CN114957673A - Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin composition containing same - Google Patents
Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin composition containing same Download PDFInfo
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Abstract
The invention relates to a polysiloxane-polycarbonate copolymer, a preparation method and a polycarbonate resin composition containing the same, wherein the main chain of the polysiloxane-polycarbonate copolymer comprises a structural unit shown in a formula (I) and a structural unit shown in a formula (II), and the residual weight of free siloxane of the polysiloxane-polycarbonate copolymer is less than 200 ppm. The polysiloxane-polycarbonate copolymer of the present invention is blended with bisphenol A type polycarbonate to obtain a polycarbonate resin composition having a siloxane content of 3.5% and an impact strength at-60 ℃ (ASTM D256) > 500J/m。
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polycarbonate-polysiloxane copolymer, a preparation method thereof and a resin composition containing the copolymer.
Background
Polycarbonate (PC) is a high molecular polymer containing carbonate bonds in molecular chains, and can be divided into aliphatic, alicyclic, aliphatic-aromatic and aromatic polycarbonates, wherein the aromatic polycarbonate has excellent mechanical properties, heat resistance, impact toughness, electrical insulation and light transmission, low creep resistance and water absorption, good dimensional stability, excellent dielectric properties and the like, can be used as a thermoplastic engineering plastic and is widely applied to the fields of automobiles, electronic equipment, buildings, office supplies, optical discs, sports equipment, medical care, computers, aerospace and the like. However, common PC also has certain defects, such as poor solvent resistance, easy occurrence of stress cracking after touching a solvent, poor impact performance at low temperature, limitation of application in low temperature places, and the like, and needs to be modified in order to widen the application field thereof.
It is known that the low-temperature impact resistance, chemical resistance and the like of polycarbonate materials can be improved by modifying the polycarbonate materials, such as by adding silicon-based modification and improving the low-temperature impact strength of polycarbonate by blending; the low-temperature resistance of the modified polycarbonate can be improved by copolymerizing polycarbonate and polysiloxane, and compared with the blending modification means, the modified polycarbonate has more reliable and more excellent performance and is remarkable in flame retardance, low-temperature impact resistance, chemical corrosion resistance, aging resistance and the like. Has been widely used for producing products such as consumer electronics cover plates, sheaths, brackets, helmets, new energy vehicles charging piles, charging guns and the like.
Chinese patent CN201710159031.5 discloses a low temperature resistant non-transparent high impact random copolycarbonate and a preparation method thereof, wherein the preparation method is to add polysiloxane monomer in one step, and the polymer prepared by the method is easy to have the problem of peeling; chinese patent CN 201080029663.6 proposes that when the average size of a polydiorganosiloxane phase region in a polyorganosiloxane-polycarbonate copolymer is 5-40 nm and the standardized dispersion is below 30%, the polyorganosiloxane-polycarbonate copolymer has good light transmission, but the low-temperature impact resistance and chemical resistance of the copolymer are poor.
In view of the above, it is desirable to develop a polysiloxane-polycarbonate copolymer having excellent low-temperature impact resistance and chemical resistance and a method for preparing the same, and to develop a resin composition comprising the polysiloxane-polycarbonate copolymer.
Disclosure of Invention
The present inventors have conducted extensive studies on the phase domains/domains of siloxane formed by the siloxane segments of a polysiloxane-polycarbonate copolymer, and as the siloxane phase domains are larger, the low temperature impact resistance and chemical resistance of the polysiloxane-polycarbonate copolymer material are better, but the siloxane monomers remaining in the polymer solution during the polymerization process are difficult to remove during the post-treatment process, i.e., the polymer solution is purified and devolatilized to obtain a polymer solid containing free polysiloxane monomers, and have found that the effect of such free polysiloxane monomers introduced during the polymerization process and the siloxane monomers introduced subsequently by blending (e.g., by twin screw extrusion after mixing silicon copolpc powder with silicone oil) is not the same as the effect on the material properties, especially on the low temperature impact resistance and chemical resistance of the material.
The inventor of the invention researches the phase region of polysiloxane-polycarbonate copolymer containing residual siloxane monomer in the polymerization process to find that the residual siloxane monomer can be aggregated with polysiloxane chain segments bonded on the main chain of the polymer to form silicon domains, free siloxane monomer plays the role of a lubricant in the silicon domains to reduce the stability of the silicon domains, and when the material is impacted, especially at low temperature, the silicon domains are more likely to slide molecular chains, namely, partial siloxane chain segments are staggered with each other to reduce the silicon domains, which macroscopically shows that the low-temperature impact resistance of the material is reduced.
The present invention has been accomplished by finding that the low temperature impact resistance and chemical resistance of a material can be improved by controlling the content of free siloxane monomer in a polysiloxane-polycarbonate copolymer.
An object of the present invention is to provide a polysiloxane-polycarbonate copolymer having a small free siloxane residue, and a polycarbonate resin composition containing the same has excellent low-temperature impact resistance and chemical resistance.
It is still another object of the present invention to provide a method for preparing such a polysiloxane-polycarbonate copolymer.
It is still another object of the present invention to provide a polycarbonate resin composition containing such a polysiloxane-polycarbonate copolymer, which has excellent low-temperature impact resistance and chemical resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polysiloxane-polycarbonate copolymer comprising polycarbonate structural units of formula (I) and polysiloxane structural units of formula (II), wherein the polysiloxane-polycarbonate copolymer has a residual free siloxane content of less than 200ppm, preferably a polysiloxane block moiety content of 5 to 45% by mass,
in the formula (I), R 1 And R 2 Each independently represents hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; a and b independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alicyclic group having 6 to 20 carbon atoms, or a group represented by the formula (a):
wherein R is ’ And R "Independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; or R ’ And R' together form a C4-20 alicyclic ring, said C4-20 alicyclic ring optionally substituted with one or more C1-20 alkyl, C6-20 aryl, C7-21 aralkyl, C5-20 cycloalkyl groups, or combinations thereof;
R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue.
In a specific embodiment, the polycarbonate structural unit shown in the formula (I) is a structural unit derived from bisphenol A shown in the formula (III),
in a particular embodiment, the polysiloxane structural unit of formula (II) is a structural unit derived from polydimethylsiloxane of formula (IV), the polydimethylsiloxane end group is a phenolic hydroxyl group, Y is an organic residue derived from phenols having ethylenically unsaturated carbon-carbon bonds, preferably allylphenols or eugenols;
wherein, R is connected on a benzene ring 5 The structure (A) represents the residue of said phenol after removal of the hydroxyl group from the phenyl ring, R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; preferably, R 5 The type selection and the position of the phenol correspond to the substituent groups on the phenol benzene ring one by one; wherein p is 0 to 5, preferably 0 to 3; n is the average number of repetitions, n is an integer of 20 to 150, preferably 40 to 100;
preferably, the structural unit represented by formula (IV) is derived from any one of allylphenol-polydimethylsiloxane, preferably 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, and more preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane.
In a specific embodiment, the polysiloxane-polycarbonate copolymer has a viscosity average molecular weight of 15000 to 55000g/mol, preferably 18000 to 35000 g/mol.
On the other hand, the preparation method of the polysiloxane-polycarbonate copolymer adopts an interfacial phosgene continuous method process, and the reaction process comprises continuous two-stage photochemical reaction and three-stage polycondensation reaction.
In a particular embodiment, the method comprises the following steps:
(1) preparing a monomer solution: respectively preparing siloxane monomer solution, phosgene solution, alkali metal hydroxide salt solution of diphenol compound, end capping agent solution, alkali metal hydroxide solution and catalyst solution with certain concentration;
(2) carrying out a continuous polymerization reaction:
step A-1: siloxane monomer solution and phosgene solution are continuously input into the system, are contacted with continuously input alkali metal hydroxide salt solution of diphenol compound after being preliminarily mixed, and mixed reaction liquid enters a primary photochemical reaction kettle R-1 to carry out primary photochemical reaction;
step A-2: the reaction liquid continuously output from the first-stage photochemical reaction kettle R-1 is contacted with the continuously input alkali metal hydroxide salt solution, the end capping agent solution, the alkali metal hydroxide solution and the phosgene solution of the dihydric phenol compound, and the mixture enters a second-stage photochemical reaction kettle R-2;
step A-3: mixing the reaction liquid continuously output from the second-stage photochemical reaction kettle R-2 with the input alkali metal hydroxide solution, then contacting and mixing with the catalyst solution, continuously feeding the mixed reaction liquid into the first-stage polycondensation reaction kettle R-3, staying for a certain time, feeding the mixed reaction liquid into the second-stage polycondensation reaction kettle R-4, staying for a certain time, feeding the mixed reaction liquid into the third-stage polycondensation reaction kettle R-5, and after staying for a certain time, feeding the reaction liquid into a post-treatment process;
(3) and (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain polysiloxane-polycarbonate copolymer;
in a preferred embodiment, the method comprises the following steps:
(1) preparing a monomer solution: in D-1, a polysiloxane monomer terminated by end phenol is dissolved in an inert organic solvent to prepare a siloxane monomer solution with a certain concentration; dissolving phosgene in inert organic solvent in D-2 and D-7 to prepare phosgene solution with certain concentration; dissolving the diphenol compound in the D-3 and D-4 aqueous solution of alkali metal hydroxide to prepare an alkali metal hydroxide salt solution of the diphenol compound with a certain concentration; dissolving a blocking agent in an inert organic solvent in D-5 to prepare a blocking agent solution with a certain concentration; dissolving alkali metal hydroxide in water in D-6 and D-8 to prepare an alkali metal hydroxide solution with a certain concentration; dissolving a catalyst in an inert organic solvent in D-9 to prepare a catalyst solution with a certain concentration;
(2) carrying out a continuous polymerization reaction:
step A-1: continuously inputting a siloxane monomer solution in the D-1 and a phosgene solution in the D-2 into a system, mixing the siloxane monomer solution and the phosgene solution in the D-2 in a pipeline through a mixer, contacting with an alkali metal solution hydroxide salt solution of a dihydric phenol compound continuously input from the D-3, and carrying out heat exchange and mixing on a mixed reaction liquid, and then, entering a primary photochemical reaction kettle R-1 for carrying out primary photochemical reaction;
step A-2: the reaction liquid continuously output from the first-stage photochemical reaction kettle R-1 is contacted with reactants continuously input from D-4, D-5, D-6 and D-7 in a pipeline, and the reactants enter a second-stage photochemical reaction kettle R-2 after being mixed;
step A-3: after the reaction liquid continuously output from the second-stage photochemical reaction kettle R-2 is mixed with the reactant input from D-8, the reaction liquid is contacted with the catalyst continuously input from D-9, after mixing, the mixed reaction liquid continuously enters the first-stage polycondensation reaction kettle R-3, after staying for a certain time, the mixed reaction liquid enters the second-stage polycondensation reaction kettle R-4, after staying for a certain time, the mixed reaction liquid enters the third-stage polycondensation reaction kettle R-5, and after staying for a certain time, the reaction liquid enters the post-treatment process;
(3) and (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain the polysiloxane-polycarbonate copolymer.
In a particular embodiment, the amount of each reactant satisfies the following formula:
wherein, Y 1 M is the weight fraction of the continuous output of the diphenolic compound in D-3 per unit time 1 Is the molar molecular weight of the dihydric phenol compound in D-3, Y 2 Is the weight fraction of the continuous output of the diphenolic compound in D-4 per unit time, M 2 Is the molar molecular weight of the dihydric phenol compound in D-4, Z 1 Is the weight fraction of siloxane monomer continuously added to the system per unit time.
In a specific embodiment, the end-capping agent is selected from any one of phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, preferably p-tert-butylphenol or p-cumylphenol;
preferably, the catalyst is selected from any one of tertiary amine and quaternary amine, preferably triethylamine or tetrabutylammonium chloride;
preferably, the alkali metal hydroxide solution is selected from aqueous solutions of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, preferably aqueous sodium hydroxide;
preferably, the inert organic solvent is selected from halogenated hydrocarbon solvents that can dissolve the resulting polycarbonate resin, preferably any one of dichloromethane (methylene dichloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, dichlorobenzene, and more preferably dichloromethane.
In a specific embodiment, the diphenol compound has a structure represented by formula (V),
wherein R is 1 、R 2 A, b and X are as defined in formula (I);
preferably, the diphenol compound of formula (v) is at least one selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane [ bisphenol a ], bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, bis (hydroxyphenyl) alkane of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4,4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone, preferably bisphenol a.
In a specific embodiment, the concentration of the diphenol compound in the alkali metal hydroxide salt solution of the diphenol compound is 150 to 200g/L, preferably 160 to 170 g/L;
the siloxane monomer solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the mass concentration of the siloxane monomer solution is 10-20%, preferably 15%;
the mass concentration of the catalyst solution is 1-10%, preferably 2-5%;
the mass concentration of the end-capping reagent solution is 10-20%, preferably 10-15%;
the mass concentration of the alkali metal hydroxide solution is 25-40%, and preferably 30-35%.
In a specific embodiment, in the step (2), step A-1, the mole fraction of phosgene discharged from D-2 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the mole fraction of the diphenolic compound discharged from D-3 per unit time and the mole fraction of the siloxane monomer discharged from D-1 per unit time;
in the step (2), step A-2, the molar fraction of phosgene discharged from D-7 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the molar fraction of the diphenol compound discharged from D-4 per unit time and the molar fraction of the blocking agent discharged from D-5 per unit time;
the input amount of the alkali metal hydroxide solution in the D-6 needs to ensure that the pH value in the system is 11-13, and preferably 11.5-12.8;
the molar ratio of the total amount of the diphenol compound to the total amount of the end-capping reagent is 20-40, preferably 27-30;
the reaction residence time in R-1, R-2, R-3, R-4 and R-5 is 10-60 min, preferably 20-40 min;
more preferably, the structural formula of the polysiloxane monomer is shown as a formula (VI),
wherein R is 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is the average repetition number of the siloxane monomer and is selected from 30 to 150, preferably 40 to 90; z represents a halogen atom, -R 5 OH、-R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, said R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; the R is 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1.
In still another aspect, a polycarbonate resin composition comprises the polysiloxane-polycarbonate copolymer or the polysiloxane-polycarbonate copolymer prepared by the method and optionally an aromatic polycarbonate, wherein the polysiloxane-polycarbonate copolymer accounts for 5 to 100% by mass, and the aromatic polycarbonate accounts for 0 to 95% by mass; preferably, the aromatic polycarbonate is a polycarbonate containing no siloxane component, preferably a bisphenol a type homopolycarbonate prepared by a phosgene interface method or a bisphenol a type homopolycarbonate prepared by a melt transesterification method; more preferably, the polysiloxane-polycarbonate copolymer is blended with a bisphenol A polycarbonate to a polycarbonate composition having a siloxane content of 3.5% and an impact strength at-60 ℃ (ASTM D256) > 500J/m.
In a specific embodiment, the polycarbonate resin composition further contains 0 to 5 wt% of at least any one selected from the group consisting of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment, and a filler, based on the total weight of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the invention adopts an interface phosgene continuous process, two-stage photochemical reaction and three-stage polycondensation reaction, and controls the parameters of two-stage photochemical reaction stage (the weight part Y of the dihydric phenol compound continuously input in unit time of the first-stage photochemical reaction stage) 1 And the molar molecular weight M of the dihydric phenol compound 1 The added weight portion of the siloxane monomer in the unit time of the first-stage photochemical reaction stage and the weight portion Y of the dihydric phenol compound continuously input in the unit time of the second-stage photochemical reaction stage 2 And molar mass M of the dihydric phenol compound 2 ) The following formula is satisfied in the following manner,
Drawings
FIG. 1 is a schematic flow diagram of a method for preparing a polysiloxane-polycarbonate copolymer according to the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
As shown in FIG. 1, the method for preparing polysiloxane-polycarbonate copolymer by interfacial phosgene continuous process of the present invention comprises continuous two-stage photochemical reaction and three-stage polycondensation reaction, and specifically comprises the following steps:
(1) preparing a monomer solution: in D-1, polysiloxane monomer terminated by end phenol is dissolved in inert organic solvent to prepare comonomer solution with certain concentration; dissolving phosgene in inert organic solvent in D-2 and D-7 to prepare phosgene inert organic solvent solution with certain concentration; dissolving the diphenol compound in the D-3 and D-4 aqueous solution of alkali metal hydroxide to prepare an alkali metal hydroxide salt solution of the diphenol compound with a certain concentration; dissolving a blocking agent in an inert organic solvent in D-5 to prepare a blocking agent solution with a certain concentration; dissolving alkali metal hydroxide in water in D-6 and D-8 to prepare an alkali metal hydroxide solution with a certain concentration; dissolving a catalyst in an inert organic solvent in D-9 to prepare a solution with a certain concentration;
(2) carrying out a continuous polymerization reaction:
step A-1: siloxane monomer solution in D-1 and phosgene solution in D-2 are continuously input into the system, mixed in a pipeline through a mixer M-1 and then contacted with alkali metal hydroxide solution of a diphenol compound continuously input from D-3, mixed reaction liquid enters a primary photochemical reaction kettle R-1 through a heat exchanger E-1 and the mixer M-2 to carry out primary photochemical reaction, and partial reaction liquid in the primary photochemical reaction kettle is conveyed to the heat exchanger through a conveying pump to carry out heat exchange;
step A-2: the reaction liquid continuously output from the first-stage photochemical reaction kettle R-1 is contacted with reactants continuously input from D-4, D-5, D-6 and D-7 in a pipeline, and the reactants are mixed by a mixer M-3 and then enter a second-stage photochemical reaction kettle R-2;
step A-3: after the reaction liquid continuously output from the second-stage photochemical reaction kettle R-2 and the reactant input from D-8 are mixed by a mixer M-4, the reaction liquid is contacted with the catalyst continuously input from D-9, after the reaction liquid is mixed by a mixer M-5, the mixed reaction liquid continuously enters a first-stage polycondensation reaction kettle R-3, stays for a certain time, enters a second-stage polycondensation reaction kettle R-4, stays for a certain time, enters a third-stage polycondensation reaction kettle R-5, and stays for a certain time, the reaction liquid enters a post-treatment process;
(3) and (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain the product.
In the above preparation process:
the end capping agent is phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, preferably p-tert-butylphenol and p-cumylphenol;
the catalyst is a tertiary amine (e.g., triethylamine, etc.), a quaternary amine (e.g., trimethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, etc.), preferably triethylamine, tetrabutylammonium chloride;
the alkali liquor is selected from aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide, and is preferably aqueous solution of sodium hydroxide;
the inert organic solvent is selected from solvents that can dissolve the obtained polycarbonate resin, and specific examples thereof include halogenated hydrocarbon solvents such as methylene chloride (methylene dichloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, dichlorobenzene, and preferably methylene chloride.
The preparation method of the polysiloxane-polycarbonate copolymer meets the following formula:
wherein in the formula, Y 1 Is the weight fraction of the continuous output of the diphenolic compound in D-3 per unit time, M 1 Is the molar molecular weight of the dihydric phenol compound in D-3, Y 2 Is the weight fraction of the continuous output of the diphenolic compound in D-4 per unit time, M 2 Is the molar molecular weight of the dihydric phenol compound in D-4, Z 1 The amount (parts by weight) of the siloxane monomer continuously added to the system per unit time;
the concentration of the diphenol compound in the alkali metal hydroxide salt solution of the diphenol compound is 150-200 g/L, preferably 160-170 g/L;
the polysiloxane solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the concentration of the solution is 10-20%, preferably 15%;
the concentration of the catalyst solution is 1-10%, preferably 2-5%;
the concentration of the end-capping reagent solution is 10-20%, preferably 10-15%;
the concentration of the alkali liquor is 25-40%, and preferably 30-35%;
in the step (2), step A-1, the molar fraction of phosgene discharged from D-2 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the molar fraction of the diphenol compound discharged from D-3 per unit time and the molar fraction of the siloxane monomer discharged from D-1 per unit time;
in the step (2), step A-2, the molar fraction of phosgene discharged from D-7 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the molar fraction of the diphenol compound discharged from D-4 per unit time and the molar fraction of the end-capping agent discharged from D-5 per unit time;
the input amount of the alkali metal hydroxide solution in the D-6 needs to ensure that the pH value in the system is 11-13, and preferably 11.5-12.8;
the molar ratio of the total amount of the diphenol compound to the total amount of the end-capping reagent is 20-40, preferably 27-30;
the reaction residence time in R-1, R-2, R-3, R-4 and R-5 is 10-60 min, preferably 20-40 min;
the mixer used in the preparation method is not limited, and can be a static mixer or a dynamic mixer as long as the mixer can perform shearing and mixing functions on a two-phase liquid substance;
the structural formula of the polyorganosiloxane monomer is shown as the following formula (V),
wherein, in the formula (V), R 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Y represents a single bond, an aliphatic or aromatic organic residue; n is the average number of repetitions. Z represents a halogen atom, -R 5 OH、 -R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, above R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; r is as defined above 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1;
the polyorganosiloxane monomer represented by the general formula (v) can be purchased as a commercial product, or can be easily produced by subjecting a phenol having an ethylenically unsaturated carbon-carbon bond (preferably, vinylphenol, allylphenol, eugenol, isopropenylphenol, or the like) and a terminal of a polyorganosiloxane chain having a predetermined degree of polymerization n to a hydrosilylation reaction; the above phenols are more preferably allylphenol or eugenol; in this case, Y in the above formula (II) and formula (V) becomes an organic residue derived from allylphenol or eugenol;
in step (3), the post-treatment may be performed by a method conventional in the art, for example: the copolymer emulsion is first oil-water separated, and the oil phase is washed with alkali, acid and water successively, and the solvent is eliminated from the washed oil phase, crushed and dried to obtain qualified powder.
The analytical evaluation methods referred to in examples or comparative examples are as follows:
(1) weight average molecular weight: testing by Gel Permeation Chromatography (GPC);
(2) the impact properties were determined according to the standard test method for Izod impact testing of plastics as specified in ASTM D256-1997;
(3) test for solvent resistance
According to ASTM D543, after sun cream (Banan Boat) is applied to a test piece (test piece thickness 3.2mm) for tensile strength test in a 1.0% strain jig, appearance change is observed, and four grades of A (no crack), B (crack), C (severe crack) and D (fracture) are divided according to the weight of crack generation;
(4) siloxane content test
By nuclear magnetic analysis of copolymers 1 An H-NMR spectrum calculated by comparing the integral ratio of the peak derived from the dihydric phenol (I) with the integral ratio of the peak derived from the hydroxyaryl-terminal polydiorganosiloxane (II);
(5) free siloxane monomer content test
(i) 6g of the polycarbonate-polysiloxane copolymer obtained in each example was dissolved in 50mL of methylene chloride to obtain a polymer solution, and a mixed solution of 50mL of n-hexane and 150mL of n-hexane was added to the polymer solution, and the mixture was stirred and mixed uniformly and allowed to stand for 30 minutes;
(ii) recovering the filtrate by suction filtration with filter paper (No.5A), concentrating the recovered filtrate to dry, measuring the weight of the resulting dry solid, dissolving the dry solid in deuterated chloroform, and performing nuclear magnetic hydrogen spectrometry to calculate the proportion z (%) of unreacted siloxane monomer from the integral value x of the proton (. delta.6.7 ppm) ortho to the phenolic hydroxyl group of the unreacted phenol-modified polysiloxane and the integral value y of the proton (. delta.0.6 ppm) of the methylene chain;
z＝2*x/y*100％
(iii) a standard sample was prepared by adding a phenol-terminated polysiloxane monomer to a silicon copolymerized PC (addition ratio 150 to 3000 ppm by mass), and the same operation as described above was performed to obtain a relational expression between z and the amount of unreacted PDMS.
(iv) calculating the mass (ppm) of the siloxane monomer remaining in the polymer from the relational expression between z obtained in (ii) and z obtained in (iii).
Comonomers used in examples and comparative examples
(1) < eugenol-terminated polyorganosiloxane monomer >
Eugenol-terminated PDMS monomers can be prepared by reference to published literature, for example, the preparation method described in chinese patent CN 201710159031.5.
The preparation method comprises the following steps: octamethylcyclotetrasiloxane (1420g, 4.80mol), tetramethyldisiloxane (40.2g, 0.3mol) and clay catalyst Filtrol 20(23.4g, 1.6 wt%) were added to a reaction vessel equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was heated up to 50 ℃ at a rate of 5 ℃/min and stirred at that temperature for 3 hours, and then the temperature of the reaction system was continuously heated up to 120 ℃ at a rate of 5 ℃/min and stirred vigorously at that temperature for 5 hours, after which the clay catalyst was removed by filtration. The material after removal of the clay catalyst was then put into a reaction tank equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2g, 1.02mol) and karstedt's platinum catalyst (0.67g) was added dropwise at a rate of 20 g/min with stirring, after which the reaction was stirred at a temperature of 80 ℃ for 13 hours. Followed by distillation at 200 ℃ under reduced pressure to 0.2kPa to remove unreacted starting materials, to give eugenol-terminated polysiloxane in a yield of 99%, with a degree of polymerization of PDMS 55 as determined by nuclear magnetic detection, herein defined for convenience as PDMS-55;
other conditions were not changed, and a monomer having a degree of polymerization of siloxane of 95 and a monomer having a degree of polymerization of siloxane of 20, which are defined herein as PDMS-95 and PDMS-20 for convenience, were prepared by changing the amount of tetramethyldisiloxane.
Preparation of examples/comparative examples:
an interfacial phosgene continuous method preparation process is shown in figure 1;
(1) preparing a solution: the concentration of BPA is 170 g/L; the concentration of the polydimethylsiloxane monomer solution is 15 percent, the concentration of the triethylamine solution is 5 percent, and the adding amount of the triethylamine is 0.4 percent of the total weight of the polymer; the concentration of the p-tert-butylphenol solution is 11 percent; the concentration of the sodium hydroxide solution is 32%; the concentration of the phosgene solution was 10%.
In the following table: the siloxane monomer used in examples 1-9, 10 and comparative examples 1-3 was PDMS-55; the siloxane monomer used in example 11 was PDMS-90; the siloxane monomer used in example 9 was PDMS-20;
Z 1 a-1, continuously inputting the weight parts of siloxane monomers into a polymerization reaction system in unit time;
Y 1 a-1 part by weight of bisphenol A continuously fed into a polymerization reaction system per unit time;
X 1 a-1, continuously inputting phosgene into a polymerization reaction system in unit time;
Y 2 a-2 part by weight of bisphenol A continuously fed into a polymerization reaction system per unit time;
X 2 a-2, continuously inputting phosgene into a polymerization reaction system in unit time;
P 1 a-2 part by weight of PTBP continuously fed into a polymerization reaction system per unit time;
D 1 a-2, continuously inputting 32% sodium hydroxide solution into a polymerization reaction system in unit time;
N 1 a-3, namely continuously inputting the triethylamine into a polymerization reaction system in unit time;
D 2 a-3, continuously inputting the weight part of sodium hydroxide with the mass content of 32% into a polymerization reaction system in unit time;
k: k is a formula
The ratio of (A) to (B);
weight parts of materials charged in each example
Comparative example charging weight parts
(2) Carrying out a polymerization reaction: according to the feeding proportion shown in the table, continuously adding a bisphenol A sodium phenolate solution, a phosgene solution, a siloxane monomer solution and the like into a polymerization reaction system, wherein the reaction time of the reaction liquid in R-1-R-5 is 10min, and the reaction temperature is maintained at 30 ℃;
(3) and (3) post-treatment: performing oil-water separation on the copolymer solution prepared in the step (2), performing alkali washing, acid washing and water washing on an oil phase, milling the washed polymer solution by using a kneader to obtain PC slurry, and centrifugally drying the slurry to obtain a product;
the above examples tests are shown in the following table:
examples 12 to 22 and comparative examples 4 to 8
The samples prepared in examples 1 to 11 and comparative examples 1 to 3 and the commercial products FG1760 and D0013 were mixed with a certain proportion
2100 general-grade PC resin,
2150 general purpose PC resin, antioxidant, and mold release agent, mixing, extruding with Cobelron CTE35 extruder at 280 deg.CAnd extruding and granulating, and testing low-temperature impact resistance and chemical resistance after the obtained particles are subjected to injection molding.
The formulations of examples 12-22 and comparative examples 4-8 have the following compositions:
the performance data for examples 12-22 and comparative examples 4-8 are shown in the following table:
| impact properties at 60 ℃ (J/m) | Chemical resistance | |
| Example 12 | 625 | A |
| Example 13 | 650 | A |
| Example 14 | 672 | A |
| Example 15 | 796 | A |
| Example 16 | 643 | A |
| Example 17 | 603 | A |
| Example 18 | 706 | A |
| Example 19 | 742 | A |
| Example 20 | 661 | A |
| Example 21 | 698 | A |
| Example 22 | 736 | A |
| Comparative example 4 | 490 | C |
| Comparative example 5 | 460 | C |
| Comparative example 6 | 428 | C |
| Comparative example 7 | 440 | C |
| Comparative example 8 | 520 | B |
As can be seen from the comparison of the above data, the polysiloxane-polycarbonate copolymer prepared according to the present invention and the polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer prepared according to the present invention have excellent low temperature impact resistance and chemical resistance properties, and have an impact strength at-60 ℃ (ASTM D256) > 500J/m, preferably more than 600J/m, while the impact strength at-60 ℃ (ASTM D256) of conventional PC is less than 200J/m, and some silicon PC products on the market are also generally less than 400J/m, preferably not more than 500J/m.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (12)
1. A polysiloxane-polycarbonate copolymer, which is characterized by comprising a polycarbonate structural unit shown in a formula (I) and a polysiloxane structural unit shown in a formula (II), wherein the residual weight of free siloxane in the polysiloxane-polycarbonate copolymer is less than 200ppm, preferably, the mass percent of a polysiloxane block part is 5-45%,
in the formula (I), R 1 And R 2 Each independently represents hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; a and b independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alicyclic group having 6 to 20 carbon atoms, or a group represented by the formula (a):
wherein R is ’ And R' each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; or R ’ And R' together form a C4-20 alicyclic ring, said C4-20 alicyclic ring optionally substituted with one or more C1-20 alkyl, C6-20 aryl, C7-21 aralkyl, C5-20 cycloalkyl groups, or combinations thereof;
R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue.
2. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polycarbonate structural unit represented by formula (I) is a structural unit derived from bisphenol A represented by formula (III),
3. the polysiloxane-polycarbonate copolymer according to claim 1, wherein the polysiloxane structural unit of formula (II) is a structural unit derived from polydimethylsiloxane of formula (IV), the polydimethylsiloxane end group is a phenolic hydroxyl group, Y is an organic residue derived from phenols having an ethylenically unsaturated carbon-carbon bond, preferably allylphenols or eugenols;
wherein, R is connected on a benzene ring 5 The structure (D) represents the residue of the phenol after removal of the hydroxyl group on the phenyl ring, R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; preferably, R 5 The type selection and the position of the phenol correspond to the substituent groups on the phenol benzene ring one by one; wherein p is 0 to 5, preferably 0 to 3; n is the average number of repetitions, n is an integer of 20 to 150, preferably 40 to 100;
preferably, the structural unit represented by formula (IV) is derived from any one of allylphenol-polydimethylsiloxane, preferably 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, and more preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane.
4. The polysiloxane-polycarbonate copolymer according to claims 1 to 3, characterized in that the polysiloxane-polycarbonate copolymer has a viscosity average molecular weight of 15000 to 55000g/mol, preferably 18000 to 35000 g/mol.
5. The method for preparing the polysiloxane-polycarbonate copolymer according to any one of claims 1 to 4, wherein an interfacial phosgene continuous process is adopted, and the reaction process comprises continuous two-stage photochemical reaction and three-stage polycondensation reaction; preferably, the method comprises the following steps:
(1) preparing a monomer solution: respectively preparing siloxane monomer solution, phosgene solution, alkali metal hydroxide salt solution of diphenol compound, end capping agent solution, alkali metal hydroxide solution and catalyst solution with certain concentration;
(2) carrying out a continuous polymerization reaction:
step A-1: siloxane monomer solution and phosgene solution are continuously input into the system, are contacted with continuously input alkali metal hydroxide salt solution of diphenol compound after being preliminarily mixed, and mixed reaction liquid enters a primary photochemical reaction kettle R-1 to carry out primary photochemical reaction;
step A-2: the reaction liquid continuously output from the first-stage photochemical reaction kettle R-1 is contacted with the continuously input alkali metal hydroxide salt solution, the end capping agent solution, the alkali metal hydroxide solution and the phosgene solution of the dihydric phenol compound, and the mixture enters a second-stage photochemical reaction kettle R-2;
step A-3: mixing the reaction liquid continuously output from the second-stage photochemical reaction kettle R-2 with the input alkali metal hydroxide solution, then contacting and mixing with the catalyst solution, continuously feeding the mixed reaction liquid into the first-stage polycondensation reaction kettle R-3, staying for a certain time, feeding the mixed reaction liquid into the second-stage polycondensation reaction kettle R-4, staying for a certain time, feeding the mixed reaction liquid into the third-stage polycondensation reaction kettle R-5, and after staying for a certain time, feeding the reaction liquid into a post-treatment process;
(3) and (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain polysiloxane-polycarbonate copolymer;
more preferably, the method comprises the following steps:
(1) preparing a monomer solution: in D-1, a polysiloxane monomer terminated by end phenol is dissolved in an inert organic solvent to prepare a siloxane monomer solution with a certain concentration; dissolving phosgene in inert organic solvent in D-2 and D-7 to prepare phosgene solution with certain concentration; dissolving the diphenol compound in the D-3 and D-4 aqueous solution of alkali metal hydroxide to prepare an alkali metal hydroxide salt solution of the diphenol compound with a certain concentration; dissolving a blocking agent in an inert organic solvent in D-5 to prepare a blocking agent solution with a certain concentration; dissolving alkali metal hydroxide in water in D-6 and D-8 to prepare an alkali metal hydroxide solution with a certain concentration; dissolving a catalyst in an inert organic solvent in D-9 to prepare a catalyst solution with a certain concentration;
(2) carrying out a continuous polymerization reaction:
step A-1: the siloxane monomer solution in D-1 and the phosgene solution in D-2 are continuously input into the system, mixed by a mixer in a pipeline and then contacted with the alkali metal hydroxide solution of the diphenol compound continuously input from D-3, and the mixed reaction liquid enters a primary photochemical reaction kettle R-1 for primary photochemical reaction after heat exchange and mixing;
step A-2: the reaction liquid continuously output from the first-stage photochemical reaction kettle R-1 is contacted with reactants continuously input from D-4, D-5, D-6 and D-7 in a pipeline, and the reactants enter a second-stage photochemical reaction kettle R-2 after being mixed;
step A-3: after the reaction liquid continuously output from the second-stage photochemical reaction kettle R-2 is mixed with the reactant input from D-8, the reaction liquid is contacted with the catalyst continuously input from D-9, after mixing, the mixed reaction liquid continuously enters the first-stage polycondensation reaction kettle R-3, after staying for a certain time, the mixed reaction liquid enters the second-stage polycondensation reaction kettle R-4, after staying for a certain time, the mixed reaction liquid enters the third-stage polycondensation reaction kettle R-5, and after staying for a certain time, the reaction liquid enters the post-treatment process;
(3) and (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain the polysiloxane-polycarbonate copolymer.
6. The method of claim 5, wherein the amount of each reactant satisfies the following formula:
wherein Y is 1 Is the weight fraction of the continuous output of the diphenolic compound in D-3 per unit time, M 1 Is the molar molecular weight of the dihydric phenol compound in D-3, Y 2 Is the weight fraction of the continuous output of the diphenolic compound in D-4 per unit time, M 2 Is the molar molecular weight of the dihydric phenol compound in D-4, Z 1 Is the weight fraction of siloxane monomer continuously added to the system per unit time.
7. The method for producing a polysiloxane-polycarbonate copolymer according to claim 5, wherein the end-capping agent is selected from any one of phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, preferably p-tert-butylphenol or p-cumylphenol;
preferably, the catalyst is selected from any one of tertiary amine and quaternary amine, preferably triethylamine or tetrabutylammonium chloride;
preferably, the alkali metal hydroxide solution is selected from aqueous solutions of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, preferably aqueous sodium hydroxide;
preferably, the inert organic solvent is selected from halogenated hydrocarbon solvents that can dissolve the resulting polycarbonate resin, preferably any one of dichloromethane (methylene dichloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, dichlorobenzene, and more preferably dichloromethane.
8. The method for producing a polysiloxane-polycarbonate copolymer according to claim 5, wherein the dihydric phenol compound has a structure represented by formula (V),
wherein R is 1 、R 2 A, b and X are as defined in formula (I);
preferably, the diphenol compound of formula (v) is at least one selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane [ bisphenol a ], bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, bis (hydroxyphenyl) alkane of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4,4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone, and preferably is bisphenol a.
9. The method for producing the polysiloxane-polycarbonate copolymer according to claims 5 to 8, wherein the concentration of the dihydric phenol compound in the alkali metal hydroxide salt solution of the dihydric phenol compound is 150 to 200g/L, preferably 160 to 170 g/L;
the siloxane monomer solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the mass concentration of the siloxane monomer solution is 10-20%, preferably 15%;
the mass concentration of the catalyst solution is 1-10%, preferably 2-5%;
the mass concentration of the end-capping reagent solution is 10-20%, preferably 10-15%;
the mass concentration of the alkali metal hydroxide solution is 25-40%, and preferably 30-35%.
10. The method for producing a polysiloxane-polycarbonate copolymer according to claim 5,
in the step (2), step A-1, the molar fraction of phosgene discharged from D-2 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the molar fraction of the diphenol compound discharged from D-3 per unit time and the molar fraction of the siloxane monomer discharged from D-1 per unit time;
in the step (2), step A-2, the molar fraction of phosgene discharged from D-7 per unit time is 1.1 to 1.5 times, preferably 1.15 to 1.3 times, the sum of the molar fraction of the diphenol compound discharged from D-4 per unit time and the molar fraction of the blocking agent discharged from D-5 per unit time;
the input amount of the alkali metal hydroxide solution in the D-6 needs to ensure that the pH value in the system is 11-13, and preferably 11.5-12.8;
the molar ratio of the total amount of the diphenol compound to the total amount of the end-capping reagent is 20-40, preferably 27-30;
the reaction residence time in R-1, R-2, R-3, R-4 and R-5 is 10-60 min, preferably 20-40 min;
more preferably, the structural formula of the polysiloxane monomer is shown as a formula (VI),
wherein R is 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is the average repetition number of the siloxane monomer and is selected from 30 to 150, preferably 40 to 90; z represents a halogen atom, -R 5 OH、-R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, said R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; said R is 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1.
11. A polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer according to any one of claims 1 to 4 or the polysiloxane-polycarbonate copolymer prepared by the method according to any one of claims 5 to 10, and optionally an aromatic polycarbonate, wherein the polysiloxane-polycarbonate copolymer is 5 to 100% by mass, and the aromatic polycarbonate is 0 to 95% by mass; preferably, the aromatic polycarbonate is a polycarbonate containing no siloxane component, preferably a bisphenol a type homopolycarbonate prepared by a phosgene interface method or a bisphenol a type homopolycarbonate prepared by a melt transesterification method; more preferably, the polysiloxane-polycarbonate copolymer is blended with a bisphenol A polycarbonate to a polycarbonate composition having a siloxane content of 3.5% and an impact strength at-60 ℃ (ASTM D256) > 500J/m.
12. The polycarbonate resin composition according to claim 11, further comprising 0 to 5 wt% of at least any one selected from the group consisting of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment, and a filler, based on the total weight of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate.
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| CN103930466A (en) * | 2011-10-18 | 2014-07-16 | 出光兴产株式会社 | Polycarbonate-polyorganosiloxane copolymer and method for producing same |
| WO2016080496A1 (en) * | 2014-11-20 | 2016-05-26 | 出光興産株式会社 | Method for producing polycarbonate-polyorganosiloxane copolymer |
| CN106977710A (en) * | 2012-07-05 | 2017-07-25 | 出光兴产株式会社 | Polycarbonate-polyorganosiloxane copolymer |
| CN113201127A (en) * | 2021-06-21 | 2021-08-03 | 万华化学集团股份有限公司 | Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin |
| CN114196001A (en) * | 2022-01-11 | 2022-03-18 | 万华化学集团股份有限公司 | Polycarbonate-polyorganosiloxane copolymer, manufacturing method and resin composition containing same |
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| CN103930466A (en) * | 2011-10-18 | 2014-07-16 | 出光兴产株式会社 | Polycarbonate-polyorganosiloxane copolymer and method for producing same |
| CN106977710A (en) * | 2012-07-05 | 2017-07-25 | 出光兴产株式会社 | Polycarbonate-polyorganosiloxane copolymer |
| WO2016080496A1 (en) * | 2014-11-20 | 2016-05-26 | 出光興産株式会社 | Method for producing polycarbonate-polyorganosiloxane copolymer |
| CN113201127A (en) * | 2021-06-21 | 2021-08-03 | 万华化学集团股份有限公司 | Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin |
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