CN105482091A - Preparation method of low-molecular-weight halogen flame-retardant polycarbonate - Google Patents
Preparation method of low-molecular-weight halogen flame-retardant polycarbonate Download PDFInfo
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- CN105482091A CN105482091A CN201510999482.0A CN201510999482A CN105482091A CN 105482091 A CN105482091 A CN 105482091A CN 201510999482 A CN201510999482 A CN 201510999482A CN 105482091 A CN105482091 A CN 105482091A
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- molecular weight
- retardant polycarbonate
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
Abstract
The invention relates to a preparation method of low-molecular-weight halogen flame-retardant polycarbonate, which is characterized by comprising the following steps: a. adding polyhalo bisphenol A into a sodium hydroxide solution-haloalkane mixed system, completely dissolving by stirring at normal temperature, and meanwhile, adding a catalyst; b. introducing phosgene, meanwhile, dropwisely adding a sodium hydroxide solution to keep the pH value of the system at 7-14, and carrying out prepolymerization reaction at 0-20 DEG C for 0.2-1.5 hours; c. increasing the reaction temperature to 10-40 DEG C, adding a blocking agent, and meanwhile, dropwisely adding a sodium hydroxide solution to keep the pH value of the system at 7-14; d. after the reaction finishes, standing to stratify to obtain an organic phase, adding fatty alcohol, washing to obtain a white solid, filtering, and drying to obtain the product. By strictly controlling the prepolymerization and polycondensation reaction temperatures and the pH value of the reaction system, the synthesized product has small fluctuation of the molecular weight, and the molecular weight can be fixed within a certain range. The synthesis technique has the advantages of short period, simple operating technique and high efficiency.
Description
Technical field
The present invention relates to chemical field, especially a kind of preparation method of lower molecular weight halogen flame retardant polycarbonate.
Background technology
The halogen flame retardant polycarbonate oligomer decomposition temperature obtained by many halogen dihydroxyphenyl propane and phosgene interface method is moderate, adapt with the decomposition temperature of various superpolymer, fire retardation can be played in gas phase and condensed phase in the best time simultaneously, addition is little, and blend processing fluidity is good, can meet the little and requirement of complicated shape of processing, simultaneously the consistency of itself and polyester is good, do not separate out, product surface can not produce bloom phenomenon, good flame retardation effect.Firing except polycarbonate except producing difficulty with polycarbonate blending, also can be used for ABS, high impact polystyrene, polyethylene terephthalate, polymeric amide, aromatic polyester, urethane and polystyrene etc., producing firing-difficult matter.
Halogen flame retardant polycarbonate mainly contains three kinds of preparation methods: phosgenation, ester-interchange method, BTC method, its study on the synthesis is more.Chang Zhi etc. are with triphosgene (BTC, be commonly called as solid phosgene, also trimerization carbonyl chloride is) and many halogen dihydroxyphenyl propane (tetrabromo-bisphenol) halogen flame retardant polycarbonate that has been Material synthesis, but the pH value that prepolymerization reaction phosgene passes into reaction system in process and polycondensation process is not followed the tracks of.(" chemistry and biotechnology ", 2005,22(5): 24-26).Chen Baiqiu etc. are with phosgene and many halogen dihydroxyphenyl propane (tetrabromo-bisphenol) the halogen flame retardant polycarbonate that has been Material synthesis, but its molecular weight distribution wider (2.7 ~ 4.6), in product, polymeric small molecule content is more, its flame retardant effect is reduced for easily oozing out in high flame retardant material, and can produce when oozing out poison or to environment (" fine-chemical intermediate ", 2013,43(4): 51-62).Liu Zhanyu is with triphosgene and many halogen dihydroxyphenyl propane (tetrabromo-bisphenol) the halogen flame retardant polycarbonate oligomer that has been Material synthesis, but its reaction time (3 ~ 4h) oversize (Shandong University's M Sc thesis).Up to the present, with phosgene and many halogen dihydroxyphenyl propane for raw material, utilize phosgene interface method at normal pressure, strictly control reaction system pH and temperature of reaction, the document of the halogen flame retardant polycarbonate oligomer of preparation narrow molecular weight distribution rarely has report.
Preparation method and the common phosgenation polycarbonate of halogen flame retardant polycarbonate oligomer are quite similar, but bisphenol-a polycarbonate is than being easier to synthesis, but the synthesis of halogen flame retardant polycarbonate is much more difficult.At identical conditions, the molecular weight of the polycarbonate that phosgene and bisphenol-a reaction obtain can be very large, and the problem such as the molecular weight of the halogen flame retardant polycarbonate that phosgene and many halogen dihydroxyphenyl propane synthesize is very little, molecular weight distribution is wider, reaction time is long, product qualification rate is low.
Summary of the invention
The object of the invention is for solving the problem, a kind of preparation method of lower molecular weight halogen flame retardant polycarbonate is provided.
For achieving the above object, the technical scheme that the present invention takes is: a, to be added by many halogen dihydroxyphenyl propane in the mixed system of sodium hydroxide solution and halogenated alkane composition, many halogen dihydroxyphenyl propane by mass percentage: halogenated alkane is 1:1 ~ 26.5, stirring and dissolving is complete at normal temperatures, add catalyzer, catalyst charge is 0.01 ~ 0.10% of many halogen dihydroxyphenyl propane quality simultaneously;
B, phosgene is passed in above-mentioned mixed system, phosgene intake is many halogen dihydroxyphenyl propane in molar ratio: phosgene is 1:1 ~ 10, and drip concentration is the sodium hydroxide solution of 10 ~ 40% simultaneously, keeps system pH7 ~ 14, it is 0 ~ 20 DEG C that prepolymerization reaction temperature controls, stirring reaction 0.2 ~ 1.5h;
C, temperature of reaction is risen to 10 ~ 40 DEG C, add end-capping reagent, end-capping reagent consumption is 1 ~ 10% of many halogen dihydroxyphenyl propane quality, and drip concentration is the sodium hydroxide solution of 10 ~ 30% simultaneously, keeps system pH7 ~ 14, stirring reaction 0.2 ~ 1.5h;
D, terminate reaction, static layering obtains organic phase, and washs with process water and mineral acid, adds fatty alcohol, washes out white solid, filtration, drying, obtain number-average molecular weight 2000 ~ 7000 halogen flame retardant polycarbonate.
Described many halogen dihydroxyphenyl propane is any one of trichlorine dihydroxyphenyl propane, tetrachlorobisphenol A or tetrabromo-bisphenol.
Described catalyzer is any one of tertiary ammonium salt, quaternary ammonium salt or tertiary amine.
Described end-capping reagent be phenol, p-tert-butylphenol, tribromophenol, isopropyl-phenol any one.
Described halogenated alkane is methylene dichloride or ethylene dichloride.
Described mineral acid is any one of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
Described fatty alcohol is any one of methyl alcohol, ethanol, propyl alcohol, butanols or neopentyl alcohol.
Principle: with phosgene and many halogen dihydroxyphenyl propane for raw material, prepolymerization reaction and the temperature of polycondensation, the pH etc. of system is controlled at ambient pressure by strict, with halogenated alkane and water for solvent, utilize and regulate the consumption of catalyzer and end-capping reagent to carry out control inerface polymerization velocity, do Precipitation agent at aliphatic alcohols and obtain the product that molecular weight distribution is narrower, reaction time is short, product qualification rate is high.
The invention has the beneficial effects as follows:
(1) adopt interfaciacial phosgenation method synthesis halogen flame retardant polycarbonate, the pH value passing into reaction system in process and polycondensation process at prepolymerization reaction phosgene is followed the tracks of, and determines optimization control parameter.
(2) by the strict pH value controlling pre-polymerization and polycondensation temperature and reaction system thereof, synthesize the molecular weight product fluctuation obtained little, can realize molecular weight being fixed in certain scope, be beneficial to the target product of preparation of industrialization specified molecular weight, product molecular weight distribution is narrow, the synthesis technique cycle is short, and operating procedure is simple, and efficiency is high.
Embodiment
Embodiment 1: with in six mouthfuls of flasks of electric mixer, add many halogen dihydroxyphenyl propane 100g, water 200g, methylene chloride 530g, dissolves completely with sodium hydroxide solution under agitation, adds catalyst of triethylamine 0.73g, system temperature is controlled at 10 DEG C, pass into phosgene 33g, regulate the pH of mixed system between 7 ~ 14 with sodium hydroxide solution, prepolymerization reaction time 20min simultaneously.Improve temperature of reaction to 18 DEG C after treating prepolymerization reaction, add end-capping reagent p-tert-butylphenol 1.37g, drip sodium hydroxide solution simultaneously, keep system pH7 ~ 14, stirring reaction 30min; React complete, by water oil two phase stratification, oil phase washs after three times with process water and hydrochloric acid soln respectively, oil phase is added in precipitation agent, wash out white solid, filtration drying, obtains the halogen flame retardant polycarbonate of number-average molecular weight 4945, weight-average molecular weight 8852, molecular weight dispersity 1.80 after testing.
Embodiment 2: with in six mouthfuls of flasks of electric mixer, add many halogen dihydroxyphenyl propane 100g, water 250g, methylene chloride 460g, dissolves completely with sodium hydroxide solution under agitation, adds catalyst of triethylamine 0.5g, system temperature is controlled at 11 DEG C, pass into phosgene 35g, regulate the pH of mixed system between 7 ~ 14 with sodium hydroxide solution, prepolymerization reaction time 15min simultaneously.Improve temperature of reaction to 20 DEG C after treating prepolymerization reaction, add end-capping reagent phenol 0.86g, drip sodium hydroxide solution simultaneously, keep system pH7 ~ 14, stirring reaction 30min; React complete, by water oil two phase stratification, oil phase washs after three times with process water and hydrochloric acid soln respectively, oil phase is added in precipitation agent, wash out white solid, filtration drying, obtains the halogen flame retardant polycarbonate of number-average molecular weight 5443, weight-average molecular weight 9873, molecular weight dispersity 1.81 after testing.
Embodiment 3: with in six mouthfuls of flasks of electric mixer, add many halogen dihydroxyphenyl propane 100g, water 300g, methylene chloride 400g, dissolves completely with sodium hydroxide solution under agitation, adds catalyst of triethylamine 1g, system temperature is controlled at 12 DEG C, pass into phosgene 30g, regulate the pH of mixed system between 7 ~ 14 with sodium hydroxide solution, prepolymerization reaction time 20min simultaneously.Improve temperature of reaction to 16 DEG C after treating prepolymerization reaction, add end-capping reagent phenol 0.86g, drip sodium hydroxide solution simultaneously, keep system pH7 ~ 14, stirring reaction 20min; React complete, by water oil two phase stratification, oil phase washs after three times with process water and hydrochloric acid soln respectively, oil phase is added in precipitation agent, wash out white solid, filtration drying, obtains the halogen flame retardant polycarbonate of number-average molecular weight 5445, weight-average molecular weight 9824, molecular weight dispersity 1.80 after testing.
Embodiment 4: with under embodiment 1 the same terms, add end-capping reagent after prepolymerization reaction terminates half an hour, polycondensation simultaneously extends to 1 ~ 4h, obtains number-average molecular weight 10000-40000, weight-average molecular weight 40000-80000; The halogen flame retardant polycarbonate of molecular weight dispersity 1-5.
Embodiment 5: by the halogen flame retardant polycarbonate that obtains under embodiment 1 condition and general purpose grade polycarbonate blending, halogen flame retardant polycarbonate consumption is 5 ~ 20%(W/W of general purpose grade polycarbonate).Its oxygen index of product is obtained between 30 ~ 40 by extruding pelletization, injection molding.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for lower molecular weight halogen flame retardant polycarbonate, is characterized in that comprising the following steps:
A, many halogen dihydroxyphenyl propane added in the mixed system of sodium hydroxide solution and halogenated alkane composition, many halogen dihydroxyphenyl propane by mass percentage: halogenated alkane is 1:1 ~ 26.5, stirring and dissolving is complete at normal temperatures, and add catalyzer, catalyst charge is 0.01 ~ 0.10% of many halogen dihydroxyphenyl propane quality simultaneously;
B, phosgene is passed in above-mentioned mixed system, phosgene intake is many halogen dihydroxyphenyl propane in molar ratio: phosgene is 1:1 ~ 10, and drip concentration is the sodium hydroxide solution of 10 ~ 40% simultaneously, keeps system pH7 ~ 14, it is 0 ~ 20 DEG C that prepolymerization reaction temperature controls, stirring reaction 0.2 ~ 1.5h;
C, temperature of reaction is risen to 10 ~ 40 DEG C, add end-capping reagent, end-capping reagent consumption is 1 ~ 10% of many halogen dihydroxyphenyl propane quality, and drip concentration is the sodium hydroxide solution of 10 ~ 30% simultaneously, keeps system pH7 ~ 14, stirring reaction 0.2 ~ 1.5h;
D, terminate reaction, static layering obtains organic phase, and washs with process water and mineral acid, adds fatty alcohol, washes out white solid, filtration, drying, obtain number-average molecular weight 2000 ~ 7000 halogen flame retardant polycarbonate.
2. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: many halogen dihydroxyphenyl propane is any one of trichlorine dihydroxyphenyl propane, tetrachlorobisphenol A or tetrabromo-bisphenol.
3. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: described catalyzer is any one of tertiary ammonium salt, quaternary ammonium salt or tertiary amine.
4. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: described end-capping reagent be phenol, p-tert-butylphenol, tribromophenol, isopropyl-phenol any one.
5. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: described halogenated alkane is methylene dichloride or ethylene dichloride.
6. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: described mineral acid is any one of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
7. the preparation method of lower molecular weight halogen flame retardant polycarbonate as claimed in claim 1, is characterized in that: described fatty alcohol is any one of methyl alcohol, ethanol, propyl alcohol, butanols or neopentyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955150A (en) * | 2017-11-23 | 2018-04-24 | 清远初曲智能科技有限公司 | A kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof |
| CN115785426A (en) * | 2022-11-21 | 2023-03-14 | 万华化学集团股份有限公司 | Polycarbonate and preparation method thereof |
| CN116425965A (en) * | 2023-05-06 | 2023-07-14 | 沧州大化股份有限公司 | Flame-retardant copolycarbonate and preparation method thereof |
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| JPH06157737A (en) * | 1992-11-25 | 1994-06-07 | Teijin Chem Ltd | Production of carbonate-type flame retardant |
| CN1100437A (en) * | 1993-05-24 | 1995-03-22 | 通用电气公司 | Method for making flame retardant polycarbonate |
| US6414178B1 (en) * | 2000-07-25 | 2002-07-02 | General Electric Company | Method for the continuous preparation of chloroformate products of halogenated dihdroxy compounds |
| CN103848983A (en) * | 2014-02-17 | 2014-06-11 | 南通大学 | Synthetic method of bromo-polycarbonate |
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Patent Citations (4)
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| JPH06157737A (en) * | 1992-11-25 | 1994-06-07 | Teijin Chem Ltd | Production of carbonate-type flame retardant |
| CN1100437A (en) * | 1993-05-24 | 1995-03-22 | 通用电气公司 | Method for making flame retardant polycarbonate |
| US6414178B1 (en) * | 2000-07-25 | 2002-07-02 | General Electric Company | Method for the continuous preparation of chloroformate products of halogenated dihdroxy compounds |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955150A (en) * | 2017-11-23 | 2018-04-24 | 清远初曲智能科技有限公司 | A kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof |
| CN115785426A (en) * | 2022-11-21 | 2023-03-14 | 万华化学集团股份有限公司 | Polycarbonate and preparation method thereof |
| CN115785426B (en) * | 2022-11-21 | 2024-04-16 | 万华化学集团股份有限公司 | Polycarbonate and preparation method thereof |
| CN116425965A (en) * | 2023-05-06 | 2023-07-14 | 沧州大化股份有限公司 | Flame-retardant copolycarbonate and preparation method thereof |
| CN116425965B (en) * | 2023-05-06 | 2024-02-13 | 沧州大化股份有限公司 | Flame-retardant copolycarbonate and preparation method thereof |
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Application publication date: 20160413 |