CN100500735C - A kind of method for preparing aliphatic oligocarbonate polyol - Google Patents
A kind of method for preparing aliphatic oligocarbonate polyol Download PDFInfo
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- CN100500735C CN100500735C CN 200710061701 CN200710061701A CN100500735C CN 100500735 C CN100500735 C CN 100500735C CN 200710061701 CN200710061701 CN 200710061701 CN 200710061701 A CN200710061701 A CN 200710061701A CN 100500735 C CN100500735 C CN 100500735C
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- polyhydric alcohol
- aliphatic polyol
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920005862 polyol Polymers 0.000 title claims abstract description 19
- 150000003077 polyols Chemical class 0.000 title abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- -1 aliphatic polyols Chemical class 0.000 claims abstract description 23
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 150000005677 organic carbonates Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 229940051250 hexylene glycol Drugs 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000005472 straight-chain saturated fatty acid group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种制备脂肪族低聚碳酸酯多元醇的方法是在常压条件下，按以脂肪族多元醇质量计催化剂的量为0.001%～10%，先将脂肪族多元醇和催化剂加入反应器中，升至反应温度80℃～200℃；将有机碳酸酯单体按有机碳酸酯单体与脂肪族多元醇的摩尔比为1∶0.1～10加入反应器中；反应时间为3h～24h；反应从常压减压至压力为10Pa～105Pa，反应温度为100℃～200℃；反应时间为2h～10h。本发明具有所使用的催化剂是一种高效、无毒、低用量，制备PCDL简单经济，所得的产品质量高的优点。A method for preparing aliphatic oligocarbonate polyols is to add the aliphatic polyols and the catalyst to the reactor at normal pressure, with the amount of the catalyst based on the mass of the aliphatic polyols being 0.001% to 10%. Rise to a reaction temperature of 80°C to 200°C; add the organic carbonate monomer to the reactor at a molar ratio of 1:0.1 to 10; the reaction time is 3h to 24h; the reaction starts from The normal pressure is reduced to a pressure of 10 Pa to 10 5 Pa, the reaction temperature is 100°C to 200°C, and the reaction time is 2h to 10h. The invention has the advantages that the catalyst used is high-efficiency, non-toxic and low in dosage, the preparation of PCDL is simple and economical, and the obtained product has the advantages of high quality.
Description
Technical field
The present invention relates to the method that a kind of transesterification by organic carbonate and aliphatic polyol prepares fatty oligo-ester carbonate polyhydric alcohol.
Background technology
Fatty oligo-ester carbonate polyhydric alcohol is prolonged well known as important intermediate product in producing plastics, lacquer and tackiness agent.They generally can be by the prepared in reaction of aliphatic polyol and phosgene (DE-A 1 595 446), two-chloro-formic ester (DE-A 857 948), diaryl carbonate (DE-A 1 915 908), cyclic carbonate (DE-A 2 523 352), ethylene carbonate or dialkyl carbonate (DE-A 2 555 805).
Make diaryl carbonate (as: diphenyl carbonate) and aliphatic polyol (as: 1, when 6-hexylene glycol) reacting, by the alkylol cpd (as: phenol) that in reaction process, removes by-product, can reach enough reaction conversion ratio (EP-A 0 533 275).But 13% the effective constituent of only having an appointment in the diphenyl carbonate is deposited in the product, and remaining is distilled out as phenol.If use dialkyl carbonate, then there is the effective constituent of higher proportion to be deposited in afterwards the product, but need to use transesterification catalyst usually, comprise basic metal or alkaline-earth metal and their oxide compound, alkoxide, carbonate, borate or organic acid salt, also have the organometallic compound (US-A 5 847 069) of III, IV, V family.
But known transesterification catalyst has some shortcomings.When using highly basic such as basic metal or alkaline-earth metal or its alkoxide, reaction must be gone catalyst neutralisation with other processing step after finishing.On the other hand, if use the Ti compound as catalyzer, then when storing products obtained therefrom undesirable discoloration (flavescence) may take place.Recently think that organo-tin compound is the potential carcinogen in the human body, and its catalytic activity not very high.(Chinese patent 02152740.7)
Summary of the invention
The purpose of this invention is to provide a kind of nontoxic, method that the transesterification of passing through organic carbonate and aliphatic polyol that catalytic activity is high prepares fatty oligo-ester carbonate polyhydric alcohol.
Method of the present invention is divided into two step of reaction: synthesis under normal pressure stage and decompression step of reaction.
The synthesis under normal pressure stage is under condition of normal pressure, is 0.001%～10% by the amount in aliphatic polyol quality catalyzer, be preferably 0.05%～5%, be preferably 0.01%～2% especially, earlier aliphatic polyol and catalyzer added in the reactor, rise to 80 ℃～200 ℃ of temperature of reaction; Is 1:0.1～10 with the organic carbonate monomer by the mol ratio of organic carbonate monomer and aliphatic polyol, is preferably 1:0.5～2 and adds in the reactors; Reaction times is 3h～24h, is preferably 6h～18h;
The decompression step of reaction, reaction is 10Pa～10 from atmospheric depressurized to pressure
5Pa is preferably 10
3Pa～10
5Pa, temperature of reaction is 100 ℃～200 ℃;-the reaction times is 2h～10h.
Aforesaid organic carbonate is aryl carbonates (a for example diphenyl carbonate), alkyl carbonate (for example methylcarbonate, diethyl carbonate), carbonic acid alkylene ester (for example ethylene carbonate).Be preferably diphenyl carbonate, methylcarbonate and diethyl carbonate.Most preferably be methylcarbonate and diethyl carbonate.
Aforesaid aliphatic polyol is straight chain or ramose, saturated or undersaturated C
2～C
25Fatty Alcohol(C12-C14 and C12-C18), its OH functionality 〉=2.Straight chain saturated Fatty Alcohol(C12-C14 and C12-C18) is as ethylene glycol, 1,3-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether, Triethylene glycol; The saturated Fatty Alcohol(C12-C14 and C12-C18) of branch as: 1,3---butyleneglycol, 2-ethyl-hexylene glycol, TriMethylolPropane(TMP) etc.; Branch undersaturated Fatty Alcohol(C12-C14 and C12-C18) is as dihydroxyphenyl propane.The mixture of various above-mentioned polyvalent alcohols also can be used as starting raw material.Be preferably 1,5-pentanediol, 1,6-hexylene glycol, TriMethylolPropane(TMP).
What the present invention used is a kind of KF heterogeneous catalyst that is supported on the carrier.Carrier is as γ-Al
2O
3, SiO
2, ZnO, ZrO
2, Fe
2O
3, TiO
2, NaX etc.Be preferably γ-Al
2O
3, SiO
2And ZrO
2
Aforesaid Preparation of catalysts method is as follows: the method by dipping is supported on KF on the carrier, uses Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.Concrete preparation method sees Journal ofMolecular Catalysis A:Chemical 255 (2006) 1-9.
The present invention compared with prior art has following advantage:
Employed is a kind of new catalyst of efficient, nontoxic, low consumption, can remove by simple filtration, and products obtained therefrom is had no adverse effect.Prepare the PCDL simple economy with this method, the quality product height of gained.
Embodiment
Embodiment 1
Method by dipping is immersed in 10g γ-Al with 4.8g KF
2O
3On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 59.63g (0.57mol), the catalyzer that has prepared of 5-pentanediol and 0.12g (0.20%), after temperature rises to 160 ℃, the methylcarbonate of 60.42g (0.67mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 14 hours down.At this moment the cat head from fractionating system distillates the methyl alcohol of by-product and the methylcarbonate of being taken out of by methanol azeotropic.Then the temperature of reaction system is risen to 180 ℃, pressure and reduce to 1.01 * 10
4Pa continues reaction 4 hours, with methyl alcohol and the unreacted methylcarbonate of removing by-product.Products obtained therefrom being removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature is a kind of white solid product, and its hydroxyl value is 109.74, and its number-average molecular weight is 1019.42.
Embodiment 2
Method by dipping is immersed in 10g SiO with 4.8g KF
2On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 63.61g (0.54mol), the catalyzer that has prepared of 6-hexylene glycol and 3.1805g (5%), after temperature rises to 100 ℃, the diethyl carbonate of 59.07g (0.5mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 24 hours down.At this moment distillate the ethanol of by-product from the cat head of fractionating system.Then the temperature of reaction system is risen to 120 ℃, pressure and reduce to 1.01 * 10
3Pa continues reaction 10 hours, with ethanol and the unreacted diethyl carbonate of removing by-product.Products obtained therefrom is removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature be-kind of white solid product, its hydroxyl value is 54.61, and its number-average molecular weight is 2050.57.
Embodiment 3
Method by dipping is immersed in 10g ZrO with 4.8g KF
2On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In-individual the reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 29.54g (0.25mol), 1 of 6-hexylene glycol, 29.79g (0.29mol), the catalyzer that 5-pentanediol and 5.34g (9%) have prepared, after temperature rises to 180 ℃, the methylcarbonate of 60.42g (0.67mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 3 hours down.At this moment the cat head from fractional column distillates the methyl alcohol of by-product and the methylcarbonate of being taken out of by methanol azeotropic.Then the temperature of reaction system is risen to 200 ℃, pressure and reduce to 5.07 * 10
4Pa continues reaction 3 hours, with methyl alcohol and the unreacted methylcarbonate of removing by-product.Products obtained therefrom being removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature is a kind of colourless transparent liquid, and its hydroxyl value is 55.42, and its number-average molecular weight is 2021.54.
Embodiment 4
Method by dipping is immersed in 10g γ-Al with 4.8g KF
2O
3On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 57.90g (0.49mol), the catalyzer that has prepared of the TriMethylolPropane(TMP) of 6-hexylene glycol, 6.70g (0.05mol) and 0.10g (0.15%), after temperature rises to 160 ℃, the methylcarbonate of 60.42g (0.67mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 10 hours down.At this moment the cat head from fractional column distillates the methyl alcohol of by-product and the methylcarbonate of being taken out of by methanol azeotropic.Then the temperature of reaction system is risen to 180 ℃, pressure and reduce to 1.01 * 10
4Pa continues reaction 4 hours, with methyl alcohol and the unreacted methylcarbonate of removing by-product.Products obtained therefrom being removed by filter catalyzer promptly obtain polycarbonate polyol, at room temperature is a kind of white solid product, and its hydroxyl value is 60.72, and its number-average molecular weight is 1940.13.
Embodiment 5
Method by dipping is immersed in 10g γ-Al with 4.8g KF
2O
3On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 59.63g (0.57mol), the catalyzer that has prepared of 5-pentanediol and 0.12g (0.20%), after temperature rises to 160 ℃, the methylcarbonate of 90.08g (1.00mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 14 hours down.At this moment the cat head from fractionating system distillates the methyl alcohol of by-product and the methylcarbonate of being taken out of by methanol azeotropic.Then the temperature of reaction system is risen to 180 ℃, pressure and reduce to 1.01 * 10
4Pa continues reaction 4 hours, with methyl alcohol and the unreacted methylcarbonate of removing by-product.Products obtained therefrom being removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature is a kind of white solid product, and its hydroxyl value is 36.71, and its number-average molecular weight is 3056.42.
Embodiment 6
Method by dipping is immersed in 10g γ-Al with 4.8g KF
2O
3On, under 353K, use Rotary Evaporators to be dried then, and under 393K dry 12h, last under 773K roasting 3h promptly get required catalyzer.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1 of 63.61g (0.54mol), the catalyzer that has prepared of 6-hexylene glycol and 0.12g (0.20%), after temperature rises to 160 ℃, the methylcarbonate of 33.33g (0.37mol) was added continuously in the reactor by constant rate in the reaction times, and normal pressure reacted 14 hours down.At this moment the cat head from fractionating system distillates the methyl alcohol of by-product and the methylcarbonate of being taken out of by methanol azeotropic.Then the temperature of reaction system is risen to 180 ℃, pressure and reduce to 1.01 * 10
4Pa continues reaction 4 hours, with methyl alcohol and the unreacted methylcarbonate of removing by-product.Products obtained therefrom being removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature is a kind of white solid product, and its hydroxyl value is 181.14, and its number-average molecular weight is 619.42.
Claims (7)
1, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol is characterized in that comprising the steps:
(1) the synthesis under normal pressure stage under condition of normal pressure, is 0.001%～10% by the amount in aliphatic polyol quality catalyzer, earlier aliphatic polyol and catalyzer is added in the reactor, rises to 80 ℃～200 ℃ of temperature of reaction; Is that 1:0.1～10 add in the reactors with the organic carbonate monomer by the mol ratio of organic carbonate monomer and aliphatic polyol; Reaction times is 3h～24h;
(2) decompression step of reaction, reaction is 10Pa～10 from atmospheric depressurized to pressure
5Pa, temperature of reaction is 100 ℃～200 ℃; Reaction times is 2h～10h;
Described catalyzer is a kind of KF heterogeneous catalyst that is supported on the carrier.
2, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1, the amount that it is characterized in that described catalyzer is by counting 0.05%～5% with the aliphatic polyol quality.
3, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 2, the amount that it is characterized in that described catalyzer is by counting 0.01%～2% with the aliphatic polyol quality.
4, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1, the mol ratio that it is characterized in that described organic carbonate monomer and aliphatic polyol is 1:0.5～2.
5, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1, the reaction times that it is characterized in that the described synthesis under normal pressure stage is 6h～18h.
6, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described decompression step of reaction, and reaction is 10 from atmospheric depressurized to pressure
3Pa～10
5Pa.
7,, it is characterized in that described organic carbonate is aryl carbonates, alkyl carbonate or carbonic acid alkylene ester as each described a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol of claim 1-6.
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| CN102576202B (en) * | 2009-07-10 | 2015-08-19 | 巴斯夫欧洲公司 | Toner resins for electronic copying purposes |
| CN107683300A (en) * | 2015-05-21 | 2018-02-09 | 巴斯夫公司 | The preparation of hyperbranched polycarbonates polyalcohol and its purposes |
| CN106800646A (en) * | 2017-01-16 | 2017-06-06 | 美瑞新材料股份有限公司 | A kind of process for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
| CN1431240A (en) * | 2001-11-19 | 2003-07-23 | 中国科学院山西煤炭化学研究所 | Method for preparing polyether ester polyalcohol |
| CN1451676A (en) * | 2003-04-30 | 2003-10-29 | 中国科学院山西煤炭化学研究所 | Process for preparing ionized polyester polyol |
| CN1760169A (en) * | 2005-10-12 | 2006-04-19 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol |
| CN1807487A (en) * | 2005-12-21 | 2006-07-26 | 中国科学院山西煤炭化学研究所 | Method for preparing polyester type polymer polyatomic alcohol |
-
2007
- 2007-04-13 CN CN 200710061701 patent/CN100500735C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
| CN1431240A (en) * | 2001-11-19 | 2003-07-23 | 中国科学院山西煤炭化学研究所 | Method for preparing polyether ester polyalcohol |
| CN1451676A (en) * | 2003-04-30 | 2003-10-29 | 中国科学院山西煤炭化学研究所 | Process for preparing ionized polyester polyol |
| CN1760169A (en) * | 2005-10-12 | 2006-04-19 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol |
| CN1807487A (en) * | 2005-12-21 | 2006-07-26 | 中国科学院山西煤炭化学研究所 | Method for preparing polyester type polymer polyatomic alcohol |
Non-Patent Citations (2)
| Title |
|---|
| Alumina-supported potassium iodide as a heterogeneouscatalyst for biodiesel production from soybean oil. Wenlei Xie.Journal of Molecular Catalysis A:Chemical,No.255. 2006 * |
| 国内外碳酸二甲酯酯交换反应催化剂研究进展. 钱锦华.分子催化，第19卷第4期. 2005 * |
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| CN101029127A (en) | 2007-09-05 |
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