CN101701062A - Method for synthesizing aliphatic polycarbonate polyols - Google Patents
Method for synthesizing aliphatic polycarbonate polyols Download PDFInfo
- Publication number
- CN101701062A CN101701062A CN200910309859A CN200910309859A CN101701062A CN 101701062 A CN101701062 A CN 101701062A CN 200910309859 A CN200910309859 A CN 200910309859A CN 200910309859 A CN200910309859 A CN 200910309859A CN 101701062 A CN101701062 A CN 101701062A
- Authority
- CN
- China
- Prior art keywords
- acetate
- polycarbonate polyols
- carbonate
- synthetic fat
- polyols according
- 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.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a method for synthesizing aliphatic polycarbonate polyols by transesterification synthesis. The transesterification is carried out on carbonate and aliphatic diols under the catalysis of a high-efficient catalyst, and the polycarbonate polyols with a plurality of structures and adjustable molecular weights and degrees of hydroxyl functional groups can be obtained by regulating the types of the diols. The method has the advantages of short reaction time, high utilization rate of equipment and reduced production cost, thereby leading the large-scale production and the applications of the aliphatic polycarbonate polyols to be possible. The method for preparing the aliphatic polycarbonate polyols comprises the following steps: adding a catalyst, butanediol and the carbonate into a reactor according to a certain material ratio, introducing nitrogen for replacing air in the reactor, increasing the temperature at normal pressure to 180-190 DEG C, carrying out reaction for 2-4h, dropping the pressure to 100-20000Pa, carrying out the reaction for 4-10h, and introducing the nitrogen for cooling a product, thereby obtaining the polycarbonate polyols.
Description
Technical field
The present invention relates to a kind of method of carrying out transesterify synthetic fat polycarbonate polyols by aliphatic polyol and organic carbonate.
Background technology
Aliphatic polycarbonate polybasic alcohol is that two ends of molecule are all hydroxyl, molecular backbone chain contains the polymkeric substance of aliphatics alkylidene group and carbonate group repeating unit, very big with traditional polycarbonate material difference, and close with aliphatic polyester polyols and polyether glycol, be widely used in fields such as synthetic leather, TPU, SPANDEX, binding agent, coating.Its important derived product polyurethane material is widely used in fields such as building, chemical industry, light industry, electromechanics, metallurgy, health care by feat of excellent property, characteristics various in style.Compare with traditional polyvalent alcohol (polyester polyol, polyether glycol) institute synthetic urethane, polycarbonate polyurethane by the polycarbonate polyol preparation has better thermotolerance, weathering resistance, water tolerance, germ resistance, scale resistance and mechanical property, and some kind also has favorable biological degradability.
Because the raw material phosgene severe toxicity that uses, and a large amount of hydrogenchloride of by-product cause heavy corrosion to equipment, formation condition is abominable, pollute bigger, phosgenation be eliminated substantially (DE1595446A1).The cost of synthesizing annular carbonate is higher, and therefore, cyclic carbonate ring-opening polymerization polycarbonate synthesis polyvalent alcohol does not have great industrial application value.Carbonic acid gas is the very abundant and cheap C1 resource of reserves on the earth, but the carbonic acid gas epoxide regulate the polycarbonate polyol that copolymerization method can only synthesize specific epoxide structure (CN101024685A, CN1060299A).By adjusting the kind of aliphatic dihydroxy alcohol, ester-interchange method can synthesize the polycarbonate polyol of multiple structure, and the adjustability height of relative molecular weight, and product colourity is low, and the hydroxy functional group degree is relatively near theoretical value.Therefore, ester-interchange method polycarbonate synthesis polyvalent alcohol has been subjected to extensive concern.
U.S. Pat 065360A1 discloses with titanium isopropylate and has made catalyst methylcarbonate and binary alcohol esters exchange polycarbonate synthesis glycol, but productive rate is low.U.S. Pat 0125576 discloses with the organic compound of rare earth element and VIIIB metallic element and has made catalyst methylcarbonate or diethyl carbonate and binary alcohol esters exchange polycarbonate synthesis glycol, the organic compound of ytterbium and lanthanum has relative catalytic activity preferably to reaction, but poor selectivity.European patent EP 1134248 discloses organo-tin compound and has made catalyst methylcarbonate and binary alcohol esters exchange polycarbonate synthesis glycol, but poor activity, and organo-tin compound is the potential carcinogen in the human body.Chinese patent CN101029127A discloses a kind of KF heterogeneous catalyst catalyzed carbon dimethyl phthalate or diethyl carbonate and binary alcohol esters exchange polycarbonate synthesis glycol that is supported on the carrier, but long reaction time, poor activity.The boiling point of methylcarbonate (90.1 ℃) and diethyl carbonate (125.8 ℃) is lower, and is volatile in the reaction process.Methylcarbonate can generate azeotrope with by-product carbinol, and azeotrope consists of methylcarbonate 30% (mass percent), methyl alcohol 70% (mass percent), and azeotropic temperature is 64 ℃ (Luo Zhi etc., gas chemical industry, 2008,33 (2), 66～70).Diethyl carbonate can not form azeotrope with by product ethanol, ethanol is nontoxic, but diethyl carbonate can enter body by gi tract, skin and respiratory tract and show as moderate toxicity, and diethyl carbonate steam can form explosive mixture (S.R.Nam etal with air, FuelProcessingTechnology, 2003,83,27～38).P.Piotr etc. have studied the catalytic performance of basic metal inorganic salt to NSC 11801 and binary alcohol esters exchange polycarbonate synthesis glycol, and are wherein best with the catalytic activity of lithium salts, secondly are sodium salts, be sylvite (P.Piotret al, Polymer, 2004 at last, 45,3125～3137).But NSC 11801 is unstable in ethylene glycol, can decompose (old blue sky etc., petrochemical technology and application, 2008,26 (3), 216～218).
Summary of the invention
The objective of the invention is to solve the deficiency and the problem that exist in the above-mentioned technology, the method of a kind of low toxicity, reliable and practical ester-interchange method synthetic fat polycarbonate polyols is provided, so that obtain to contain more carbonate unit with relatively low economic cost, the aliphatic polycarbonate polybasic alcohol that molecular weight and hydroxy functionality all can be adjusted on demand.
The present invention is achieved by the following technical solutions:
The method of synthetic fat polycarbonate polyols of the present invention, its step is as follows: (1) is under condition of normal pressure, catalyzer, aliphatic polyol and organic carbonate are joined in the reactor, feed nitrogen to get rid of the air in the reactor, under nitrogen atmosphere, temperature is risen to 100～200 ℃, back flow reaction 2～4 hours; (2) reduce pressure to 100～20000Pa, simultaneously, temperature rises to 120～200 ℃, reacts 4～10 hours.
Described catalyst consumption counts 0.01%～7% with the organic carbonate quality.
The mol ratio of described aliphatic polyol and organic carbonate is 1.06～2.
Described catalyzer is alkali metal acetate, alkaline-earth metal acetate, transition metal acetate or organic titanic compound.
Described organic carbonate is alkyl carbonate, aryl carbonates or alkylene carbonic ether.
Described aliphatic polyol is straight chain or ramose, saturated or undersaturated C
3～C
25Aliphatic polyol or its mixture, wherein, hydroxy functionality 〉=2, the aliphatic dihydroxy alcohol that wherein said straight chain is saturated is 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,6-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol or their mixture, preferred 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or their mixture.
Described alkali metal acetate is Lithium Acetate, sodium-acetate or Potassium ethanoate; Alkaline-earth metal acetate is magnesium acetate, calcium acetate or barium acetate; Transition metal acetate is chromium acetate, manganese acetate, iron acetate, Cobaltous diacetate, nickel acetate, neutralized verdigris, zinc acetate, plumbic acetate or Burow Solution; Organic titanic compound is metatitanic acid methyl esters, titanium ethanolate, isopropyl titanate, butyl (tetra) titanate, metatitanic acid phenyl ester or methyl ethyl diketone oxygen titanium.
Described alkyl carbonate is methylcarbonate or diethyl carbonate, and aryl carbonates is a diphenyl carbonate, and the alkylene carbonic ether is a NSC 11801.
The present invention compared with prior art has the following advantages:
(1) owing to adopted the organic titanium catalyzer of a kind of efficient, low toxicity, low consumption, the reaction times is short, and the synthesis under normal pressure time was generally 2～4 hours, and the decompression polycondensation time is generally 4～10 hours, thereby has improved usage ratio of equipment, has reduced production cost.
(2) molecular weight of product and hydroxy functional group degree can be regulated on request.
Embodiment
Example 1
With 1 of 150g (1.7mol), the diphenyl carbonate of 4-butyleneglycol, 300g (1.4mol) and the methyl ethyl diketone oxygen titanium of 0.9g (0.003mol) join in the reactor that is equipped with heated and stirred system, temp measuring system and fractionating system.Logical repeatedly nitrogen is to discharge air (at least 3 times) in the reactor, and normal pressure is warming up to 180～190 ℃ under nitrogen atmosphere, back flow reaction 2～4h.Reduce pressure to 5500Pa, temperature is 180～190 ℃, reaction 6h.Logical nitrogen cools off by product, promptly obtains polycarbonate polyol, is a kind of slightly yellowy solid under the room temperature, and its hydroxyl value is 79.04mg KOH/g, and number-average molecular weight is 1419.45.
Example 2
With 1 of 180g (2.0mol), the diphenyl carbonate of 4-butyleneglycol, 300g (1.4mol) and the butyl (tetra) titanate of 0.9g (0.003mol) join in the reactor that is equipped with heated and stirred system, temp measuring system and fractionating system.Logical repeatedly nitrogen is to discharge air (at least 3 times) in the reactor, and normal pressure is warming up to 180～190 ℃ under nitrogen atmosphere, back flow reaction 2～4h.Reduce pressure to 5500Pa, temperature is 180～190 ℃, reaction 6h.Logical nitrogen cools off by product, promptly obtains polycarbonate polyol, is a kind of slightly yellowy solid under the room temperature, and its hydroxyl value is 94.58mg KOH/g, and number-average molecular weight is 1186.24.
Example 3
With 1 of 230g (2.2mol), the diphenyl carbonate of 5-butyleneglycol, 300g (1.4mol) and the metatitanic acid methyl esters of 0.4g (0.002mol) join in the reactor that is equipped with heated and stirred system, temp measuring system and fractionating system.Logical repeatedly nitrogen is to discharge air (at least 3 times) in the reactor, and normal pressure is warming up to 180～190 ℃ under nitrogen atmosphere, back flow reaction 2～4h.Reduce pressure to 5500Pa, temperature is 180～190 ℃, reaction 6h.Logical nitrogen cools off by product, promptly obtains polycarbonate polyol, is a kind of slightly yellowy solid under the room temperature, and its hydroxyl value is 130.15mg KOH/g, and number-average molecular weight is 862.07.
Example 4
With 1 of 200g (1.7mol), the diphenyl carbonate of 6-butyleneglycol, 300g (1.4mol) and the methyl ethyl diketone oxygen titanium of 2.1g (0.008mol) join in the reactor that is equipped with heated and stirred system, temp measuring system and fractionating system.Logical repeatedly nitrogen is to discharge air (at least 3 times) in the reactor, and normal pressure is warming up to 180～190 ℃ under nitrogen atmosphere, back flow reaction 2～4h.Reduce pressure to 5500Pa, temperature is 180～190 ℃, reaction 6h.Logical nitrogen cools off by product, promptly obtains polycarbonate polyol, is a kind of slightly yellowy solid under the room temperature, and its hydroxyl value is 54.73mg KOH/g, and number-average molecular weight is 2050.14.
Claims (10)
1. the method for a synthetic fat polycarbonate polyols, its feature comprises following two steps: (1) is under condition of normal pressure, catalyzer, aliphatic polyol and organic carbonate are joined in the reactor, feed nitrogen to get rid of the air in the reactor, under nitrogen atmosphere, temperature is risen to 100～200 ℃, back flow reaction 2～4 hours; (2) reduce pressure to 100～20000Pa, simultaneously, temperature rises to 120～200 ℃, reacts 4～10 hours.
2. the method for synthetic fat polycarbonate polyols according to claim 1 is characterized in that described catalyst consumption counts 0.01%～7% with the organic carbonate quality.
3. the method for synthetic fat polycarbonate polyols according to claim 1, the mol ratio that it is characterized in that described aliphatic polyol and organic carbonate is 1.06～2.
4. the method for synthetic fat polycarbonate polyols according to claim 1 is characterized in that described catalyzer is alkali metal acetate, alkaline-earth metal acetate, transition metal acetate or organic titanic compound.
5. the method for synthetic fat polycarbonate polyols according to claim 1, it is characterized in that described aliphatic polyol is aliphatic polyol or its mixture of straight chain or ramose, saturated or undersaturated C3～C25, wherein, hydroxy functionality 〉=2.
6. the method for synthetic fat polycarbonate polyols according to claim 1 is characterized in that described organic carbonate is alkyl carbonate, aryl carbonates or alkylene carbonic ether.
7. the method for synthetic fat polycarbonate polyols according to claim 4 is characterized in that described alkali metal acetate is Lithium Acetate, sodium-acetate or Potassium ethanoate; Alkaline-earth metal acetate is magnesium acetate, calcium acetate or barium acetate; Transition metal acetate is chromium acetate, manganese acetate, iron acetate, Cobaltous diacetate, nickel acetate, neutralized verdigris, zinc acetate, plumbic acetate or Burow Solution; Organic titanic compound is metatitanic acid methyl esters, titanium ethanolate, isopropyl titanate, butyl (tetra) titanate, metatitanic acid phenyl ester or methyl ethyl diketone oxygen titanium.
8. the method for synthetic fat polycarbonate polyols according to claim 5, it is characterized in that the saturated aliphatic dihydroxy alcohol of described straight chain is 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,6-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol or their mixture.
9. the method for synthetic fat polycarbonate polyols according to claim 6 is characterized in that described alkyl carbonate is methylcarbonate or diethyl carbonate, and aryl carbonates is a diphenyl carbonate, and the alkylene carbonic ether is a NSC 11801.
10. the method for synthetic fat polycarbonate polyols according to claim 8 is characterized in that the saturated aliphatic dihydroxy alcohol of described straight chain is 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910309859A CN101701062A (en) | 2009-11-17 | 2009-11-17 | Method for synthesizing aliphatic polycarbonate polyols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910309859A CN101701062A (en) | 2009-11-17 | 2009-11-17 | Method for synthesizing aliphatic polycarbonate polyols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101701062A true CN101701062A (en) | 2010-05-05 |
Family
ID=42155992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910309859A Pending CN101701062A (en) | 2009-11-17 | 2009-11-17 | Method for synthesizing aliphatic polycarbonate polyols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101701062A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120818A (en) * | 2011-01-05 | 2011-07-13 | 河北工业大学 | Preparation method of aliphatic polycarbonate diol |
| CN103204987A (en) * | 2012-01-17 | 2013-07-17 | 常州化学研究所 | Method for synthesizing high-molecular-weight aliphatic polycarbonate |
| CN103923307A (en) * | 2014-05-05 | 2014-07-16 | 李亮 | Method for preparing polycarbonate diol |
| CN104419001A (en) * | 2013-09-06 | 2015-03-18 | 常州化学研究所 | Novel biodegradable polycarbonate copolymer and preparation method thereof |
| WO2016075968A1 (en) * | 2014-11-11 | 2016-05-19 | 宇部興産株式会社 | Polycarbonate polyol |
| CN105694020A (en) * | 2016-02-01 | 2016-06-22 | 中山大学 | Aliphatic polycarbonate dibasic alcohol and preparation method thereof |
| WO2016161585A1 (en) * | 2015-04-09 | 2016-10-13 | 中国科学院成都有机化学有限公司 | Preparation method for aliphatic polycarbonate |
| CN107057050A (en) * | 2016-12-24 | 2017-08-18 | 四川中腾能源科技有限公司 | Preparation method and equipment of polycarbonate dihydric alcohol |
| CN107189052A (en) * | 2017-07-18 | 2017-09-22 | 温州南力实业有限公司 | A kind of preparation of loaded catalyst and its application in poly- carbonic acid hexylene glycol ester polyol is prepared |
| CN107236120A (en) * | 2017-06-09 | 2017-10-10 | 海聚高分子材料科技（广州）有限公司 | A kind of liquid PCDL and preparation method thereof |
| CN110054766A (en) * | 2019-05-22 | 2019-07-26 | 河南省科学院化学研究所有限公司 | A method of utilizing the complex-catalyzed preparation aliphatic Copolycarbonate polyalcohol of stannous chloride |
| CN110894288A (en) * | 2019-12-09 | 2020-03-20 | 东莞市竤穗实业投资有限公司 | Ultraviolet light curing polycarbonate acrylate and preparation method thereof |
| US10689488B2 (en) | 2018-01-02 | 2020-06-23 | Industrial Technology Research Institute | Method for preparing polycarbonate polyol and composition comprising the polycarbonate polyol |
| CN112029083A (en) * | 2020-08-26 | 2020-12-04 | 烟台大学 | Polyether carbonate polyol and preparation method thereof |
| CN113292714A (en) * | 2021-06-01 | 2021-08-24 | 山东元利科技有限公司 | Preparation method of polycarbonate diol |
| CN113372547A (en) * | 2021-06-01 | 2021-09-10 | 山东元利科技有限公司 | Method for synthesizing polycarbonate diol by adopting compound catalyst |
| CN114149576A (en) * | 2021-11-26 | 2022-03-08 | 南京桐君新材料科技有限公司 | Fluorine-containing polycarbonate diol and preparation method thereof |
| CN115044028A (en) * | 2022-08-02 | 2022-09-13 | 河南省科学院化学研究所有限公司 | Polycarbonate dihydric alcohol and preparation method thereof |
| CN115232301A (en) * | 2022-08-03 | 2022-10-25 | 山东海科创新研究院有限公司 | Method for preparing polycarbonate diol with rapid and controllable molecular weight and application thereof |
| CN115466181A (en) * | 2022-09-05 | 2022-12-13 | 天津凯美特化工科技有限公司 | Method for producing dimethyl carbonate by ester exchange using long-acting catalyst |
-
2009
- 2009-11-17 CN CN200910309859A patent/CN101701062A/en active Pending
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120818A (en) * | 2011-01-05 | 2011-07-13 | 河北工业大学 | Preparation method of aliphatic polycarbonate diol |
| CN102120818B (en) * | 2011-01-05 | 2012-08-01 | 河北工业大学 | Preparation method of aliphatic polycarbonate diol |
| CN103204987A (en) * | 2012-01-17 | 2013-07-17 | 常州化学研究所 | Method for synthesizing high-molecular-weight aliphatic polycarbonate |
| CN103204987B (en) * | 2012-01-17 | 2015-12-02 | 常州化学研究所 | A kind of method of synthesizing high-molecular aliphatic polycarbonate |
| CN104419001A (en) * | 2013-09-06 | 2015-03-18 | 常州化学研究所 | Novel biodegradable polycarbonate copolymer and preparation method thereof |
| CN103923307A (en) * | 2014-05-05 | 2014-07-16 | 李亮 | Method for preparing polycarbonate diol |
| CN103923307B (en) * | 2014-05-05 | 2015-08-12 | 李亮 | The preparation method of polycarbonate diol |
| WO2016075968A1 (en) * | 2014-11-11 | 2016-05-19 | 宇部興産株式会社 | Polycarbonate polyol |
| US10344122B2 (en) | 2015-04-09 | 2019-07-09 | Chengdu Organic Chemicals Co., Ltd., Cas | Preparing method of aliphatic polycarbonate |
| WO2016161585A1 (en) * | 2015-04-09 | 2016-10-13 | 中国科学院成都有机化学有限公司 | Preparation method for aliphatic polycarbonate |
| CN105694020A (en) * | 2016-02-01 | 2016-06-22 | 中山大学 | Aliphatic polycarbonate dibasic alcohol and preparation method thereof |
| CN107057050A (en) * | 2016-12-24 | 2017-08-18 | 四川中腾能源科技有限公司 | Preparation method and equipment of polycarbonate dihydric alcohol |
| CN107236120A (en) * | 2017-06-09 | 2017-10-10 | 海聚高分子材料科技（广州）有限公司 | A kind of liquid PCDL and preparation method thereof |
| CN107236120B (en) * | 2017-06-09 | 2019-06-25 | 海聚高分子材料科技（广州）有限公司 | A kind of liquid polycarbonate glycol and preparation method thereof |
| CN107189052A (en) * | 2017-07-18 | 2017-09-22 | 温州南力实业有限公司 | A kind of preparation of loaded catalyst and its application in poly- carbonic acid hexylene glycol ester polyol is prepared |
| US10689488B2 (en) | 2018-01-02 | 2020-06-23 | Industrial Technology Research Institute | Method for preparing polycarbonate polyol and composition comprising the polycarbonate polyol |
| CN110054766A (en) * | 2019-05-22 | 2019-07-26 | 河南省科学院化学研究所有限公司 | A method of utilizing the complex-catalyzed preparation aliphatic Copolycarbonate polyalcohol of stannous chloride |
| CN110054766B (en) * | 2019-05-22 | 2021-08-17 | 河南省科学院化学研究所有限公司 | Method for preparing aliphatic copolymerized carbonate polyol by using stannous chloride complex as catalyst |
| CN110894288A (en) * | 2019-12-09 | 2020-03-20 | 东莞市竤穗实业投资有限公司 | Ultraviolet light curing polycarbonate acrylate and preparation method thereof |
| CN112029083A (en) * | 2020-08-26 | 2020-12-04 | 烟台大学 | Polyether carbonate polyol and preparation method thereof |
| CN113292714A (en) * | 2021-06-01 | 2021-08-24 | 山东元利科技有限公司 | Preparation method of polycarbonate diol |
| CN113372547A (en) * | 2021-06-01 | 2021-09-10 | 山东元利科技有限公司 | Method for synthesizing polycarbonate diol by adopting compound catalyst |
| CN114149576A (en) * | 2021-11-26 | 2022-03-08 | 南京桐君新材料科技有限公司 | Fluorine-containing polycarbonate diol and preparation method thereof |
| CN115044028A (en) * | 2022-08-02 | 2022-09-13 | 河南省科学院化学研究所有限公司 | Polycarbonate dihydric alcohol and preparation method thereof |
| CN115044028B (en) * | 2022-08-02 | 2023-03-14 | 河南省科学院化学研究所有限公司 | Polycarbonate dihydric alcohol and preparation method thereof |
| CN115232301A (en) * | 2022-08-03 | 2022-10-25 | 山东海科创新研究院有限公司 | Method for preparing polycarbonate diol with rapid and controllable molecular weight and application thereof |
| CN115232301B (en) * | 2022-08-03 | 2024-01-30 | 山东海科创新研究院有限公司 | Preparation method and application of quick and molecular weight-controllable polycarbonate diol |
| CN115466181A (en) * | 2022-09-05 | 2022-12-13 | 天津凯美特化工科技有限公司 | Method for producing dimethyl carbonate by ester exchange using long-acting catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101701062A (en) | Method for synthesizing aliphatic polycarbonate polyols | |
| CN104513393B (en) | Method for preparing biodegradable thermoplastic poly(ether-urethane) by employing a non-isocyanate process | |
| KR101241248B1 (en) | Polymer of polycarbonate diol having an alicyclic structure and production process thereof | |
| CN103204987B (en) | A kind of method of synthesizing high-molecular aliphatic polycarbonate | |
| CN102120818B (en) | Preparation method of aliphatic polycarbonate diol | |
| CN101570595B (en) | Terpolymer containing polyester chain links and polycarbonate chain links and synthetic method thereof | |
| JP5803107B2 (en) | Polycarbonate diol and polycarbonate diol copolymer | |
| CN1980979B (en) | Oligocarbonate polyols having terminal secondary hydroxyl groups | |
| CN100560634C (en) | A kind of preparation method of PCDL | |
| CN104910348A (en) | Polycarbonate polyurethane and green preparation method thereof | |
| CN111825836B (en) | Preparation method of polycarbonate | |
| CN100491440C (en) | Method for preparing polyols of acyclic oligo carbonic ester | |
| KR101136951B1 (en) | Fluorinated polycarbonate diol, its preparation and method for preparing fluorinated polyurethane using the same | |
| JP5073218B2 (en) | Polycarbonate diol polymer having alicyclic skeleton and method for producing the same | |
| CN102093549A (en) | Catalyst for preparing polycarbonate polyol | |
| CN105694020B (en) | A kind of aliphatic polycarbonate diol and preparation method thereof | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| KR101307559B1 (en) | Synthesis of glycerol carbonate using high active catalysts | |
| CN101450317A (en) | Carbonic allyl ester preparation catalyst through catalyzing urea and 1,2-propylene glycol | |
| JP5509868B2 (en) | Polycarbonate diol and polycarbonate diol copolymer | |
| CN114479026A (en) | Preparation method of PBS (Poly Butylene succinate) without generation of by-product tetrahydrofuran | |
| CN101735434A (en) | Poly(alkene carbonate) diol-polybutylene succinate copolymer and preparation method thereof | |
| CN110256662B (en) | Preparation method of low-molecular-weight aliphatic polycarbonate polyol | |
| CN104861160A (en) | Method for preparing aliphatic polycarbonate through melt transesterification and polycondensation | |
| CN106317406B (en) | The method that the preparation of non-isocyanate method has benzene ring structure biodegradable thermoplastic polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100505 |