CN102372848B - A kind of method of preparing polycarbonate through melt transesterification technology - Google Patents
A kind of method of preparing polycarbonate through melt transesterification technology Download PDFInfo
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- CN102372848B CN102372848B CN201010248387.4A CN201010248387A CN102372848B CN 102372848 B CN102372848 B CN 102372848B CN 201010248387 A CN201010248387 A CN 201010248387A CN 102372848 B CN102372848 B CN 102372848B
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- polycarbonate
- reaction
- dihydroxy compound
- polycondensation
- transesterify
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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 Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of method of preparing polycarbonate through melt transesterification technology.With diphenyl carbonate and dihydroxyphenyl propane for raw material, under catalyst action, point transesterify and polycondensation two stage synthetic aroma polycarbonate.Used catalyst is basic metal acetyl acetone complex, and relative to every mole of aroma dihydroxy, the usage quantity of catalyzer is 10
-7-10
-3mol, temperature of reaction, between 100-250 DEG C, reduces pressure stage by stage.Product prepared by the present invention has higher viscosity-average molecular weight, colourless, lower viscosity-average molecular weight and number-average molecular weight ratio.
Description
Technical field
The present invention relates to the method that melt transesterification process prepares the clear polycarbonate of high molecular.
Background technology
Polycarbonate (PC) has high strength, high tenacity, high heat resistance, antidetonation and good processability, has fabulous shape and the transparent resin of stability.It both can be used alone, and also can blend and alloy mode use.Can be divided into several large classes such as aliphatics, Zhi Huan race, aromatic series, at present, applying maximum is bisphenol A-type PC.In the development course of more than 50 years, the Application Areas of PC is constantly expanded.In recent years due to the improvement of production technique and technology, PC material achieves and is in progress faster in perfect performance and personalized designs, the application of PC goods has penetrated among the industry such as optical instrument of building, medical science, clothes, disc plate, automotive material, material of construction, wrapping material, loose ripple printing opacity, is improving rapidly and is promoting the quality of life of people.
The conventional synthesis route of polycarbonate is that phosgene and dihydroxyphenyl propane carry out interfacial polycondensation in the two-phase system formed with water and methylene dichloride, not only employ phosgene and the noxious solvent methylene dichloride of severe toxicity, and during product separation, produce a large amount of waste water, all there is serious environmental problem.Non-phosgene preparation technology, directly uses the diphenyl carbonate (DPC) of non-phosgene synthesis and BPA to carry out ester exchange polycondensation synthesis PC.Avoid the use of phosgene of severe toxicity, do not use noxious solvent, product can directly granulation, and technique simply and have green environmental protection, has become the direction of Future Development.
Melt transesterification production technique is in order to obtain the product of high molecular, and generally under high temperature, high vacuum condition, starting monomer and product remain molten state, pressure reduction with classification removing byproduct of reaction phenol.Along with the carrying out of reaction, reaction system viscosity constantly increases, and mass transfer, heat transfer become more and more difficult, cause local superheating, easily produces branching, the side reaction such as crosslinked, produces, affect quality product with variegated material; In addition usually because catalyst distribution inequality causes reaction heterogeneity, make the molecular weight distribution of polymkeric substance wider, affect the performance of product.Patent US2003022659 discloses and adopts quaternary alkylphosphonium salt and NaOH mixed catalyst, and under 310 DEG C of conditions, the Fu Lisizhi U content of PC product is less than 1000ppm; DE19612139.6 adopts PPh
4bPh
4be catalyzer with sodium phenylate, at 320 DEG C, reaction 5.0h, obtaining Fu Lisizhi U content is 17ppm, and yellowness index is 1.22; Patent JP2002119514, adopts Cs
2cO
3make catalyzer, at 285 DEG C, the M of reaction 4.0h, PC
ηfor 25000gmol
-1left and right, and M
η/ Mn is about 3.0, and tone YI value is 1.25.
Summary of the invention
What the present invention adopted is that basic metal acetyl acetone complex makes catalyzer, and temperature of reaction is within 250 DEG C, and the reaction times is less than 2.0h, and the M of the PC produced
η/ Mn is low, the M of the PC that the present invention produces
η/ Mn is minimum reaches 1.43, and product is colourless.
The invention provides a kind of method preparing polycarbonate, the method comprises and uses diaryl carbonate and aroma dihydroxy compound to carry out melt transesterification to prepare polycarbonate, relate to the melt polymerization preparing polycarbonate, and basic metal acetyl acetone complex catalyzer.
Concrete technical scheme is:
In the methods of the invention, the aroma dihydroxy compound that can be used for preparing polycarbonate can represent with general formula below:
Wherein R is H or hydrocarbyl group.
X
1for halogen atom, nitro, hydrocarbyl group or hydrocarbonoxy radical.
N is the integer of 0-5.
Preferred aroma dihydroxy compound includes but not limited to 2,2-bis-(4-hydroxy phenyl) propane, 3,3-bis-(4-hydroxy phenyl) pentane, 2,2-bis-(the bromo-4-hydroxy phenyl of 3,5-bis-) propane, 2,2-bis-(3,5-dimethyl-4-hydroxy phenyl) propane, 2,2-bis-(3-methoxyl group-4-hydroxy phenyl) propane, 2,2-bis-(3,5-phenylbenzene-4-hydroxy phenyl) propane, and composition thereof.
Diaryl carbonate can represent with general formula below:
Wherein: X
2for halogen atom, nitro, hydrocarbyl group,-oxyl group or multiple group coexist,
M is the integer of 0-5.
Preferred diaryl carbonate includes but not limited to two (4-chloro-phenyl-) ester of diphenyl carbonate, carbonic acid two (methyl salicyl) ester, carbonic acid, two (O-Nitrophenylfluorone) ester of carbonic acid, two (4-tert-butyl-phenyl) ester of carbonic acid, carbonic acid dinaphthyl ester, two (biphenyl) ester of carbonic acid, two (o-methoxyphenyl) ester of carbonic acid, and composition thereof.
Catalyst body is metal acetylacetonate title complex, and its structural formula is:
Wherein M is alkali metal.
N be greater than zero positive integer.
The usage quantity of preferred catalyst is every mole of aroma dihydroxy compound 10
-7-10
-3mol catalyst.Can be that pressed powder state adds, be dissolved into solvent in advance as in water etc., make solution state and add again.Catalyzer can disposablely before reactions add, and also can add in other stages of reaction or add in batches.
The reaction conditions of described melt transesterification process polycarbonate synthesis not by specific restriction, and can be implemented under operational condition widely.Temperature of reaction is generally between 100 DEG C to about 250 DEG C.The mol ratio of reactant monomer aroma dihydroxy compound and diaryl carbonate between 1-0-1.2, more preferably between 1.05 to 1.10.Reaction pressure controls between 1Pa to 100000Pa, and between preferred 100Pa to 10000Pa, occurrence can adjust according to the different steps of reaction.Reaction is between 1000Pa to normal atmosphere in the transesterify stage, between preferred 4000Pa to 10000Pa, polycondensation phase pressure is between 1Pa to 6000Pa, more preferably between 4000 to 100Pa, in churned mechanically situation, total reaction time 1-4h, preferred 1-2h, the concrete time regulates according to catalyst activity.
The present invention has the following advantages:
1. with aroma dihydroxy compound and diaryl carbonate for raw material, by melt transesterification process polycarbonate synthesis, do not use the phosgene of severe toxicity and do not need solvent can straight forming;
2. use acetyl acetone complex to make catalyzer, soluble, active high, and also alkalescence is moderate, and side reaction is few, does not need catalyst quenchers;
3. temperature of reaction is low, and the reaction times is short, less energy consumption;
4. the product colour that obtains of present method is transparent, molecular weight is high, even molecular weight distribution.
Embodiment
Further illustrate the present invention below by embodiment, but enforcement of the present invention is not limited to following examples:
Embodiment 1
Reaction system is made up of heating system, stirring system, condenser system, vacuum system.Ester exchange polycondensation reaction is carried out in 50ml three-necked bottle.
Take the DPC of 43.2mmolBPA and 1.08 times, add 2.5 × 10
-4(ACAC is methyl ethyl diketone C to the LiACAC of mol/molBPA
5h
8o
2univalent anion) (concentration is 4.323 × 10 to the aqueous solution
-3molml
-1) make catalyzer, being evacuated to pressure is be heated to 130 DEG C in 4000Pa, 5.0min.Start to stir Deng after reactant fusing, after reaction 30min, start to heat up, 5min is raised to 160 DEG C, reaction 20min, 5min is raised to 180 DEG C again, reaction 10min, and then decompression is raised to 220 DEG C to 100Pa, 5min, reaction 5min, then 5min is warmed up to 250 DEG C, reaction 5min, then stopped reaction.
By product carry out following mensuration:
Viscosity-average molecular weight (M
η):
According to " measuring method of HG-T2234-1991 polycarbonate dilute solution viscosity number ", with CH in 25 DEG C of constant temperature waters
2cl
2for solvent, be the viscosity-average molecular weight of the determination of ubbelohde viscometer product of 0.37mm with capillary inner diameter.
Number-average molecular weight (Mn):
The Mn of product is characterized with gel permeation chromatography (GPC).Be dissolved in THF by product, and be eluent with THF, flow is 0.35ml/min, and sample size is 10.0 μ l, and working time is 13.0min.
The results are shown in table one and table two.
Embodiment 2-4
Under the same conditions, the experimental result of basic metal methyl ethyl diketone catalyzer lists in table one:
The experimental result of table 1 embodiment 1-4 and comparative example 1-4 thereof
Comparative example 1-4
Under the same terms, with KOH and and the acetyl acetone complex of alkaline-earth metal, transition metal and the lanthanide series metal experimental result of making catalyzer list in table one:
Embodiment 5-8
Under the same terms, the experimental result of the methyl ethyl diketone lithium catalyst of different amounts lists in table two:
The experimental result of table 2 different amounts methyl ethyl diketone lithium catalyst
Claims (4)
1. prepare a method for aromaticity polycarbonate, it is characterized in that, under the existence of metal acetylacetonate composition catalyst, aroma dihydroxy compound and aromatic carbon acid diesters are through transesterify and polycondensation polycarbonate synthesis;
The structural formula of described metal acetylacetonate composition catalyst is:
Wherein n be greater than zero positive integer, M is alkali metal;
The metallic element of described metal acetylacetonate catalyzer is basic metal M, and described basic metal M is Li, Na, Cs one wherein;
The mol ratio of described aroma dihydroxy compound and aromatic carbon acid diesters is 1:1.08, and the usage quantity of described catalyzer is every mole of aroma dihydroxy compound 10
-7-10
-3mol catalyst.
2. method according to claim 1, is characterized in that, described aroma dihydroxy compound formula is:
Wherein R is the alkane group of H or C1-C20, X
1for halogen atom, nitro, hydrocarbyl group or hydrocarbonoxy radical, n is the integer of 0-5.
3. method according to claim 1, is characterized in that, described in claim 1, aromatic carbon acid diesters general formula is:
Wherein X
2for halogen atom, nitro, hydrocarbyl group or hydrocarbonoxy radical, m is the integer of 0-5.
4. method according to claim 1, is characterized in that, described method is divided into transesterify and two stages of polycondensation, and transesterify heats up stage by stage, reduce pressure, and temperature range is at 100 DEG C-250 DEG C, and pressure is between 10000Pa-6000Pa; The temperature range of polycondensation phase is 200 DEG C-300 DEG C, pressure between 6000Pa-100Pa, total reaction time 1-4 hour.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010248387.4A CN102372848B (en) | 2010-08-09 | 2010-08-09 | A kind of method of preparing polycarbonate through melt transesterification technology |
| PCT/CN2011/001201 WO2012019424A1 (en) | 2010-08-09 | 2011-07-22 | A method of melt transesterification for preparing a polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010248387.4A CN102372848B (en) | 2010-08-09 | 2010-08-09 | A kind of method of preparing polycarbonate through melt transesterification technology |
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| Publication Number | Publication Date |
|---|---|
| CN102372848A CN102372848A (en) | 2012-03-14 |
| CN102372848B true CN102372848B (en) | 2016-03-16 |
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| WO (1) | WO2012019424A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846858B2 (en) * | 2012-12-21 | 2014-09-30 | Saudi Basic Industries Corporation | Method for alcoholysis of polycarbonate compositions containing flame retardant or acrylonitrile-butadiene-styrene |
| EP2746249B1 (en) * | 2012-12-21 | 2017-06-07 | Saudi Basic Industries Corporation | Manufacture of dihydroxy aromatic compounds by alcoholysis of flame retardant-containing polycarbonate compositions |
| CN105085895A (en) * | 2015-08-28 | 2015-11-25 | 华东理工大学 | Melting ester exchange method of preparing catalysts for polycarbonate and application thereof |
| CN111393628B (en) * | 2020-05-07 | 2021-11-09 | 中国科学院过程工程研究所 | Application of organic metal complex and preparation method of polycarbonate prepolymer |
| CN113801313B (en) * | 2021-09-22 | 2023-06-13 | 宁波浙铁大风化工有限公司 | Preparation method of high molecular weight polycarbonate and polycarbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57183745A (en) * | 1981-05-06 | 1982-11-12 | Asahi Chem Ind Co Ltd | Production of carbonic ester |
| EP1241202A1 (en) * | 2001-03-13 | 2002-09-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polycarbonate resin |
| CN101125917A (en) * | 2007-08-06 | 2008-02-20 | 天津大学 | Method for preparing polycarbonate by fusing ester exchange method and catalyst used for the same |
| CN101125918A (en) * | 2007-08-06 | 2008-02-20 | 天津大学 | Neutralization treatment method for catalyst used for preparing polycarbonate from aromatics dihydroxy compounds and diester carbonate, and neutralizing agent used for the same |
-
2010
- 2010-08-09 CN CN201010248387.4A patent/CN102372848B/en active Active
-
2011
- 2011-07-22 WO PCT/CN2011/001201 patent/WO2012019424A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57183745A (en) * | 1981-05-06 | 1982-11-12 | Asahi Chem Ind Co Ltd | Production of carbonic ester |
| EP1241202A1 (en) * | 2001-03-13 | 2002-09-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polycarbonate resin |
| CN101125917A (en) * | 2007-08-06 | 2008-02-20 | 天津大学 | Method for preparing polycarbonate by fusing ester exchange method and catalyst used for the same |
| CN101125918A (en) * | 2007-08-06 | 2008-02-20 | 天津大学 | Neutralization treatment method for catalyst used for preparing polycarbonate from aromatics dihydroxy compounds and diester carbonate, and neutralizing agent used for the same |
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| Publication number | Publication date |
|---|---|
| WO2012019424A1 (en) | 2012-02-16 |
| CN102372848A (en) | 2012-03-14 |
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Address after: 211900 Yangzhou Chemical Industrial Park, Jiangsu, Yizheng Road, No. 3 Patentee after: Jiangsu oxiranchem Co., Ltd. Address before: 211900 Yangzhou Chemical Industrial Park, Jiangsu, Yizheng Road, No. 3 Patentee before: Oxiranchem (Yangzhou) Co., Ltd. |
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