CN101029127A - Production of fatty oligo-ester carbonate polyhydric alcohol - Google Patents
Production of fatty oligo-ester carbonate polyhydric alcohol Download PDFInfo
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- CN101029127A CN101029127A CN 200710061701 CN200710061701A CN101029127A CN 101029127 A CN101029127 A CN 101029127A CN 200710061701 CN200710061701 CN 200710061701 CN 200710061701 A CN200710061701 A CN 200710061701A CN 101029127 A CN101029127 A CN 101029127A
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- polyhydric alcohol
- oligo
- carbonate
- ester carbonate
- reaction
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Abstract
Production of fatty oligo-ester carbonate polyol is carried out by putting fatty oligo-ester carbonate polyol 0.001-10wt% and catalyst into reactor, raising temperature to 80-200degree, and putting organic ester carbonate monomer in proportion of ester carbonate: fatty oligo-polyol=1:0.1-10 into reactor at 10Pa-105Pa and 100-200degree for 3-24hrs. It's simple, efficient and non-toxic.
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 the 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 add 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 ℃; 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, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether, Triethylene glycol; Branch saturated Fatty Alcohol(C12-C14 and C12-C18) is as 1,3 butylene glycol, 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 being removed by filter catalyzer promptly obtain polycarbonate diol, at room temperature is a kind of white solid product, and 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 a 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 one pentanediols 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 (16)
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 1: 0.1～10 to add in the reactors 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.
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.
8, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 7 is characterized in that described aryl carbonates is a diphenyl carbonate, and alkyl carbonate is methylcarbonate or diethyl carbonate, and carbonic acid alkylene ester is an ethylene carbonate.
9,, it is characterized in that described aliphatic polyol is straight chain or ramose, saturated or undersaturated C as each described a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol of claim 1-6
2～C
25Fatty Alcohol(C12-C14 and C12-C18) polyvalent alcohol or its mixture, OH functionality 〉=2 wherein.
10, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 9, it is characterized in that the saturated Fatty Alcohol(C12-C14 and C12-C18) of described straight chain is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether or Triethylene glycol.
11, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 10 is characterized in that the saturated Fatty Alcohol(C12-C14 and C12-C18) of described straight chain is 1,5-pentanediol or 1,6-hexylene glycol.
12, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 9 is characterized in that the saturated Fatty Alcohol(C12-C14 and C12-C18) of described branch is 1,3 butylene glycol, 2-ethyl-hexylene glycol or TriMethylolPropane(TMP); The undersaturated Fatty Alcohol(C12-C14 and C12-C18) of branch is a dihydroxyphenyl propane.
13, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 12 is characterized in that the saturated Fatty Alcohol(C12-C14 and C12-C18) of described branch is a TriMethylolPropane(TMP).
14,, it is characterized in that described catalyzer is a kind of KF heterogeneous catalyst that is supported on the carrier as each described a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol of claim 1-6.
15, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 14 is characterized in that described carrier is γ-Al
2O
3, SiO
2, ZnO, ZrO
2, Fe
2O
3, TiO
2Or NaX.
16, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 15 is characterized in that described carrier is γ-Al
2O
3, SiO
2Or ZrO
2
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| CN 200710061701 CN100500735C (en) | 2007-04-13 | 2007-04-13 | Production of fatty oligo-ester carbonate polyhydric alcohol |
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|---|---|---|---|
| CN 200710061701 CN100500735C (en) | 2007-04-13 | 2007-04-13 | Production of fatty oligo-ester carbonate polyhydric alcohol |
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| CN100500735C CN100500735C (en) | 2009-06-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576202A (en) * | 2009-07-10 | 2012-07-11 | 巴斯夫欧洲公司 | Toner resins for electronic copying 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 |
| CN107683300A (en) * | 2015-05-21 | 2018-02-09 | 巴斯夫公司 | The preparation of hyperbranched polycarbonates polyalcohol and its purposes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4137317A1 (en) * | 1991-11-13 | 1993-05-19 | Henkel Kgaa | ESTERS OF FATTY ACIDS WITH ETHOXYLATED POLYOLS |
| CN1176970C (en) * | 2001-11-19 | 2004-11-24 | 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 |
| CN100491440C (en) * | 2005-10-12 | 2009-05-27 | 中国科学院山西煤炭化学研究所 | Method for preparing polyols of acyclic oligo carbonic ester |
| CN100376616C (en) * | 2005-12-21 | 2008-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing polyester type polymer polyatomic alcohol |
-
2007
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576202A (en) * | 2009-07-10 | 2012-07-11 | 巴斯夫欧洲公司 | Toner resins for electronic copying purposes |
| US8865856B2 (en) | 2009-07-10 | 2014-10-21 | Basf Se | Toner resins for electronic copying purposes |
| 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 |
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| CN100500735C (en) | 2009-06-17 |
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