1,1-two (2-butyl-4-hydroxy-5-methyl base phenyl) butane,

1,1-two (the 2-tertiary butyl-4-hydroxy-stupid base of 5-methyl) butane,

1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Trimethylmethane,

1,1-two (2-tert-pentyl-4-hydroxy-5-methyl base phenyl) butane,

2,2-two (3,5-two chloro-4-hydroxyphenyl) butane,

2,2-two (3,5-two bromo-4-hydroxyphenyl) butane, 4,4-two (4-hydroxyphenyl) heptane,

1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) heptane, 2,2-two (4-hydroxyphenyl) octane,

1,1-(4-hydroxyphenyl) ethane etc.; Two (hydroxyaryl) naphthenic hydrocarbon as

1,1-two (4-hydroxyphenyl) pentamethylene, 1,1-two (4-hydroxyphenyl) hexanaphthene,

1,1-two (3-methyl-4-hydroxyphenyl) hexanaphthene,

1,1-two (3-cyclohexyl-4-hydroxyphenyl) hexanaphthene,

1,1-two (3-phenyl-4-hydroxyphenyl) hexanaphthene,

1,1-two (4-hydroxyphenyl)-3,5,5-trimethyl-cyclohexane etc.; Two (hydroxyaryl) ether is as two (4-hydroxyphenyl) ether, two (4-hydroxy-3-methyl phenyl) ether etc.; Two (hydroxyaryl) thioether is as two (4-hydroxyphenyl) thioether, two (3-methyl-4-hydroxyphenyl) thioether etc.; Two (hydroxyaryl) sulfoxide is as two (hydroxyphenyl) sulfoxide, two (3-methyl-4-hydroxyphenyl) sulfoxide, two (3-phenyl-4-hydroxyphenyl) sulfoxide etc.; Two (hydroxyaryl) sulfone is as two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, two (3-phenyl-4-hydroxyphenyl) sulfone etc.; Or dihydroxybiphenyl is as 4 ', 4 ' dihydroxybiphenyl, 4, and 4 '-dihydroxyl-2,2 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3,3 '-dicyclohexyl biphenyl, 3,3 '-two fluoro-4,4 '-dihydroxybiphenyl etc.

Except the compound shown in the formula 2, aromatic dihydroxy compound can be by the dihydroxy-benzene of dihydroxy-benzene, halogen or alkyl replacement.This aromatic dihydroxy compound can be a Resorcinol, the 3-methylresorcinol, the 3-ethyl resorcinol, 3-propyl group Resorcinol, 3-butyl Resorcinol, the 3-tert-butyl resorcin, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,3,4,6-tetrafluoro Resorcinol, 2,3,4,6-tetrabromo Resorcinol, pyrocatechol, Resorcinol, the 3-methyl hydroquinone, 3-ethyl Resorcinol, 3-propyl group Resorcinol, the 3-butylhydroquinone, the 3-Tert. Butyl Hydroquinone, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,5-two chlorohydroquinones, 2,3,5, the 6-duroquinol, 2,3,5,6-tetra-tert Resorcinol, 2,3,5,6-tetrafluoro Resorcinol, 2,3,5,6-tetrabromo Resorcinol etc.

According to the embodiment of the present invention, aromatic dihydroxy compound can be a dihydroxyphenyl propane.

The diaryl carbonate that is used for one of transesterify starting material can be the compound shown in compound shown in the formula 5 or the formula 6:

[formula 5]

Ar wherein¹And Ar²Be independently of one another aryl and

[formula 6]

Ar wherein³And Ar⁴Be independently of one another aryl and

D¹Be that the aromatic dihydroxy compound shown in the formula 2 is removed the residue that obtains behind two hydroxyls.

Diaryl carbonate shown in formula 5 or the formula 6 can be diphenyl carbonate, xylyl carbonate, two (chloro-phenyl-) carbonic ether, two (tolyl) carbonic ether, dinaphthyl carbonic ether, two (phenylbenzene) carbonic ether, dihydroxyphenyl propane-bis-phenol carbonic ether etc.

For example, according to the embodiment of the present invention, the diaryl carbonate that is used for one of transesterify starting material can be a diphenyl carbonate.

Based on 1mol diaryl carbonate compound, the concentration of dicarboxylic acid compound is 10^-4To 1mol, preferred 10^-3To 0.5mol, more preferably 0.05 to 0.1mol.If the concentration of dicarboxylic acid compound is outside above-mentioned scope, modified polycarbonate can not show gratifying physicals.

Based on the 1mol dihydroxy compound, the concentration of diaryl carbonate is in 1.0 to 1.5mol scopes, and preferred 1.0 to 1.3mol, and more preferably 1.0 to 1.2mol.If the concentration of diaryl carbonate is outside above-mentioned scope, the polymerization degree that is drawn by following formula is low:

[formula 1]

{\overset{&OverBar;}{X}}_{n} = \frac{1 + r}{1 + r - 2 rp}

Wherein r is the mol ratio of oxy-compound and carbonate group, and Xn is the polymerization degree, and p is a level of response.When p was 1.0, formula 1 became formula 2.In the case, when r ten minutes near 1.0 the time, can make polymerization degree maximization at short notice:

[formula 2]

{\overset{&OverBar;}{X}}_{n} = \frac{1 + r}{1 - r}

According to the embodiment of the present invention, when preparing modified polycarbonate resin, if desired, can use additive in addition, as terminator, antioxidant etc. by esterification and transesterify.

Terminator can be neighbour-normal-butyl phenol, between-normal-butyl phenol, right-normal-butyl phenol, neighbour-isobutyl-phenol, between-isobutyl-phenol, right-isobutyl-phenol, neighbour-tert.-butyl phenol, between-tert.-butyl phenol, p-tert-butylphenol, neighbour-n-pentyl phenol, between-n-pentyl phenol, right-n-pentyl phenol, neighbour-n-hexyl phenol, between-n-hexyl phenol, right-n-hexyl phenol, neighbour-cyclohexylphenol, between-cyclohexylphenol, right-cyclohexylphenol, neighbour-phenylphenol, between-phenylphenol, right-phenylphenol, neighbour-n-nonyl phenol, between-n-nonyl phenol, right-n-nonyl phenol, neighbour-cumyl phenol, between-cumyl phenol, right-cumyl phenol, neighbour-naphthyl phenol, between-naphthyl phenol, right-naphthyl phenol, 2,6-two-tert.-butyl phenol, 2,5-two-tert.-butyl phenol, 2,4-two-tert.-butyl phenol, 3,5-two-tert.-butyl phenol, 3,5-two-cumyl phenol, 3, the 5-dicumyl phenol, compound shown in the formula 7, compound shown in the formula 8, compound shown in the formula 9, compound shown in the formula 10, compound shown in the formula 11, compound shown in the formula 12, or monovalent phenol, suc as formula 13 or formula 14 shown in dimethylbiphenyl pyranyl phenol (croman) derivative:

[formula 7]

[formula 8]

[formula 9]

Wherein n is 7 to 30 integer,

[formula 10]

C_nH_2n+1——OH

Wherein n is 7 to 30 integer,

[formula 11]

R wherein¹³Be that C1～C12 alkyl and k are 1 to 3 integers,

[formula 12]

R wherein¹³Be that C1～C12 alkyl and k are 1 to 3 integers,

[formula 13]

With

[formula 14]

What for example, terminator can be p-tert-butylphenol, right-cumyl phenol, right-phenylphenol and formula 11 to the compound shown in the formula 14 is a kind of.

Be used for the aromatic dihydroxy compound of transesterify process starting material based on 1mol, according to embodiment of the present invention, the concentration of terminator is 0.01 to 10mol%.

Can when beginning, transesterify add whole terminators.Selectively, in whole transesterify process, progressively add terminator in batches.Selectively, the specified time after aromatic dihydroxy compound and diaryl carbonate transesterify begin adds whole terminators.

Antioxidant can be the phosphino-antioxidant.The example of phosphino-antioxidant comprises trialkyl phosphite such as trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite monooctyl ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, tricresyl phosphite (octadecyl) ester, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite (2-chloroethyl) ester or tricresyl phosphite (2,3-two chloropropyls) ester etc.; Tricresyl phosphite cycloalkyl ester such as tricresyl phosphite cyclohexyl etc.; Triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tricresyl phosphite (ethylphenyl) ester, tricresyl phosphite (butyl phenyl) ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (hydroxyphenyl) ester etc.; Monoalkyl diaryl phosphorous acid ester such as 2-ethylhexyl phenylbenzene phosphorous acid ester etc.; Trialkylphosphate such as trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate (octadecyl) ester, bisphosphate distearyl pentaerythritol ester, tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2,3-two chloropropyls) ester etc.; Tricresyl phosphate cycloalkyl ester such as tricyclohexyl phosphate etc.; Or triaryl phosphate such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid 2-ethylphenyl diphenyl etc.

According to the method for preparing modified polycarbonate resin of embodiment of the present invention, make aromatic dihydroxy compound and diaryl carbonate in the presence of polymerizing catalyst, carry out transesterify.In this case, can also add additive, as terminator, branching agent, antioxidant etc.

The temperature of transesterify without limits, transesterify can be carried out under 100 to 330 ℃, preferred 180 to 300 ℃, more preferably in the temperature that progressively rises to 300 ℃ from 180 ℃.If temperature of reaction is lower than 100 ℃, transesterify is carried out slowly.If temperature of reaction is higher than 330 ℃, the modified polycarbonate resin that side reaction or generation may occur may be painted.

The pressure of transesterify and can be controlled according to use monomeric vapour pressure and temperature of reaction without limits.When transesterify began, pressure can be for 1 to 10atm, and when transesterify finished, pressure can reduce to 0.1 to 100mbar.

The transesterification reaction time can prolong until obtaining desired molecular weight, and described molecular weight is 1,500 to 15,000g/mol.The reaction times of transesterify is in 0.2 to 10 hour scope.

Transesterify can be carried out under the condition of inert solvent not having.Yet if desired, transesterify can be carried out in the presence of the inert solvent that based on the modified polycarbonate all wts for preparing be 1～150% weight.Inert solvent can be an aromatic substance, as phenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene, methylnaphthalene etc.; Or naphthenic hydrocarbon is as three ring (5,2,10) decane, cyclooctane, cyclodecane etc.

In some cases, transesterify can be carried out in inert atmosphere.Rare gas element can be gas such as Ar₂, CO₂, N₂O or N₂Chlorofluorocarbon (chlorofluoro hydrocarbonate); Alkane is as ethane or propane; Or alkene such as ethene or propylene.

The result of transesterify under the above-mentioned condition separates from reactor and the corresponding phenol of diaryl carbonate or its ester, water and the inert solvent that use.These isolating compositions can be separated, purifying and regeneration.Transesterify can be used predetermined equipment intermittence or carry out continuously.

Step 2: polycondensation

Making the weight-average molecular weight that is prepared from by transesterify is 1,500 to 20, and the lower molecular weight modified polycarbonate prepolymer that comprises ester group of 000g/mol under the high temperature reduced pressure, or carries out polycondensation in nitrogen atmosphere.Result as polycondensation, removed the diaryl carbonate that exists with the unreacted form in the transesterify process, the polymerization degree is less than the by product that generates in 3 byproduct of reaction and the reaction process, as phenol, make the intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group that molecular weight is higher than the low molecular weight amorphous polycarbonate prepolymer.

In polycondensation, because the relatively low unreacted diaryl carbonate that has neither part nor lot in reaction of its boiling point and the polymerization degree are evaporated to outside the reactor together less than 3 byproduct of reaction and byproduct of reaction phenol.Compare with ordinary method, this exclusion process in the solid state polymerization processes more helps increasing the molecular weight of modified polycarbonate.

In the method for routine, untapped excessive diaryl carbonate and the polymerization degree are not got rid of by polycondensation process less than 3 byproduct of reaction in the transesterify process before solid state polymerization.In addition, along with the growth of prepolymer molecular weight, the molecular fraction difference between aryl carbonates end group and the aromatic hydroxy end group increases.Therefore, the solid state polymerization processes that is used to prepare the high molecular modified polycarbonate that comprises ester group is extended.

The present embodiment according to the present invention, polycondensation can use conventional condensation reactor, as rotational circle disc type reactor or rotation cage reactor or film reactor.

Polycondensation can be at 180 to 330 ℃, carry out under preferred 200 to 300 ℃.

In polycondensation process, at 0～50mmHg, under the decompression of preferred 0～20mmHg and in above-mentioned high temperature range, remove unreacted dialkyl group (aryl) carbonic ether that exists after transesterify and the esterification, the polymerization degree less than 3 byproduct of reaction, the by-product phenol and the water of generation.

According to the specific embodiment of the present invention, can use nitrogen to inject and replace decompression to remove byproduct of reaction.In the case, the nitrogen amount of injection is 0.01 to 1.0Nm³/ kgh.Reaction times is with change in reaction conditions, can be in 2 to 120 minutes scopes.

The intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group of said process preparation, its weight-average molecular weight can be 3,000 to 20,000g/mol.

According to the embodiment of the present invention, if the non-crystalline state modified polycarbonate that uses in the spray crystallization method is the non-crystalline state modified polycarbonate that comprises siloxanes, the method that then prepares the non-crystalline state modified polycarbonate that comprises siloxanes comprises:

A ') transesterify of carrying out under the condition of catalyzer between diaryl carbonate, dihydroxyl polysiloxane and the aromatic dihydroxy compound is being arranged, with the preparation weight-average molecular weight is 1,500～20, the non-crystalline state modification carbonic ether prepolymer that comprises siloxanes of 000g/mol; With

B ') polycondensation comprises the non-crystalline state modified polycarbonate prepolymer (a ' obtains by operation) of siloxanes

Below, describe the method that preparation comprises the non-crystalline state modified polycarbonate of siloxanes in detail.

Step 1: transesterify

The polymerizing catalyst that uses in the embodiments of the present invention can be metal compound as catalyst, nonmetallic compound catalyzer or the mixture of the two.Metal compound as catalyst can be a salt compound, as oxyhydroxide, acetate, alkoxide, carbonate, hydride, hydrate or the oxide compound of basic metal or alkaline-earth metal; Contain transition metal, as the organometallic compound of Zn, Cd, Ti or Pb; Aluminum hydride; Or hydroborate.

The nonmetallic compound catalyzer can be a quaternary ammonium salt, as tetramethylammonium hydroxide, acetic acid tetramethylammonium, tetramethyl-ammonium formate, carbonic acid tetramethylammonium, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, tetrabutylammonium hydroxide, hydroxide four puratized agricultural sprays, hydroxide trimethylphenyl ammonium etc.; Quaternary alkylphosphonium salt such as Qing oxidation Si Jia Phosphonium, acetic acid Si Jia Phosphonium, formic acid Si Jia Phosphonium, carbonic acid Si Jia Phosphonium, Qing oxidation Si Yi Phosphonium, Qing oxidation Si Bing Phosphonium, hydroxide Si Ding Phosphonium, hydroxide Si Ben Phosphonium, hydroxide trimethyl Ben Ji Phosphonium etc.; The primary, the second month in a season or tertiary amine compound; Perhaps nitrogenous aromatic derivative is as pyridine.

Based on the dihydroxy compound that is used for transesterify process starting material, can be 10 according to the specific embodiment of the present invention nonmetallic compound catalyst concentration^-6To 10^-1Mol, preferred 10^-5To 10^-2Mol, more preferably 10^-4To 10^-3Mol.If based on 1mol dihydroxy compound nonmetallic compound, catalyst concentration is less than 10^-6Mol, then the nonmetallic compound catalyzer is difficult to effectively bring into play its activity when the reaction beginning; If based on 1mol dihydroxy compound nonmetallic compound catalyst concentration greater than 10^-1Mol, then production cost height.

Comprising basic metal or alkaline earth metal compounds can be, but is not limited only to, and contains oxyhydroxide, carbonate, acetate, alkoxide or the borohydride compound of Li, Na, K, Ru, Cs, Be, Mg, Ca, Sr, Ba etc. separately.

According to the embodiment of the present invention, the concentration that comprises basic metal or alkaline earth metal compounds is 10^-8To 10^-3Mol, preferred 10^-7To 10^-4Mol, more preferably 10^-6To 10^-5Mol is used for the aromatic dihydroxy compound of transesterify process starting material based on 1mol.If based on the 1mol dihydroxy compound, the concentration that comprises basic metal or alkaline earth metal compounds is less than 10^-8Mol, then catalyzer is difficult to effectively bring into play its activity in the reaction later stage; If the concentration that comprises basic metal or alkaline earth metal compounds is greater than 10^-3Mol, production cost height then, and as the physicals of the modified polycarbonate that comprises siloxanes of the finished product, may be bad as thermotolerance and hydrolytic resistance.

According to the embodiment of the present invention, can be as the aromatic dihydroxy compound of one of transesterify starting material by formula 2 expressions.

The diaryl carbonate that is used for one of transesterify starting material can be the compound shown in compound shown in the formula 5 or the formula 6.

The polysiloxane compound that is used for the transesterify starting material can be the compound shown in the formula 15.

[formula 15]

Wherein n is 1 to 500 integer.

R⁴, R^{4 '}, R⁵And R^{5 '}Be hydrogen atom or C1～C20 alkyl independently of one another, wherein the part or all of hydrogen atom of alkyl can be replaced by halogen atom; With

R⁶And R⁷Be independently of one another C1-C20 alkylidene group, the monocycle of linearity or branching or encircle the C6-C30 arylidene more or-R⁸-X-R⁹-, R wherein⁸And R⁹Be to replace or last C1-C20 alkylidene group or replacement or the unsubstituted C6-C30 arylidene that replaces independently of one another; With

X is-O-,-S-,-SO-,-SO₂-or-CO-.

Polysiloxane compound shown in the formula 15 can be polydialkysiloxane～dialkoxy alcohol etc.

According to the embodiment of the present invention, the polysiloxane compound that is used for one of transesterify starting material can be the compound shown in the formula 16:

[formula 16]

Wherein x is 1 to 500 integer.

Based on the 1mol dihydroxy compound, the concentration of diaryl carbonate can be 1.0 to 1.5mol, and preferred 1.0 to 1.3mol, and more preferably 1.0 to 1.2mol.If the concentration of diaryl carbonate is outside above-mentioned scope, then the polymerization degree is low.Identical with the modified polycarbonate that comprises ester group, the polymerization degree is drawn by formula 1 and 2.

Based on dihydroxy compound, the concentration of the polysiloxane of interpolation is 0.01 to 20mol%, and preferred 0.1 to 15mol%, and more preferably 0.5 to 5mol%.If concentration is less than 0.01mol%, then the effect of modification is insignificant.If concentration is greater than 20mol%, then local increase of the concentration of polysiloxane and polysiloxane become gel.This gelation is unfavorable for reaction.

According to the embodiment of the present invention, when preparing modified polycarbonate resin, if desired, can use additive in addition, as terminator, oxidation inhibitor, branching agent etc. by transesterify.The example of additive, condition etc. are as mentioned above.

In addition, the reaction conditions of step of transesterification, as temperature of reaction, reaction pressure etc. as mentioned above.

Step 2: polycondensation

Making the weight-average molecular weight that is prepared from by transesterify is 1,500 to 20, and the lower molecular weight modified polycarbonate prepolymer that comprises siloxanes of 000g/mol under the decompression hot conditions, or carries out polycondensation in nitrogen atmosphere.Result as polycondensation, removed unreacted diaryl carbonate in the transesterify process, the polymerization degree is less than the by product that generates in 3 byproduct of reaction and the reaction process, as phenol, make the intermediate molecular weight non-crystalline state modified polycarbonate that comprises siloxanes that molecular weight is higher than the low molecular weight amorphous modified polycarbonate prepolymer that comprises siloxanes.

In polycondensation, have neither part nor lot in the unreacted diaryl carbonate of reaction and the polymerization degree owing to boiling point is lower and be evaporated to outside the reactor together less than 3 byproduct of reaction and byproduct of reaction phenol.With respect to ordinary method, this method for removing in the solid state polymerization processes more helps increasing the molecular weight of modified polycarbonate.

In the method for routine, untapped excessive diaryl carbonate and the polymerization degree are got rid of through polycondensation process less than 3 byproduct of reaction in the transesterify process before solid state polymerization.In addition, along with the growth of prepolymer molecular weight, the aryl carbonates end group of the prepolymer that makes and the molecular fraction difference between the aromatic hydroxy end group increase.Therefore, the solid state polymerization processes that is used to prepare the high molecular modified polycarbonate that comprises siloxanes is extended.

In polycondensation process,, under the decompression of preferred 0～20mmHg and in above-mentioned high temperature range, remove untapped dialkyl group (aryl) acid esters that exists after the transesterify, the polymerization degree less than 3 byproduct of reaction, the byproduct phenol of generation at 0～50mmHg.

According to the embodiment of the present invention, can use nitrogen injection to replace decompression to remove byproduct of reaction.In the case, the nitrogen amount of injection is 0.01 to 1.0Nm³/ kgh.Reaction times is with change in reaction conditions, can be in 2 to 120 minutes scopes.

The weight-average molecular weight of the intermediate molecular weight non-crystalline state modified polycarbonate prepolymer that comprises siloxanes of said process preparation is 1,000 to 30,000g/mol.

Further describe the present invention with reference to the following example.Described embodiment only is an exemplary illustrated, is not used for limiting the scope of the invention.

Embodiment

Embodiment 1

(preparation comprises the non-crystalline state modified polycarbonate prepolymer of ester group)

With 1,500g (6.57mol) dihydroxyphenyl propane, 1,463g (6.83mol) diphenyl carbonate and 15.89g (6.9 * 10^-2Mol) 1, the 10-sebacic acid mixes, and mixture is joined in the reactor of nitrogen atmosphere.Add 2.5 * 10 based on every mol dihydroxyphenyl propane to reactor then^～4The dibutyltin oxide of mol is as polymerizing catalyst.The reactant that obtains is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4 Hg decompression, carried out esterification and transesterification reaction 30 minutes then.As a result, having prepared number-average molecular weight is 3, the low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group of 452g/mol.

(the non-crystalline state modified polycarbonate that comprises ester group by the polycondensation preparation)

The low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group that makes is filled into temperature is 300 ℃, at 1mmHg or more in the film reactor under the low reaction pressure.Polycondensation was carried out 30 minutes.As a result, having prepared number-average molecular weight is 5, the intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group of 342g/mol.

(strengthening the high molecular modified polycarbonate that method for solid phase polymerization-preparation comprises ester group)

The number-average molecular weight that will make by melt phase polycondensation is 5, and the modified polycarbonate that comprises ester group of 342g/mol (polydispersity index (PDI)=2.69) stirring and dissolving obtains the solution of 15wt% in the 2L methylene dichloride.As shown in Figure 1, with solution with the compressed nitrogen that injects with 400L/h speed through nozzle spray to strengthening solid state polymerization reactor.The solution that makes spraying contact with the hot nitrogen of being supplied with by reactor bottom evaporating whole solvents, thus the crystalline modified polycarbonate that comprises ester group of collection dry particulate form in the coagulation vessel under reactor.

200 ℃ of hot nitrogens being supplied with by the polymerized unit bottom are cooled to 140 ℃ by temperature control unit, and refrigerative nitrogen contacts with solution then.After solvent that evaporates in the drying unit and nitrogen process were installed in the cyclonic separator of reactor upper end, the unit that is condensed again was divided into liquid solvent and gasiform nitrogen.Liquid solvent is back in the dissolving chamber that agitator is housed, and gasiform nitrogen is back to well heater by compressor.In drying unit, had on a small quantity less than 5% low-crystallinity with less than the particle of the diameter of 80 μ m, described particle is by collecting and be back to agitator in the cyclonic separator that is installed in reactor top.The size of the crystalline particle of bottom use scanning electron microscope and image dissector analysis reactor, collecting.As a result, find the crystalline particle size evenly, mean diameter is 400 ± 35.In addition, use differential scanning calorimeter to measure the degree of crystallinity of crystalline particle, degree of crystallinity is 22.8%.

Crystalline particle after the solid state polymerization 12 hours, is measured molecular weight in reactor.As a result, the number-average molecular weight that comprises the high molecular modified polycarbonate of ester group is 20, and 463g/mol, PDI are 3.06.

Number-average molecular weight and the PDI of differential responses time are as shown in table 1.

The comparative example 1

(transesterify-preparation comprises the modified polycarbonate prepolymer of ester group)

With 1,500g (6.57mol) dihydroxyphenyl propane, 1,463g (6.83mol) diphenyl carbonate and 15.89g (6.9 * 10^～2Mol) 1, the 10-sebacic acid mixes, and mixture is joined in the reactor of nitrogen atmosphere.Reactant mixed and under 230 ℃ jacket temperature the reaction 5 minutes.Under 1 to 4 Hg decompression, carried out esterification and transesterification reaction 30 minutes then.As a result, having prepared number-average molecular weight is 3, the low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group of 452g/mol.

(crystallization～preparation comprises the crystalline modified polycarbonate of ester group)

To be dissolved in through the lower molecular weight modified polycarbonate prepolymer (PDI=2.38) that comprises ester group that transesterification reaction makes in the methylene dichloride to concentration be 0.1g/mL.Come the precipitated crystal particle by in solution, adding methyl alcohol as non-solvent.The amount of methyl alcohol is greater than 2 times of solution.In the case, the mean diameter that comprises the crystalline modified polycarbonate of ester group is 570 μ m, observes the crystalline particle of many diameters greater than 10mm.Therefore, in order to carry out solid state polymerization, the crystalline particle piece must grind and classification.Grinding and fractionated particle diameter are 200 ± 42, and the degree of crystallinity of using differential scanning calorimeter to measure is 20.2%.

(solid state polymerization processes-preparation comprises the high molecular modified polycarbonate of ester group)

The modified polycarbonate that comprises ester group after the crystallization, grinding and the classification that make is added in the solid state polymerization reactor, from the bottom of reactor with the continuous nitrogen injection of the speed of 3L/min.Under 200 ℃ of constant temperature, carry out solid state polymerization processes and comprise the high molecular modified polycarbonate of ester group with preparation.The result is as shown in table 1.

Table 1

The solid state polymerization time	Embodiment 1		The comparative example 1
	Embodiment 1		The comparative example 1		Number-average molecular weight	Polydispersity index	Number-average molecular weight	Polydispersity index
	0	5,342	2.69	3,452	Number-average molecular weight	Polydispersity index	Number-average molecular weight	Polydispersity index	2.38
2	0	5,342	2.69	3,452	11,899	2.75	10,328	2.62	2.38
2	4	15,574	2.82	11,846	11,899	2.75	10,328	2.62	2.86
6	4	15,574	2.82	11,846	16,623	2.89	11,980	3.06	2.86
6	8	17,878	2.94	12,560	16,623	2.89	11,980	3.06	3.34
10	8	17,878	2.94	12,560	19,744	3.00	12,788	3.59	3.34
10	12	20,463	3.06	12,532	19,744	3.00	12,788	3.59	3.84

As shown in table 1, the non-crystalline state modified polycarbonate that comprises ester group among the embodiment 1 is melted polycondensation and spray crystallization, made the high molecular modified polycarbonate that comprises ester group through solid state polymerization then, after solid state polymerization 4 hours, the number-average molecular weight that comprises the modified polycarbonate of ester group surpasses 15,000g/mol.On the contrary, contrast implements to comprise in 1 the non-crystalline state modified polycarbonate of ester group by transesterify and by conventional non-solvent precipitated crystal, carry out solid state polymerization then, the number-average molecular weight that comprises the modified polycarbonate of ester group is difficult to reach 13,000g/mol is even the solid state polymerization time was above 10 hours.

Comparing embodiment 1 and comparative example 1, discovery is to be suitable for 20% to 30% of solid state polymerization according to the degree of crystallinity of the crystalline particle of the embodiment of the invention 1 preparation.In addition, different with comparative example 1 result, the crystalline particle of embodiment 1 preparation has deviation less than mean diameter 80～3, and 20% the narrow diameter of 000 μ m distributes, and this is to control by changing spray condition under the situation of not grinding.

And the present invention does not need the necessary other drying process of ordinary method and grinds classification process, and therefore, operating time and running cost obviously reduce.Finally, after 12 hours, the number-average molecular weight of the high molecular modified polycarbonate that comprises ester group of embodiment 1 preparation reaches 20,463g/mol at solid state polymerization.

After solid state polymerization, the polydispersity index that comprises the modified polycarbonate of ester group among the embodiment 1 only increases by 14.0%, its be that polydispersion is given advice increasing value 61.3% among the comparative example 1 1/4th.Therefore, in embodiment 1, can prevent the formation of low-quality product, low-quality product is indicated by high polydispersity index, and can stablize the product that obtains having homogeneous molecular weight and physicals in a large number.

Embodiment 2

(preparation comprises the non-crystalline state modified polycarbonate prepolymer of siloxanes)

With 1,484g (6.50mol) dihydroxyphenyl propane, 1,478g (6.9mol) diphenyl carbonate and 5.08g (1.13 * 10^～3Mol) dihydroxyl polysiloxane (Dow Corning 3058) mixes, and mixture is joined in the reactor of nitrogen atmosphere.Add 1 * 10 based on every mol dihydroxyphenyl propane to reactor then^～6Mol sodium acetate and 2.5 * 10^～4Mol hydroxide 4-butyl-phosphonium is as polymerizing catalyst.Reactant is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4 Hg decompression, carried out transesterification reaction 30 minutes then.As a result, having made weight-average molecular weight is 8, the non-crystalline state modified polycarbonate prepolymer that comprises siloxanes of 804g/mol.

(the non-crystalline state modified polycarbonate that comprises siloxanes by the polycondensation preparation)

It is film reactor under 300 ℃ of 1mmHg or the more decompression power that the low molecular weight amorphous modified polycarbonate prepolymer that will comprise siloxanes is filled into temperature.Polycondensation was carried out 30 minutes.As a result, having prepared weight-average molecular weight is 15, the non-crystalline state modified polycarbonate that has siloxanes of 578g/mol.

(strengthening the high molecular modified polycarbonate that method for solid phase polymerization～preparation comprises siloxanes)

The weight-average molecular weight that will make by melt phase polycondensation is 15, and the non-crystalline state modified polycarbonate (PDI=2.79) that comprises siloxanes of 578g/mol is dissolved in and obtains 15wt% solution in the 2L methylene dichloride.With reference to Fig. 1, with solution with the compressed nitrogen that injects with 400L/h speed through nozzle injection reinforcing solid state polymerization reactor.Spray solution is contacted with the hot nitrogen of being supplied with by reactor bottom evaporating whole solvents, thereby make the crystalline modified polycarbonate that comprises siloxanes of dry particulate form.

The size of the crystalline particle that use scanning electron microscope and image dissector measure.As a result, find the crystalline particle size evenly, mean diameter is 400 ± 35.In addition, use differential scanning calorimeter to measure the degree of crystallinity of crystalline particle, degree of crystallinity is 23.2%.

Crystalline particle stopped 10 hours at polymerized unit, measured the resulting high molecular modified polycarbonate that comprises siloxanes.As a result, the weight-average molecular weight of high-molecular weight siloxanes Copolycarbonate is 39, and 500g/mol, PDI are 3.19.

Weight-average molecular weight and the PDI of differential responses time are as shown in table 2.

The comparative example 2

(transesterify-preparation comprises the modified polycarbonate prepolymer of siloxanes)

With 1,484g (6.50mol) dihydroxyphenyl propane, 1,478g (6.9mol) diphenyl carbonate and 5.08g (1.13 * 10^～3Mol) dihydroxyl polysiloxane (Dow Corning 3058) mixes, and mixture is joined in the reactor of nitrogen atmosphere.Reactant is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4 Hg decompression, carried out transesterification reaction 30 minutes then.As a result, making weight-average molecular weight is 8, the low molecular weight amorphous modified polycarbonate prepolymer that comprises siloxanes of 804g/mol.

(crystallization-preparation comprises the crystalline modified polycarbonate of siloxanes)

To be dissolved in through the lower molecular weight modified polycarbonate prepolymer (PDI=2.40) that comprises siloxanes that transesterification reaction makes in the methylene dichloride to concentration be 0.1g/mL.Make the crystalline solids precipitation by the methyl alcohol that adds as non-solvent.Quantity of methyl alcohol is greater than 2 times of solution.Thereby make the pulverous crystalline modified polycarbonate that comprises siloxanes.In the case, the mean diameter of crystalline particle is 570 μ m, and has generated the crystalline particle of many diameters greater than 10mm.Therefore, in order to carry out solid state polymerization, the crystalline particle piece must grind and classification.Grinding and fractionated particle diameter are 200 ± 42, and the degree of crystallinity of using differential scanning calorimeter to measure is 20.5%.

(solid state polymerization processes-preparation comprises the high molecular modified polycarbonate of siloxanes)

The crystalline modified polycarbonate that will comprise siloxanes is filled in the typical solid state polymerization reactor, injects hot nitrogen from the bottom of reactor continuously with the speed of 3L/min.In the case, under 200 ℃ of constant temperature, carry out solid state polymerization comprises siloxanes with preparation high molecular modified polycarbonate.The result is as shown in table 2.

Table 2

Time	Embodiment 2		The comparative example 2
	Embodiment 2		The comparative example 2		Weight-average molecular weight	PDI	Weight-average molecular weight	PDI
	0	15578	2.79	8804	Weight-average molecular weight	PDI	Weight-average molecular weight	PDI	2.4
2	0	15578	2.79	8804	33876	2.88	30225	2.69	2.4
2	4	35957	2.97	30982	33876	2.88	30225	2.69	2.96

6	38002	3.04	33324	3.23
6	38002	3.04	33324	3.23	8	38624	3.12	33996	3.52
10	39500	3.19	34523	3.8	8	38624	3.12	33996	3.52

As shown in table 2, according to embodiment 2, having made weight-average molecular weight in 4 hours is 35, the modified polycarbonate that comprises siloxanes of 000g/mol.On the contrary, according to comparative example 2, be 35 even be difficult to obtain weight-average molecular weight later in 10 hours in reaction, the modified polycarbonate that comprises siloxanes of 000g/mol.

Comparing embodiment 2 and comparative example 2 are found to compare with comparative example 2, are to be suitable for 20% to 30% of solid state polymerization according to the degree of crystallinity of the crystalline particle of embodiments of the invention 2 preparations.In addition, the crystalline particle of embodiment 2 preparation has deviation in mean diameter 80～3, and 20% the narrow diameter of 000 μ m distributes, this do not grind with the fractionated situation under control by changing spray condition.

And the present invention does not need the necessary other drying process of ordinary method, process of lapping and classification process, and therefore, operating time and running cost obviously reduce.Finally, after 10 hours, the weight-average molecular weight among the embodiment 2 is increased to 39,500g/mol at solid state polymerization.

In embodiment 2, after solid state polymerization, polydispersity index only increases by 14.5%, its be among the comparative example 2 polydispersity index increasing value 58.1% 1/4th.Therefore, in embodiment 2, can prevent the formation of low-quality product, low-quality product is indicated by high polydispersity index, and can stablize the product that obtains having homogeneous molecular weight and physicals in a large number.

Industrial applicibility

The invention provides and a kind ofly stablize, ensure the quality of products and only need the short time can prepare the modified polycarbonate preparation method of HMW modified polycarbonate.

Claims

1, a kind of method for preparing the high molecular modified polycarbonate resin, it comprises: with modified polycarbonate be dissolved in obtain solution in the solvent after, spray crystallization and solid state polymerization non-crystalline state modified polycarbonate simultaneously.

2, method according to claim 1, wherein said non-crystalline state modified polycarbonate are the polycarbonate that comprises ester group or siloxanes in a kind of chemical structure.

3, method according to claim 1, wherein said solvent are the mixtures of methylene dichloride, chloroform, tetrahydrofuran (THF), meta-cresol, hexanaphthene, diox, dimethyl aldehyde, pyridine or above-mentioned solvent.

4, method according to claim 1, the concentration of wherein said non-crystalline state modified polycarbonate solution are 5.0 to 50 weight %.

5, method according to claim 1, the crystallization of wherein said non-crystalline state modified polycarbonate comprises by nozzle spray non-crystalline state modified polycarbonate solution, and it is contacted with evaporating solvent with high-temperature gas, and remove thus and desolvate, make crystalline modified polycarbonate.

6, method according to claim 5, wherein said nozzle are pressure nozzle or air-blast atomizer.

7, method according to claim 6, wherein nozzle is the pressure nozzle and the non-crystalline state modified polycarbonate solution of spraying under 2.0～51.0kgf/ spray pressure.

8, method according to claim 6, wherein said nozzle are air-blast atomizers and inject pressurized gas with 200～800L/ hour injection speed.

9, method according to claim 8, wherein said pressurized gas comprises at least a N of being selected from₂, air and CO₂Gas.

10, method according to claim 5, wherein said high-temperature gas are that temperature is 40～250 ℃ N₂, air or CO₂

11, method according to claim 5, the mean diameter of wherein said crystalline modified polycarbonate pellets are 80-3000 μ m, and its limit of error is less than 30%.

12, a kind of method for preparing modified polycarbonate resin, this method comprises:

Spray crystallization non-crystalline state modified polycarbonate is to generate crystalline modified polycarbonate; With

The crystalline modified polycarbonate of solid state polymerization is to generate the high molecular modified polycarbonate.

13, according to the method for claim 12, wherein said non-crystalline state modified polycarbonate is that number-average molecular weight is 3,000-20, the non-crystalline state modified polycarbonate that comprises ester group of 000g/mol, and the modified polycarbonate of described solid state polymerization is that number-average molecular weight is 15,000-200, the modified polycarbonate that comprises ester group of 000g/mol.

14, method according to claim 12, wherein said non-crystalline state modified polycarbonate is that weight-average molecular weight is 10,000-30, the non-crystalline state modified polycarbonate that comprises siloxanes of 000g/mol, and the modified polycarbonate of described solid state polymerization is that weight-average molecular weight is 20,000-200, the modified polycarbonate that comprises siloxanes of 000g/mol.

15, method according to claim 12, wherein said non-crystalline state modified polycarbonate forms by the transesterify of interfacial polymerization process, dialkyl group (aryl) carbonic ether and aromatic dihydroxy compound or the transesterify and the condensation prepared of dialkyl group (aryl) carbonic ether and aromatic dihydroxy compound.

16, method according to claim 12, the spray crystallization of wherein said non-crystalline state modified polycarbonate comprises: the non-crystalline state modified polycarbonate is dissolved in makes solution in the solvent; By nozzle spray solution; And the solution of spraying is contacted with evaporating solvent with high-temperature gas, and remove thus and desolvate, make crystalline modified polycarbonate.