CN100491440C - Method for preparing polyols of acyclic oligo carbonic ester - Google Patents
Method for preparing polyols of acyclic oligo carbonic ester Download PDFInfo
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- CN100491440C CN100491440C CNB2005100129047A CN200510012904A CN100491440C CN 100491440 C CN100491440 C CN 100491440C CN B2005100129047 A CNB2005100129047 A CN B2005100129047A CN 200510012904 A CN200510012904 A CN 200510012904A CN 100491440 C CN100491440 C CN 100491440C
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- carbonate
- polyhydric alcohol
- ester
- oligo
- preparing fatty
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
A process for preparing the aliphatic oligocarbonate polyol includes such steps as proportionally adding aliphatic polyol and catalyst to reactor, heating to 80-200 deg.C, proportionally and continuously adding organic carbonate while reacting for 3-24 hr, vacuumizing, and reacting at 100-200 deg.C for 2-10 hr.
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-A1595446), two-chloro-formic ester (DE-A 857 948), diaryl carbonate (DE-A 1 915908), 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 have only about 13% diphenyl carbonate to be deposited in the product, remaining is distilled out as phenol.If use dialkyl carbonate, then there is the dialkyl carbonate 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, in case oligomerization takes place, its product must neutralize with other processing step.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 use bimetallic cyanide complex catalyst, prepare the method for fatty oligo-ester carbonate polyhydric alcohol by the transesterification of organic carbonate and aliphatic polyol.
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, be under condition of normal pressure, by the amount in aliphatic polyol quality catalyzer is 0.01ppm～10,000ppm, be preferably 0.1ppm～5000ppm, be preferably 1ppm～1000ppm 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 reactor continuously by the constant flow in the reaction times, the reaction times is 3h～24h, is preferably 6h～18h;
The decompression step of 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, alkyl ester or alkylene ester etc., as: diphenyl carbonate, methylcarbonate, diethyl carbonate, ethylene carbonate etc.Be preferably diphenyl carbonate, methylcarbonate and diethyl carbonate.Most preferably be methylcarbonate and diethyl carbonate.Aforesaid aliphatic polyol is straight chain, ring-type, ramose, unbranched, saturated or undersaturated C
2～C
25Fatty Alcohol(C12-C14 and C12-C18), its OH functionality 〉=2 one kind or its mixture.As: ethylene glycol, 1,3-propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2-ethyl-hexylene glycol, dihydroxyphenyl propane, TriMethylolPropane(TMP) etc.The mixture of various above-mentioned polyvalent alcohols also can be used as starting raw material.Be preferably 1,5-pentanediol or 1,6-hexylene glycol and TriMethylolPropane(TMP).
The bimetallic cyanide complex catalyst that the present invention uses is designated as dmc catalyst as the catalyzer that CN 1233529A provides.Be the class effective catalyst that is used for the olefin oxide ring-opening polymerization (, it has been successfully used to the suitability for industrialized production of high molecular low-unsaturated polyether polyatomic alcohol.Through our research, this catalyzer of surprised discovery to organic carbonate particularly the transesterification of dialkyl carbonate and aliphatic polyol good catalytic activity is also arranged, can be used for preparing fatty oligo-ester carbonate polyhydric alcohol, and product can xanthochromia.Other transesterification catalyst is relatively more cheap relatively for this catalyzer in addition, and amount ratio is less.
The general formula of dmc catalyst be Ma[M ' (CN)
6] bxMXcyH
2OzL, wherein, M, M ' they are metal ion, and MXc is water miscible metal-salt, and L is an organic ligand, and a, b, c are positive integer, x, y, z are scale-up factor.
Aforesaid Preparation of catalysts method is as follows:
Cyano complex salt brine solution and the organism of the MXc aqueous solution, M ', under stirring fast, be added in the reactor simultaneously and mix, precipitation separation after for some time, after the mixture washing of precipitation with organism and water, drying promptly gets dmc catalyst.Detailed preparation method sees CN1233529A
The bimetallic cyanide complex that can be used in the preparation bimetallic cyanide complex catalyst is mainly Zn
3[Co (CN)
6]
2And Zn
3[Fe (CN)
6]
2, be preferably Zn
3[Co (CN)
6]
2This class catalyzer is represented as:
Zn
3[Co(CN)
6]
2·x?ZnCl
2·y?H
2O·zL
Wherein x, y, z are scale-up factor, and L is an organic ligand.
Catalyzer used in the present invention can use with solid form or liquid form (as: being dissolved in the starting raw material).The present invention can use the mixture of dmc catalyst and other one or more transesterification catalysts.
The present invention compared with prior art has following advantage:
Employed is a kind of efficient, low consumption and without the new catalyst of aftertreatment, and prepares the PCDL simple economy, the quality product height of gained with this method.
Embodiment
Embodiment 1
The 8g Cobalt Potassium Cyanide is dissolved in the 140ml deionized water, makes 0.17mol/l hexacyanocobaltate acid potassium solution; The 25g zinc chloride is dissolved in the 40ml deionized water, makes the 4.59mol/l liquor zinci chloridi, simultaneously the 100ml trimethyl carbinol, hexacyanocobaltate acid potassium solution, liquor zinci chloridi are added to stir in the reactor to generate and precipitate, separate; Isolated throw out is isolated throw out with the mixture pulping and washing of the 180ml trimethyl carbinol and 20ml water; And then with 180ml trimethyl carbinol pulping and washing throw out, isolated throw out is under 60 ℃ of temperature, and vacuum-drying obtains catalyzer Zn to weight
3[Co (CN)
6]
20.08ZnCl
21.0H
2O2.5L (L is the trimethyl carbinol)
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1, the 5-pentanediol of 59.63g (0.57mol) and the Zn that has prepared of 0.0078g (131ppm)
3[Co (CN)
6]
20.08ZnCl
21.0H
2O2.5L (L is the trimethyl carbinol) catalyzer after temperature rises to 160 ℃, is added continuously to the methylcarbonate of 60.42g (0.67mol) in the reactor by constant rate in the reaction times, normal pressure reaction 10 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.In temperature is that 180 ℃, pressure are 1.01 * 10
4Pa reacted 4 hours down, 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
The 8g Cobalt Potassium Cyanide is dissolved in the 140ml deionized water, makes 0.17mol/l hexacyanocobaltate acid potassium solution; The 25g zinc chloride is dissolved in the 40ml deionized water, makes the 4.59mol/l liquor zinci chloridi, simultaneously 100ml tertiary amyl alcohol, hexacyanocobaltate acid potassium solution, liquor zinci chloridi are added to stir in the reactor to generate and precipitate, separate; Isolated throw out is isolated throw out with the mixture pulping and washing of 180ml tertiary amyl alcohol and 20ml water; And then with 180ml tertiary amyl alcohol pulping and washing throw out, isolated throw out is under 60 ℃ of temperature, and vacuum-drying obtains catalyzer Zn to weight
3[Co (CN)
6]
20.09ZnCl
21.0H
2O2.7L (L is a tertiary amyl alcohol)
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1, the 6-hexylene glycol of 63.61g (0.54mol) and the Zn that has prepared of 0.0078g (123ppm)
3[Co (CN)
6]
20.09ZnCl
21.0H
2O2.7L (L is a tertiary amyl alcohol) catalyzer after temperature rises to 160 ℃, is added continuously to the diethyl carbonate of 59.07g (0.5mol) in the reactor by constant rate in the reaction times, normal pressure reaction 14 hours down.At this moment distillate the ethanol of by-product from the cat head of fractionating system.In temperature is that 180 ℃, pressure are 1.01 * 10
4Pa reacted 4.5 hours down, 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
The 8g Cobalt Potassium Cyanide is dissolved in the 140ml deionized water, makes 0.17mol/l hexacyanocobaltate acid potassium solution; The 25g zinc chloride is dissolved in the 40ml deionized water, makes the 4.59mol/l liquor zinci chloridi, simultaneously 100ml diethylene glycol diethyl ether, hexacyanocobaltate acid potassium solution, liquor zinci chloridi are added to stir in the reactor to generate and precipitate, separate; Isolated throw out is isolated throw out with the mixture pulping and washing of 180ml diethylene glycol diethyl ether and 20ml water; And then with 180ml diethylene glycol diethyl ether pulping and washing throw out, isolated throw out is under 60 ℃ of temperature, and vacuum-drying obtains catalyzer Zn to weight
3[Co (CN)
6]
20.08ZnCl
21.0H
2O1.5L (L is a diethylene glycol diethyl ether)
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add 1, the 6-hexylene glycol of 63.61g (0.54mol) and the Zn that has prepared of 0.0078g (123ppm)
3[Co (CN)
6]
20.08ZnCl
21.0H
2O1.5L (L is a diethylene glycol diethyl ether) catalyzer after temperature rises to 160 ℃, is added continuously to the methylcarbonate of 60.42g (0.67mol) in the reactor by constant rate in the reaction times, normal pressure reaction 10 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.In temperature is that 180 ℃, pressure are 1.01 * 10
4Pa reacted 4 hours down, 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 57.43, and its number-average molecular weight is 1951.68.
Embodiment 4
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add the prepared Zn of 1,5-pentanediol of 1,6-hexylene glycol, 29.79g (0.29mol) of 29.54g (0.25mol) and 0.0078g (131ppm) embodiment 3
3[Co (CN)
6]
20.08ZnCl
21.0H
2O1.5L (L is a diethylene glycol diethyl ether) catalyzer after temperature rises to 160 ℃, is added continuously to the methylcarbonate of 60.42g (0.67mol) in the reactor by constant rate in the reaction times, normal pressure reaction 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.In temperature is that 180 ℃, pressure are 1.01 * 10
4Pa reacted 4 hours down, 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 5
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and fractionating system, add the prepared Zn of embodiment 3 of the TriMethylolPropane(TMP) of 1,6-hexylene glycol, 38.86g (0.29mol) of 29.54g (0.25mol) and 0.0078g (114ppm)
3[Co (CN)
6]
20.08ZnCl
21.0H
2O1.5L (L is a diethylene glycol diethyl ether) catalyzer after temperature rises to 160 ℃, is added continuously to the methylcarbonate of 60.42g (0.67mol) in the reactor by constant rate in the reaction times, normal pressure reaction 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.In temperature is that 180 ℃, pressure are 1.01 * 10
4Pa reacted 4 hours down, 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 70.11, and its number-average molecular weight is 2030.30.
Claims (12)
1, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol is characterized in that comprising the steps:
Under condition of normal pressure, be 0.01ppm～10 by amount in aliphatic polyol quality catalyzer, 000ppm adds aliphatic polyol and catalyzer in the reactor earlier, rises 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; Add reactor continuously by the constant flow in the reaction times, the reaction times is 3h～24h;
From atmospheric depressurized to pressure is 10Pa～10
5Pa, temperature of reaction is 100 ℃～200 ℃; Reaction times is 2h～10h;
Described organic carbonate is aryl carbonates, alkyl carbonate or carbonic acid alkylene ester;
Described catalyzer is one of following catalyzer, Zn
3[Co (CN)
6]
20.08 ZnCl
21.0H
2O2.5L, L are the trimethyl carbinol; Zn
3[Co (CN)
6]
20.09 ZnCl
21.0H
2O2.7L, L are tertiary amyl alcohol; Zn
3[Co (CN)
6]
20.08 ZnCl
21.0H
2O1.5L, L are diethylene glycol diethyl ether.
2, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that the add-on of described catalyzer is counted 0.1ppm～5000ppm with the aliphatic polyol quality.
3, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 2, it is 1ppm～1000ppm that the add-on that it is characterized in that described catalyzer is counted 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 is characterized in that described is 6h～18h in the following reaction times of condition of normal pressure.
6, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described is 10 from atmospheric depressurized to pressure
3Pa～10
5Pa.
7, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described aryl carbonates is a diphenyl carbonate; Alkyl carbonate is methylcarbonate or diethyl carbonate; Carbonic acid alkylene ester is an ethylene carbonate.
8, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described organic carbonate is diphenyl carbonate, methylcarbonate or diethyl carbonate.
9, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described organic carbonate is methylcarbonate or diethyl carbonate.
10, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 1 is characterized in that described aliphatic polyol is straight chain, ring-type, ramose, unbranched, saturated or undersaturated C
2～C
25Fatty Alcohol(C12-C14 and C12-C18), a kind of or its mixture in its OH functionality 〉=2.
11, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 10 is characterized in that described C
2～C
25, its OH functionality 〉=2 Fatty Alcohol(C12-C14 and C12-C18) be a kind of or its mixture in ethylene glycol, 1,3-propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2-ethyl-hexylene glycol, the TriMethylolPropane(TMP).
12, a kind of method for preparing fatty oligo-ester carbonate polyhydric alcohol as claimed in claim 10 is characterized in that described C
2～C
25, its OH functionality 〉=2 Fatty Alcohol(C12-C14 and C12-C18) be 1,5-pentanediol or 1,6-hexylene glycol and TriMethylolPropane(TMP).
Priority Applications (1)
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|---|---|---|---|
| CNB2005100129047A CN100491440C (en) | 2005-10-12 | 2005-10-12 | Method for preparing polyols of acyclic oligo carbonic ester |
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|---|---|---|---|
| CNB2005100129047A CN100491440C (en) | 2005-10-12 | 2005-10-12 | Method for preparing polyols of acyclic oligo carbonic ester |
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| CN100491440C true CN100491440C (en) | 2009-05-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100491441C (en) * | 2006-11-10 | 2009-05-27 | 中国科学院山西煤炭化学研究所 | Method for preparing aliphatic oligo carbonate polyol |
| CN101024685B (en) * | 2007-02-12 | 2010-06-30 | 江苏中科金龙化工股份有限公司 | Method for preparing fatty group polycarbonate polylol |
| CN100500735C (en) * | 2007-04-13 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Production of fatty oligo-ester carbonate polyhydric alcohol |
| EP3298065A4 (en) * | 2015-05-21 | 2019-02-27 | Basf Se | Preparation of hyperbranched polycarbonate polyols and their use |
| US9493608B1 (en) | 2015-12-21 | 2016-11-15 | Covestro Llc | DMC catalyzed alkoxylation of esters |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233529A (en) * | 1998-04-29 | 1999-11-03 | 中国科学院山西煤炭化学研究所 | Double metal cyanide catalyst and its prepn. method |
| CN1420134A (en) * | 2001-11-20 | 2003-05-28 | 拜尔公司 | Use of catalyst for preparing polylol aliphatic oligocarbonate |
| JP2003183376A (en) * | 2001-12-13 | 2003-07-03 | Ube Ind Ltd | Liquid copolycarbonatediol and thermoplastic polyurethane obtained by using the same |
| CN1430637A (en) * | 2000-05-24 | 2003-07-16 | 旭化成株式会社 | Polycarbonate diol having high proportion of primary terminal OH |
| CN1616396A (en) * | 2003-09-19 | 2005-05-18 | 拜尔材料科学股份公司 | Method for producing aliphatic oligocarbonate polyols |
-
2005
- 2005-10-12 CN CNB2005100129047A patent/CN100491440C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233529A (en) * | 1998-04-29 | 1999-11-03 | 中国科学院山西煤炭化学研究所 | Double metal cyanide catalyst and its prepn. method |
| CN1430637A (en) * | 2000-05-24 | 2003-07-16 | 旭化成株式会社 | Polycarbonate diol having high proportion of primary terminal OH |
| CN1420134A (en) * | 2001-11-20 | 2003-05-28 | 拜尔公司 | Use of catalyst for preparing polylol aliphatic oligocarbonate |
| JP2003183376A (en) * | 2001-12-13 | 2003-07-03 | Ube Ind Ltd | Liquid copolycarbonatediol and thermoplastic polyurethane obtained by using the same |
| CN1616396A (en) * | 2003-09-19 | 2005-05-18 | 拜尔材料科学股份公司 | Method for producing aliphatic oligocarbonate polyols |
Non-Patent Citations (1)
| Title |
|---|
| 双金属氰化络合物（DMC）催化剂的合成及应用研究. 王文浩等人.化学推进剂与高分子材料，第2卷第5期. 2004 * |
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