CN105968337A - Method for preparing sulfur-containing polycarbonate - Google Patents
Method for preparing sulfur-containing polycarbonate Download PDFInfo
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- CN105968337A CN105968337A CN201610169144.9A CN201610169144A CN105968337A CN 105968337 A CN105968337 A CN 105968337A CN 201610169144 A CN201610169144 A CN 201610169144A CN 105968337 A CN105968337 A CN 105968337A
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- bisphenol
- polycarbonate
- monomer
- sodium
- phenol
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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
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing sulfur-containing polycarbonate. The method is mainly used for preparing polycarbonate containing S at the main chain or side chain by melt-transesterification of diphenyl carbonate, an S-containing monomer and bisphenol A under the action of a catalyst. The polycarbonate has a flame retardant property, and can be directly used as a flame retardant material or can undergo melt blending with polycarbonate to prepare a flame-retardant polycarbonate composite material. The catalyst used in the invention is an alkaline compound which can react with bisphenol A or phenol to generate a volatile substance, and sodium phenolate and sodium bisphenolate. Reaction time is 1-10 h, reaction temperature is 140-300 DEG C, and vacuum degree is 10-10,000 Pa.
Description
Technical field
The present invention discloses a kind of method being applied to and preparing sulfur-bearing Merlon, and the method is mainly used in is urging
Under agent effect by diphenyl carbonate, prepare containing S monomer and bisphenol-A melt transesterification copolymerization main chain or
Containing the Merlon of S on side chain, this Merlon has fire resistance, can directly as fire proofing or
It is blended with polycarbonate melt and prepares fire-retardant polycarbonate composite.
Background technology
Merlon (PC) is the thermoplastic engineering plastic of a kind of high comprehensive performance, itself and and its
The mixture of his high polymer in machinery industry, electronic apparatus, automobile making, build, weave and the row such as light industry
Industry obtains a wide range of applications, and the proportion that wherein flame retardant grade PC occupies is increasing.
PC fire resistance reaches the V-2 level of UL-94 standard, and its oxygen index (OI) LOI is 21%～24%,
Still it is difficult to meet the occasion that many flame-retardancy requirements are higher or the highest.Although United States Patent (USP) 4195156 was mentioned
These activated monomers containing S can be copolymerized on the chain of Merlon, but it is by phosgenation system
Standby, phosgene and the CH of toxic and volatile of a large amount of severe toxicity is used yet with phosgenation2Cl2, locate at present
In developmental limitation state.United States Patent (USP) US6476249B1 is the preparation of siliceous fire-retardant melted Copolycarbonate
It is illustrated as emphasis, has referred only to these activated monomers containing S and can be copolymerized to Merlon
On chain.United States Patent (USP) US6753405B2 refer to the compound energy containing dihydroxydiphenyl group and carbonic acid
Diphenyl ester, bisphenol-A carry out melted copolymerization Merlon, and with 4,4-dihydroxybiphenyl, carbonic acid two
Phenyl ester, bisphenol-A melted copolymerization as a example by be illustrated.(the Journal of applied polymer such as Liaw
Science, 1997,35:2453-2460.) first bisphenol S is carried out different pretreatment, obtain a series of
The derivant of bisphenol S, then under the catalytic action of zinc acetate, melts copolymerization with diphenyl carbonate respectively
It is prepared for a series of PC, but the molecular weight of products obtained therefrom is the highest, wherein the highest being only of intrinsic viscosity
0.29dL/g.Zhang Tingjian etc. (polymer material science and engineering, 2014,30 (7): 22-25.) are with double
Phenol S, bisphenol-A and diphenyl carbonate are monomer, pass through melt transesterification process under the catalytic action of KOH
Copolymerization has the PC of anti-flammability, but the products obtained therefrom transparency and polydispersity are poor, and bisphenol S
Reactivity is relatively low, and along with the increase of its addition, the molecular weight of product constantly declines, when bisphenol S with
After the mol ratio of bisphenol-A increases to 20: 80, the relative molecular weight of product is down to less than 10000.
Summary of the invention
It is an object of the invention to provide a kind of method preparing sulfur-bearing Merlon.
The present invention be with diphenyl carbonate, containing S monomer, bisphenol-A as raw material, catalyst can be can and bis-phenol
A or phenol reactant generate the alkali compounds of volatile material and sodium phenate and bis-phenol sodium, are handed over by melted ester
The method of changing is prepared in main chain or side chain containing the Merlon of ignition-proof element S, and 4,4 '-dihydroxy diphenyl sulfide, 4,4 '
The reactivities such as-dihydroxy diphenyl disulfide are more or less the same with bisphenol-A, and reactivity is higher, when it adds
When measuring more, the most all replace bisphenol-A and remain to obtain the PC product that molecular weight is higher, and use carbonic acid
When sodium is catalyst, the transparency of product is the best.Synthesis step is: add certain proportion in reaction bulb
Diphenyl carbonate, containing S monomer and bisphenol-A, described diphenyl carbonate is total with containing S monomer and bisphenol-A
Mol ratio be 1～1.2, wherein the monomer Han S accounts for the 0.05～1 of bisphenol-A and its total mole number, then uses
In vacuum pump discharge bottle after air, regulation temperature of reaction system and pressure, carry out ester exchange pre-polymerization and polycondensation is anti-
Should, described reaction temperature is 140～300 DEG C, and reaction pressure is 10～10000Pa.
Detailed description of the invention
The present invention will be further described by the following examples.
Embodiment 1
In 200ml three neck round bottom, add 10.0g diphenyl carbonate, 8.88g bisphenol-A, 0.99g 4,4 '
-dihydroxy diphenyl sulfide, 3.2mg sodium carbonate, after air in vacuum pump discharge bottle, regulation system pressure
For 4000Pa, it is rapidly heated to 140 DEG C, opens stirring after the fusing of question response thing, after fine melt, be warming up to 150 DEG C
Keeping 50min, the most gradually heat up, every 10min heats up 20 DEG C, until temperature rises to 210 DEG C, and dimension
Hold 50min.Then reaction system pressure is down to below 130Pa, is rapidly heated to 245 DEG C.Maintain 20min
After be again rapidly heated to 270 DEG C, to be seen start polycondensation to sample after react 20min, stop heating also
System pressure is become normal pressure.Gel permeation chromatography (GPC) is used to analyze products obtained therefrom, number-average molecular weight
(Mn) being 26999, weight average molecular weight (Mw) is 54169, and polydispersity coefficient (PDI) is 2.00,
Glass transition temperature (Tg) is 143.37 DEG C, and at 700 DEG C, carbon yield is 23.13%.
Embodiment 2
Add 10g diphenyl carbonate, 4.94g bisphenol-A, 4.72g 4,4 '-dihydroxy diphenyl sulfide, 5.5mg acetic acid
Lithium, other condition is identical with example 1, and obtaining product Mn is 27216, and Mw is 49035, and PDI is
1.80, Tg is 132.12 DEG C, and at 700 DEG C, carbon yield is 27.37%.
Embodiment 3
Add 10g diphenyl carbonate, 1.97g bisphenol-A, 7.55g4,4 '-dihydroxy diphenyl sulfide, 5.5mg hydrogen-oxygen
Changing sodium, other condition is identical with example 1, and obtaining product Mn is 28704, and Mw is 59424, PDI
Being 2.11, Tg is 117.11 DEG C, and at 700 DEG C, carbon yield is 29.26%.
Embodiment 4
Addition 10.00g diphenyl carbonate, 9.87g 4,4 '-dihydroxy diphenyl sulfide, 3.16mg sodium phenate, other
Condition is identical identical with example 1, and products obtained therefrom does not dissolves in THF, dichloromethane equal solvent, and fusing point is
225.99 DEG C, at 700 DEG C, carbon yield is 35.38%.
Embodiment 5
Add 10g diphenyl carbonate, 2.96g bisphenol-A, 5.66g 4,4 '-dihydroxy diphenyl sulfide, 1.10g bis-phenol
S, 3.2mg sodium carbonate, other condition is identical with example 1, and obtaining product Mn is 14593, and Mw is
30753, PDI is 2.11.
Embodiment 6
In 5L reactor, add 1124.0g diphenyl carbonate, 998.0g bisphenol-A, 106.5g 4,4 '-dihydroxy
Base diphenyl sulfide, 0.3608g sodium carbonate, other conditions are identical with example 1, and obtaining product Mn is 26999,
Mw is 54169, and PDI is 2.00, and bending strength is 77.9MPa, and limited oxygen index (LOI) is 36.9,
The products formed of thickness 3.2mm carries out residual flame time t during vertical combustion testfFor 23S.
Embodiment 7
In 5L reactor, add 925.0g diphenyl carbonate, 182.5g bisphenol-A, 698.5g 4,4 '-dihydroxy
Diphenyl sulfide, 0.2295g sodium acetate, other conditions are identical with example 1, and products obtained therefrom Mn is 26367,
Mw is 50074, and PDI is 1.90, prepares polycarbonate composite material by following weight: poly-carbon
Acid esters 100 parts, sulfur-bearing Merlon 20 parts, prepared containing S amount as 1.63wt%'s by melting mixing
Merlon.
Claims (4)
1. the method preparing sulfur-bearing Merlon, it is characterised in that: with diphenyl carbonate, containing S monomer,
Bisphenol-A is raw material, carries out melt transesterification copolyreaction under catalyst action.
Method the most according to claim 1, it is characterised in that catalyst is: can be with bisphenol-A or phenol
Reaction generates the alkali compounds of volatile material, the most alkali-metal acetic acid compound, carbonic acid
Compound, hydroxide, alkoxide, sodium phenate or bis-phenol sodium.
Method the most according to claim 1 and 2, it is characterised in that the reactant structure containing S monomer is special
Levy for:Wherein A can be-S-,-S-S-,-SO-；Containing S
Monomer and bisphenol-A mol ratio are 0.05～1: 0.95～0.
Method the most according to claim 1 and 2, it is characterised in that melting state transesterification reaction system, instead
Being 1～10h between Ying Shi, reaction temperature is 140～300 DEG C, and vacuum is 10～10000Pa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2015101078417 | 2015-03-12 | ||
| CN201510107841 | 2015-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105968337A true CN105968337A (en) | 2016-09-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610169144.9A Pending CN105968337A (en) | 2015-03-12 | 2016-03-14 | Method for preparing sulfur-containing polycarbonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957419A (en) * | 2017-04-13 | 2017-07-18 | 郭峰 | A kind of method that utilization graphene oxide cladding stannic acid lanthanum prepares fire retardation PC |
| CN106987109A (en) * | 2017-04-13 | 2017-07-28 | 郭峰 | The method that a kind of nanometer of dawsonite/stannic acid lanthanum/graphene oxide composite flame-proof is modified PC/ABS alloys |
| US11649322B2 (en) | 2018-11-30 | 2023-05-16 | Shpp Global Technologies B.V. | Sulfur-stabilized copolycarbonates and articles formed therefrom |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227834A (en) * | 1997-12-24 | 1999-09-08 | 通用电气公司 | Process for the production of bisphenols and polycarbonates |
| CN101175790A (en) * | 2005-08-24 | 2008-05-07 | 通用电气公司 | Method for making polycarbonate articles by rotational molding and rotationally molded articles made by this method |
-
2016
- 2016-03-14 CN CN201610169144.9A patent/CN105968337A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227834A (en) * | 1997-12-24 | 1999-09-08 | 通用电气公司 | Process for the production of bisphenols and polycarbonates |
| CN101175790A (en) * | 2005-08-24 | 2008-05-07 | 通用电气公司 | Method for making polycarbonate articles by rotational molding and rotationally molded articles made by this method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957419A (en) * | 2017-04-13 | 2017-07-18 | 郭峰 | A kind of method that utilization graphene oxide cladding stannic acid lanthanum prepares fire retardation PC |
| CN106987109A (en) * | 2017-04-13 | 2017-07-28 | 郭峰 | The method that a kind of nanometer of dawsonite/stannic acid lanthanum/graphene oxide composite flame-proof is modified PC/ABS alloys |
| US11649322B2 (en) | 2018-11-30 | 2023-05-16 | Shpp Global Technologies B.V. | Sulfur-stabilized copolycarbonates and articles formed therefrom |
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Application publication date: 20160928 |
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