CN104861160A - Method for preparing aliphatic polycarbonate through melt transesterification and polycondensation - Google Patents
Method for preparing aliphatic polycarbonate through melt transesterification and polycondensation Download PDFInfo
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Abstract
The invention relates to a method for preparing aliphatic polycarbonate through melt transesterification and polycondensation. The method is characterized in that the aliphatic polycarbonate is prepared from dialkyl carbonate and aliphatic diol by adopting a composite oxide catalyst; the composite oxide catalyst is prepared through a sol gel technology, a co-precipitation technology or a uniform precipitation technology; and the used carbonate can be dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dihexyl carbonate, dioctyl carbonate, diphenyl carbonate, phenylethyl carbonate or methylethyl carbonate, and the diol can be ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, 2-methylpropylene glycol or alicyclic diol. The aliphatic polycarbonate is synthesized through normal pressure melt transesterification and low pressure polycondensation processes.
Description
Technical field
The present invention discloses a kind of method that high-molecular aliphatic polycarbonate is prepared in melt transesterification polycondensation.Present method adopts composite oxides catalyst based, with aliphatic dihydroxy alcohols such as the carbonic ether such as diphenyl carbonate and methylcarbonate and BDOs for raw material, with the method synthetic fat adoption carbonic ether of melt transesterification polycondensation.
Background technology
Polycarbonate roughly can be divided into aromatic copolycarbonate (PC) and aliphatic polycarbonate (APC) two class.Aromatic copolycarbonate (PC), as one of five large general engineering plastic, has good use properties and realizes industrialization.Aliphatic polycarbonate (APC) is that one can photodegradation and biological degradation plastics, the aliphatic polycarbonate (APC) of high molecular is widely used in the fields such as the modification of Dispoable medical material, packaging material for food, agricultural mulching, pharmaceutical carrier, castable ceramic and other macromolecular materials (such as, urethane).
At present, the synthetic method of fat adoption carbonic ether (APC) mainly contains the transesterify of aliphatic dihydroxy alcohol and phosgene reaction, cyclic carbonate monomer ring-opening polymerization (ROP), epoxide and carbon dioxide copolymerization, aliphatic dihydroxy alcohol and carbonic acid dialkyl ester.Aliphatic dihydroxy alcohol and phosgene reaction synthesize the processing method of APC, and because raw material phosgene is poisonous, obtain molecular weight product low (Mn ≈ 2000), productive rate low (43%), poor-performing, is eliminated.Under cyclic carbonate monomer ring-opening polymerization (ROP) and epoxide and carbon dioxide copolymerization operational path, available monomeric species is limited, the APC kind obtained is also less, and different structure and the aliphatic dihydroxy alcohol compared with Long carbon chain under the ester exchange process route of aliphatic dihydroxy alcohol and carbonic acid dialkyl ester, can be utilized, considerably increase with additive method complementation the kind can synthesizing APC.
At present, the research of synthetic fat race polycarbonate catalyst mainly concentrates on the copolyreaction of epoxide and carbonic acid gas, the catalyzer of emphasis mainly this reaction system of its research.Patent CN102718960B, CN102617845A, CN1250603C have employed rare-earth ternary catalyst, obtain the aliphatic polycarbonate of molecular weight higher (Mw > 201600), carbon dioxide fixation rate more than 40%, glass transition temp 9.8 ~ 116 DEG C; Patent CN101768261B, CN101780419B, CN101058636B adopt zinc carboxylate class catalyzer to obtain molecular weight higher (120000 ~ 160000), the product of epoxy compounds alternating copolymerization rate higher (being greater than 95%).The people such as Lv little Bing (Angew.Chem., Int.Ed., 2004,43 (27): 3574 ~ 3577.) have prepared [(Salen) CoX] catalyzer, and for CO
2with meso epoxide polyreaction at ambient temperature, polymkeric substance Mn reaches 31600g/mol.But the aliphatic polycarbonate of synthesis, due to the restriction by epoxide ad hoc structure, limits processing characteristics and the physicals of this base polymer.Complementary with the method for epoxide and carbon dioxide copolymerization synthetic fat adoption carbonic ether, carbonic acid dialkyl ester and aliphatic dihydroxy alcohol transesterify are also the approach obtaining high-molecular aliphatic polycarbonate.Similar with additive method, the key issue of ester-interchange method is also the exploitation of efficient catalyst for ester exchange reaction.But at present, the research that the catalyzer of high-molecular aliphatic polycarbonate is synthesized in the transesterify for aliphatic dihydroxy alcohol and carbonic acid dialkyl ester is only limitted to the reaction system of methylcarbonate and aliphatic dihydroxy alcohol.Both at home and abroad, the patent of the mandate of transesterify synthesis high-molecular aliphatic polycarbonate only has the people such as CN101643542B and Park (Macromolecules, 2013,2013,46 (9): 3301 ~ 3308.) reporting with a kind of gel based titanium dioxide and silica composite oxide and sodium alkoxide is respectively agent catalysis, obtains by methylcarbonate and binary aliphatic alcohol transesterification reaction the aliphatic polycarbonate that weight-average molecular weight is up to 166000.The research of the catalyzer of high-molecular aliphatic polycarbonate is synthesized for other carbonic ethers (such as diphenyl carbonate) and aliphatic dihydroxy alcohol transesterify, disclosing of patent CN 103204987A is only had to report with zinc compounds to be catalyzer, to obtain by diphenyl carbonate and binary aliphatic alcohol transesterification reaction the aliphatic polycarbonate that number-average molecular weight is up to 137300.
The aliphatic polycarbonate of high molecular has been synthesized in aliphatic dihydroxy alcohol and methylcarbonate (DMC) transesterify, DMC boiling point is lower, pressurization is needed in the transesterify stage, simultaneously can with methanol azeotropic, therefore at reaction conditions, the volatile loss of DMC, raw material availability is lower, and processing condition are harsh.Diphenyl carbonate (DPC) and the phenol recoverable in aliphatic dihydroxy alcohol ester-interchange method, reaction process is solvent-free, is a kind of process for cleanly preparing, but in reaction monomers DPC, carbonyl utilization ratio is lower.The present invention attaches most importance to for the research of transesterify synthesis high-molecular aliphatic polycarbonate catalyzer, utilize composite oxides to the high efficiency of transesterification reaction, not only realize the efficient preparation of high-molecular aliphatic polycarbonate, also expand the kind of available carboxylic acid alkyl ester, improve carbonyl utilization ratio, operational path is simplified, reduces product cost, there is certain prospects for commercial application.
Summary of the invention
The object of the present invention is to provide the method using the catalyst based ester exchange polycondensation of a kind of composite oxides to prepare high-molecular aliphatic polycarbonate.
The present invention is that the composite oxides adopting silicon-dioxide and the titanium dioxide regulated through organic compounds containing nitrogens such as hexanolactams are catalyst preparing aliphatic polycarbonate with carbonic ether and aliphatic dihydroxy alcohol for raw material.The feature of the method is the carbonic ether adopted is methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid dihexyl, carbonic acid dioctyl ester, diphenyl carbonate, carbonic ether phenethyl ester and Methyl ethyl carbonate.Dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, 2-methyl propanediol, cycloaliphatic diols.
Sol-gel method, sluggish precipitation can be passed through through the silicon-dioxide of organic compounds containing nitrogen adjustment such as hexanolactam and the composite oxides of titanium dioxide, or coprecipitation method preparation.The feature of the method is for catalyzer with the composite oxides of the silicon-dioxide regulated through organic compounds containing nitrogens such as hexanolactams and titanium dioxide.In this catalyzer, silicon titanium molar ratio range is 1: 1 ~ 20: 1, and in catalyzer, nitrogen titanium molar ratio range is 1: 1 ~ 15: 1.
The titanium source of the active ingredient titanium dioxide of the silicon-dioxide regulated through the organic compounds containing nitrogen such as hexanolactam and the composite oxide catalysts of titanium dioxide can be inorganic titanium compound, also can be organic titanic compound.Inorganic titanium compound is titanous chloride, titanium tetrafluoride, titanium tetrachloride or titanyl sulfate.Organic titanic compound is tetraethyl titanate, tetrabutyl titanate, titanium isopropylate, tetraphenyl titanate or cyclopentadienyl titanium dichloride.
Organic compounds containing nitrogen can be: hexanolactam, monomethyl pyrrolidone, quadrol, polyvinylpyrrolidone, Schiff's base, Salen-part or quinoline.
The present invention has following features:
(I) the composite oxide catalysts activity of the silicon-dioxide regulated through the organic compounds containing nitrogen such as hexanolactam that uses of the inventive method and titanium dioxide is high, the kind that can be used for synthetic fat adoption carbonic ether is many, high to ester group selectivity in polycarbonate.The present invention uses composite catalyst can not only can also synthetic aroma adoption carbonic ether for the synthesis of aliphatic polycarbonate, and synthesizing carbonate ester Mw is 10000 ~ 150000, and molecular weight distribution is 1.3 ~ 2.2, and ester group content is up to 98%.
(II) composite oxide catalysts of the silicon-dioxide regulated through the organic compounds containing nitrogen such as hexanolactam that uses of the inventive method and titanium dioxide, because activity is high, consumption is few, and the purity of products obtained therefrom is high.The polycarbonate prepared can through simple elution or the processing use being directly used in polycarbonate material.
(III) composite oxide catalysts of the silicon-dioxide regulated through the organic compounds containing nitrogen such as hexanolactam that uses of the inventive method and titanium dioxide, the quality stabilizability of polycarbonate synthesis is higher, can ensure the homogeneity of quality product.
(IV) the inventive method belongs to mass polymerization, and without the need to solvent, the phenol produced in reaction almost reclaims completely, environmentally safe, and no coupling product generates.
Embodiment
The present invention will be further described by the following examples.
Carbonic acid dialkyl ester and aliphatic dihydroxy alcohol transesterify and polycondensation process as follows:
1 normal pressure transesterify precondensation stage: first, a certain amount of BDO, diphenyl carbonate and metal oxide based composite catalyst are joined with nitrogen conduit, thermometer, magneton stir and condensation tower 100mL round-bottomed flask in; Then, pass into nitrogen with air in metathesis reactor, under normal pressure, system temperature is risen to 180 ~ 240 DEG C, keep reaction until cut no longer steams, cut gas chromatograph carries out qualitative and quantitative analysis.
2 vacuum polycondensation phase: first, control system temperature at 190 ~ 240 DEG C; Then, system pressure is reduced to 3.0 × 10 gradually
3pa, keeps 0.5h.Finally rapid within system pressure drop to 300Pa, keep 2h.Polymkeric substance methylene dichloride dissolves, and obtains polymeric articles by dehydrated alcohol precipitation.
Embodiment 1
Sol-gel method is adopted to prepare TiO
2-SiO
2composite catalyst, Ti: Si=1: 9, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, to obtain product Mn be 58111, Mw is 99743, and polydispersity coefficient is 1.72.
Embodiment 2
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=2, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 43358, Mw is 79972, and polydispersity coefficient is 1.84.
Embodiment 3
The precipitator method are adopted to prepare TiO
2-SiO
2(polyvinylpyrrolidone is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=4, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 47977, Mw is 100427, and polydispersity coefficient is 2.09.
Embodiment 4
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=4, use it for methylcarbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 26004, Mw is 31411, and polydispersity coefficient is 1.21.
Embodiment 5
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 9, N: Ti=8, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 51418, Mw is 81038, and polydispersity coefficient is 1.58.
Embodiment 6
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 2, N: Ti=4, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 59375, Mw is 75209, and polydispersity coefficient is 1.27.
Embodiment 7
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=4, use it for diphenyl carbonate and 1,3-PD mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 13070, Mw is 21235, and polydispersity coefficient is 1.62.
Embodiment 8
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=4, use it for diphenyl carbonate and hexylene glycol mass polymerization is prepared in the reaction of aliphatic polycarbonate, to obtain product Mn be 25207, Mw is 38786, and polydispersity coefficient is 1.54.
Embodiment 9
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=4, use it for diphenyl carbonate and ethylene glycol mass polymerization is prepared in the reaction of aliphatic polycarbonate, to obtain product Mn be 27583, Mw is 39495, and polydispersity coefficient is 1.43.
Embodiment 10
The precipitator method are adopted to prepare TiO
2-SiO
2(hexanolactam is precipitation agent) composite catalyst, Ti: Si=1: 4, N: Ti=8, use it for diphenyl carbonate and BDO mass polymerization is prepared in the reaction of aliphatic polycarbonate, obtaining product Mn is 54495, Mw is 73619, and polydispersity coefficient is 1.35.
Embodiment 11
Adopt sol-gel method preparation containing zinc oxide composite catalyst, and prepare in the reaction of aliphatic polycarbonate for diphenyl carbonate and BDO mass polymerization, to obtain product Mn be 93781, Mw is 176593, and polydispersity coefficient is 1.88.
Specific embodiment of the present invention; particular content of the present invention is further described; it should be emphasized that; specific embodiment listed by the present invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment, replacement, improvement etc. made, all should be included within protection scope of the present invention.
Claims (4)
1. a method for aliphatic polycarbonate is prepared in melt transesterification polycondensation, to it is characterized in that with carbonic ether and aliphatic dihydroxy alcohol, for raw material, adopting the composite oxides regulated through organic compounds containing nitrogens such as hexanolactams to be catalyst preparing aliphatic polycarbonate.
2. method according to claim 1, it is characterized in that described catalyzer is made up of composite oxides and organic compounds containing nitrogen two portions, described oxide compound is the calcium of period 4 in the periodic table of elements, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, the oxide compound of nickel or the composite oxides of wherein two oxides arbitrarily; Composite oxides are mainly: titania-silica, and its mol ratio is 1: 1 ~ 20; Zinc oxide-calcium oxide, its mol ratio is 1: 1 ~ 20; Manganse Dioxide-silicon-dioxide, its mol ratio is 1: 1 ~ 20; Cobalt sesquioxide-silicon-dioxide, its mol ratio is 1: 1 ~ 20; Organic compounds containing nitrogen is quadrol, Ursol D, polyvinylpyrrolidone, Schiff's base, pyridine, N-Methyl pyrrolidone, hexanolactam, Ursol D, amino-benzene; In described catalyzer, itrogenous organic substance and oxide mol ratio are 1 ~ 15: 1.
3. method according to claim 1, it is characterized by described carbonic ether is methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid dihexyl, carbonic acid dioctyl ester, diphenyl carbonate, carbonic ether phenylethylester, carbonate methyl ester or Methyl ethyl carbonate; Described aliphatic dihydroxy alcohol is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, 2-methyl propanediol or cycloaliphatic diols.
4. method according to claim 1, it is characterized by: account for 0.001% ~ 5% of reactant total mass with composite oxide catalysts consumption described in claim 1, temperature of reaction is 140 ~ 300 DEG C, and reaction pressure is 10Pa ~ 100000Pa, and the reaction times is 0.5h ~ 48h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674190A (en) * | 2016-08-01 | 2018-02-09 | 中国科学院成都有机化学有限公司 | The synthetic method and its catalyst of a kind of high-molecular-weight polycarbonate and application |
| CN114133549A (en) * | 2021-12-10 | 2022-03-04 | 石河子大学 | Fully biodegradable branched aliphatic polycarbonate and preparation method and application thereof |
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|---|---|---|---|---|
| CN101891884A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Polyester polycondensation catalyst and preparation method and application thereof |
| CN103120934A (en) * | 2011-11-11 | 2013-05-29 | 奥克化学扬州有限公司 | Method for preparing TiO2/SiO2 catalyst for exchanging and synthesizing diphenyl carbonate by dimethyl carbonate and phenol ester |
| CN103204525A (en) * | 2012-01-17 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Application of lactam as solvent in nano-grade material preparation |
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2014
- 2014-12-27 CN CN201410857778.4A patent/CN104861160A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891884A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Polyester polycondensation catalyst and preparation method and application thereof |
| CN103120934A (en) * | 2011-11-11 | 2013-05-29 | 奥克化学扬州有限公司 | Method for preparing TiO2/SiO2 catalyst for exchanging and synthesizing diphenyl carbonate by dimethyl carbonate and phenol ester |
| CN103204525A (en) * | 2012-01-17 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Application of lactam as solvent in nano-grade material preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674190A (en) * | 2016-08-01 | 2018-02-09 | 中国科学院成都有机化学有限公司 | The synthetic method and its catalyst of a kind of high-molecular-weight polycarbonate and application |
| CN107674190B (en) * | 2016-08-01 | 2020-03-27 | 中国科学院成都有机化学有限公司 | Synthetic method of high molecular weight polycarbonate, catalyst and application thereof |
| CN114133549A (en) * | 2021-12-10 | 2022-03-04 | 石河子大学 | Fully biodegradable branched aliphatic polycarbonate and preparation method and application thereof |
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Application publication date: 20150826 |