CN1095403C - Process for preparing zinc bicarboxylate catalyst - Google Patents
Process for preparing zinc bicarboxylate catalyst Download PDFInfo
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- CN1095403C CN1095403C CN00130811A CN00130811A CN1095403C CN 1095403 C CN1095403 C CN 1095403C CN 00130811 A CN00130811 A CN 00130811A CN 00130811 A CN00130811 A CN 00130811A CN 1095403 C CN1095403 C CN 1095403C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 239000011701 zinc Substances 0.000 title abstract description 29
- 229910052725 zinc Inorganic materials 0.000 title abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract description 9
- 239000004593 Epoxy Substances 0.000 abstract description 6
- 229920005646 polycarboxylate Polymers 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 235000011089 carbon dioxide Nutrition 0.000 description 12
- 230000009466 transformation Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- SCRKTTJILRGIEY-UHFFFAOYSA-N pentanedioic acid;zinc Chemical compound [Zn].OC(=O)CCCC(O)=O SCRKTTJILRGIEY-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- -1 zinc carboxylate Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UXDZLUCNRYCZCG-UHFFFAOYSA-L zinc;phthalate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O UXDZLUCNRYCZCG-UHFFFAOYSA-L 0.000 description 2
- PKMTWMDBJHRDBM-ODZAUARKSA-N (z)-but-2-enedioic acid;zinc Chemical compound [Zn].OC(=O)\C=C/C(O)=O PKMTWMDBJHRDBM-ODZAUARKSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- AGFGXVAAIXIOFZ-UHFFFAOYSA-L zinc;butanedioate Chemical compound [Zn+2].[O-]C(=O)CCC([O-])=O AGFGXVAAIXIOFZ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing zinc polycarboxylate catalysts, particularly to a method for preparing binary zinc polycarboxylate catalysts used in carbon dioxide and epoxy ether copolymerization. ZnO, Zn(OH)2 or Zn (NO3)2.6H2O is put in aprotic solvents and reacts with dicarboxylic acid or acid anhydride at the temperature of 10 to 95 DEG C to prepare the binary zinc polycarboxylate. The method is characterized in that ultrasonic wave whose frequency is from 10KHz to 180KHz is adopted to oscillate and stir during the reaction. The method has the advantages that the reaction speed can be quickened, the conversion rate of reactants is enhanced, the crystallisation of the binary zinc polycarboxylate is promoted, the crystallisation defect is reduced and the quality is enhanced.
Description
The present invention relates to a kind of preparation method of zinc polycarboxylate catalyst, especially the preparation method of the binary zine carboxylate catalyst that uses in carbonic acid gas and the ether epoxy copolymerization.
Carbonic acid gas is the waste gas of contaminate environment, but also is a kind of carbon resource of preciousness, and it is also more than the summation of coal, oil and natural gas at the reserves of the earth.The utilization of carbonic acid gas is a heat subject, and many scientific workers have carried out the research of this respect.Carbonic acid gas all obtains utilizing in the production of food, urea, methyl alcohol, carbonate and other organic compound, it is aspect Polymer Synthesizing that another kind utilizes the method for carbonic acid gas, and it is synthesized aliphatic polycarbonate as a kind of monomer and ether epoxy copolymerization.1969, Inoue, Koinuma and Tsuruta had utilized since the carbonic acid gas polycarbonate synthesis first, and many researchists have carried out the polymerization studies of carbonic acid gas and ether epoxy.
Carbonic acid gas and ether epoxy copolymerization, need activate the inertia of carbonic acid gas with catalyzer, many effective catalyzer have now been developed, wherein the catalyzed polymerization speed of binary zine carboxylate catalyst is fast, the molecular weight product height, product be the ratio of carbonic acid gas and ether epoxy compounds near 1: 1 alternating copolymer, be a class ideal catalyzer.Binary zine carboxylates such as zinc succinate, pentanedioic acid zinc, hexanodioic acid zinc, maleic acid zinc and zinc phthalate are the representatives of this class catalyzer, and are wherein the highest with pentanedioic acid zinc activity.
ZnO, Zn (OH) are used in the preparation of binary zine carboxylate catalyst usually
2, or Zn (NO
3)
2.6H
2O and corresponding di-carboxylic acid or acid anhydrides carry out in aprotic solvent.Be reflected under the suitable temperature, adopt high speed machine to stir.Because ZnO, Zn (OH)
2All be insoluble to the solvent that is adopted with the product binary zine carboxylate, as toluene, benzene, acetone, butyl ether, methyl alcohol, ethanol, tetrahydrofuran (THF) etc., so its reaction is the inhomogeneous reaction of " slurry type ".In so-called " mud " reaction, speed of response is ZnO, Zn (OH)
2Molecular diffusion speed is controlled, and under mechanical stirring, speed of response is slow, is difficult to even thoroughly carry out.When selecting Zn (NO for use
3)
2.6H
2When O is raw material,, need to strengthen the consumption of di-carboxylic acid and with the NO that generates although its raw material all is dissolved in tetrahydrofuran (THF)
2In time get rid of, reaction could be carried out smoothly.
The preparation method who the purpose of this invention is to provide a kind of binary zine carboxylate catalyst, it can overcome churned mechanically shortcoming, and fast reaction speed improves the transformation efficiency of reactant, and promotes the binary zine carboxylate crystallization to reduce crystal defect, improves its quality.
The present invention adopts ZnO, Zn (OH)
2Or Zn (NO
3)
2.6H
2O in aprotic solvent with di-carboxylic acid or acid anhydrides prepared in reaction binary zine carboxylate under 10～95 ℃ of temperature, adopting frequency when it is characterized in that reacting is that 10～180KHz ultra-sonic oscillation stir.
Temperature of reaction can be decided on requirement of experiment in 10～95 ℃ of scopes.The heat that ultrasonic wave produced can be heated for reaction solution, during as if shortage of heat or surplus, can suitably heat or cool off, to satisfy the temperature requirement of control.For different reactants, its best temperature of reaction is different.Adopt ZnO and Zn (OH)
2During for raw material, optimal reaction temperature is 52～56 ℃, selects Zn (NO for use
3)
2.6H
2When O was raw material, optimal reaction temperature was 60～70 ℃.
Frequency of ultrasonic can be selected for use in 10～180KHz scope, and preferred 30～50KHz can select the ultrasonic wave of a certain fixed frequency or conversion frequency for use.
Reaction is carried out in the water-bath under the ultra-sonic oscillation usually, when enough big as if reactor, ultrasonic generator directly can be placed the reaction solution in the reactor, so that effectively utilize its energy.
After reaction finishes, cross the elimination mother liquor, and wash and remove remaining di-carboxylic acid, the solvent that is used to wash can be selected the aprotic solvent that used di-carboxylic acid is had strong dissolving power for use.Binary zine carboxylate drying behind the washing and filtering, standby.
The present invention adopts the ultrasonic stirring method to replace mechanical stirring, has promoted ZnO and Zn (OH) effectively
2Dispersion of particles, the diffusion or the NO of quickening molecule
2Discharge, and promote the crystallization of resultant binary zine carboxylate to reduce crystal defect, thus the carrying out of accelerated reaction and improve the quality of product.The using ultrasound ripple stirs and compares with mechanical stirring, and following advantage is arranged:
(1) ZnO, Zn (OH)
2, or Zn (NO
3)
2.6H
2O and di-carboxylic acid reaction, identical if di-carboxylic acid generates the conversion of zinc carboxylate when other reaction conditions is identical, adopt ultrasonic stirring, can shorten the reaction times 40～60%, or reduce temperature of reaction more than 5 ℃.
(2) adopt the present invention, to reactant ZnO and Zn (OH)
2Size of particles is not strict with, and in the time, the transformation efficiency of reactant all can reach 100% in certain reaction, and mechanical stirring then is difficult to accomplish.
(3) adopt the ultrasonic stirring method, help the zinc carboxylate crystalline and carry out, reduce the formation of crystal defect, improve the quality of zinc polycarboxylate catalyst.With pentanedioic acid zinc catalysis carbonic acid gas and the propylene oxide copolymerization that this law makes, obtain the polycarbonate of complete alternating structure, its second-order transition temperature and 5% thermal weight loss temperature are respectively 39.39 ℃ and 275.0 ℃, are the maximum of all reports.
(4) adopt supersonic method to prepare zinc carboxylate, ultrasonic generator can be arranged on inside reactor or outside, is suitable for multiple conversion unit and reaction conditions and different solvents, and is flexible and changeable.
(5) adopt supersonic method, equipment is simple, and is easy to operate, the heat heating that also can utilize ultrasonic wave to produce, but stirring heating has both the saving energy.
Enforcement of the present invention can not only obtain fine binary zine carboxylate catalyst crystal, reduces the cost with the carbonic acid gas polycarbonate synthesis, and can reduce facility investment and energy expenditure, and it is applied will have favorable economic benefit and social benefit.
Embodiment 1
Get ZnO (99.5%) 20mmol, pentanedioic acid (99.0%) 19.6mmol, solvent toluene 30ml is loaded in the flask of 50ml, and water-bath is 10 hours in frequency 45KHz ultrasonic cleaner tank, and temperature of reaction is 50～55 ℃.After reaction is finished, the elimination mother liquor, and with washing with acetone for several times, the transformation efficiency that pentanedioic acid generates pentanedioic acid zinc is 100%.
Embodiment 2
ZnO 50mmol, pentanedioic acid 49mmol, toluene 75ml, reactor volume 100ml, reaction conditions and material purity such as embodiment 1, the transformation efficiency of pentanedioic acid are 99.9%.
Embodiment 3
Five duplicate samples, its reactant and solvent are: pentanedioic acid (99.5%) 22mmol, Zn (NO
3)
2.6H
2O (99.0%) 20mmol, tetrahydrofuran (THF) 45ml.Respectively at 40～49 ℃, 50～55 ℃, 56～60 ℃, water-bath is 15 hours in 60～70 ℃ and 70～80 ℃ of temperature sections, and reaction is the ultrasonic stirring of 42KHz with frequency.Product filters the back with the tetrahydrofuran (THF) washing for several times.Zn (NO
3)
2.6H
2The transformation efficiency of O is respectively: 39.7%, 41.6%, 65.7%, 99.0% and 84.3%.
Embodiment 4
Tetra hydro Phthalic anhydride (99.7%) 19.6mmol, ZnO (99.5%) 20mmol, tetrahydrofuran (THF) 30ml, reaction conditions are with embodiment 1, and it is remaining sour with the tetrahydrofuran (THF) flush away that reactant filters the back.The transformation efficiency that Tetra hydro Phthalic anhydride generates zinc phthalate is 73.6%.
Embodiment 5
4 parts of ZnO (99.5%) 20mmol, respectively with di-carboxylic acid: Succinic Acid (99.0%), hexanodioic acid (99.0%) and pentanedioic acid (99.0%) reaction, the di-carboxylic acid consumption is 19.6mmol, the solvent of preceding two kinds of carboxylic acids and ZnO reaction is a tetrahydrofuran (THF), latter's portion is an acetone, and another part is methyl alcohol.Reaction conditions is with embodiment 1, and the reactant binary zine carboxylate is all used its selected solvent wash.The di-carboxylic acid transformation efficiency of above-mentioned four duplicate samples is respectively 81.5%, 59.6%, and 48.3% and 80.6%.
Embodiment 6
The reactant of five duplicate samples and solvent composition are: pentanedioic acid (99.0%) 19.6mmol, ZnO (99.5%) 20mmol, toluene 30ml.In oscillation frequency is under the ultrasonic wave effect of 45KHz, respectively at 20～29 ℃, and 30～40 ℃, 41～49 ℃, 50～55 ℃, water-bath is 10 hours in 56～65 ℃ of temperature sections, and the transformation efficiency of its pentanedioic acid is respectively: 88.7%, 95.4%, 98.9%, 100% and 99.3%.
Embodiment 7
Pentanedioic acid (99.0%) 19.6mmol, Zn (OH)
2(99.0%) 20mmol, toluene 30ml, the reaction times is 30 hours, other reaction conditions and experimental technique are with embodiment 1.The transformation efficiency that pentanedioic acid generates its zinc carboxylate is 76.8%.
Embodiment 8
Pentanedioic acid (99.0%) 19.6mmol, ZnO (99.0%) 20mmol, two parts in the sample of toluene 30ml, its temperature of reaction is 50～55 ℃, and the reaction times is 4 hours, and wherein first part is adopted mechanical stirring, another part adopts ultrasonic stirring, its appointed condition such as embodiment 1.The transformation efficiency of pentanedioic acid is respectively: 35.8% and 75.9%.
Claims (3)
1, a kind of preparation method of binary zine carboxylate catalyst adopts ZnO, Zn (OH)
2Or Zn (NO
3)
2.6H
2O in aprotic solvent with di-carboxylic acid or acid anhydrides prepared in reaction binary zine carboxylate under 10～95 ℃ of temperature, it is characterized in that reacting that to adopt frequency be that the ultra-sonic oscillation of 10～180KHz stir.
2,, it is characterized in that adopting ZnO and Zn (OH) according to the method described in the claim 1
2During for raw material, temperature of reaction is 52～56 ℃; Adopt Zn (NO
3)
2.6H
2When O was raw material, temperature of reaction was 60～70 ℃.
3,, it is characterized in that frequency of ultrasonic is 30～50KHz, selects the ultrasonic wave of fixed frequency or conversion frequency for use according to the method described in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130811A CN1095403C (en) | 2000-11-22 | 2000-11-22 | Process for preparing zinc bicarboxylate catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130811A CN1095403C (en) | 2000-11-22 | 2000-11-22 | Process for preparing zinc bicarboxylate catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1302694A CN1302694A (en) | 2001-07-11 |
| CN1095403C true CN1095403C (en) | 2002-12-04 |
Family
ID=4594316
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00130811A Expired - Fee Related CN1095403C (en) | 2000-11-22 | 2000-11-22 | Process for preparing zinc bicarboxylate catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1095403C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300214C (en) * | 2002-06-20 | 2007-02-14 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410294C (en) * | 2006-04-18 | 2008-08-13 | 中国科学院广州化学研究所 | Polymers of methylethylene and ethylene carbonate and its prepn. method |
| CN102911351A (en) * | 2011-08-05 | 2013-02-06 | 湛江师范学院 | Method for preparing dicarboxylic acid zinc catalyst with rheological phase reaction method |
| KR20140062130A (en) * | 2011-09-09 | 2014-05-22 | 바스프 에스이 | Method for producing zinc dicarboxylate |
| CN105418907B (en) * | 2015-11-30 | 2017-06-23 | 中国科学院长春应用化学研究所 | A kind of preparation method of binary zine carboxylate catalyst, modified binary zine carboxylate catalyst and carbon dioxide epoxy compound composition copolymer |
-
2000
- 2000-11-22 CN CN00130811A patent/CN1095403C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300214C (en) * | 2002-06-20 | 2007-02-14 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate using same |
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| Publication number | Publication date |
|---|---|
| CN1302694A (en) | 2001-07-11 |
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