CN119431802A

CN119431802A - A polycarbonate-polyorganosiloxane copolymer and its preparation method and application

Info

Publication number: CN119431802A
Application number: CN202411832714.9A
Authority: CN
Inventors: 吴国章; 王辉; 王新宇; 王进森; 张洁
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2024-12-13
Filing date: 2024-12-13
Publication date: 2025-02-14

Abstract

The invention provides a polycarbonate-polyorganosiloxane copolymer, a preparation method and application thereof, and belongs to the technical field of polycarbonate material preparation. The polycarbonate-polyorganosiloxane copolymer comprises a polycarbonate block and a polyorganosiloxane block. According to the invention, the high-boiling point solvent capable of simultaneously dissolving the polyorganosiloxane and the polycarbonate is added, the high-boiling point cosolvent capable of improving the intersolubility of the polyorganosiloxane and other monomers (aromatic bisphenol compound and/or aliphatic diol compound and carbonic diester) is introduced into the melt transesterification polycondensation method, the intersolubility of the reaction monomers is improved in the transesterification stage, the conversion rate of the polyorganosiloxane is improved, and the transparency and the molecular weight of the copolymer are improved.

Description

Polycarbonate-polyorganosiloxane copolymer and preparation method and application thereof

Technical Field

The invention belongs to the technical field of preparation of polycarbonate materials, and particularly relates to a polycarbonate-polyorganosiloxane copolymer, a preparation method and application thereof.

Background

The polycarbonate has excellent optical transparency, impact toughness, dimensional stability, creep resistance and other performances, and has wide application, but bisphenol A polycarbonate has rigid benzene rings and carbonate bonds which are easy to attack by nucleophiles in the main chain, has higher melt viscosity and poor processing fluidity, is difficult to obtain thin-wall large-size products, has poor solvent resistance and weather resistance, is easy to generate stress cracking in the environment, and limits the use of the polycarbonate under certain special conditions. The polysiloxane is nontoxic and safe, has good environment, and the flexible siloxane long chain and side chain methyl groups can bring excellent lubrication and pollution resistance, low-temperature impact resistance and melt fluidity to the polymer, so that the defects of the polycarbonate can be effectively overcome.

In many cases, a polycarbonate-polyorganosiloxane copolymer is produced by the phosgene method, and although the polycarbonate-polyorganosiloxane produced by the phosgene method is excellent in transparency and mechanical properties, the phosgene method requires the use of highly toxic phosgene (phosgene) as a carbonate source, and also requires the use of methylene chloride, which is an environmentally heavy burden, as a solvent in the reaction, and a large amount of water is required for the post-treatment, which is economically and environmentally disadvantageous.

In order to avoid the above problems, production of a polycarbonate-polyorganosiloxane copolymer by a production method other than the phosgene method, for example, a melt polymerization method has been studied. However, since the solubility parameter of the polyorganosiloxane is 7.3cal ^1/2cm^3/2, the solubility parameter of the polycarbonate is 9.5cal ^1/2cm^3/2, the difference is large, the copolymer system is a thermodynamically incompatible system, microphase separation is caused, and the polyorganosiloxane and other monomers (such as carbonate monomers) cannot be completely mutually dissolved in melt polycondensation, so that the problem that the conversion rate of the polyorganosiloxane is not high (60-82%) exists, the surface property (such as hydrophobicity) and the optical transparency of the copolymer (the transmittance of a 3mm film of a polycarbonate-polyorganosiloxane copolymer prepared by a melt transesterification method is lower than 50%) are affected, and the free polyorganosiloxane in the processing process also causes mold pollution.

Disclosure of Invention

In view of the above, the present invention aims to provide a polycarbonate-polyorganosiloxane (PC-PDMS) copolymer, a preparation method and an application thereof. The method provided by the invention has higher conversion rate of the polyorganosiloxane, and the prepared polycarbonate-polyorganosiloxane copolymer has high molecular weight, small chromatic aberration and higher heat-resistant temperature.

In order to achieve the above object, the present invention provides the following solutions:

The invention provides a polycarbonate-polyorganosiloxane copolymer, which comprises a polycarbonate block and a polyorganosiloxane block, wherein the polycarbonate block is provided with a repeating unit with a structure shown in a formula A, and the polyorganosiloxane block is provided with a repeating unit with a structure shown in a formula B;

R ₁ in the formula A is an aliphatic alkylene group with 2-40 carbon atoms, an alicyclic alkylene group with 3-40 carbon atoms or a hydroxyl-substituted arylene group with 6-20 carbon atoms;

R ₂ in formula B has a structure represented by formula 1:

In the formula 1, n is 5-60, m is 1-20, and a, a1, b and b1 are independently 0 or 1;

r ₃～R₆ is independently-H, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms or aralkyl having 6 to 10 carbon atoms;

R ₇ and R ₈ are independently arylene groups having 6 to 20 carbon atoms, linear alkylene groups having 1 to 10 carbon atoms or alkyl-substituted arylene groups;

R ₉ and R ₁₀ are independently arylene groups having 6 to 20 carbon atoms, linear alkylene groups having 2 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms or alkyl-substituted arylene groups;

the light transmittance of the polycarbonate-polyorganosiloxane copolymer is 50% or more.

Preferably, R ₁ is an aliphatic alkylene group having 2 to 40 main chain carbon atoms, a cycloaliphatic alkylene group having 3 to 40 main chain carbon atoms or a hydroxy-substituted arylene group having 6 to 20 main chain carbon atoms.

Preferably, the mass of the polyorganosiloxane block is 0.5-20% of the total mass of the polycarbonate-polyorganosiloxane copolymer.

The invention provides a preparation method of the polycarbonate-polyorganosiloxane copolymer, which comprises the following steps:

Mixing carbonic acid diester, diol monomer, cosolvent and catalyst under protective atmosphere, and performing transesterification reaction to obtain a polycarbonate prepolymer, wherein the boiling point of the cosolvent is 200-400 ℃;

The diol monomer comprises a first component and a second component, wherein the first component is an aromatic bisphenol compound and/or an aliphatic diol compound, and the second component is polyorganosiloxane, and the polyorganosiloxane has a structure shown in a formula 2;

And (3) carrying out polycondensation reaction on the polycarbonate prepolymer to obtain the polycarbonate-polyorganosiloxane copolymer.

Preferably, the cosolvent comprises one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, 2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, bicyclohexane, 1,2, 3-tribromopropane, biphenyl, naphthalene and alpha-methylnaphthalene.

Preferably, the transesterification reaction comprises the steps of heating from 160 ℃ to 180 ℃, preserving heat for 1-3 hours, heating to 210 ℃ and preserving heat for 1-3 hours.

Preferably, the polycondensation reaction comprises the steps of heating from 210 ℃ to 275 ℃, simultaneously decompressing to be less than or equal to 50Pa, and then preserving heat and pressure for 0.5-5 h.

Preferably, the carbonic acid diester includes diphenyl carbonate or dimethyl carbonate.

Preferably, the aromatic bisphenol compound includes one or more of 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane and 1, 1-bis (4-hydroxyphenyl) cyclododecene;

The aliphatic diol compound comprises one or more of isosorbide, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-propanediol and 1, 4-butanediol.

The invention provides an application of the polycarbonate-polyorganosiloxane copolymer prepared by the scheme or the preparation method of the scheme in engineering plastics.

R ₂ in formula B has a structure represented by formula 1:

R ₃～R₆ is independently-H, alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, aryl with 6-12 carbon atoms or aralkyl with 6-10 carbon atoms, R ₇ and R ₈ are independently arylene with 6-20 carbon atoms, linear alkylene with 1-10 carbon atoms or alkyl-substituted arylene, R ₉ and R ₁₀ are independently arylene with 6-20 carbon atoms, linear alkylene with 2-10 carbon atoms, branched alkylene with 3-10 carbon atoms or alkyl-substituted arylene, and the light transmittance of the polycarbonate-polyorganosiloxane copolymer is above 50%.

The reason why the conversion of the polyorganosiloxane is not high is that the polyorganosiloxane is not compatible with the carbonic acid diester and other diol monomers, and therefore the polyorganosiloxane cannot be sufficiently contacted with other monomers to react during the reaction. According to the invention, the high-boiling point solvent capable of simultaneously dissolving the polyorganosiloxane and the polycarbonate is added, the high-boiling point cosolvent capable of improving the intersolubility of the polyorganosiloxane and other monomers (aromatic bisphenol compound and/or aliphatic diol compound and carbonic diester) is introduced into the melt transesterification polycondensation method, the intersolubility of the reaction monomers is improved in the transesterification stage, the conversion rate of the polyorganosiloxane is improved, and the transparency and the molecular weight of the copolymer are improved.

The method provided by the invention has higher conversion rate of the polyorganosiloxane (namely lower free polysiloxane residue), the conversion rate of the polyorganosiloxane can reach more than 95%, and the prepared polycarbonate-polyorganosiloxane copolymer has high molecular weight, small chromatic aberration and higher heat-resistant temperature.

Further, the polycondensation reaction of the present invention is carried out at a high temperature under a high vacuum condition, and the solvent can be entirely removed.

The preparation method provided by the invention has little pollution.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a structure and a hydrogen spectrum of a polycarbonate-polyorganosiloxane copolymer obtained in example 1 of the present invention;

FIG. 2 is a structure and a hydrogen spectrum of a polycarbonate-polyorganosiloxane copolymer obtained in example 5 of the present invention;

FIG. 3 is a structure and a hydrogen spectrum of a polycarbonate-polyorganosiloxane copolymer obtained in example 6 of the present invention;

FIG. 4 is a structure and a hydrogen spectrum of a polycarbonate-polyorganosiloxane copolymer obtained in example 10 of the present invention;

FIG. 5 is a structure and a hydrogen spectrum of a polycarbonate-polyorganosiloxane copolymer obtained in example 11 of the present invention.

Detailed Description

R ₁ in the formula A is an aliphatic alkylene group having 2 to 40 carbon atoms, an alicyclic alkylene group having 3 to 40 carbon atoms or a hydroxy-substituted arylene group having 6 to 20 carbon atoms.

In the present invention, R ₁ is preferably an aliphatic alkylene group having 2 to 40 carbon atoms in the main chain, an alicyclic alkylene group having 3 to 40 carbon atoms in the main chain, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms in the main chain.

R ₂ in formula B has a structure represented by formula 1:

R ₇ and R ₈ are independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 1 to 10 carbon atoms or an alkyl-substituted arylene group, wherein the number of carbon atoms of the alkyl group in the alkyl-substituted arylene group is preferably 1 to 10, more preferably a dimethylene group, a methyl-substituted dimethylene group or a trimethylene group, and still more preferably a trimethylene group (- (CH ₂)₃).

R ₉ and R ₁₀ are independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms or an alkyl-substituted arylene group, wherein the alkyl group in the alkyl-substituted arylene group has preferably 1 to 10 carbon atoms, more preferably phenyl group, a dimethylene group (- (CH ₂)₂ -), a methyl-substituted dimethylene group (- (CH ₂ CHMe-), a trimethylene group (- (CH ₂)₃ -) or a tetramethylene group (- (CH ₂)₄ -), still more preferably trimethylene group (- (CH ₂)₃ -).

In the present invention, the selection of the above-described polyorganosiloxane structure can improve its affinity with other glycol monomers, thereby achieving uniform polymerization.

In the present invention, the mass of the polyorganosiloxane block is preferably 0.5 to 20%, more preferably 3 to 15%, and still more preferably 5 to 10% of the total mass of the polycarbonate-polyorganosiloxane copolymer.

In the present invention, the structure of the polycarbonate-polyorganosiloxane copolymer preferably has a structure represented by the formula a to formula:

in formula a, n=18, m=12.

In formula b, n=30.

In formula c, n=30.

In formula d, n=31.

In formula e, n=30.

In the present invention, the light transmittance of the polycarbonate-polyorganosiloxane copolymer is 50% or more, preferably 55 to 100%, and more preferably 60 to 85%.

Under the protective atmosphere, mixing carbonic diester, diol monomer, cosolvent and catalyst, and performing transesterification reaction to obtain polycarbonate prepolymer;

The materials and equipment used in the present invention are all commercially available products unless otherwise specified.

In the invention, carbonic diester, diol monomer, cosolvent and catalyst are mixed under protective atmosphere to carry out transesterification reaction, thus obtaining polycarbonate prepolymer.

In the present invention, the protective atmosphere preferably includes nitrogen. In the present invention, the carbonic acid diester preferably includes diphenyl carbonate or dimethyl carbonate, the diol monomer includes a first component and a second component, the first component is an aromatic bisphenol compound and/or an aliphatic diol compound, the second component is polyorganosiloxane, and the aromatic bisphenol compound preferably includes one or more of 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane and 1, 1-bis (4-hydroxyphenyl) cyclododecene, and the aliphatic diol compound preferably includes isosorbide, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, 3, 9-bis (1, 1-dimethyl-2-hydroxy-ethyl) -2, 8, 4-oxa-1, 5-butanediol, 1, 5-undecane, or 1, 5-butanediol.

In the present invention, the polyorganosiloxane has a structure represented by formula 2;

in the present invention, the polyorganosiloxane preferably includes one or more of phenolic hydroxyl silicone oil, alcoholic hydroxyl silicone oil and polyether silicone oil.

In the present invention, the preparation of the polyorganosiloxane preferably comprises the steps of:

and mixing polysiloxane, allyl-hydroxyl-containing compound and catalyst in a protective atmosphere, and carrying out polymerization reaction to obtain the polyorganosiloxane.

In the invention, the protective atmosphere preferably comprises nitrogen, and the polysiloxane preferably has a structure shown in a formula I;

In the present invention, the polysiloxane of the structure of formula I preferably comprises a polysiloxane having a siloxane average chain length of 18, a polysiloxane having a siloxane average chain length of 30, a polysiloxane having a siloxane average chain length of 42, or a polysiloxane having a siloxane average chain length of 31,

In the present invention, the allyl-hydroxyl group-containing compound preferably includes a compound having a structure represented by formula II, 2-allylphenol, or eugenol.

In the present invention, the compound of the structure shown in formula II preferably comprises allyl polyethylene glycol or ethylene glycol monoallyl ether having an average oxyethylene chain length of 12. In the present invention, the catalyst preferably comprises H ₂PtCl₆. In the present invention, the molar ratio of the polysiloxane to the allyl-hydroxyl-containing compound is preferably 1:2.2, and the molar amount of the catalyst is preferably 5ppm of the molar amount of the polysiloxane. In the present invention, the temperature of the polymerization reaction is preferably 110℃and the time is preferably 5 hours.

In the present invention, the molar ratio of the carbonic acid diester to the diol monomer is preferably (0.9 to 1.2): 1, more preferably (0.95 to 1.2): 1, and still more preferably (1 to 1.1): 1. In the present invention, if the molar ratio is less than 0.9, the terminal-OH groups of the resulting polycarbonate-polyorganosiloxane copolymer are increased, and the heat stability and water resistance of the polymer are poor, and if the molar ratio is more than 1.2, the transesterification reaction rate is decreased or a polycarbonate-polyorganosiloxane of a desired molecular weight is not obtained under the same conditions, and the residual amount of carbonic acid diester in the produced polycarbonate-polyorganosiloxane is increased.

In the present invention, the mass of the polyorganosiloxane is preferably 6% of the total mass of the diol monomers. In the invention, the boiling point of the cosolvent is 200-400 ℃, and the cosolvent preferably comprises one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, 2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, bicyclohexane, 1,2, 3-tribromopropane, biphenyl, naphthalene and alpha-methylnaphthalene. In the present invention, the molar ratio of the cosolvent to the diol monomer is preferably (0 to 10): 1, and is not 0, more preferably (2 to 8:1), and still more preferably (3 to 6): 1.

According to the invention, the high-boiling point solvent capable of simultaneously dissolving the polyorganosiloxane and the polycarbonate is added, the high-boiling point cosolvent capable of improving the intersolubility of the polyorganosiloxane and other monomers (aromatic bisphenol compound and/or aliphatic diol compound and carbonic diester) is introduced into the melt transesterification polycondensation method, the intersolubility of the reaction monomers is improved in the transesterification stage, the conversion rate of the polyorganosiloxane is improved, and the transparency and the molecular weight of the copolymer are improved.

The invention controls the mole ratio of the cosolvent and the diol monomer within the above range, can improve the affinity of the cosolvent and the diol monomer, thereby realizing uniform polymerization and having the advantage of economy.

In the present invention, the catalyst preferably includes one or more of a group IA metal compound, a group IIA metal compound, a group IB metal compound or a group IIB metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an organic amine compound, and an ionic liquid compound.

In the present invention, the group IA metal compound preferably includes one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylboride, potassium phenylboride, lithium phenylboride, cesium phenylboride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, cesium hydrogen phosphate, disodium phenyl phosphate, dilithium phenyl phosphate, sodium alkoxide, potassium alkoxide, lithium alkoxide, cesium alkoxide, sodium phenoxide, potassium phenoxide, lithium phenoxide, cesium phenoxide, disodium salt of bisphenol a, dipotassium salt, dilithium salt, and cesium salt.

In the present invention, the group IIA metal compound preferably includes one or more of calcium acetate, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium chloride, magnesium chloride, zinc chloride, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

In the present invention, the group IB metal compound preferably includes one or more of copper hydroxide, copper oxide, copper chloride, copper nitrate, copper stearate, copper sulfate, copper sulfite, copper benzoate, copper carbonate, copper bicarbonate, copper fluoride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper oxalate, and copper phosphate.

In the present invention, the group IIB metal compound preferably includes one or more of zinc hydroxide, zinc oxide, zinc chloride, zinc nitrate, zinc stearate, zinc sulfate, zinc sulfite, zinc benzoate, zinc carbonate, zinc bicarbonate, zinc fluoride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc oxalate, and zinc phosphate.

In the present invention, the basic boron compound preferably includes one or more of sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt and strontium salt of a boron compound, and the boron compound preferably includes one or more of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltritylboron and butyltriphenylboron.

In the present invention, the basic phosphorus compound preferably includes one or more of triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine and a quaternary phosphonium salt, more preferably a quaternary phosphonium salt.

In the present invention, the basic ammonium compound preferably includes one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide, and more preferably tetramethylammonium hydroxide from the viewpoint of reactivity and color of the resulting polycarbonate resin.

In the present invention, the organic amine compound preferably includes one or more of 4-aminopyridine, 2-aminopyridine, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.

In the present invention, the anion of the ionic liquid compound is preferably an amino acid-based anion or an amide-based anion.

In the present invention, the amino acid-based anion is preferably a lysine anion, a threonine anion, a valine anion, an alanine anion, a serine anion, a histidine anion, or an aspartic acid anion.

In the present invention, the amide-based anion is preferably N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-azacyclic ketone, 1, 8-naphthalenedicarboximide, 1, 2-cyclopentanediimide, 3-pentamethylene glutaiimide, 3-tetramethylene glutaiimide, 1,2,3, 6-tetrahydrophthalimide, hexahydrophthalimide, diacetamide, succinimide, glutarimide, adipoimide, maleimide, succinimide, phthalimide or bistrifluoroacetamide.

In the present invention, the cation of the ionic liquid compound is preferably a quaternary ammonium cation, a quaternary phosphonium cation, an imidazole cation, a pyridine cation or a piperidine cation.

In the present invention, the quaternary ammonium cation is preferably a tetraethylammonium cation, a tetrabutylammonium cation or a choline cation, the quaternary phosphine cation is preferably a tetrabutylphosphonium cation or a trihexyl (tetradecyl) phosphine cation, the imidazole cation is preferably a 1-ethyl-3-methylimidazole cation, a 1-propyl-3-methylimidazole cation, a 1-butyl-3-methylimidazole cation, a 1-pentyl-3-methylimidazole cation, a 1-hexyl-3-methylimidazole cation, a 1-benzyl-3-methylimidazole cation, a 1-ethyl acetate-3-methylimidazole cation, a 1-allyl-3-methylimidazole cation or a 1-2 (hydroxyethyl) -3-methylimidazole cation, the pyridine cation is preferably an N-ethylpyridine cation, and the piperidine cation is preferably an N-butyl-N-methylpiperidine cation.

In the present invention, when the catalyst comprises a group IA metal compound, a group IIA metal compound, a group IB metal compound or a group IIB metal compound, the molar amount of the catalyst is preferably 0.1 to 50ppm, more preferably 3 to 40ppm, still more preferably 10 to 30ppm, based on the total molar amount of the carbonic acid diester and the diol monomer, and when the catalyst comprises a basic phosphorus compound, a basic ammonium compound, an organic amine compound or an ionic liquid compound, the molar amount of the catalyst is preferably 1 to 1500ppm, more preferably 50 to 1000ppm, still more preferably 100 to 500ppm, based on the total molar amount of the carbonic acid diester and the diol monomer _.

In the invention, the transesterification reaction preferably comprises the steps of heating from 160 ℃ to 180 ℃, preserving heat for 1-3 hours, then heating to 210 ℃ and preserving heat for 1-3 hours. In the embodiment of the invention, the temperature is raised from 160 ℃ to 180 ℃, the temperature is kept for 1.5 hours, then the temperature is raised to 210 ℃, the temperature is kept for 1 hour, and the pressure of the transesterification reaction is preferably normal pressure.

After the polycarbonate prepolymer is obtained, the polycarbonate prepolymer is subjected to polycondensation reaction to obtain the polycarbonate-polyorganosiloxane copolymer.

In the invention, the polycondensation reaction preferably comprises the steps of heating from 210 ℃ to 275 ℃ and simultaneously decompressing to be less than or equal to 50Pa, and then preserving heat and pressure for 0.5-5 h. In the embodiment of the invention, the temperature is raised from 210 ℃ to 275 ℃ and reduced to less than or equal to 50Pa, and then the temperature and the pressure are maintained for 0.5h.

After the polycondensation reaction is completed, the obtained copolymer is preferably dissolved in methylene dichloride, the copolymer is sufficiently dissolved and then slowly dripped into ethanol to remove unreacted polyorganosiloxane monomers and oligomers, and then the obtained precipitate is repeatedly washed for three times, filtered and dried to obtain the polycarbonate-polyorganosiloxane copolymer. In the present invention, the temperature of the drying is preferably 100 ℃ and the time is preferably 24 hours.

In the present invention, since the copolymer is insoluble in ethanol and the oligomer and the polyorganosiloxane monomer are soluble in ethanol, the oligomer and the polyorganosiloxane monomer can be removed by separating the copolymer from the ethanol solution.

In the transesterification reaction, glycol monomers such as polyorganosiloxane, bisphenol A, isosorbide and the like react with carbonic acid diester such as diphenyl carbonate in a molten state, the glycol monomers remove a hydrogen and the diphenyl carbonate removes a phenoxy, so that the glycol monomers obtain a carbonate bond, and the byproduct is phenol, and the reaction is continued until the monomer reaction is complete.

In the present invention, in order to prevent yellowing and thermal deterioration, an additive may be added to the reaction system at the time of polymerization, at the end of polymerization or at the late stage of polymerization, and the additive preferably includes one or more of a hindered phenol antioxidant stabilizer, a phosphite antioxidant stabilizer, a heat stabilizer, a catalyst activity quencher, a UV absorber, a light stabilizer, a mold release agent and a hue adjuster. In the present invention, the hindered phenol based antioxidant stabilizer preferably includes an antioxidant 1010; the phosphite antioxidant stabilizer preferably comprises one or more of an antioxidant 36, an antioxidant 168 and bisphenol A phosphite; the heat stabilizer preferably comprises one or more of phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphate, tris (nonylphenyl) phosphate, tridecyl phosphite, trioctyl phosphite, didecyl phosphate, monophenyl phosphate, dioctyl monophenyl phosphate, diisopropyl monophenyl phosphate, monobutyl diphenyl phosphate, monodecyl diphenyl phosphate, monooctyl diphenyl phosphate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, 2-methylenebis (4, 6-di-tert-butylphenyl) octyl phosphate, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phosphate, diethyl phenylphosphate and dipropyl phenylphosphate, the catalytically active quencher preferably comprising methyl benzene sulfonic acid, the UV stabilizer preferably comprising P-salicylic acid, the UV stabilizer preferably comprising UV absorber P-UV absorber UV light stabilizer comprising UV-UV absorber P-UV absorber 46, the light stabilizer 944 and the light temperature agent BW-10LD, the release agent preferably comprises one or more of E-1338, E-3149 and E-3161, and the hue regulator preferably comprises one or more of bluing agent, ultramarine, permanent violet, phthalocyanine violet and cobalt violet.

The method of adding the above additives is not particularly limited, and the method is well known in the art. In the examples of the present invention, the addition is carried out in a twin-screw extruder, specifically, when the addition is selected at the time of polymerization and before the start of the reaction, i.e., when the transesterification reaction is started, and the addition is carried out again when the addition is selected at the end or later stage of the polymerization, i.e., the obtained material is mixed with the additive and then fed into the twin-screw extruder to be extruded.

The present invention is not particularly limited in the amount of the above-mentioned additives, and may be adjusted according to the kind of the additives.

For further explanation of the present invention, a polycarbonate-polyorganosiloxane copolymer, a method for producing the same, and applications thereof, which are provided in the present invention, are described in detail below with reference to examples and drawings, but they are not to be construed as limiting the scope of the present invention.

The structural formulas of PDMS-1 to PDMS-6 in examples 1 to 6 of the present invention are shown in Table 1.

Table 1 PDMS-1 to PDMS-6 structural formula

Preparation 1 preparation of PDMS-1 (polyorganosiloxane-1):

Allyl polyethylene glycol (100.2 g) having an average oxyethylene chain length of 12 (i.e., m is 12 in formula II) of the structure shown in formula II was added to a polysiloxane (80 g) having an average silicone chain length of 18 (i.e., n is 18 in formula I) in the presence of nitrogen in an amount of 2.2 times by mol relative to the polysiloxane, and 5ppm of H ₂PtCl₆ catalyst relative to the molar amount of silicone was added thereto, and the mixture was sufficiently stirred at 110℃for 5 hours to obtain colorless transparent polyether-modified polysiloxane PDMS-1.

Preparation 2 preparation of PDMS-2:

The only difference from preparation 1 is that "the polysiloxane having a siloxane average chain length of 18 as shown in formula I" is replaced with "the polysiloxane having a siloxane average chain length of 30 as shown in formula I (i.e., n is 30 in formula I)".

Preparation 3 preparation of PDMS-3:

The only difference from preparation 1 is that "the polysiloxane having a siloxane average chain length of 18 as shown in formula I" is replaced with "the polysiloxane having a siloxane average chain length of 42 as shown in formula I (i.e., n is 42 in formula I)".

Preparation 4 preparation of PDMS-4:

The difference from preparation 1 is only that "the polysiloxane having a siloxane average chain length of 18 represented by formula I" is replaced with "the polysiloxane having a siloxane average chain length of 31 represented by formula I (i.e., n is 31 in formula I)", and "the allyl polyethylene glycol having an average oxyethylene chain length of 12 represented by formula II" is replaced with "ethylene glycol monoallyl ether (CH ₂＝CHCH₂-O-CH₂CH₂ -OH) (i.e., m is 1 in formula II)".

Preparation 5 preparation of PDMS-5:

The only difference from preparation 1 is that "the polysiloxane having a siloxane average chain length of 18 represented by formula I" is replaced with "the polysiloxane having a siloxane average chain length of 30 represented by formula I (i.e., n is 30 in formula I)", and "the allylpolyethylene glycol having an average oxyethylene chain length of 12 represented by formula II" is replaced with "2-allylphenol".

Preparation 6 preparation of PDMS-6:

The difference from preparation 1 is only that "the polysiloxane having a siloxane average chain length of 18 represented by formula I" is replaced with "the polysiloxane having a siloxane average chain length of 30 represented by formula I (i.e., n is 30 in formula I)", and "the allyl polyethylene glycol having an average oxyethylene chain length of 12 represented by formula II" is replaced with "eugenol".

Example 1

7.583G of diphenyl carbonate, 8.002g of bisphenol A (BPA), 0.569g of PDMS-1 (polyorganosiloxane), 5.608g of cyclohexylbenzene (cosolvent), 10ppm of cesium carbonate and 100ppm of tetramethylammonium hydroxide are added into a 100mL three-neck flask at room temperature, and transesterification reaction is carried out under the protection of nitrogen atmosphere, wherein the mixture is heated to 160 ℃ and then stirred for 20min for melting, then heated to 180 ℃ and then heated to 180 ℃ for 1.5h, and then heated to 210 ℃ and then heated for 1h (30 min is heated to 210 ℃ from 180 ℃) to obtain polycarbonate prepolymer;

And (3) carrying out polycondensation reaction on the polycarbonate prepolymer, raising the temperature from 210 ℃ to 275 ℃ (2 h from 210 ℃ to 275 ℃), reducing the pressure to be less than or equal to 50Pa while raising the temperature, and after the temperature and the pressure reach the requirements (namely, raising the temperature to 275 ℃ and reducing the pressure to be less than or equal to 50 Pa), preserving the heat and the pressure for 0.5h, and finishing the reaction to obtain the copolymer.

The resulting copolymer was dissolved in 50mL of methylene chloride, and after sufficient dissolution, was slowly dropped into 500mL of ethanol to remove unreacted polyorganosiloxane monomer and oligomer (the copolymer was not dissolved in ethanol, but the oligomer and the polyorganosiloxane monomer were dissolved in ethanol, and the copolymer was separated from the ethanol solution to remove the oligomer and the polyorganosiloxane monomer), and the resulting precipitate was repeatedly washed three times, suction-filtered and vacuum-dried at 100℃for 24 hours to obtain the polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 2.

As shown in fig. 1, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in example 1 are shown, n=18, m=12 in fig. 1. The hydrogen spectrum data are as follows:

Wherein 0ppm is the chemical shift in the backbone of the polyorganosiloxane repeat unit (Si-CH ₃), 0.45ppm is the first methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 1.45ppm is the chemical shift in the BPA repeat unit where-CH ₃ is superimposed with the second methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 3.6ppm are the chemical shifts of the third methylene group of the polyorganosiloxane near the Si-O-Si bond with the polyether group, and 7.1 and 7.2ppm are the chemical shifts of the four protons of the benzene ring on the BPA repeat unit, respectively.

From the above data and analysis of the spectra, the obtained product was the target product carbonate-polyorganosiloxane copolymer having the structure shown in FIG. 1.

Example 2

The same procedure as in example 1 was repeated except that 7.617g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-2, 5.608g of cyclohexylbenzene, 10ppm of potassium carbonate and 100ppm of tetraethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 2.

The structure of the polycarbonate-polyorganosiloxane copolymer obtained in example 2 is similar to that of example 1, except that the chain length of the PDMS-2 portion differs, i.e., the a-peak height in FIG. 1.

Example 3

The same procedure as in example 1 was repeated except that 7.609g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-3, 5.608g of cyclohexylbenzene, 10ppm of potassium hydroxide and 100ppm of tetrabutylammonium hydroxide were charged into a 100mL three-necked flask at room temperature, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 2.

The structure of the polycarbonate-polyorganosiloxane copolymer obtained in example 3 is similar to that of example 1, except that the chain length of the PDMS-3 moiety differs, i.e., the a-peak height in FIG. 1.

Example 4

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-4, 5.608g of cyclohexylbenzene, 5ppm of cesium hydroxide and 150ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer at the end of the reaction, and the evaluation results are shown in Table 2.

The structure of the polycarbonate-polyorganosiloxane copolymer obtained in example 4 was similar to that of example 1, except that the chain length of the PDMS-3 moiety was different, i.e., the peak height of a was different in FIG. 1, and the peak e+f was smaller.

Example 5

The same procedure as in example 1 was repeated except that 7.637g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-5, 5.608g of cyclohexylbenzene, 15ppm of cesium carbonate and 50ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer at the end of the reaction, and the evaluation results are shown in Table 2.

As shown in fig. 2, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in example 5 are shown, where n=30 in fig. 2. The hydrogen spectrum data are as follows:

Wherein 0ppm is the chemical shift in the backbone of the polyorganosiloxane repeat unit (Si-CH ₃), 0.45ppm is the first methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 1.45ppm is the chemical shift in the BPA repeat unit where-CH ₃ is superimposed with the second methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 2.6ppm is the chemical shift of the third methylene group of the polyorganosiloxane repeating unit near the Si-O-Si bond, and 7.1 and 7.2ppm are the chemical shifts of the four protons of the benzene ring on the BPA repeating unit and the four protons of the benzene ring in the polyorganosiloxane repeating unit, respectively.

From the above data and analysis of the spectra, the obtained product was the target product carbonate-polyorganosiloxane copolymer having the structure shown in FIG. 2.

Example 6

The same procedure as in example 1 was repeated except that 7.636g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-6, 5.608g of cyclohexylbenzene, 2ppm of cesium hydroxide and 100ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer at the end of the reaction, and the evaluation results are shown in Table 2.

As shown in fig. 3, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in example 6 of the present invention are shown, where n=30 in fig. 3.

The hydrogen spectrum data are as follows:

Wherein 0ppm is the chemical shift in the backbone of the polyorganosiloxane repeat unit (Si-CH ₃), 0.45ppm is the first methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 1.45ppm is the chemical shift in the BPA repeat unit where-CH ₃ is superimposed with the second methylene of the polyorganosiloxane repeat unit adjacent to the Si-O-Si bond, 2.6ppm is the chemical shift of the polyorganosiloxane repeat unit near the third methylene of the Si-O-Si bond and 3.8ppm is the chemical shift of-CH ₃ on the polyorganosiloxane repeat unit. 7.1 and 7.2ppm are chemical shifts of four protons of benzene rings on the BPA repeat unit and three protons of benzene rings in the polyorganosiloxane repeat unit, respectively.

From the above data and analysis of the spectra, the obtained product was a target product carbonate-polyorganosiloxane copolymer having a structure shown in FIG. 3.

Example 7

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-4, 4.844g of isophorone and 10ppm of cesium carbonate were charged into a 100mL three-necked flask at room temperature, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 2.

Example 8

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 8.002g of BPA, 0.569g of PDMS-4, 4.206g of sulfolane and 5ppm of cesium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer at the end of the reaction, and the evaluation results are shown in Table 2.

Example 9

The same procedure as in example 1 was repeated except that 7.603g of diphenyl carbonate, 4.547g of Isosorbide (ISB), 0.505g of 1, 4-Cyclohexanedimethanol (CHDM), 0.569g of PDMS-3, 4.206g of cyclohexylbenzene and 10ppm of potassium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

Example 10

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 4.547g of ISB, 0.505g of CHDM, 0.569g of PDMS-4, 4.206g of cyclohexylbenzene and 1000ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

As shown in fig. 4, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in example 10 of the present invention are shown, where n=31 in fig. 4.

The hydrogen spectrum data are as follows:

Wherein 0ppm is the chemical shift of the polyorganosiloxane repeating unit backbone (Si-CH ₃), 0.45ppm is the first methylene of the polyorganosiloxane repeating unit near the Si-O-Si bond, 1.45ppm is the chemical shift of the polyorganosiloxane repeating unit near the second methylene of the Si-O-Si bond, 1, 1.5ppm is the cis-and trans-chemical shift of-CH ₂ -on CHDM, three nuclear magnetic peaks between 3 and 4ppm are the chemical shift of three-CH ₂ -on the polyorganosiloxane repeating unit, 4ppm is the chemical shift of-CH ₂ -on isosorbide, and 4.85 and 4.5ppm are the two H proton peaks on isosorbide. 5ppm is the H proton peak of isosorbide near ether linkage.

From the above data and analysis of the spectra, the obtained product was the target product carbonate-polyorganosiloxane copolymer having the structure shown in FIG. 4.

Example 11

The same procedure as in example 1 was repeated except that 7.637g of diphenyl carbonate, 4.547g of ISB, 0.505g of CHDM, 0.569g of PDMS-5, 4.206g of cyclohexylbenzene, 10ppm of calcium chloride and 100ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

As shown in FIG. 5, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in example 11 of the present invention are shown.

The hydrogen spectrum data are as follows:

Wherein 0ppm is the chemical shift on the polyorganosiloxane repeating unit backbone (Si-CH ₃), 0.45ppm is the first methylene of the polyorganosiloxane repeating unit near the Si-O-Si bond, 1.45ppm is the chemical shift of the second methylene of the polyorganosiloxane repeating unit near the Si-O-Si bond, 1, 1.5ppm is the cis-and trans-chemical shift of-CH ₂ -on CHDM, 2.6ppm is the chemical shift of the third-CH ₂ -on the polyorganosiloxane repeating unit, 4ppm is the chemical shift of-CH ₂ -on isosorbide, and 4.85, 4.5ppm are the two H proton peaks on isosorbide. 5ppm is the H proton peak of isosorbide near ether linkage. The chemical shift of benzene ring protons on polyorganosiloxane is around 7 ppm.

From the above data and analysis of the spectra, the obtained product was a target product carbonate-polyorganosiloxane copolymer having a structure shown in FIG. 5.

Example 12

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 3.586g of ISB, 1.516g of CHDM, 0.569g of PDMS-4, 4.837g of isophorone, 10ppm of sodium hydroxide and 100ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

Example 13

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 3.586g of ISB, 1.516g of CHDM, 0.569g of PDMS-4, 4.212g of sulfolane, 10ppm of calcium acetate and 100ppm of tetramethylammonium hydroxide were charged into a 100mL three-necked flask at room temperature to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

Example 14

The same procedure as in example 1 was repeated except that 7.616g of diphenyl carbonate, 3.586g of ISB, 1.516g of CHDM, 0.569g of PDMS-4, 4.212g of N-methylpyrrolidone, 10ppm of potassium carbonate and 100ppm of tetrabutylammonium hydroxide were charged into a 100mL three-necked flask at room temperature, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 3.

TABLE 2 Properties of polycarbonate-polyorganosiloxane copolymers prepared in examples 1 to 8

TABLE 3 Properties of polycarbonate-polyorganosiloxane copolymers prepared in examples 9 to 14

In tables 2 to 3, wt% of the polyorganosiloxane (B) is represented, and the amount of the polyorganosiloxane (B) to be charged contained in the mass (theoretical value) of the obtained polycarbonate-polyorganosiloxane copolymer is calculated by the following formula.

Polycarbonate-polyorganosiloxane copolymer mass (theoretical value) =total diol monomer mass+carbonic acid diester mass-produced phenol mass (2 times mole of carbonic acid diester phenol), units are g.

Amount of polyorganosiloxane (B) =mass of polyorganosiloxane (i.e. amount dosed, unit g)/[ mass of polycarbonate-polyorganosiloxane copolymer (theoretical value) ].

Comparative example 1

The procedure of example 1 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 2

The procedure of example 2 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 3

The procedure of example 3 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 4

The same procedure as in example 4 was followed except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the results are shown in Table 4.

Comparative example 5

The procedure of example 5 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 6

The procedure of example 6 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 7

The procedure of example 9 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 8

The procedure of example 10 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 9

The procedure of example 11 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Comparative example 10

The procedure of example 12 was repeated except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer, and the evaluation results are shown in Table 4.

Table 4 Properties of the polycarbonate-polyorganosiloxane copolymers prepared in comparative examples 1 to 10

In table 4, wt% of the polyorganosiloxane (B) is represented, and the amount of the fed polyorganosiloxane (B) contained in the mass (theoretical value) of the obtained polycarbonate-polyorganosiloxane copolymer is calculated by the following formula.

The performance test methods in the examples and comparative examples of the present invention are as follows:

(1) Intrinsic viscosity number

The polycarbonate-polyorganosiloxane copolymer was dissolved in chloroform to a concentration C of 0.01g/mL and measured at a temperature of 25.+ -. 0.5 ℃ using a Ubbelohde viscometer. Wherein, the intrinsic viscosity [ eta ] is determined according to the following formula.

Where t is the flow time of the solution and t ₀ is the flow time of the solvent alone.

(2) Transmittance of light

The transmittance of the 0.1mm thick polycarbonate-polyorganosiloxane copolymer film was measured in the range of 380 to 780nm using an ultraviolet/visible spectrophotometer (UV 1900, youke Instrument), and the total transmittance T _total (%) of the copolymer film in the visible light region was calculated by the following.

Wherein T (lambda) represents the transmittance of the corresponding wavelength, and 780nm and 380nm both represent the wavelength.

(3) Chromatic aberration

0.1G of the polycarbonate-polyorganosiloxane copolymer was sufficiently dissolved in 10mL of chloroform. The solution was measured using an ultraviolet/visible spectrophotometer (UV 1900, youke Instrument) and the color difference (Δc) was calculated according to the following formula.

Wherein T ₆₀₀、T₅₅₅ and T ₄₄₅ represent the transmittance of the solution at 600,555,4475 nm, respectively, and t=t ₆₀₀+T₅₅₅+T₄₄₅.

(4) Method for quantifying conversion of polyorganosiloxane

For example, the method for quantifying the polydimethylsiloxane having undergone the transesterification reaction contained in the polycarbonate-polyorganosiloxane copolymer obtained in example 1.

A is an integral value of methyl groups of the dimethylsiloxane portion observed in the vicinity of delta-0.02 to 0.3;

B, an integrated value of H protons of ISB observed in the vicinity of δ4.3-4.6;

c, an integral value of methylene at the end of dimethylsiloxane observed in the vicinity of δ0.4 to 0.6;

d, an integral value of methylene of CHDM observed in the vicinity of δ0.8-1.5;

e, integration value of methylene of PEG part observed near delta 3.3-3.8;

a=a/6b=B c=C/4d=D/4e=E/4;

T=a+b+c+d+e;

f=a/T×100g=b/T×100h=c/T×100i=d/T×100j=e/T×100;

TW=f×74.1+g×172+h×116+i×170+j×44;

The mass ratio of polyorganosiloxane blocks in the copolymer W _PDMS = g x 74.1/TW x 100;

Conversion (%) =w _PDMS/W₀,W₀ is the mass ratio of diol monomer to polyorganosiloxane (B) in tables 2 to 4.

In summary, the polycarbonate-polyorganosiloxane copolymer of the present invention has a higher molecular weight (expressed as intrinsic viscosity) and a higher heat-resistant temperature (expressed as glass transition temperature) than a polycarbonate-polyorganosiloxane copolymer without adding a cosolvent, and the polyorganosiloxane conversion is improved by 2 to 20%, and particularly, the use of cyclohexylbenzene as a cosolvent has an optimal effect on the improvement of the conversion, and the polyorganosiloxane conversion in a part of the polycarbonate-polyorganosiloxane copolymer is improved by 95% or more, while the transparency (expressed as light transmittance) and the light resistance (expressed as color difference) are also improved due to the addition of the cosolvent, and thus, the polycarbonate-polyorganosiloxane copolymer is useful as a molding material for various injection molding, extrusion molding, compression molding and the like in the engineering plastic field.

Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.

Claims

1. A polycarbonate-polyorganosiloxane copolymer comprises a polycarbonate block and a polyorganosiloxane block, wherein the polycarbonate block has a repeating unit with a structure shown in a formula A, and the polyorganosiloxane block has a repeating unit with a structure shown in a formula B;

R ₂ in formula B has a structure represented by formula 1:

2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein R ₁ is an aliphatic alkylene group having 2 to 40 main chain carbon atoms, a cycloaliphatic alkylene group having 3 to 40 main chain carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 main chain carbon atoms.

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the mass of the polyorganosiloxane block is 0.5 to 20% of the total mass of the polycarbonate-polyorganosiloxane copolymer.

4. The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3, comprising the steps of:

5. The method according to claim 4, wherein the cosolvent comprises one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethylsulfoxide, 2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, dicyclohexyl, 1,2, 3-tribromopropane, biphenyl, naphthalene, and α -methylnaphthalene.

6. The method according to claim 4 or 5, wherein the transesterification reaction comprises heating from 160 ℃ to 180 ℃, maintaining the temperature for 1 to 3 hours, and then heating to 210 ℃ and maintaining the temperature for 1 to 3 hours.

7. The method according to claim 4, wherein the polycondensation reaction comprises heating from 210 ℃ to 275 ℃ while reducing the pressure to 50Pa or less, and then maintaining the temperature for 0.5 to 5 hours.

8. The method of claim 4 or 5, wherein the carbonic acid diester comprises diphenyl carbonate or dimethyl carbonate.

9. The production method according to claim 4 or 5, wherein the aromatic bisphenol compound comprises one or more of 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane and 1, 1-bis (4-hydroxyphenyl) cyclododecene;

10. The use of the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3 or the polycarbonate-polyorganosiloxane copolymer prepared by the preparation method according to any one of claims 4 to 9 in engineering plastics.