EP1012202A1 - Systeme catalyseur pour preparer des carbonates de polyalkylene - Google Patents
Systeme catalyseur pour preparer des carbonates de polyalkyleneInfo
- Publication number
- EP1012202A1 EP1012202A1 EP98949897A EP98949897A EP1012202A1 EP 1012202 A1 EP1012202 A1 EP 1012202A1 EP 98949897 A EP98949897 A EP 98949897A EP 98949897 A EP98949897 A EP 98949897A EP 1012202 A1 EP1012202 A1 EP 1012202A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- catalyst
- catalyst system
- dicarboxylic acids
- acid
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229920001281 polyalkylene Polymers 0.000 title claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 title claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 150000002118 epoxides Chemical class 0.000 claims abstract 2
- 150000003751 zinc Chemical class 0.000 claims abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 150000003752 zinc compounds Chemical class 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- -1 aliphatic dicarboxylic acids Chemical class 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000012661 block copolymerization Methods 0.000 claims description 4
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 4
- 229940007718 zinc hydroxide Drugs 0.000 claims description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229960001296 zinc oxide Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 150000002924 oxiranes Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004651 carbonic acid esters Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
Definitions
- the invention relates to a catalyst system for the production of polyalkylene carbonates by co-, ter- and block copolymerization of epoxides with carbon dioxide.
- carbon dioxide can be converted to polymers containing carbonic acid ester groups by anionic polymerization with epoxides. These polymers are known as polyalkylene carbonates or as aliphatic polycarbonates.
- Diethylzinc / phenoisystems are also known and have been described by Inoue et al. (Macromolekules, 4, 658, 1971; Macromolecules, 169, 69, 1973) were also examined.
- Soga et al. also described zinc carboxylates, made from zinc oxide and various dicarboxylic acids with and without supporting inert metal oxides, as highly effective for the copolymerization of epoxides and carbon dioxide.
- a number of dicarboxylic acids have been tested for the synthesis of this catalyst system. Only adipic acid and glutaric acid proved to be suitable in principle, the activities achieved being only slightly higher than in the systems mentioned above.
- US Pat. No. 5,026,676 describes an improved process for the preparation of zinc carboxylates for the copolymerization of epoxides with carbon dioxide.
- a catalyst activity of approximately 22 grams of product per gram of catalyst used was achieved.
- this turnover is not yet sufficient for a commercially viable application.
- the catalyst systems mentioned still produce too many by-products, such as, for example, the cyclic monomer.
- This cyclic monomer has a negative influence on the product properties. For example, it seriously lowers the glass point of the polyalkylene carbonate and thus changes certain processing properties and thus disadvantageously also possible applications.
- the aim of the invention is to find a catalyst system for the co-, ter- and block copolymerization of one or more epoxides with carbon dioxide, which does not have the disadvantages mentioned.
- the object of the invention is to make the catalyst system so multifunctional that it is suitable for carrying out a copolymerization, a terpolymerization as well as for a block copolymerization of one or more epoxides with carbon dioxide. It is also an object of the invention to develop a suitable process for the preparation of this catalyst system, so that a high activity of the catalyst and thus economically sensible polymer conversions with high product purity and interesting property profile for a variety of application options can be achieved.
- the catalyst system according to the invention consisting of an inorganic zinc compound which is brought into contact with a mixture of at least two dicarboxylic acids, leads to above-average yields of polymers with an excellent degree of purity.
- the zinc compounds include, for example, zinc carbonate, zinc hydroxycarbonate, zinc oxide, zinc hydroxide, zinc sulfate and other divalent zinc compounds.
- Zinc hydroxycarbonate, zinc oxide and zinc hydroxide are preferably used.
- the dicarboxylic acid mixture consists of at least two dicarboxylic acids, which can be present aliphatic or aromatic or as a mixture thereof.
- the dicarboxylic acids can be mixed with one another in any ratio, preferably combinations of three are to be used.
- the aliphatic dicarboxylic acids from C 2 -C10 and the aromatic dicarboxylic acids phthalic acid, terephthalic acid, preferably isophthalic acid, are suitable.
- Mellitic acid is also advantageous in small amounts.
- a special effect with regard to the resulting product properties can also be achieved by adding small amounts of monocarboxylic acids.
- Monocarboxylic acids of C -C-io, in particular those with an odd C number, can preferably be used for this.
- a mixture of zinc oxide (> 99%) or another zinc compound mentioned above with a mixture of at least two finely ground ( ⁇ 15 ⁇ m) dicarboxylic acids are in a three-necked flask, the molar fraction of the zinc compound in this mixture always ⁇ 0.5 must be submitted.
- the liquid monocarboxylic acids are slowly added via a dropping funnel.
- the solvent used should form an azeotrope with water or be immiscible with it, since the water of reaction formed must be removed.
- the three-necked flask is equipped with a stirrer, reflux cooling, water separator and gas inlet valve. The gas space is then flushed several times with nitrogen. The reaction mixture is stirred for 90 minutes at room temperature, then the temperature is raised to 53 ° C. and held for about 3 hours with vigorous stirring.
- reaction temperatures between 15 ° C. and 80 ° C. and reaction times of up to 10 hours are possible.
- the solid is filtered off and dried in a drying cabinet under vacuum at 120 ° C. for 12 hours.
- the product is a fine white powder and can be stored in tightly closed containers for a long time. After a longer storage period, it is advisable to temper the catalyst again in a vacuum drying cabinet at 120 ° C. for 5 hours before use.
- the catalyst and a suitable solvent, in which the resulting polymer advantageously dissolves are placed in a pressure reactor rinsed several times with carbon dioxide.
- the solid catalyst can be metered in as a suspension with the solvent, for example via a lock, or it is filled in dryly before the solvent through a metering opening.
- the epoxy is then charged.
- the reaction mixture is saturated with carbon dioxide with stirring for 30 minutes. Then the reaction quickly brought to the appropriate polymerization temperature. If necessary, carbon dioxide must be replenished during the reaction.
- the reaction mixture is cooled and let down, the catalyst is separated off mechanically or removed by washing with dilute sulfuric acid.
- the resulting polymer is finely divided with a suitable precipitant, such as ethanol and dried.
- the residual solvent content in the polymer must not exceed 5 ppm.
- the mass of the resulting polymer is determined by weighing and expressed as the activity of gram of polymer per gram of catalyst, based on the mass of the catalyst used.
- a carboxylic acid mixture consisting of 0.2 mol of succinic acid, 0.3 mol of adipic acid and 0.1 mol of mellitic acid was mixed intimately with zinc hydroxycarbonate and boiled in toluene under reflux. The temperature was kept at 65 ° C. and the reaction time was 6 hours. The catalyst was worked up as described in Example 1.
- Propylene oxide and ethylene oxide were block copolymerized with carbon dioxide, the propylene oxide and 60% of the catalyst which corresponded to that of Example 5 being introduced.
- the polymerization was carried out under usual conditions. After 3 hours, the ethylene oxide and the remainder of the catalyst were metered into the reactor under pressure. The reaction was complete after a total of 5.5 hours. 360 g of polymer were obtained. When using a total of 12.5 g of catalyst, this corresponds to a catalyst activity of 28.8 g per 1 g of polymer.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
L'invention concerne un système catalyseur comprenant au moins deux acides dicarboxyliques pouvant être aliphatique ou aromatique ou un mélange des deux, qui sont mis en combinaison avec un sel de zinc inorganique bivalent. Utilisé dans le cadre de la copolymérisation, de la tripolymérisation et de la copolymérisation séquencée d'un ou de plusieurs époxydes avec du dioxyde de carbone de manière continue ou discontinue, ce système catalyseur permet d'obtenir des rendements importants, significatifs pour un usage commercial. Les polymères obtenus sont dans une large mesure exempts de produits secondaires et présentent un degré de pureté de 99 %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997137547 DE19737547A1 (de) | 1997-08-28 | 1997-08-28 | Katalysatorsystem zur Herstellung von Polyalkylencarbonaten |
| DE19737547 | 1997-08-28 | ||
| PCT/DE1998/002368 WO1999011694A1 (fr) | 1997-08-28 | 1998-08-14 | Systeme catalyseur pour preparer des carbonates de polyalkylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1012202A1 true EP1012202A1 (fr) | 2000-06-28 |
Family
ID=7840475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98949897A Withdrawn EP1012202A1 (fr) | 1997-08-28 | 1998-08-14 | Systeme catalyseur pour preparer des carbonates de polyalkylene |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1012202A1 (fr) |
| DE (1) | DE19737547A1 (fr) |
| WO (1) | WO1999011694A1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10147712A1 (de) * | 2001-09-27 | 2003-04-17 | Basf Ag | Verfahren zur Herstellung aliphatischer Polycarbonate |
| KR100722380B1 (ko) | 2002-06-20 | 2007-05-28 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
| KR100722381B1 (ko) | 2002-06-20 | 2007-05-28 | 주식회사 포스코 | 지방족 폴리카보네이트 중합용 촉매의 제조 방법 및 이를사용한 지방족 폴리카보네이트의 중합 방법 |
| CN104193980B (zh) | 2008-05-09 | 2018-11-13 | 康奈尔大学 | 环氧乙烷与二氧化碳的聚合物 |
| WO2011107577A2 (fr) * | 2010-03-05 | 2011-09-09 | Basf Se | Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation |
| ES2728648T3 (es) | 2011-04-04 | 2019-10-28 | Henkel Ag & Co Kgaa | Catalizador para la polimerización de un epóxido y para la copolimerización de epóxido con dióxido de carbono |
| US10047196B2 (en) | 2013-11-18 | 2018-08-14 | Lg Chem, Ltd. | Organic zinc catalyst, and manufacturing method thereof and manufacturing method of polyalkylene carbonate resin using the same (as amended) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4783445A (en) * | 1987-12-14 | 1988-11-08 | Arco Chemical Company | Soluble epoxide/carbon dioxide copolymerization catalysts |
| EP0358326B1 (fr) * | 1988-08-09 | 1996-12-27 | Mitsui Petrochemical Industries, Ltd. | Procédé pour préparer un catalyseur solide contenant du zinc et procédé pour la préparation de carbonate de polyalkylène |
| US4960862A (en) * | 1989-03-31 | 1990-10-02 | Air Products And Chemicals, Inc. | Regeneration of metallo-organic catalyst for carbon dioxide-epoxide copolymerization |
| US5026676A (en) * | 1989-06-07 | 1991-06-25 | Air Products And Chemicals, Inc. | Catalyst for the copolymerization of epoxides with CO2 |
| US4943677A (en) * | 1989-06-08 | 1990-07-24 | Air Products And Chemicals, Inc. | Making poly(alkylene carbonates) of controlled molecular weight |
-
1997
- 1997-08-28 DE DE1997137547 patent/DE19737547A1/de not_active Withdrawn
-
1998
- 1998-08-14 WO PCT/DE1998/002368 patent/WO1999011694A1/fr not_active Ceased
- 1998-08-14 EP EP98949897A patent/EP1012202A1/fr not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9911694A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999011694A1 (fr) | 1999-03-11 |
| DE19737547A1 (de) | 1999-03-04 |
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