CN117487171A - Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same - Google Patents

Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same Download PDF

Info

Publication number
CN117487171A
CN117487171A CN202311481827.4A CN202311481827A CN117487171A CN 117487171 A CN117487171 A CN 117487171A CN 202311481827 A CN202311481827 A CN 202311481827A CN 117487171 A CN117487171 A CN 117487171A
Authority
CN
China
Prior art keywords
polycarbonate
group
carbon atoms
copolymer
polysiloxane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311481827.4A
Other languages
Chinese (zh)
Inventor
魏志涛
梁允超
李晓飞
仇志伟
曾伟
王磊
黎源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202311481827.4A priority Critical patent/CN117487171A/en
Publication of CN117487171A publication Critical patent/CN117487171A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a polycarbonate-polyorganosiloxane copolymer, which comprises a polysiloxane chain segment and a polycarbonate chain segment, wherein in the preparation process of the polycarbonate-polyorganosiloxane copolymer, when the weight average molecular weight of a polycarbonate-polyorganosiloxane reaction intermediate is 8000-15000 g/mol, the following conditions are satisfied: r is less than or equal to 2000; and the value of the effective factor gamma is required to meet gamma being more than or equal to 20. The polycarbonate-polyorganosiloxane copolymer provided by the invention has larger silicon domain under the condition of certain molecular weight and siloxane content, so that the polycarbonate resin composition containing the polysiloxane-polycarbonate copolymer prepared by the method has excellent chemical resistance and low-temperature impact resistance.

Description

Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same
Technical Field
The invention relates to a copolymer, in particular to a polycarbonate-polyorganosiloxane copolymer, a preparation method and a resin composition containing the copolymer, and belongs to the technical field of high polymer materials.
Background
Polycarbonate (PC) is a high molecular polymer containing carbonate bonds in a molecular chain, has excellent mechanical properties, heat resistance, impact toughness, electrical insulation, light transmittance, low creep resistance, low water absorption, good dimensional stability, excellent dielectric properties and the like, 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, the common aromatic polycarbonate material also has certain defects such as poor solvent resistance, easy occurrence of stress cracking after touching the solvent, poor impact performance at low temperature, limitation of the application of the material in low-temperature places and the like. In order to widen the application area thereof, it needs to be modified.
There are two main methods for modifying polycarbonate at present, one is to prepare polycarbonate composite materials by physical blending modification, for example: the low-temperature impact strength of the polycarbonate is improved by adding a silicon-based modifier and blending; by alloying with PBT, the chemical resistance of polycarbonate materials and the like are improved. However, physical blending modification is limited in improvement of polycarbonate resin properties and may sacrifice some properties. The other modification is chemical copolymerization modification, namely functional groups are introduced into a polycarbonate molecular chain from genes, so that the performance of the polycarbonate resin is improved, the most applied and commercialized product is siloxane copolycarbonate, namely a polydimethylsiloxane chain segment is introduced into a PC molecular chain, and compared with general-purpose PC, the silicon copolyPC has excellent low-temperature impact resistance, chemical resistance, ageing resistance and the like.
At present, a great number of patent reports on silicon copolypc are provided, chinese patent CN201080055804.1 proposes a siloxane copolycarbonate, the siloxane content is 1-30%, the viscosity average molecular weight of the copolymer is 13000-26000, and the impact performance of a resin composition containing the copolymer at low temperature needs to be further improved; chinese patent CN201710159031.5 discloses a low temperature resistant non-transparent high impact random copolycarbonate and its preparation method, wherein polysiloxane monomer is added in one step, and the polymer prepared by this method is easy to peel; chinese patent CN 201080029663.6 proposes that the average size of the polydiorganosiloxane phase region in the polyorganosiloxane-polycarbonate copolymer is 5-40 nm and that the normalized dispersion is below 30%, the copolymer has good light transmittance, but the low-temperature impact resistance and chemical resistance of the copolymer are poor.
In summary, there is a need to further improve the properties of polycarbonate-polysiloxane copolymers based on the prior art.
Disclosure of Invention
In order to solve the above technical problems, the present invention proposes a polycarbonate-polyorganosiloxane copolymer to improve chemical resistance, low temperature impact resistance, and aging resistance of a polycarbonate resin composition comprising the polycarbonate-polyorganosiloxane copolymer.
As a result of comprehensive studies on the structure and properties of the siloxane segment of the polycarbonate-polyorganosiloxane copolymer, the inventors have found that, in the case where the molecular weight of the polycarbonate-polyorganosiloxane copolymer and the polyorganosiloxane content are constant, 10000 times the ratio of the molecular weight distribution peak area S1 of the polycarbonate-polyorganosiloxane copolymer at any wavelength in the range of 288 to 300nm to the molecular weight distribution peak area S2 at any wavelength in the range of 254 to 266nm, and that the effective factor gamma value is required to satisfy gamma not less than 20, when the polycarbonate-polyorganosiloxane oligomer intermediate satisfies specific parameters (i.e., when the weight average molecular weight of the polycarbonate-polyorganosiloxane reaction intermediate is 8000 to 15000g/mol, the ratio of the number of moles of acyl chloride groups of the reaction intermediate to the number of moles of phenolic hydroxyl groups of the polyorganosiloxane segment in the reaction system) satisfies the conditions that R value is not more than 2000, R value is defined as, and that the polycarbonate-polysiloxane intermediate has a molecular weight distribution peak area S2 at any wavelength in the range of 288 to 266nm in the UV-GPC test, the copolymer has outstanding properties and low resistance to impact.
Based on the above researches, the technical scheme adopted by the invention is as follows:
a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate segment of formula i and a polysiloxane segment of formula ii, and having the following structural characteristics: in the preparation process of the polycarbonate-polyorganosiloxane copolymer, when the weight average molecular weight of the polycarbonate-polyorganosiloxane reaction intermediate is 8000-15000 g/mol, the following conditions are satisfied:
(1) R is less than or equal to 2000, and is defined as 10000 times the ratio of the molecular weight distribution peak area S1 of the polycarbonate-polysiloxane intermediate at any wavelength in the range of 288-300nm to the molecular weight distribution peak area S2 at any wavelength in the range of 254-266nm in a UV-GPC test; the method comprises the steps of,
(2) The effective factor gamma value is more than or equal to 20, and the gamma value is defined as the ratio of the mole number of acyl chloride groups of a reaction intermediate to the mole number of phenolic hydroxyl groups of a polyorganosiloxane chain segment in a reaction system;
in the above, R 1 And R is 2 Each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 4 to 20 carbon atoms or aryl of 6 to 20 carbon atoms;
a and b independently represent an integer of 0 to 4;
x is present or absent and, when present, represents an ether group, a carbonyl group, a thioether group, 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, orA group represented by the formula (the attachment site is a C atom in the formula); wherein R is ’ And R' independently represent 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 being optionally substituted with one or more C1-20 alkyl groups, C6-20 aryl groups, C7-21 aralkyl groups, C5-20 cycloalkyl groups or combinations thereof;
R 3 and R is 4 Each independently represents hydrogen, a halogen atom or 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 organic residue optionally comprising an aliphatic or aromatic substituent;
n is selected from 30 to 120, preferably 40 to 90.
Further, in the copolymer, the total mass content of the polysiloxane segment is 18-40%;
further, the polycarbonate segment is a structural unit derived from bisphenol a, and comprises a unit structure represented by formula iii:
further, the polysiloxane segment is a structural unit derived from a phenolic hydroxyl-terminated polydimethylsiloxane, as shown in formula iv; the phenolic hydroxyl groups are derived from phenols having an ethylenically unsaturated carbon-carbon bond, preferably allyl phenol, eugenol, vinyl phenol or isopropenyl phenol, more preferably allyl phenol or eugenol. The allylphenol is, for example, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-methoxy-5-allylphenol, 2-methoxy-6-allylphenol, preferably 2-allylphenol, 2-methoxy-4-allylphenol or the like;
in the formula IV, R is connected on benzene ring 5 The structure represents the residue after the hydroxyl group is removed from the phenols, 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 selection and the position of the benzene ring correspond to the substituent groups on the benzene ring of the phenols one by one. Wherein p is 0 to 5, preferably 0 to 3.
Further, the weight average molecular weight of the copolymer is 20000 to 40000g/mol, preferably 22000 to 35000g/mol.
A process for the preparation of a polycarbonate-polyorganosiloxane copolymer as described hereinbefore, comprising monomer solution formulation, photochemical reaction, pre-polycondensation reaction, and post-treatment:
1) Preparing a monomer solution:
respectively preparing a phenol sodium salt solution of a bisphenol compound, a phenolic hydroxyl end-capped polysiloxane monomer solution, an end capping agent solution, a catalyst solution and an alkali metal hydroxide solution;
2) Photochemical reaction: adding a certain amount of pre-prepared bisphenol compound phenol sodium salt solution, polysiloxane monomer solution, inert organic solvent and phosgene into an photochemical reaction kettle for photochemical reaction to prepare polycarbonate-polysiloxane oligomer emulsion with a certain molecular weight;
3) Pre-polycondensation reaction: adding the oligomer emulsion prepared in the step 2) and a certain amount of end-capping reagent solution into a pre-polycondensation reaction kettle for pre-polycondensation reaction, adding an alkali metal hydroxide solution in the reaction process, maintaining the reaction pH to be more than 12, and starting a circulating pump to circularly react the reaction solution through a two-stage mixer;
4) Polycondensation reaction: adding the pre-polycondensation reaction liquid prepared in the step 3) into a polycondensation reaction kettle, adding a certain amount of catalyst solution for polycondensation reaction, adding alkali metal hydroxide solution in the whole reaction process, maintaining the reaction pH at 11-13, and ending the reaction when no acyl chloride group exists in a reaction system;
5) Post-treatment: purifying the copolymer solution prepared in the step 4) and removing the organic solvent to obtain a target product.
In some embodiments, the method comprises:
1) Preparing a monomer solution:
respectively preparing a phenol sodium salt solution of a bisphenol compound, a phenolic hydroxyl end-capped polysiloxane monomer solution, an end capping agent solution, a catalyst solution and an alkali metal hydroxide solution;
further, the sodium phenolate solution of the bisphenol compound is prepared by dissolving the bisphenol compound in an aqueous solution of an alkali metal hydroxide, preferably at a concentration of 150 to 200g/L, more preferably 160 to 170g/L, based on the mass concentration of the bisphenol compound; the bisphenol compound is preferably 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol A), bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4' -dihydroxybiphenyl one or more of 2, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthylmethane;
the concentration of the phenolic hydroxyl-terminated polysiloxane monomer solution is preferably 10-20%, more preferably 10-15%; among them, the phenolic hydroxyl-terminated polysiloxane monomer can be purchased from commercial products, and can be easily and simply produced by subjecting a phenolic-terminated agent having an ethylenically unsaturated carbon-carbon bond (e.g., allylphenol, eugenol, vinylphenol, isopropenylphenol, etc.) to hydrosilylation reaction with the terminal end of a polysiloxane chain having a prescribed degree of polymerization, and the production method is widely disclosed in the prior art, as in publication [ Li Tao, zhou Nan, yuanhua et al [ J ]. Organosilicon material of a eugenol-terminated polysiloxane, 2016,30 (5): 5 ] and the production process mentioned in publication patent CN110776640A, CN 111848956A;
the concentration of the capping agent solution is preferably 10-20%, more preferably 10-15%; wherein the end-capping agent is one or more of phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol and p-cyanophenol, preferably p-tert-butylphenol or p-cumylphenol;
the concentration of the catalyst solution is preferably 1 to 10%, more preferably 2 to 5%; the catalyst is one or more of triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, preferably triethylamine;
the inert organic solvent used for preparing the solution is one or more of dichloromethane, chloroform, dichloroethane and trichloroethane, preferably dichloromethane;
the concentration of the alkali metal hydroxide solution is preferably 25 to 40%, more preferably 30 to 35%; the alkali metal hydroxide is one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide, preferably sodium hydroxide;
2) Photochemical reaction: adding a certain amount of pre-prepared bisphenol compound phenol sodium salt solution, polysiloxane monomer solution, inert organic solvent and phosgene into an photochemical reaction kettle for photochemical reaction to prepare polycarbonate-polysiloxane oligomer emulsion with a certain molecular weight;
wherein the mass ratio of the bisphenol compound to the phenolic hydroxyl terminated polysiloxane monomer is 1.3-4.1, preferably 2-3.5;
phosgene usage phosgene to bisphenol based compound molar ratio, phosgene: the bisphenol compound molar ratio is 1.01-1.3, preferably 1.1-1.2;
the inert organic solvent is added in an amount such that the solid content of the reaction liquid is 10-30%, preferably 15-20%;
the temperature of the photochemical reaction is 20-40 ℃, preferably 25-35 ℃;
the weight average molecular weight of the polycarbonate-polyorganosiloxane copolymer oligomer prepared by the photochemical reaction is 1000-6000 g/mol, preferably 1000-3000;
3) Pre-polycondensation reaction: adding the oligomer emulsion prepared in the step 2) and a certain amount of end-capping agent solution into a pre-polycondensation reaction kettle for pre-polycondensation reaction, adding an alkali metal hydroxide solution in the reaction process, maintaining the reaction pH to be more than 12, and starting a circulating pump to circularly react the reaction solution through a two-stage mixer to obtain a pre-polycondensation reaction solution containing a polycarbonate-polyorganosiloxane reaction intermediate;
the molar ratio of bisphenol compound to capping agent is 20-40, preferably 27-30;
the flow rate of the reaction liquid passing through the two-stage mixer is required to meet the requirement that the circulation time is 10-25 times/min, preferably 15-20 times/min;
the two-stage mixer is used by matching a static mixer and a dynamic mixer, and the dynamic mixer is not limited to the two types, such as Primix, bruce FA25 and the like; the static mixer may be of the SM-V type, SM-K type, SM-X type, SM-L type, SM-H type, for example, depending on the structure of the mixing unit; the mixer is not limited to the above-listed types;
wherein the Reynolds number in the outlet pipeline of the static mixer is 4000-10000, preferably 5000-8000;
the conversion of the polyorganosiloxane in the polycarbonate-polyorganosiloxane reaction intermediate prepared by the pre-polycondensation reaction in step 3) is more than 75%, preferably more than 80%;
the weight average molecular weight of the polycarbonate-polyorganosiloxane reaction intermediate prepared by the pre-polycondensation is 8000-15000 g/mol, preferably 9000-12000 g/mol; and satisfies the following conditions:
(1) R is less than or equal to 2000, and is defined as 10000 times the ratio of the molecular weight distribution peak area S1 of the polycarbonate-polysiloxane intermediate at any wavelength in the range of 288-300nm to the molecular weight distribution peak area S2 at any wavelength in the range of 254-266nm in a UV-GPC test; the method comprises the steps of,
(2) The effective factor gamma value is more than or equal to 20, and the gamma value is defined as the ratio of the mole number of acyl chloride groups of a reaction intermediate to the mole number of phenolic hydroxyl groups of a polyorganosiloxane chain segment in a reaction system;
4) Polycondensation reaction: adding the pre-polycondensation reaction liquid prepared in the step 3) into a polycondensation reaction kettle, adding a certain amount of catalyst solution for polycondensation reaction, adding alkali metal hydroxide solution in the whole reaction process, maintaining the reaction pH at 11-13, and ending the reaction when no acyl chloride group exists in a reaction system;
the catalyst is used in a molar amount of 1-10 per mill, preferably 3-6 per mill, of the bisphenol compound;
5) Post-treatment: purifying the copolymer solution prepared in the step 4) and removing the organic solvent to obtain a target product;
the post-treatment may be performed by methods conventional in the art, for example: the copolymer emulsion is firstly subjected to oil-water separation, oil phase is sequentially subjected to alkali washing, acid washing and multiple water washing, the solvent of the oil phase is removed after the water washing, and qualified powder is obtained after crushing and drying.
Further, the present invention also relates to a polycarbonate resin composition comprising the above polysiloxane-polycarbonate copolymer.
A polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer described above or the polysiloxane-polycarbonate copolymer produced by the method described above, which comprises 5 to 100% by mass of the polysiloxane-polycarbonate copolymer and 0 to 95% by mass of other aromatic polycarbonate;
preferably, the other aromatic polycarbonate is a siloxane-free polycarbonate, such as bisphenol a-type homopolycarbonate prepared by a known phosgene interface method or bisphenol a-type homopolycarbonate prepared by a melt transesterification method, or the like;
preferably, the resin composition further comprises an optional addition agent, wherein the addition agent is 0-5% of the total mass of the polysiloxane-polycarbonate copolymer and other aromatic polycarbonates. The additive auxiliary agent is selected from one or more of a release agent, a flow auxiliary agent, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment and a filler.
The invention has the beneficial effects that:
according to the invention, by controlling key parameter indexes of the polycarbonate-polyorganosiloxane intermediate in the preparation process of the silicon copolymerized PC, the polycarbonate-polysiloxane copolymer with more excellent performance is prepared under the condition that the molecular weight of the polycarbonate-polyorganosiloxane copolymer and the content of the polyorganosiloxane are certain, and in addition, the polycarbonate resin composition containing the polycarbonate-polyorganosiloxane copolymer has excellent chemical resistance, low-temperature impact resistance and ageing resistance.
Drawings
FIG. 1 is a schematic illustration of a process flow diagram for preparing a polycarbonate-polyorganosiloxane copolymer according to the present invention.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The analytical evaluation methods involved in the examples or comparative examples are as follows:
(1) The polymer molecular weight was obtained by Agilent Technologies 1260infinity test, UV and RI detectors were formulated with methylene chloride as the mobile phase at a flow rate of 1mL/min and column temperature and box temperature of 30 ℃.
(2) The Izod impact properties were determined according to the standard test methods for Izod impact properties detection of plastics as specified in ASTM D256-1997.
(3) Aging resistance test
After 1000 hours of aging of double 85, the material was tested for retention of impact strength.
(4) Solvent resistance test
The appearance change was observed after applying a sunscreen (Banan coat) to a test piece for tensile strength test (test piece thickness 3.2 mm) in accordance with ASTM D543 using a 1.0% strain clamp, and the time at which cracking began to occur was recorded.
(5) Acyl chloride group content test
Testing by titration;
(6) Polysiloxane content test
Determination of copolymer by Nuclear magnetism 1 The H-NMR spectrum was calculated by comparing the integral ratio of the peak derived from the bisphenol compound (I) with the integral ratio of the peak derived from the phenolic hydroxyl group-terminated polysiloxane (II).
Preparation of eugenol-blocked polysiloxane monomer
Octamethyl cyclotetrasiloxane (1420 g,4.80 mol), tetramethyl disiloxane (40.2 g,0.3 mol) and clay catalyst filter 20 (23.4 g,1.6 wt%) were added to a reaction kettle equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was warmed to 50 ℃ at a rate of 5 ℃/min and stirred at this temperature for 3 hours, then the temperature of the reaction system was continuously warmed to 120 ℃ at a rate of 5 ℃/min and reacted vigorously at this temperature for 5 hours, after which the clay catalyst was removed by filtration. The mass after removal of the clay catalyst was then placed in a reaction kettle equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2 g,1.02 mol) and karstedt platinum catalyst (0.67 g) was added dropwise with stirring at a rate of 20 g/min, followed by stirring at a temperature of 80℃for 13 hours. Unreacted starting material was then distilled off under reduced pressure to 0.2kPa at 200 ℃ to give eugenol-terminated polysiloxane in 99% yield, with a degree of polymerization of PDMS, as measured by nuclear magnetism, of 48, defined herein as PDMS-48, for convenience;
other conditions were unchanged, and by varying the amount of tetramethyldisiloxane, a monomer having a siloxane polymerization degree of 95 (corresponding to an amount of tetramethyldisiloxane of 20 g), defined herein as PDMS-95, was prepared.
[ examples 1 to 7 ]
Referring to the process flow shown in fig. 1, a polycarbonate-polyorganosiloxane copolymer is prepared:
(1) Preparing a monomer solution:
in the BPA phenol sodium salt solution, the mass concentration of BPA is 170g/L; the polysiloxane monomer concentration was 15%; the concentration of the triethylamine solution was 3%; the concentration of the end capping agent p-tert-butylphenol solution is 11%; the concentration of sodium hydroxide solution was 32%; the organic solvent is dichloromethane.
(2) Photochemical reaction: according to the feeding amount shown in table 1, adding a pre-prepared bisphenol compound sodium phenolate solution, a pre-prepared polysiloxane monomer solution, methylene dichloride and phosgene into an photochemical reaction kettle, wherein the solid content of the reaction solution is 16%, carrying out photochemical reaction, controlling the reaction temperature to be 30 ℃ and the reaction time to be 40min, preparing a polycarbonate-polysiloxane oligomer emulsion with a certain molecular weight, testing the weight average molecular weight of polycarbonate oligomer generated by the photochemical reaction, and testing the result table 4;
TABLE 1 charge of raw material monomers in examples
(3) Pre-polycondensation reaction: adding the oligomer emulsion prepared in the step 2) and the end capping agent solution into a pre-polycondensation reaction kettle for pre-polycondensation reaction, adding sodium hydroxide solution in the reaction process, maintaining the pH of the reaction at 12-13, and performing the circulation reaction by starting a circulating pump, wherein the reaction solution passes through a two-stage mixer (a dynamic mixer is fluororuker FA60, and a static mixer is SM-X type). The control parameters for each example are shown in table 2; taking the reaction solution after the pre-polycondensation reaction (before adding the catalyst), and testing the weight average molecular weight, the siloxane conversion rate, the R value and the gamma value, wherein the test data are shown in Table 4;
TABLE 2 control parameters for the stage of the precondensation reaction in the examples
(4) Polycondensation reaction: respectively adding the pre-polycondensation reaction liquid prepared in the step 3) into a polycondensation reaction kettle, adding 269g of triethylamine solution for polycondensation reaction, adding alkali metal hydroxide solution in the whole reaction process, maintaining the reaction pH at 11-13, and ending the reaction when no acyl chloride group exists in a reaction system;
(5) Post-treatment: purifying the copolymer solution prepared in the step (4), removing the organic solvent, and drying to obtain the product.
Comparative examples 1 to 3
Comparative examples 1 to 3 the same as example 2 except that the parameters in table 3 were different;
table 3 comparative examples 1 to 3 control parameters
The test data for the examples and comparative examples are shown in table 4 below:
definition: in the following table 4, the contents of the table,
m1 represents: weight average molecular weight of the photochemically reacted oligomer;
m2 represents: weight average molecular weight of the polycarbonate-polyorganosiloxane intermediate prepared by the pre-polycondensation reaction;
t represents: conversion of polyorganosiloxane in the polycarbonate-polyorganosiloxane intermediate prepared by the pre-polycondensation reaction;
table 4 test data for examples and comparative examples
[ examples 8 to 14 and comparative examples 4 to 6 ]
The copolymer prepared in each example and the commercially available polycarbonate-polyorganosiloxane copolymer product were used as raw materials, respectively, to prepare a resin composition according to the following formulation:
polycarbonate-polyorganosiloxane copolymer powder, clarnateGeneral-purpose PC resin and ClarnateAfter thoroughly mixing 9g of general-purpose PC resin, 9g of antioxidant (Irgafos 168, available from Ciba-Geigy) and 6g of mold release agent (Glycuber P-ETS, available from Lonza) (the material formulation is shown in Table 5), pellets were extruded and cut at 280℃using a Kebelone CTE35 type extruder, and the obtained pellets were subjected to low-temperature impact resistance and chemical resistance tests and aging resistance after injection molding, and the results are shown in Table 6.
Table 5 polycarbonate composition formulation
TABLE 6 Performance test of resin compositions
As is apparent from the comparison of the above data, the polysiloxane-polycarbonate copolymer prepared by the present invention has excellent properties by controlling the parameters of the intermediate in the pre-polycondensation reaction stage within a certain range under the condition of a certain siloxane content and a certain molecular weight, and the polycarbonate resin composition comprising the polycarbonate-polyorganosiloxane copolymer prepared by the present invention has excellent low temperature impact resistance and chemical resistance.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (7)

1. A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate segment of formula i and a polysiloxane segment of formula ii, and having the following structural characteristics: in the preparation process of the polycarbonate-polyorganosiloxane copolymer, when the weight average molecular weight of the polycarbonate-polyorganosiloxane reaction intermediate is 8000-15000 g/mol, the following conditions are satisfied:
(1) R is less than or equal to 2000, and is defined as 10000 times the ratio of the molecular weight distribution peak area S1 of the polycarbonate-polysiloxane intermediate at any wavelength in the range of 288-300nm to the molecular weight distribution peak area S2 at any wavelength in the range of 254-266nm in a UV-GPC test; the method comprises the steps of,
(2) The effective factor gamma value is more than or equal to 20, and the gamma value is defined as the ratio of the mole number of acyl chloride groups of a reaction intermediate to the mole number of phenolic hydroxyl groups of a polyorganosiloxane chain segment in a reaction system;
in the above, R 1 And R is 2 Each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 4 to 20 carbon atoms or aryl of 6 to 20 carbon atoms;
a and b independently represent an integer of 0 to 4;
x is present or absent and, when present, represents an ether group, a carbonyl group, a thioether group, 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, orA group represented; wherein R is ’ And R' independently represent 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 being optionally substituted with one or more C1-20 alkyl groups, C6-20 aryl groups, C7-21 aralkyl groups, C5-20 cycloalkyl groups or combinations thereof;
R 3 and R is 4 Each independently represents hydrogen, a halogen atom or 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 organic residue optionally comprising an aliphatic or aromatic substituent;
n is selected from 30 to 120, preferably 40 to 90.
2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein the total mass content of polysiloxane segments in the copolymer is 18 to 40%.
3. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the polycarbonate segment is a structural unit derived from bisphenol a, comprising a unit structure represented by formula iii:
4. the polycarbonate-polyorganosiloxane copolymer of any of claims 1-3, wherein the polysiloxane segment is a structural unit derived from a phenolic hydroxyl-terminated polydimethylsiloxane, as shown in formula iv;
in the formula IV, R is connected on benzene ring 5 The structure represents the residue of a phenol after removal of the hydroxyl group, wherein p is 0-5.
5. The polycarbonate-polyorganosiloxane copolymer according to any of claims 1 to 4, wherein the weight average molecular weight of the copolymer is 20000 to 40000g/mol, preferably 22000 to 35000g/mol.
6. A polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer of any one of claims 1 to 5, wherein the resin composition comprises 5 to 100% by mass of the polysiloxane-polycarbonate copolymer and 0 to 95% by mass of other aromatic polycarbonate;
preferably, the other aromatic polycarbonate is a siloxane-free polycarbonate.
7. The polycarbonate resin composition according to claim 6, further comprising an additive, wherein the additive is contained in an amount of 0 to 5% by mass based on the total mass of the polysiloxane-polycarbonate copolymer and the other aromatic polycarbonate.
CN202311481827.4A 2023-11-09 2023-11-09 Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same Pending CN117487171A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311481827.4A CN117487171A (en) 2023-11-09 2023-11-09 Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311481827.4A CN117487171A (en) 2023-11-09 2023-11-09 Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same

Publications (1)

Publication Number Publication Date
CN117487171A true CN117487171A (en) 2024-02-02

Family

ID=89673983

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311481827.4A Pending CN117487171A (en) 2023-11-09 2023-11-09 Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same

Country Status (1)

Country Link
CN (1) CN117487171A (en)

Similar Documents

Publication Publication Date Title
JP7081882B2 (en) Method for manufacturing polycarbonate-based resin composition
CN105899575B (en) Copolycarbonate and composition comprising the Copolycarbonate
JP6457344B2 (en) Polycarbonate-polyorganosiloxane copolymer and method for producing the same
JP6355951B2 (en) Polyorganosiloxane, polycarbonate-polyorganosiloxane copolymer and method for producing the same
CN114196001B (en) Polycarbonate-polyorganosiloxane copolymer, method for producing the same, and resin composition containing the same
KR20130047612A (en) Polysiloxane-polycarbonate copolymer and method of manufacturing the same
CN110062792B (en) Polycarbonate resin composition having excellent heat resistance and flowability, and molded article comprising same
JP6765432B2 (en) Polysiloxane-polycarbonate copolymer with improved transparency and flame retardancy and its production method
CN115124707B (en) Phosphorus-silicon-containing copolycarbonate and preparation method and application thereof
KR20130074748A (en) Method of preparing polysiloxane-polycarbonate copolymer
TWI738059B (en) Polysiloxane-polycarbonate copolymer having excellent impact resistance, flame retardancy and transparency and method for preparing the same
JP6589248B2 (en) Polyorganosiloxane, polycarbonate-polyorganosiloxane copolymer and method for producing the same
CN114989407B (en) Polycarbonate-polysiloxane copolymer, method for producing same, and polycarbonate resin composition containing same
KR20110021630A (en) Urethane bond-containing hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer and method of manufacturing the same
KR102115799B1 (en) Polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance and method for preparing the same
CN117487171A (en) Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same
CN114957673B (en) Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin composition containing same
KR101184801B1 (en) Siloxane compound and branched polycarbonate manufactured using the same
CN118388773A (en) Polycarbonate-polyorganosiloxane copolymer, method for producing same, and resin composition containing same
CN107849254B (en) Polyorganosiloxane and copolycarbonate prepared using the same
KR20160002485A (en) Polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance and method for preparing the same
CN112789310B (en) Copolycarbonates and polycarbonate compositions containing the same
CN115010914B (en) Siloxane copolycarbonate, preparation method thereof and polycarbonate resin composition containing same
CN114196003B (en) Siloxane copolycarbonate and preparation method thereof
KR102213376B1 (en) Polysiloxane-polycarbonate copolymer having excellent impact resistance, flame retardancy and flowability and method for preparing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination