CN101302153A - Method for preparing carbonic ether polyatomic alcohol - Google Patents
Method for preparing carbonic ether polyatomic alcohol Download PDFInfo
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- CN101302153A CN101302153A CNA2008100553540A CN200810055354A CN101302153A CN 101302153 A CN101302153 A CN 101302153A CN A2008100553540 A CNA2008100553540 A CN A2008100553540A CN 200810055354 A CN200810055354 A CN 200810055354A CN 101302153 A CN101302153 A CN 101302153A
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Abstract
The invention discloses a method for preparing carbonate polyol. Under the condition of normal pressure, aliphatic polyol, polybasic carboxylic acid or cyclic carboxylic acid anhydride, organic carbonate and catalyst are evenly mixed, the amount of the catalyst is 50 to 10,000ppm of the mass of total raw materials, the ratio of the mole number of the aliphatic polyol to the total mole number of the polybasic carboxylic acid or the cyclic carboxylic acid anhydride and the organic carbonate is between 1 to 0.1 and 1, the mol ratio of the polybasic carboxylic acid or the cyclic carboxylic acid anhydride to the organic carbonate is between 1 to 0.01 and 100, the reaction temperature is increased to between 150 and 200 DEG C to react for 6 to 24h; the reaction pressure is reduced between 10<3> and 10<5>Pa, the reaction temperature is adjusted to be between 150 and 200 DEG C to continue reacting for 4 to 10h. The method has the advantages of no pollution, low cost, and simple process.
Description
Technical field
The present invention relates to the method that a kind of polycondensation by organic carbonate, organic cyclic carboxylic acids acid anhydride or di-carboxylic acid and aliphatic polyol prepares carbonate polyol.
Technical background
The polyurethane high molecule material is one of macromolecular material at present with fastest developing speed, because the application in producing and living of its good performance is very extensive.Polyurethane chain is made up of soft section and hard section, and is most important for the performance of polyurethane high molecule material as the molecular structure of the oligomer polyol of flexible polyurethane section.The pure and mild polycarbonate polyol of polyester polyols is in the oligomer polyol very important two kinds.Polyurethane material by polyester polyol preparation has advantages such as high-mechanical property, good thermomechanical property and high-wearing feature, and it shows relatively poor hydrolysis, anti-mould, anti-deflection and performance such as low temperature resistant again simultaneously.Polyurethane material by the polycarbonate diol preparation then has above two class advantages concurrently.But because latter's price comparison costliness, so its application is restricted.
At present, in order to obtain the oligomer polyol of high comprehensive performance, need again to reduce production costs simultaneously, a lot of research workers will study focus and turn to the synthetic of its multipolymer, the i.e. research of polyester-carbonate polyol.Study route is method and single stage method in two steps mainly.Two-step approach: at first, use the reaction of aliphatic polyol and polycarboxylic acid to generate the lower molecular weight polyester polyol; Then, this low-molecular-weight polyester polyvalent alcohol and cyclic carbonate or bischloroformate react synthesizing polyester-carbonate polyol.(US5527968; Macromol.Rapid Commun.21 (2000): 680; J.Polym.Sci.Part A Polym.Chem.39 (2001): 2508) single stage method: use aliphatic polyol, cyclic carbonate and lactone three copolyreaction preparation or aliphatic polyol, diphenyl carbonate and polybasic ester three to react generation polyester-carbonate polyol.(Prog.Polym.Sci.27 (2002): 87; Eur.Polym.J.41 (2005): 1478) prepare polyester-carbonate polyol and will cause very high production cost and cause environmental pollution, and the performance of resultant product is also not ideal enough by above two kinds of methods.
Summary of the invention
The method for preparing carbonate polyol that the purpose of this invention is to provide a kind of pollution-free, good product performance.
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: under condition of normal pressure that aliphatic polyol, polycarboxylic acid or cyclic carboxylic acids acid anhydride, organic carbonate and catalyst mix is even, rise to 150 ℃～200 ℃ of temperature of reaction, reaction 6h～24h; Amount in the quality catalyzer of total raw material is 50ppm～10000ppm, is preferably 100ppm～1000ppm; The mole number of aliphatic polyol is 1: 0.1～1 with the ratio of the total mole number of polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate, be preferably 1: 0.5～and 0.9; The mol ratio of polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate is 1: 0.01～100, be preferably 1: 0.2～and 1;
The decompression step of reaction: reaction pressure is 10
3Pa～10
5Pa; Temperature of reaction is 150～200 ℃, and the reaction times is 4h～10h.
Aforesaid organic carbonate is an alkyl carbonate, as: methylcarbonate, diethyl carbonate, dipropyl carbonate, Methyl ethyl carbonate etc.Be preferably methylcarbonate and diethyl carbonate.
Aforesaid di-carboxylic acid is hexanodioic acid, Succinic Acid or pentanedioic acid.The cyclic carboxylic acids acid anhydride is Succinic anhydried, divinyl acid anhydrides or Pyroglutaric acid etc.Be preferably hexanodioic acid or Succinic anhydried.
Aforesaid aliphatic polyol is the small molecules polyvalent alcohol, as 1, and 6-hexylene glycol, 1,5-pentanediol, 1,4-butyleneglycol, 1, ammediol, ethylene glycol etc.Be preferably 1, the 4-butyleneglycol.
The catalyzer that the present invention uses is as titanium compound, tin compound, alkali metal compound and zinc compounds etc., as positive butyl (tetra) titanate, dibutyl titanium oxide, dibutyl titanium chloride, tin chloride, di-n-butyltin dilaurate, sodium ethylate, zinc chloride.Be preferably positive butyl (tetra) titanate.
The present invention compared with prior art has the following advantages:
Employed method is the production route that a kind of cost is lower, technology is simple and easy to operate, and employed catalyzer is a catalyzer relatively more commonly used when preparing polyester polyol.Prepare polyester-carbonate polyol simple economy with this method, the products obtained therefrom performance is good.
Embodiment
Embodiment 1
With 1 of 54.07g (0.6mol), 1 of 4-butyleneglycol, 58.46g (0.4mol), the positive butyl (tetra) titanate catalyzer of the methylcarbonate of 6-hexanodioic acid, 13.51g (0.15mol) and 0.0063g (50ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 150 ℃, normal pressure is reaction 24h down.The methylcarbonate that distillates methyl alcohol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is risen to 180 ℃, pressure and reduce to 1.01 * 10
1Pa continues reaction 4h, to go out methyl alcohol, water and unreacted methylcarbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 177.05, and number-average molecular weight is 633.72.
Embodiment 2
With 1 of 54.07g (0.6mol), 1 of 4-butyleneglycol, 73.07g (0.5mol), the methylcarbonate of 6-hexanodioic acid, 13.51g (0.15mol) and 1.407g (10, di-n-butyltin dilaurate catalyzer 000ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 200 ℃, normal pressure is reaction 6h down.The methylcarbonate that distillates methyl alcohol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is reduced to 150 ℃, pressure and reduce to 1.01 * 10
3Pa continues reaction 10h, to go out methyl alcohol, water and unreacted methylcarbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 73.81, and number-average molecular weight is 1520.12.
Embodiment 3
With 1 of 62.49g (0.6mol), the sodium ethylate catalyzer of the methylcarbonate of the Succinic anhydried of 5-pentanediol, 30.02g (0.3mol), 36.01g (0.4mol) and 0.0257g (200ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 170 ℃, normal pressure is reaction 16h down.The methylcarbonate that distillates methyl alcohol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is risen to 190 ℃, pressure and reduce to 3 * 10
3Pa continues reaction 8h, to go out methyl alcohol, water and unreacted methylcarbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 84.39, and number-average molecular weight is 1329.54.
Embodiment 4
With 1 of 87.74g (0.6mol), the dibutyl titanic chloride catalyst of the diethyl carbonate of the maleic acid anhydride of 6-hexylene glycol, 19.61g (0.2mol), 47.25g (0.4mol) and 0.0124g (80ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 180 ℃, normal pressure is reaction 9h down.The diethyl carbonate that distillates ethanol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is risen to 190 ℃, pressure and reduce to 5 * 10
3Pa continues reaction 10h, to go out ethanol, water and unreacted diethyl carbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 95.23, and number-average molecular weight is 1178.20.
Embodiment 5
With 1 of 54.07g (0.6mol), 1 of 4-butyleneglycol, 52.80g (0.4mol), the di-n-butyltin dilaurate catalyzer of the methylcarbonate of 5-pentanedioic acid, 36.03g (0.4mol) and 0.0572g (400ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 170 ℃, normal pressure is reaction 13h down.The methylcarbonate that distillates methyl alcohol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is risen to 190 ℃, pressure and reduce to 1.01 * 10
3Pa continues reaction 7h, to go out methyl alcohol, water and unreacted methylcarbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 83.27, and number-average molecular weight is 1347.42.
Embodiment 6
With 1 of 54.07g (0.6mol), 1 of 4-butyleneglycol, 43.84g (0.3mol), the di-n-butyltin dilaurate catalyzer of the methylcarbonate of 6-hexanodioic acid, 13.51g (0.5mol) and 0.1407g (1000ppm) join be furnished with stirring system, in the reactor of thermometer and fractionating system, be heated to 130 ℃, normal pressure is reaction 16h down.The methylcarbonate that distillates methyl alcohol, water and carry secretly from the cat head of fractionating system then.At last, temperature of reaction system is risen to 200 ℃, pressure and reduce to 6 * 10
3Pa continues reaction 10h, to go out methyl alcohol, water and unreacted methylcarbonate.Be solid under the products therefrom room temperature, its hydroxyl value is 93.22, and number-average molecular weight is 1203.60.
Claims (14)
1, a kind of method for preparing carbonate polyol is characterized in that comprising the steps:
The synthesis under normal pressure stage: under condition of normal pressure that aliphatic polyol, polycarboxylic acid or cyclic carboxylic acids acid anhydride, organic carbonate and catalyst mix is even, rise to 150 ℃～200 ℃ of temperature of reaction, reaction 6h～24h; Amount in the quality catalyzer of total raw material is 50ppm～10000ppm, is preferably 100ppm～1000ppm; The mole number of aliphatic polyol is 1: 0.1～1 with the ratio of the total mole number of polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate, be preferably 1: 0.5～and 0.9; The mol ratio of polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate is 1: 0.01～100, be preferably 1: 0.2～and 1;
The decompression step of reaction: reaction pressure is 10
3Pa～10
5Pa; Temperature of reaction is 150～200 ℃, and the reaction times is 4h～10h.
2, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that the amount of described catalyzer is counted 100ppm～1000ppm with the quality of total raw material.
3, a kind of method for preparing carbonate polyol as claimed in claim 1, the mole number that it is characterized in that described aliphatic polyol is 1: 0.5～0.9 with the ratio of the total mole number of polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate.
4, a kind of method for preparing carbonate polyol as claimed in claim 1, the mol ratio that it is characterized in that described polycarboxylic acid or cyclic carboxylic acids acid anhydride and organic carbonate is 1: 0.2～1.
5, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that described organic carbonate is an alkyl carbonate.
6, a kind of method for preparing carbonate polyol as claimed in claim 5 is characterized in that described alkyl carbonate is methylcarbonate, diethyl carbonate, dipropyl carbonate or Methyl ethyl carbonate.
7, a kind of method for preparing carbonate polyol as claimed in claim 6 is characterized in that described alkyl carbonate is methylcarbonate and diethyl carbonate.
8, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that described di-carboxylic acid is hexanodioic acid, Succinic Acid or pentanedioic acid.
9, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that described cyclic carboxylic acids acid anhydride is Succinic anhydried, divinyl acid anhydrides or Pyroglutaric acid.
10, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that described aliphatic polyol is 1,6-hexylene glycol, 1,5-pentanediol, 1,4-butyleneglycol, 1, ammediol or ethylene glycol.
11, a kind of method for preparing carbonate polyol as claimed in claim 10 is characterized in that described aliphatic polyol is 1, the 4-butyleneglycol.
12, a kind of method for preparing carbonate polyol as claimed in claim 1 is characterized in that described catalyzer is titanium compound, tin compound, sodium ethylate or zinc chloride.
13, a kind of method for preparing carbonate polyol as claimed in claim 12 is characterized in that described titanium compound is positive butyl (tetra) titanate, dibutyl titanium oxide or dibutyl titanium chloride.
14, a kind of method for preparing carbonate polyol as claimed in claim 12 is characterized in that described tin compound is tin chloride or di-n-butyltin dilaurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100553540A CN101302153A (en) | 2008-07-04 | 2008-07-04 | Method for preparing carbonic ether polyatomic alcohol |
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|---|---|---|---|
| CNA2008100553540A CN101302153A (en) | 2008-07-04 | 2008-07-04 | Method for preparing carbonic ether polyatomic alcohol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518672A (en) * | 2016-10-11 | 2017-03-22 | 西南科技大学 | Method for synthesizing carboxylic methyl ether by reaction between acid anhydrides and dimethyl carbonate |
| CN115044029A (en) * | 2021-03-08 | 2022-09-13 | 旭化成株式会社 | Polyester polycarbonate polyols and synthetic leather |
-
2008
- 2008-07-04 CN CNA2008100553540A patent/CN101302153A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518672A (en) * | 2016-10-11 | 2017-03-22 | 西南科技大学 | Method for synthesizing carboxylic methyl ether by reaction between acid anhydrides and dimethyl carbonate |
| CN115044029A (en) * | 2021-03-08 | 2022-09-13 | 旭化成株式会社 | Polyester polycarbonate polyols and synthetic leather |
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Open date: 20081112 |