CN100355804C - Method for preparing high-molecular-weight polycarbonate - Google Patents
Method for preparing high-molecular-weight polycarbonate Download PDFInfo
- Publication number
- CN100355804C CN100355804C CNB2006100497077A CN200610049707A CN100355804C CN 100355804 C CN100355804 C CN 100355804C CN B2006100497077 A CNB2006100497077 A CN B2006100497077A CN 200610049707 A CN200610049707 A CN 200610049707A CN 100355804 C CN100355804 C CN 100355804C
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- described preparation
- ion liquid
- epoxy compounds
- reaction
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a mild high-efficiency method for preparing polycarbonates having high molecular weight. Composite ion liquid is used as catalyst and solvent, and carbon dioxide and epoxy compounds generate a copolymerization reaction to obtain polycarbonates having high molecular weight, narrow molecular weight distribution and high alternating structure under low pressure. The composite ion liquid is a duality catalytic system which is composed of main catalyst Schiff base metal compounding agent and cocatalyst ion liquid, and the mol ratio of the metal compounding agent to the ion liquid is from 0.001 to 10: 1. The catalyzing efficiency of the catalyst is beyond 1.5 * 10 <5> g copolymer per mol catalyst, the molecular weight of the copolymer is larger than 25000, the fixed rate of the carbon dioxide is larger than 0.46, the molecular weight distribution is less than 1.5, and the content of the alternating structure of the copolymer is beyond 98 percent. The present invention has the advantages of mild reaction condition, high catalytic activity, simple separation, no pollution, etc., and furthermore, the present invention is green technology for synthesizing polycarbonates.
Description
Technical field
The present invention relates to a kind of high efficiency preparation method of high-molecular-weight polycarbonate, be to be catalyzer and solvent with the compound ion liquid, under lower pressure, make carbonic acid gas and epoxy compounds generation copolyreaction obtain the method for high molecular, narrow molecular weight distributions, high alternating structure polycarbonate.
Background technology
Carbonic acid gas is topmost greenhouse gases, is again the most cheap resource.About 1,500,000,000 tons of the annual emission amount of carbon dioxide of China, being only second to the U.S. is world's Carbon emission second big country, the topsoil that causes thus is on the rise.How recycling carbonic acid gas, is the problem of countries in the world government growing interest.
Utilize the research of carbonic acid gas synthesized polymer material to start from the aboveground auspicious flat of Japanese oil sealing company in 1969, he finds under the effect of catalyzer, carbonic acid gas and epoxy compounds polymerizable generation aliphatic polycarbonate.Afterwards, many investigators have carried out extensive studies to the polyreaction of carbonic acid gas, find that carbonic acid gas can binary or terpolymer reaction, polyketone synthesis, polyethers, polyester, polycarbonate etc. take place with unsaturated hydro carbons, aminated compounds, epoxy compounds, alkene ether etc.These copolymerized macromolecule materials not only have excellent characteristic, can be used as engineering plastics and medical macromolecular materials, and biodegradable, have avoided problem of environmental pollution.Therefore, utilize the carbon dioxide copolymerization synthesized polymer material, both can alleviate Greenhouse effect, can produce complete degradable plastic again, the radical cure white pollution has good environmental protection benefit.
Carbonic acid gas and epoxy compounds copolymerization generate polycarbonate, are one of research focuses that utilizes the carbonic acid gas synthesized polymer material.Research report to the catalyst system of carbonic acid gas and epoxy compounds copolymerization is a lot, mainly comprises: zinc ethyl-auxiliary agent catalyzer, metal carboxylates catalysts, phenolic group metal catalyst, metal-diimine ligand mixture catalyst, rare earth coordination catalyst system, bimetallic catalytic system, metal Schiff's base catalyzer and catalysis of metalloporphyrin agent etc.Wherein, United States Patent (USP) 3585168 has been reported the method for employing zinc alkyl(s)-promotor catalyzed copolymerization polycarbonate synthesis, and molecular weight of copolymer is higher than 20000; Japanese Patent 02575199 adopts the metal porphyrin complex catalyzer, has obtained the catalytic efficiency of about 10000 gram polymkeric substance/mol catalysts, but the molecular weight of polymkeric substance has only about 5000, and the time of polyreaction is longer; Daresbourg etc. have reported and have adopted the copolyreaction of high sterically hindered phenates as catalyst carbonic acid gas and oxirane ring hexene, and catalytic efficiency is higher, but to the poor effect of catalysis carbonic acid gas and propylene oxide; Employings such as Coates metal-diimine ligand compound is that catalyzer carries out copolyreaction, and catalytic activity is higher, and reaction conditions is also relatively gentleer, and molecular weight of copolymer is higher than 20000, and molecular weight distribution is narrower, but also produces the by product ring-type propylene ester more than 10% simultaneously; Chinese patent CN1044663 has reported the method that adopts the reaction of bimetallic catalyst catalyzed copolymerization, though this method catalyzer is stable, catalytic efficiency is higher, and molecular weight of copolymer is lower; Chinese patent 1306021 has been reported the method that adopts the copolyreaction of ternary RE catalyst, and molecular weight is greater than 20000, and alternating structure is greater than 95%, but the molecular weight distribution broad; Chinese patent 1560111 and Daresbourg etc. have reported that the big alkaline catalysts of employing metal seat is a Primary Catalysts, Methylimidazole, Tetrabutyl amonium bromide etc. are as the method for promotor, the result shows that molecular weight of copolymer can reach more than 20000, and molecular weight distribution is narrower, catalytic efficiency is higher.
Above-mentioned preparation method, need to adopt volatile organic solvent mostly, as 1,4-dioxy six alkane, 1,3-dioxolane, methylene dichloride, hexane, toluene equal solvent, have mostly that catalytic activity is not high, long reaction time, reaction pressure height, supervene by products such as cyclic carbonate, and product and catalyst separating difficulty, catalyzer such as can not apply mechanically at shortcoming.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing high molecular, narrow molecular weight distributions, high alternating structure polycarbonate, solve the defective that exists in the prior art, as use volatile organic solvent, reaction conditions harshness, separation difficulty, catalyzer can not recycled etc. shortcoming.
The preparation method of high-molecular-weight polycarbonate provided by the invention, be to be raw material with carbonic acid gas and epoxy compounds, the compound ion liquid of forming with schiff base metal complex and ionic liquid is a catalyzer, carry out copolyreaction, the steps include: in autoclave, the compound ion liquid binary catalyst that adds epoxy compounds and certain proportioning, described bad oxygen compound is 50～20000 with the mol ratio of schiff base metal complex: 1, and schiff base metal complex and ion liquid mol ratio are 0.001～10: 1; Feed the carbonic acid gas of certain pressure then, react under certain temperature condition, behind the certain hour, the methyl alcohol termination reaction is used in cooling, and phase-splitting obtains high-molecular-weight polycarbonate of the present invention; The pressure of described reaction is 0.1～5MPa, and temperature of reaction is 10～80 ℃, and the reaction times is 2～20 hours.
The binary catalyst that employed compound ion liquid is made up of schiff base metal complex and ionic liquid among the present invention, wherein, metal complexes and ion liquid mol ratio are 0.001～10: 1, with 0.002～2: 1 is good.Employed schiff base metal complex is to synthesize (Inorg.Chem., 2004,43,6024-6034 by Schiff's base organic ligand and trivalent transition metal chloride, bromide, nitrate, acetate by known method; Inorg.Chem., 2005,44,2588-2595), trivalent metal ion is Cr
3+, Co
3+, Al
3+, Fe
3+, Ni
3+Employed Schiff's base organic ligand is by arginine, quadrol, propylene diamine, cyclohexanediamine, phenylenediamine and 3, and the 5-position is obtained by the salicylic aldehyde reaction that halogen, nitro, alkoxyl group, alkyl replace.
The ionic liquid that uses among the present invention is by formed various ionic liquids of negatively charged ion such as dialkylimidazolium class, quaternary amines positively charged ion and tetrafluoroborate, hexafluoro-phosphate radical, acetate moiety, nitrate radicals, these ionic liquids can be bought on market, perhaps can be by the synthetic (Green.Chem. of known method, 2004,6,75-77).Employed ionic liquid can be [Bmim] [BF
4], [Emim] [BF
4], [Bmim] [PF
6], [Emim] [BF
6], [Et
4N] [BF
4], [Et
4N] [PF
6], [Pr
4N] [BF
4], [Pr
4N] [PF
6], [Me
4N] [BF
4], [Me
4N] [PF
6], [Bmim] [OOCCH
3], [Emim] [OOCCH
3], [Bmim] [NO
3], [Emim] [NO
3] etc.
Employed epoxy compounds can be oxyethane, propylene oxide, epoxy chloropropane, Styrene oxide 98min., cyclohexene oxide, epoxypinane etc. among the present invention.
The mol ratio of epoxy compounds and metal complexes is generally 50～20000 among the present invention: 1, and especially with 100～10000: 1 is good.
The pressure that reacts among the present invention is generally 0.1～5MPa, is good with 0.5～3Mpa especially.
The temperature of reacting among the present invention is good with 20～60 ℃ especially for being generally 10～80 ℃.
The time of reacting among the present invention is generally 2～20 hours, is good with 3～10 hours especially.
The present invention has following technique effect:
(1) adopting ionic liquid in the copolyreaction is solvent, can avoid using the volatile organic solvent that environment is had harm.
(2) the binary compound ion liquid that adopts metal schiff bases complex and ionic liquid to form is a catalyzer, does not need to add other promotors, the catalytic activity height, and by product is few.
(3) copolyreaction mild condition, the polymkeric substance alternating structure is greater than 98%, and narrow molecular weight distribution.
(4) multipolymer separates with composite catalyst simply, utilize the phase-splitting that simply is separated to get final product, and composite catalyst can recycled.
Reaction conditions gentleness of the present invention, reaction times use conventional organic solvent greatly to shorten, and very high selectivity is arranged, and the catalytic efficiency of catalyzer surpasses 1.5 * 10
5G multipolymer/mol catalyzer, molecular weight of copolymer can reach more than 25000, and the fixed rate of carbonic acid gas is greater than 0.46, and molecular weight distribution is less than 1.5, and alternating structure is greater than 98%, and compound ion liquid separates simply with product, and can recycle.
Concrete embodiment
Following embodiment will more comprehensively describe the present invention.
Embodiment 1
In 100 milliliters autoclave, add 0.2 * 10
-3Mol Schiff's base cobalt chloride and 0.1mol[Bmim] [PF
6], add 0.4mol oxirane ring hexene then, feed carbon dioxide again, and make pressure reach 1.5Mpa, 30 ℃ of controlled temperature, react after 5 hours, unreacted carbon dioxide is slowly emitted in cooling, reclaim unreacted propylene oxide, add methylene dichloride and small amount of methanol then and make superpolymer dissolving, phase-splitting, upper strata methylene dichloride phase decompression and solvent recovery, add methyl alcohol then, separate out a large amount of precipitations, drying under reduced pressure obtains 35 gram white solids, multipolymer is 29500 with the gel chromatography determining molecular weight, molecular weight distribution is 1.16, with nmr determination hydrogen spectrum, shows multipolymer alternating structure 99%.Lower floor is the compound ion liquid phase, and not treated can overlapping is used for reaction next time.
Embodiment 2
In 100 milliliters autoclave, under the condition identical, just with [Emim] [BF with embodiment
4] replacement [Bmim] [PF
6], after 5 hours, obtaining 39 gram white solids in reaction under 30 ℃, its molecular weight is 33500, molecular weight distribution is 1.21, multipolymer alternating structure 99%.
Embodiment 3-12
Be similar to embodiment 1, with adopting different composite ionic liquid, differing temps, different condition to carry out copolyreaction, get following result (table one) after reaction finishes respectively:
Table one
| The experiment sequence number | Epoxy compounds | Schiff base metal complex | Ionic liquid | Temperature | Pressure | Time | Molecular weight | Alternating structure | Molecular weight distribution |
| 3 4 5 6 7 8 9 10 11 12 | Ethylene oxide propylene oxide epoxychloropropane epoxy styrene epoxypinane epoxide ring hexene epoxide ring hexene epoxide ring hexene epoxide ring hexene epoxide ring hexene | Salen Co Salen Co Salen Co Salen Co Salen Co Salen Al Salen Mn Salen Fe Salen Ni Salen Co | [Et 4N][BF 4] [Me 4N][BF 4] [Et 4N][PF 6] [Et 4N][PF 6] [Et 4N][BF 4] [Et 4N][BF 4] [Bmim][PF 6] [Emim][NO 3] [Bmim][PF 6] [Emim][BF 4] | 30 30 30 30 30 30 20 60 80 30 | 0.5 2.0 2.0 0.1 1.0 2.0 2.0 5.0 2.0 2.0 | 20 10 10 20 10 5 10 5 2 5 | 30500 33600 23500 28900 25400 33900 12000 21500 23600 36800 | 98 99 98 98 99 99 98 96 98 99 | 1.25 1.12 1.28 1.21 1.18 1.08 1.45 1.32 1.36 1.16 |
Claims (10)
1, a kind of preparation method of high-molecular-weight polycarbonate, it is characterized in that: this method is to be raw material with carbonic acid gas and epoxy compounds, the compound ion liquid of forming with schiff base metal complex and ionic liquid is a catalyzer, carry out copolyreaction, the steps include: in autoclave, the compound ion liquid binary catalyst that adds epoxy compounds and certain proportioning, the mol ratio of described epoxy compounds and schiff base metal complex is 50～20000: 1, and schiff base metal complex and ion liquid mol ratio are 0.001～10: 1; Feed the carbonic acid gas of certain pressure then, react under certain temperature condition, behind the certain hour, the methyl alcohol termination reaction is used in cooling, and phase-splitting obtains high-molecular-weight polycarbonate of the present invention; The pressure of described reaction is 0.1～5MPa, and temperature of reaction is 10～80 ℃, and the reaction times is 2～20 hours.
2,, it is characterized in that employed reactant epoxy compounds is a kind of of oxyethane, propylene oxide, epoxy chloropropane, Styrene oxide 98min., cyclohexene oxide, epoxypinane according to the described preparation method of claim 1.
3, according to the described preparation method of claim 1, it is characterized in that employed schiff base metal complex is to be synthesized by Schiff's base organic ligand and trivalent transition metal chloride, bromide, nitrate, acetate, metal ion is Cr
3+, Co
3+, Al
3+, Fe
3+, Ni
3+
4, according to the described preparation method of claim 3, it is characterized in that employed Schiff's base organic ligand is by quadrol, propylene diamine, cyclohexanediamine, phenylenediamine and 3, the 5-position is obtained by the salicylic aldehyde reaction that halogen, nitro, alkoxyl group, alkyl replace.
5,, it is characterized in that employed ionic liquid is [Bmim] [BF according to the described preparation method of claim 1
4], [Emim] [BF
4], [Bmim] [PF
6], [Emim] [BF
6], [Et
4N] [BF
4], [Et
4N] [PF
6], [Pr
4N] [BF
4], [Pr
4N] [PF
6], [Me
4N] [BF
4], [Me
4N] [PF
6], [Bmim] [OOCCH
3], [Emim] [OOCCH
3], [Bmim] [NO
3], [Emim] [NO
3] a kind of.
6,, it is characterized in that metal complexes and ion liquid mol ratio are 0.002～2: 1 according to the described preparation method of claim 1.
7, according to the described preparation method of claim 1, the mol ratio that it is characterized in that epoxy compounds and metal complexes is 100～10000: 1.
8,, it is characterized in that the pressure that reacts is 0.5～3MPa according to the described preparation method of claim 1.
9,, it is characterized in that the temperature of reacting is 20～60 ℃ according to the described preparation method of claim 1.
10,, it is characterized in that the time of reacting is 3～10 hours according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497077A CN100355804C (en) | 2006-03-06 | 2006-03-06 | Method for preparing high-molecular-weight polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497077A CN100355804C (en) | 2006-03-06 | 2006-03-06 | Method for preparing high-molecular-weight polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1814647A CN1814647A (en) | 2006-08-09 |
| CN100355804C true CN100355804C (en) | 2007-12-19 |
Family
ID=36907019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100497077A Expired - Fee Related CN100355804C (en) | 2006-03-06 | 2006-03-06 | Method for preparing high-molecular-weight polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100355804C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI586641B (en) * | 2016-04-13 | 2017-06-11 | 國立中興大學 | Bimetallic lanthanide complex, fabricating method and use thereof, polycarbonate and method of manufacturing polycarbonate |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463932C (en) * | 2007-02-12 | 2009-02-25 | 江苏中科金龙化工股份有限公司 | Production method of aliphatic polycarbonate resin |
| CN101302332B (en) * | 2007-05-10 | 2011-08-03 | 东丽纤维研究所（中国）有限公司 | Carbon dioxide-cyclohexene oxide copolymer brittlement modified method |
| CN103191779A (en) * | 2013-04-11 | 2013-07-10 | 南京大学 | Chiral schiff alkali metal catalyst supported by ionic liquid and preparation method and use thereof |
| CN103333329B (en) * | 2013-06-27 | 2015-06-03 | 昆明理工大学 | Method for preparing polycarbonate by copolymerizing carbon dioxide and alpha-pinene derivatives |
| CN106377976B (en) * | 2016-10-13 | 2018-11-30 | 浙江大学 | A method of realizing that NO is efficiently trapped using polyazole ylboronic acid ionic liquid |
| CN109054011B (en) * | 2018-07-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Schiff base cobalt compound, preparation method thereof and preparation method of polycarbonate |
| CN116410455B (en) * | 2023-03-03 | 2023-11-14 | 天津工业大学 | Method for preparing polyester by copolymerization of carbon dioxide and epoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560111A (en) * | 2004-02-27 | 2005-01-05 | 大连理工大学 | Preparation process of polyester carbonate with high molecular weight whole alternant structure |
| US6870004B1 (en) * | 2001-08-24 | 2005-03-22 | Northwestern University | Metal-ligand complexes and related methods of chemical CO2 fixation |
| CN1663978A (en) * | 2005-03-21 | 2005-09-07 | 大连理工大学 | Process for preparing polycarbonate with optical activity |
-
2006
- 2006-03-06 CN CNB2006100497077A patent/CN100355804C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6870004B1 (en) * | 2001-08-24 | 2005-03-22 | Northwestern University | Metal-ligand complexes and related methods of chemical CO2 fixation |
| CN1560111A (en) * | 2004-02-27 | 2005-01-05 | 大连理工大学 | Preparation process of polyester carbonate with high molecular weight whole alternant structure |
| CN1663978A (en) * | 2005-03-21 | 2005-09-07 | 大连理工大学 | Process for preparing polycarbonate with optical activity |
Non-Patent Citations (2)
| Title |
|---|
| 室温离子液体中二氧化碳与环氧化合物的电催化插入反应 杨宏洲，顾彦龙，邓友全.有机化学，第22卷第12期 2002 * |
| 锌离子液体系高效催化合成环状碳酸酯 李福伟，许传芝，夏春谷.石油与天然气化工，第33卷第S1期 2004 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI586641B (en) * | 2016-04-13 | 2017-06-11 | 國立中興大學 | Bimetallic lanthanide complex, fabricating method and use thereof, polycarbonate and method of manufacturing polycarbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1814647A (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100355804C (en) | Method for preparing high-molecular-weight polycarbonate | |
| Zhang et al. | Recent advances in the coupling of CO2 and epoxides into cyclic carbonates under halogen-free condition | |
| US8278239B2 (en) | Polycarbonates made using highly selective catalysts | |
| CN100494248C (en) | Double function catalyst for synthesizing polycarbonate | |
| CN101412809B (en) | Single site catalyst for synthesizing polycarbonate | |
| US9434665B2 (en) | Ruthenium complex and method for preparing methanol and diol | |
| CN108299375B (en) | Method for preparing cyclic carbonate by combined catalysis of succinimide and halide | |
| EP2590924A1 (en) | Conversion of alcohols | |
| CN112409190B (en) | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst | |
| KR20170039674A (en) | Alkylene oxide polymerization catalyst and method for producing polyalkylene oxides using same | |
| CN1792453A (en) | Complex catalyst for synthesizing carbonate ester by using homogeneous oxidation carbonylation of alcohol (S), its prepn. tech. and use | |
| CN111233816B (en) | Preparation method of cyclic carbonate | |
| Chang et al. | Polyvinyl alcohol-potassium iodide: an efficient binary catalyst for cycloaddition of epoxides with CO2 | |
| CN109675635B (en) | Non-covalent polymer catalyst suitable for 2,3, 6-trimethylphenol oxidation and preparation method thereof | |
| Yi et al. | Carbon dioxide capture and utilization: using dinuclear catalysts to prepare polycarbonates | |
| CN1663978A (en) | Process for preparing polycarbonate with optical activity | |
| JP2009215471A (en) | Alternating copolymerization of epoxide and carbon dioxide using metal complex | |
| CN102416348A (en) | Polymer supported imidazole ion catalyst as well as preparation method and application thereof | |
| CN1315908C (en) | Process for preparing highly ordered polycarbonate with optical activity | |
| US20040024263A1 (en) | Process for preparing aryl allyl ethers | |
| CN111377951B (en) | Rare earth metal compound, preparation method, composition and method for catalyzing olefin epoxidation | |
| CN109503532B (en) | 3-phenyl-3-benzyl benzofuranone compound and efficient synthesis method thereof | |
| KR20220074932A (en) | Catalyst composition for production of cyclic carbonates from CO2 and epoxides | |
| Kemp | Carbon dioxide as a polymer feedstock | |
| CN1318384C (en) | Polyphosphoric acid catalyzed dimethyl carbonate synthesizing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Ningbo Xinke Textile Auxiliary Co., LTd. Assignor: Zhejiang University Contract fulfillment period: 2008.2.10 to 2013.1.31 contract change Contract record no.: 2009330000575 Denomination of invention: Method for preparing high-molecular-weight polycarbonate Granted publication date: 20071219 License type: Exclusive license Record date: 2009.4.8 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.2.10 TO 2013.1.31; CHANGE OF CONTRACT Name of requester: NINGBO XINKE TEXTILE AIDS CO., LTD. Effective date: 20090408 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071219 Termination date: 20120306 |