CN101029125A - Production of polyester polyhydric alcohol - Google Patents
Production of polyester polyhydric alcohol Download PDFInfo
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- CN101029125A CN101029125A CN 200710020310 CN200710020310A CN101029125A CN 101029125 A CN101029125 A CN 101029125A CN 200710020310 CN200710020310 CN 200710020310 CN 200710020310 A CN200710020310 A CN 200710020310A CN 101029125 A CN101029125 A CN 101029125A
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- mixture
- polyester polyol
- preparation
- epoxide
- solvent
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Abstract
Production of polyester polyol is carried out by putting catalyst, epoxide, initiating agent, cyclic acid anhydride and solvent into dried high-pressure reactor, agitating while raising temperature to 30-150degree for 0.5-50hrs, and separating out non-reacted epoxide and cyclic acid anhydride to obtain the final product. The structural formula is MMlaLbXc(H2O)dPeRf(I).
Description
Technical field
The present invention relates to a kind of preparation method of polyvalent alcohol, more specifically to a kind of preparation method of polyester polyol.
Background technology
Polyester polyol is a kind of good urethane starting material, with it is that the polyurethane material of feedstock production has higher intensity, good wear resistance, scratch resistance, oil-proofness etc., and it is widely used in the industry such as urethane foam, elastomerics, coating, tackiness agent, synthon, synthetic leather, water-proof grouting agent.At present, the synthetic of this polyvalent alcohol mainly is by the condensation reaction preparation of small molecules glycol with acid, the technology more complicated, and production cost is higher.
Retrieval is found, the Chinese patent application that application number is 89100701, the applying date is on February 2nd, 1989 discloses a kind of macromolecule loading DMC catalysts that is used for the copolymerization of carbonic acid gas epoxide, and points out that this catalyzer can be used for the copolymerization vibrin (CN1022039C) of catalysis epoxidation thing and cyclic acid anhydride.Yet, when this catalyzer is used for cyclic acid anhydride and epoxide copolymerization, have long inductive phase.
Application number is that the complex compound that US 4500704 discloses a kind of iron zinc cyanide and diglyme or ethylene glycol diethyl ether is a kind of catalyzer that is used for the epoxide homopolymerization in addition, people such as Wang Xinkui are used for such catalyzer the copolyreaction of cyclic acid anhydride and epoxide, obtain polyester polyol (CN1431240) near the alternating copolymerization product, need consume a large amount of more expensive diglyme or ethylene glycol diethyl ether during such Preparation of Catalyst, production cost is higher.
Summary of the invention
The objective of the invention is to solve above-mentioned the deficiencies in the prior art and problem, a kind of novel, reliable and practical synthesis method of polyester polyol is provided,, can be used in the polyester polyol of polyurethane industrial so that obtain high performancely with cheap cost.
The present invention is achieved by the following technical solutions:
The preparation method of polyester polyol of the present invention, comprise following steps: catalyzer, epoxide, initiator, cyclic acid anhydride and solvent are added through in the autoclave of thorough drying, under stirring state, be warming up to 30～150 ℃, reacted 0.5～50 hour, and isolated unreacted epoxide and cyclic acid anhydride then and can obtain polyester polyol;
Described catalyzer is a kind of bimetallic complex catalyst, and its structural formula is shown in (I):
MM
1 aL
bX
c(H
2O)
dP
eR
f (I)
(I) in the formula:
M is one or more the mixture in two valency metallic zinc, cadmium, cobalt, nickel, copper or the iron;
M
1It is one or more the mixture in 3 valencys or variable valency metal iron, cobalt, chromium, aluminium or the tin;
L is easy and metal M
1The mixture of one or more in part alkoxyl group, halogen, cyano group, thiocyanogen or the oxalate of formation complex anion;
X is one or more the mixture in halogen atom fluorine, chlorine, bromine, iodine or the astatine;
P is the organic sequestering agent (n 〉=2) that contains n ligand atomic oxygen, sulphur, nitrogen or phosphorus, or contains the oligopolymer or the polymkeric substance of ligand atom;
R is one or more a mixture of propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, cyclopentene oxide;
A, b, c, d, e, f are 1～10 numerical value.
Further, above-mentioned bimetallic complex catalyst, P described in its structural formula (I) are one or more the mixture in etherificate, hydroformylation or the esterified derivative of polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol, polythioether or these polymkeric substance; Or one or more the mixture in polynary ether, thioether, acetal, ketone, ester or the amine.
Among the preparation method of polyester polyol of the present invention, the consumption of its described bimetallic complex catalyst is 0.001～20% of an epoxide weight, preferred 0.1～10%; Described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene or the cyclopentene oxide; Described initiator is the material that contains 1～10 reactive hydrogen atom in the molecule, the polymkeric substance of preferably water, small molecule alcohol, phenols, thio-alcohol, carboxylic-acid, hydroxyl or oligopolymer, the polymkeric substance that contains thiol or oligopolymer or carboxylic polymkeric substance or oligopolymer, or the mixture of these materials, the add-on of initiator is 0.01～20% of an epoxide weight, preferred 1～5%; Described cyclic acid anhydride is Succinic anhydried, Pyroglutaric acid, MALEIC ANHYDRIDE, face phthalate anhydride or chloro faces one or more mixture in the phthalate anhydride, and its consumption is 0.5～80% of an epoxide weight, and preferred 30～60%; Its described reaction is that mass polymerization or adding solvent carry out polymerization, when adopting mass polymerization, does not add any solvent in the reaction process; When using solvent, this solvent be can the dissolved polyester polyvalent alcohol polarity or non-polar solvent, the preferred acetone of solvent, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1, the mixture of one or more in 1-trichloroethane, vinyl trichloride, toluene, benzene, the tetracol phenixin, the add-on of solvent is 0～200% of an epoxide weight, preferred 0～50%.
The preparation method of bimetallic complex catalyst of the present invention is as follows simultaneously:
Earlier in the halide solution that contains one or more two valencys metal M mixtures, add a kind of organic sequestering agent P or its aqueous solution, or the mixture of several organic sequestering agent P or its aqueous solution, wherein in the organic sequestering agent mol ratio of contained ligating atom and two valency metal M between 0.01～500, after fully stirring, progressively drip and contain a kind of variable valency metal M
1Or several variable valency metal M
1The L complex anion part aqueous solution of mixture, wherein variable valency metal M
1Or the mol ratio of its mixture and two valency metal M is between 0.01～50, adopts centrifugal or filter method is collected the throw out that above-mentioned reaction forms, after washing removes by product, and under 0～120 ℃, under vacuum or the non-vacuum condition, dry 0.1～100 hour; After treating above-mentioned product drying, the mixture that adds one or several epoxide, wherein the mol ratio of epoxide and metal M is between 0.001～10, under well-mixed condition, 0～120 ℃ of reaction 0.1～100h, under vacuum condition or directly oven dry, remove unreacted epoxide after, promptly obtain needed bimetallic catalyst.
The present invention has following beneficial effect:
The prices of raw and semifnished materials that adopt during Preparation of Catalyst of the present invention are lower, and Catalyst Production technology is simple, and the catalyzer cost is low, account for product cost 5% in.
The present invention is owing to adopted a kind of novel dual metal complex compound catalyst, and the catalytic efficiency height can shorten polymerization time significantly, generally in 180 minutes, can further contract to about 100 minutes after the optimization, thereby improve equipment efficiency of usage, reduce production costs.
Another one advantage of the present invention be product near alternating copolymerization, the mole fraction of ester units in resin is generally 45%～50%.
Embodiment
Embodiment 1
In 100 milliliter of 5% solder(ing)acid, it is the polyether glycol of 2000,2 functionality that agitation condition adds the 0.5g molecular weight down, and dropping 40ml concentration is 20% the potassium cobalticyanide aqueous solution under agitation condition, filter and collect the white precipitate that generates, after washing 5 times with water, be dried to constant weight and obtain the 6.1g white powder, in this white powder, add the 1g propylene oxide, under 20 ℃ of agitation conditions, reacted 10 hours, vacuum-drying can obtain bimetal complex catalyst to constant weight.
In the 5000ml of thorough drying autoclave, add the bimetal complex catalyst that 5g prepares according to the method described above, add the 1500ml propylene oxide, the 2000g MALEIC ANHYDRIDE, 2000ml toluene, 150g through thorough drying, molecular weight is 300, average functionality is 3 polyether glycol (moisture content 300ppm), under agitation condition, be warming up to 90 ℃, reacted 150 minutes, decompression removes unreacted monomer, obtain the 3210g product, number-average molecular weight is 6400, and resin lactone group content is at 97% polyester polyol.
Embodiment 2
In the 5000ml of thorough drying autoclave, add the bimetal complex catalyst of 5g according to the method preparation of embodiment 1, add the 1000ml propylene oxide, the 1200g Succinic anhydried, 2000ml toluene, 150g through thorough drying, molecular weight is 300, average functionality is 3 polyether glycol (moisture content 300ppm), under agitation condition, be warming up to 120 ℃, reacted 150 minutes, decompression removes unreacted monomer, obtain product 1750g, number-average molecular weight is 3580, and ester group content is at 96% polyester polyol in the resin.
Embodiment 3
In the 5000ml of thorough drying autoclave, add the bimetal complex catalyst of 5g according to the method preparation of embodiment 1, add the 1000ml propylene oxide, the 1200g Succinic anhydried, 2000ml toluene, 500g through thorough drying, molecular weight is 300, average functionality is 3 polyether glycol (moisture content 300ppm), is warming up to 140 ℃ under agitation condition, reacted 150 minutes, decompression removes unreacted monomer, obtains product 2500g, and number-average molecular weight is 1520 polyester polyol.
More than by specific embodiment technical solution of the present invention has been done to further specify, the example that provides only is an exemplary applications, can not be interpreted as limiting the scope of the invention.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the claim scope of the present invention.
Claims (10)
1, a kind of preparation method of polyester polyol, it is characterized in that comprising following steps: catalyzer, epoxide, initiator, cyclic acid anhydride and solvent are added through in the autoclave of thorough drying, under stirring state, be warming up to 30～150 ℃, reacted 0.5～50 hour, and isolated unreacted epoxide and cyclic acid anhydride then and can obtain polyester polyol;
Described catalyzer is a kind of bimetallic complex catalyst, and its structural formula is shown in (I):
MM
1 aL
bX
c(H
2O)
dP
eR
f (I)
(I) in the formula:
M is one or more the mixture in two valency metallic zinc, cadmium, cobalt, nickel, copper or the iron;
M
1It is one or more the mixture in 3 valencys or variable valency metal iron, cobalt, chromium, aluminium or the tin;
L is easy and metal M
1The mixture of one or more in part alkoxyl group, halogen, cyano group, thiocyanogen or the oxalate of formation complex anion;
X is one or more the mixture in halogen atom fluorine, chlorine, bromine, iodine or the astatine;
P is the organic sequestering agent (n 〉=2) that contains n ligand atomic oxygen, sulphur, nitrogen or phosphorus, or contains the oligopolymer or the polymkeric substance of ligand atom;
R is one or more a mixture of propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, cyclopentene oxide;
A, b, c, d, e, f are 1～10 numerical value.
2, the preparation method of polyester polyol according to claim 1 is characterized in that P described in the structural formula (I) is one or more the mixture in etherificate, hydroformylation or the esterified derivative of polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol, polythioether or these polymkeric substance; Or one or more the mixture in polynary ether, thioether, acetal, ketone, ester or the amine.
3, the preparation method of polyester polyol according to claim 1, the consumption that it is characterized in that described bimetallic complex catalyst is 0.1～10% of an epoxide weight.
4, the preparation method of polyester polyol according to claim 1 is characterized in that described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide.
5, the preparation method of polyester polyol according to claim 1, it is characterized in that described initiator is the polymkeric substance or the oligopolymer of water, small molecule alcohol, phenols, thio-alcohol, carboxylic-acid, hydroxyl, the polymkeric substance that contains thiol or oligopolymer or carboxylic polymkeric substance or oligopolymer, or the mixture of these materials; The add-on of initiator is 0.01～20% of an epoxide weight.
6, the preparation method of polyester polyol according to claim 5, the add-on that it is characterized in that described initiator is 1～5% of an epoxide weight.
7, the preparation method of polyester polyol according to claim 1, it is characterized in that described cyclic acid anhydride is Succinic anhydried, Pyroglutaric acid, MALEIC ANHYDRIDE, faces phthalate anhydride, chloro and face one or more mixture in the phthalate anhydride that its consumption is 0.5～80% of an epoxide weight.
8, the preparation method of polyester polyol according to claim 7, the consumption that it is characterized in that described cyclic acid anhydride is 30～60% of an epoxide weight.
9, the preparation method of polyester polyol according to claim 1 is characterized in that described reaction is that mass polymerization or adding solvent carry out polymerization, when adopting mass polymerization, does not add any solvent in the reaction process; When using solvent, this solvent be can the dissolved polyester polyvalent alcohol polarity or non-polar solvent, described solvent is acetone, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1,1-trichloroethane, 1,1, the mixture of one or more in 2-trichloroethane, toluene, benzene, the tetracol phenixin, the add-on of solvent is 0～200% of an epoxide weight.
10, the preparation method of polyester polyol according to claim 9, the add-on that it is characterized in that described solvent is 0～50% of an epoxide weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710020310XA CN100484983C (en) | 2007-02-12 | 2007-02-12 | Production method of polyester polyhydric alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710020310XA CN100484983C (en) | 2007-02-12 | 2007-02-12 | Production method of polyester polyhydric alcohol |
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| Publication Number | Publication Date |
|---|---|
| CN101029125A true CN101029125A (en) | 2007-09-05 |
| CN100484983C CN100484983C (en) | 2009-05-06 |
Family
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|---|---|---|---|
| CNB200710020310XA Active CN100484983C (en) | 2007-02-12 | 2007-02-12 | Production method of polyester polyhydric alcohol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072745A (en) * | 2014-07-04 | 2014-10-01 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol for aromatic coating |
| CN107686552A (en) * | 2013-05-17 | 2018-02-13 | 英佩雷尔创新有限公司 | For preparing the method and antigravity system of polymer and block copolymer |
| CN111944134A (en) * | 2020-08-24 | 2020-11-17 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN112210073A (en) * | 2020-10-26 | 2021-01-12 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
| CN117126365A (en) * | 2023-09-22 | 2023-11-28 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5714428A (en) * | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
-
2007
- 2007-02-12 CN CNB200710020310XA patent/CN100484983C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686552A (en) * | 2013-05-17 | 2018-02-13 | 英佩雷尔创新有限公司 | For preparing the method and antigravity system of polymer and block copolymer |
| CN104072745A (en) * | 2014-07-04 | 2014-10-01 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol for aromatic coating |
| CN111944134A (en) * | 2020-08-24 | 2020-11-17 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN111944134B (en) * | 2020-08-24 | 2021-08-03 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN112210073A (en) * | 2020-10-26 | 2021-01-12 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
| CN112210073B (en) * | 2020-10-26 | 2021-11-16 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
| CN117126365A (en) * | 2023-09-22 | 2023-11-28 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
| CN117126365B (en) * | 2023-09-22 | 2024-03-08 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
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|---|---|
| CN100484983C (en) | 2009-05-06 |
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