CN104927040A - Preparation method of aliphatic polycarbonate catalyzed by DMC catalyst - Google Patents
Preparation method of aliphatic polycarbonate catalyzed by DMC catalyst Download PDFInfo
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- CN104927040A CN104927040A CN201410098251.8A CN201410098251A CN104927040A CN 104927040 A CN104927040 A CN 104927040A CN 201410098251 A CN201410098251 A CN 201410098251A CN 104927040 A CN104927040 A CN 104927040A
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Abstract
The invention relates to a preparation method of aliphatic polycarbonate catalyzed by a DMC catalyst, and is used for mainly solving the problem of low catalytic activity of a DMC catalyst in conventional methods. The problem is better solved by adopting the technical scheme that the preparation method of aliphatic polycarbonate catalyzed by the DMC catalyst includes the following steps: putting the DMC catalyst and an initiator into an autoclave, replacing air in the autoclave with nitrogen or carbon dioxide, adding an epoxide with the amount required for initiating a reaction into the autoclave, initiating polymerization, carrying out a reaction with a copolymerization monomer mixture composed of carbon dioxide gas and the epoxide, to generating aliphatic polycarbonate. The preparation method can be used in industrial production of aliphatic polycarbonate.
Description
Technical field
The present invention relates to the preparation method of the aliphatic polycarbonate of dmc catalyst catalysis.
Background technology
Aliphatic polycarbonate (APC) is the linear unformed multipolymer of one formed by carbonic acid gas and epoxy compounds catalyzed copolymerization, can be used as engineering plastics, elastomerics, coating, tackiness agent, oxygen barrier film and biodegradable material etc.It is regarded as contaminate environment for a long time always and produces the CO 2 waste gas of Greenhouse effect and product is degradable environmentally friendly plastics and gets more and more people's extensive concerning because raw material adopts.Found that carbonic acid gas and epoxide are by since copolyreaction synthetic fat adoption carbonic ether from the aboveground auspicious equality people of Japanese Scientists in 1969, domestic and international many scientists are devoted to this respect research.Carbonic acid gas is a kind of compound of chemical property quite stable, has higher thermodynamic stability, therefore finds the focus that the catalyzer that can activate carbonic acid gas becomes this research.
At present, the catalyzer for this system mainly contains ZnEt
2/ many proton compound (US3585168, US3953383), pentanedioic acid zinc class catalyzer (CN1302694A, CN1449866A), rare earth catalyst (CN101402725A) and double metal cyanide catalyst (US2006/0223973A1, US6713599B1, CN101440159A) etc.Wherein, double metal cyanide catalyst (DMC) has preparation simple and stablizes, and the advantages such as catalytic efficiency is high, and consumption is little, and working conditions is not harsh are subject to the favor of people.The old upper class (Polymer, 2004,45:6519-6524) is with Co-Zn DMC catalysis PO/CO
2copolymerization, reaction 10h catalytic efficiency reaches 1600 grams of polymkeric substance/gram catalyzer.The people such as Zhang Min (polymer material science and engineering, 2010,26(5): 5-8) adopt the copolymerization of high-crystallinity Co-Zn dmc catalyst catalysis carbon dioxide-epoxy propane, the catalytic efficiency of 100 DEG C of reaction 15h, Co-Zn DMC reaches 7000 grams of polymkeric substance/gram catalyzer.But current reported dmc catalyst catalytic efficiency is not still very high, needs to improve catalytic efficiency further, reduce catalyst levels.
Summary of the invention
Technical problem to be solved by this invention is that the problem that in the preparation method of aliphatic polycarbonate, dmc catalyst catalytic activity is low is prepared in existing carbonic acid gas-epoxy compounds copolymerization, provides a kind of preparation method of aliphatic polycarbonate of new dmc catalyst catalysis.In the method, DMC is active high and the content of carbonic acid gas in product fatty adoption carbonic ether is adjustable between 10% ~ 45%, and molecular weight distribution is narrow.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of the aliphatic polycarbonate of dmc catalyst catalysis, comprise the following steps: dmc catalyst and initiator are put into autoclave, with nitrogen or carbonic acid gas, especially the air in carbon dioxide replacement autoclave is used, the epoxide of initiation reaction required dosage is joined in autoclave after initiated polymerization, reacts the aliphatic polycarbonate described in generating with the copolymerized monomer mixture be made up of carbon dioxide and epoxide; Described copolymerized monomer mixture is obtained preferably by the mode first passing into carbonic acid gas and then pass into epoxide in autoclave.
In above-mentioned technical profession scheme, described dmc catalyst preferably has following general formula:
M
1 a[M
2 d(CN)
f].M
1 b[M
3 e(CN)
g].M
1 cX
h.Y
i.Z
j.kH
2O
In formula:
M
1, M
3be selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W,
Cu or Cr; Wherein, the preferred version of M1 is Zn, Ni or Co; M
3preferred version be Zn or Fe;
M
2be selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, be preferably Fe or Co;
X is selected from halogens, OH
-, NO
3 -, CO
3 2-, SO
4 2-or ClO
3 2-;
Y is selected from the C with tertiary alcohol structure
4~ C
10organic Alcohol, preferably side is the trimethyl carbinol or tertiary amyl alcohol;
Z is selected from aliphatic ester, aromatic series monoesters or aromatic diester, is preferably aromatic diesters, is more preferably phthalic ester;
A, b, c represent M
1number; D, e represent M respectively
2, M
3number; F, g represent the number of CN; H, i, j,
K represents X, Y, Z and H respectively
2the number of O.
In technique scheme, the gross weight that the consumption of described dmc catalyst accounts for product is 25 ~ 300ppmw.
In technique scheme, the temperature of described reaction is preferably 100 ~ 150 DEG C.Reaction pressure is preferably 1.5 ~ 5.0MPa.
In technique scheme, described epoxide is preferably one or more in propylene oxide, oxyethane, Styrene oxide 98min. or cyclohexene oxide.
In technique scheme, described initiator is preferably polyether glycol; The number-average molecular weight of described polyether glycol is preferably 200 ~ 1000, and more preferably 200 ~ 500.
In technique scheme, described polyether glycol is preferably at least one in polyether Glycols or polyether-tribasic alcohol.
Adopt in preparation method of the present invention, the activity of dmc catalyst can up to 2 × 10
4gram polymkeric substance/gram catalyzer, catalyst levels is little, and in the product fatty adoption carbonic ether of gained, the content of carbonic acid gas is adjustable between 10% ~ 45%, and the molecular weight distribution of the product fatty adoption carbonic ether of gained is narrower, between 1.1 ~ 1.6.
Below by embodiment, the invention will be further elaborated.
Embodiment
The preparation of A, bimetallic cyaniding complex dmc catalyst
Being joined in 150ml distilled water by 8g Cobalt Potassium Cyanide makes it dissolve, and then at rotating speed is to add 38.5%(weight wherein under the speed of 8000r/min) ZnCl
2aqueous solution 65g, then adds the mixed solution of the 100ml trimethyl carbinol and 100ml distilled water, after stirring 25min, then adds the mixed solution of 14.5g dimethyl phthalate and 200ml distilled water wherein, after continuing to stir 10min, uses sand core funnel vacuumizing filtration.Finally being added by the solid obtained in the mixed solution of the 150ml trimethyl carbinol and 50ml distilled water, is, after stirring 10min under the speed of 8000r/min, add 10.6g dimethyl phthalate at rotating speed, after stirring 10min, and centrifugation.The solid obtained is added the 220ml trimethyl carbinol again, is, after stirring 10min under the speed of 8000r/min, add 6.8g dimethyl phthalate at rotating speed, after stirring 10min, and centrifugation.Finally solid vacuum-drying to the constant weight obtained is obtained solid powder th-1 catalyst DMC12.7g.
The preparation of B, aliphatic polycarbonate
[embodiment 1]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.018g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 230g propylene oxide is reacted to be squeezed in autoclave by high-pressure pump.Reaction terminates rear cooling pressure release and takes out product.
It is 3685 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.7, in molar content, and the content 23.2% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 2 × 10
4gram polymkeric substance/gram catalyzer.
[embodiment 2]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.036g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 25g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 225g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3560 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.43, in molar content, and the content 25.3% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 1 × 10
4gram polymkeric substance/gram catalyzer.
[embodiment 3]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.072g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 230g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3750 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.15, in molar content, and the content 22.9% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 5000 grams of polymkeric substance/gram catalyzer.
[embodiment 4]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.036g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 100 DEG C, first 25g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 225g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3430 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.49, in molar content, and the content 22.1% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 9.6 × 10
3gram polymkeric substance/gram catalyzer.
[embodiment 5]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.036g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 130 DEG C, first 25g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 225g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3730 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.53, in molar content, and the content 22.3% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 1 × 10
4gram polymkeric substance/gram catalyzer.
[embodiment 6]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.037g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 2.5MPa needed for reaction, remaining 230g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3208 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.52, in molar content, and the content 16.7% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 9.3 × 10
3gram polymkeric substance/gram catalyzer.
[embodiment 7]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.037g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 5.0MPa needed for reaction, remaining 230g propylene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3579 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.48, in molar content, and the content 31.3% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 1.0 × 10
4gram polymkeric substance/gram catalyzer.
[embodiment 8]
The polyether Glycols initiator being 280mgKOH/g by 0.036g dmc catalyst and 80g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 5.0MPa needed for reaction, remaining 290 grams of propylene oxide are squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 1967 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.56, in molar content, and the content 21.7% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 9.2 × 10
3gram polymkeric substance/gram catalyzer.
[embodiment 9]
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.036DMC catalyzer and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g cyclohexene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 5.0MPa needed for reaction, remaining 230g cyclohexene oxide is squeezed in autoclave by high-pressure pump and react.Reaction terminates rear cooling pressure release and takes out product.
It is 3639 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.35, in molar content, and the content 40.3% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 1.03 × 10
4gram polymkeric substance/gram catalyzer.
[embodiment 10]
Except adopting carbonic acid gas to replace except nitrogen replacement air, all the other operation embodiments 1 are identical, are specially:
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.018g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumize carbon dioxide replacement, heat up, when temperature reaches temperature of reaction 110 DEG C, first 20g propylene oxide is joined initiated polymerization in reactor, when pressure drop passes into carbon dioxide to initiation pressure one half, after reaching the pressure 3.8MPa needed for reaction, remaining 230g propylene oxide is reacted to be squeezed in autoclave by high-pressure pump.Reaction terminates rear cooling pressure release and takes out product.
It is 3693 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.2, in molar content, and the content 23.1% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 3 × 10
4gram polymkeric substance/gram catalyzer.
From embodiment 1 and embodiment 10 on year-on-year basis, the molecular weight distribution obtained when substituting nitrogen replacement air with carbonic acid gas is narrow, and the activity of catalyzer is high.
[embodiment 11]
That embodiment 2 first passes into carbonic acid gas and then passes into propylene oxide and obtain copolymerized monomer mixture in autoclave with the difference of embodiment 2; And the present embodiment to be the mode first passing into propylene oxide in autoclave and then pass into carbonic acid gas obtain copolymerized monomer mixture, be specially:
The polyether-tribasic alcohol initiator being 360mgKOH/g by 0.036g dmc catalyst and 50g hydroxyl value puts into 500 milliliters of dry autoclaves, vacuumized nitrogen, heat up, when temperature reaches temperature of reaction 110 DEG C, first 25 grams of propylene oxide are joined initiated polymerization in reactor, when pressure drop is to initiation pressure one half, squeeze in autoclave by remaining 225g propylene oxide by high-pressure pump, then pass into carbon dioxide, the pressure 3.8MPa reached needed for reaction reacts.Reaction terminates rear cooling pressure release and takes out product.
It is 2859 that molecular weight of product is surveyed in sampling, and molecular weight distribution is 1.23, in molar content, and the content 11.8% of-COO-structural unit in molecule, and in this polymerization process, dmc catalyst catalytic activity is 6.5 × 10
3gram polymkeric substance/gram catalyzer.
From embodiment 2 and the present embodiment on year-on-year basis, when the mode passing into epoxide by first passing into carbonic acid gas in autoclave again obtains copolymerized monomer mixture, in the molecule of polymkeric substance, the content of-COO-structural unit is higher.
Claims (8)
- The preparation method of the aliphatic polycarbonate of 1.DMC catalyst, comprise the following steps: dmc catalyst and initiator are put into autoclave, with the air in nitrogen or carbon dioxide replacement autoclave, the epoxide of initiation reaction required dosage is joined in autoclave after initiated polymerization, reacts the aliphatic polycarbonate described in generating with the copolymerized monomer mixture be made up of carbon dioxide and epoxide.
- 2. preparation method according to claim 1, is characterized in that, described dmc catalyst has following general formula:M 1 a[M 2 d(CN) f].M 1 b[M 3 e(CN) g].M 1 cX h.Y i.Z j.kH 2OIn formula:M 1, M 3be selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W,Cu or Cr; Wherein, M 1preferred version be Zn, Ni or Co;M 2be selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V;X is selected from halogens, OH -, NO 3 -, CO 3 2-, SO 4 2-or ClO 3 2-;Y is selected from the C with tertiary alcohol structure 4~ C 10organic Alcohol;Z is selected from aliphatic ester, aromatic series monoesters or aromatic diester;A, b, c represent M 1number; D, e represent M respectively 2, M 3number; F, g represent the number of CN; H, i, j,K represents X, Y, Z and H respectively 2the number of O.
- 3. preparation method according to claim 1, is characterized in that, the gross weight that the consumption of described dmc catalyst accounts for product is 25 ~ 300ppmw.
- 4. preparation method according to claim 1, is characterized in that, temperature of reaction is 100 ~ 150 DEG C.
- 5. preparation method according to claim 1, is characterized in that, described epoxide is one or more in propylene oxide, oxyethane, Styrene oxide 98min. or cyclohexene oxide.
- 6. preparation method according to claim 1, is characterized in that, described initiator is polyether glycol.
- 7. preparation method according to claim 6, is characterized in that, the number-average molecular weight of described polyether glycol is 200 ~ 1000.Most preferably molecular weight 200 ~ 500.
- 8. preparation method according to claim 6, is characterized in that, described polyether glycol is at least one in polyether Glycols or polyether-tribasic alcohol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566184A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工股份有限公司 | Process for producing polyether polyols with low degree of unsaturation |
| CN101440159A (en) * | 2008-12-17 | 2009-05-27 | 中国科学院广州化学研究所 | Process for synthesizing aliphatic polycarbonate |
| CN103429637A (en) * | 2010-12-17 | 2013-12-04 | 拜耳知识产权有限责任公司 | Method for producing polyether carbonate polyols having primary hydroxyl end groups and polyurethane polymers produced therefrom |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566184A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工股份有限公司 | Process for producing polyether polyols with low degree of unsaturation |
| CN101440159A (en) * | 2008-12-17 | 2009-05-27 | 中国科学院广州化学研究所 | Process for synthesizing aliphatic polycarbonate |
| CN103429637A (en) * | 2010-12-17 | 2013-12-04 | 拜耳知识产权有限责任公司 | Method for producing polyether carbonate polyols having primary hydroxyl end groups and polyurethane polymers produced therefrom |
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