CN110092893A - A kind of room temperature liquid polyesters and preparation method thereof - Google Patents
A kind of room temperature liquid polyesters and preparation method thereof Download PDFInfo
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- CN110092893A CN110092893A CN201910428654.7A CN201910428654A CN110092893A CN 110092893 A CN110092893 A CN 110092893A CN 201910428654 A CN201910428654 A CN 201910428654A CN 110092893 A CN110092893 A CN 110092893A
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- Prior art keywords
- liquid polyesters
- acid
- room temperature
- temperature liquid
- preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
Abstract
The invention discloses a kind of room temperature liquid polyesters and preparation method thereof, related polyester is prepared by straight chain type monomer and containing side monomers by reaction, at room temperature in liquid, not only there is very excellent mobility, but also hydrolytic resistance is also extremely excellent.Polyurethane elastomer or the polyurethane plastics mechanical performance with higher that the indoor or outdoors as prepared by the liquid polyesters use are suitable for multiple technologies purposes, especially have good stability to hydrolysis resistance.
Description
Technical field
The present invention relates to polyester arts, and in particular in a kind of room temperature liquid polyesters and preparation method thereof.
Background technique
Polyester is based especially on the polyester of aliphatic diacid and aliphatic diol by large quantities applied to the manufacture of polyurethane
In.Polyester polyurethane plastics are a kind of materials that performance is very excellent.General preparation method is to add polyisocyanate in the polyester
Cyanate is reacted.And polyester is then by melt polycondensation or polyester by polyalcohol and polybasic carboxylic acid in metallic catalyst ester
Exchange.Although polyester polyurethane plastics have a wide range of applications in many fields.But pass through addition polyisocyanates
There is also some great difficult problems for polymerization technique into polyester.Wherein a maximum defect is in the technique, used
Aliphatic polyester is mostly crystallization or semi-crystalline polymer, is difficult to flow under room temperature, is difficult to process, and needs special heating
Equipment is melted polyester and need to be protected under atmosphere of inert gases to polyester, can just add isocyanates in this way and be gathered
Close reaction.It is complicated to eventually lead to polyester polyurethane plastic preparation process, the increase of cost.In order to solve this problem, at present
There are two the methods taken, first is that being the molecular weight for reducing polyester by the control extent of reaction, second is that passing through Molecular Design
The preferable polyester of mobility is prepared apart from both methods between increase polyester molecule.But the poly- ammonia as prepared by these polyester
The anti-hydrolytic performance of ester is excessively poor, it is difficult to meet the use demand under high wet heat condition.
Summary of the invention
To solve problems of the prior art, the present invention provides a kind of room temperature liquid polyesters and preparation method thereof.
Room temperature liquid polyesters of the invention are formed by linear monomers and containing side monomers；Wherein, the linear monomers packet
Straight chain diatomic acid and straight dihydric alcohol are included, it is described to include binary acid containing side group and diol containing side alkyl group containing side monomers.
It wherein, include-O-CH in the molecular structure of the liquid polyesters2-CH(CH3)-CH2-CH2-CH2-O-、-O-CH2-
CH(C2H5)-CH2-CH2-O-、-OC-CH(CH3)-CH2-CH2- CO- and-OC-CH (C2H5)-CH2At least one of-CO- knot
Structure.
In addition, the Straight chain diatomic acid is one or more of adipic acid, glutaric acid and succinic acid；
The straight dihydric alcohol is one or both of ethylene glycol and Isosorbide-5-Nitrae butanediol.
In addition, viscosity of the liquid polyesters at 25 DEG C is 800-20000mPas.
In addition, the binary acid containing side group be 2- methylglutaric acid, 2- ethylsuccinic acid, 2- methylglutaric acid dimethyl ester and
One or more of 2- ethylsuccinic acid dimethyl ester；The diol containing side alkyl group is 2- methyl-1,5- pentanediol, 2- ethyl-
One or more of 1,4-butanediol and triisopropanolamine；
In addition, the linear monomers and the mass ratio containing side monomers are 13: 77-77: 13.
The present invention also provides a kind of preparation method of room temperature liquid polyesters as described above, it is specific the preparation method is as follows:
All raw materials are uniformly mixed, are then heated to 180-220 DEG C under the atmosphere of nitrogen, carry out esterification or transesterification
Reaction, slips out by-product；After system acid value is lower than 20, at a temperature of 220-250 DEG C, slowly vacuumizing makes the reduction of system pressure
To 30Pa hereinafter, carrying out polycondensation reaction and slipping out extra alcohol, liquid polyesters are made.
Wherein, the average functionality of the liquid polyesters is 2-3, and hydroxyl value 25-400, acid value is less than 10.
In addition, the acid value of the liquid polyesters is 0.2-0.9.
The present invention is about room temperature liquid polyesters and preparation method thereof.Liquid polyesters of the invention have superior fluidity, by
The made polyurethane of the liquid polyesters possesses excellent lower temperature resistance and anti-hydrolytic performance.Especially by above-mentioned polyester polyol
Polyurethane elastomer or the polyurethane plastics mechanical performance with higher that prepared indoor or outdoors use are suitable for a variety of
Technological use especially has good stability to hydrolysis resistance.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail, the description of this part be only it is exemplary and explanatory, no
Reply protection scope of the present invention has any restriction effect.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1-9
Embodiment 1-9 and control group prepare raw material used in liquid polyesters and are listed in the table below in 1, by all raw material room temperature
Under be uniformly mixed, twice with air in reaction system with nitrogen, then increase system temperature to 220 DEG C, in nitrogen
It is esterified in atmosphere, slips out moisture, after system acid value is lower than 20, at a temperature of 220 DEG C, slowly vacuumized so that system pressure drops
To 30Pa hereinafter, carrying out polycondensation reaction and slipping out extra alcohol, liquid polyesters are made, and tested, as a result such as table 2.
1 embodiment 1-9 of table and control group prepare raw material used in liquid polyesters
The performance of liquid polyesters made from 2 embodiment 1-9 of table and control group
Embodiment 10-12
Raw material used in embodiment 10-12 preparation liquid polyesters is listed in Table 3 below, mixed by stirring under all raw material room temperature
It closes uniformly, twice with air in reaction system with nitrogen, then increases system temperature to 180 DEG C, under the atmosphere of normal pressure nitrogen
Ester exchange reaction is carried out, by-product carbinol is slipped out, after the quantity of methyl alcohol slipped out reaches theoretical value, at a temperature of 250 DEG C, is slowly taken out
Vacuum is down to 30Pa or less to system pressure and carries out polycondensation reaction, steams extra alcohol and liquid polyesters are made, and tested, tied
Fruit such as table 4.
3 embodiment 10-12 of table prepares raw material used in liquid polyesters
| Raw material (g) | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| 2- methylglutaric acid dimethyl ester | 26.41 | 29.04 | 18.47 |
| 2- ethylsuccinic acid dimethyl ester | 4.66 | 5.12 | 3.26 |
| Ethylene glycol | 12.12 | 14.83 | 8.49 |
| Triisopropanolamine | - | - | 9.22 |
The performance of liquid polyesters made from 4 embodiment 10-12 of table and control group
| Performance | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Hydroxyl value (mgKOH/g) | 62.8 | 122.4 | 302 |
| Acid value (mgKOH/g) | 0.4 | 0.1 | 0.8 |
| Viscosity (25 DEG C, m pas) | 7150 | 1102 | 2605 |
| Iodine color value | 3-4 | 3-4 | 3-4 |
Anti-hydrolytic performance test
Embodiment 1-12 and the made liquid polyesters of control group are mixed with the water of its quality 2%, are stored in 65 DEG C of condition
Under, the carboxyl value by measuring liquid polyesters characterizes its anti-hydrolytic performance such as table 5 with the variation of storage time.
Carboxyl end group value behind 100 days of each embodiment of table 5 and control group polyethylene glycol adipate
As data in the above table it is found that polyester prepared by the present invention is that liquid has good mobility at room temperature,
And possess excellent hydrolytic resistance.Therefore the polyurethane elastomer or poly- that the indoor or outdoors as prepared by the liquid polyesters use
Urethane plastics mechanical performance with higher is suitable for multiple technologies purposes, especially has good stability to hydrolysis resistance.It can be with
Solve the problem of current polyester polyurethane processing technology complexity and intolerant to hydrolysis.
The above is only the specific embodiment of the application, is made skilled artisans appreciate that or realizing this Shen
Please.Various modifications to these embodiments will be apparent to one skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the application.Therefore, the application
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of room temperature liquid polyesters, which is characterized in that the liquid polyesters are formed by linear monomers and containing side monomers；Its
In, the linear monomers include Straight chain diatomic acid and straight dihydric alcohol, and the side monomers that contain include binary acid containing side group and contain
Side group dihydric alcohol.
2. room temperature liquid polyesters according to claim 1, which is characterized in that wrapped in the molecular structure of the liquid polyesters
Containing-O-CH2-CH(CH3)-CH2-CH2-CH2-O-、-O-CH2-CH(C2H5)-CH2-CH2-O-、-OC-CH(CH3)-CH2-CH2-
CO- and-OC-CH (C2H5)-CH2At least one of-CO- structure.
3. room temperature liquid polyesters according to claim 1, which is characterized in that the Straight chain diatomic acid is adipic acid, penta 2
One or more of acid and succinic acid；
The straight dihydric alcohol is one or both of ethylene glycol and 1,4 butanediols.
4. according to claim 1 is room temperature liquid polyesters, which is characterized in that viscosity of the liquid polyesters at 25 DEG C
For 800-20000mPas.
5. room temperature liquid polyesters according to claim 1, which is characterized in that the binary acid containing side group is 2- methylpent two
One or more of acid, 2- ethylsuccinic acid, 2- methylglutaric acid dimethyl ester and 2- ethylsuccinic acid dimethyl ester；It is described to contain side
Base dihydric alcohol is 2- methyl-1, one or more of 5- pentanediol, 2- ethyl -1,4- butanediol and triisopropanolamine.
6. room temperature liquid polyesters according to claim 1, which is characterized in that the linear monomers and the matter containing side monomers
Amount is than being 13:77-77:13.
7. a kind of preparation method of such as room temperature liquid polyesters of any of claims 1-6, which is characterized in that the liquid
State polyester the preparation method is as follows:
All raw materials are uniformly mixed, are then heated to 180-220 DEG C under the atmosphere of nitrogen, esterification is carried out or transesterification is anti-
It answers, slips out by-product；After system acid value is lower than 20, at a temperature of 220-250 DEG C, slowly vacuumizing is reduced to system pressure
Liquid polyesters are made hereinafter, carry out polycondensation reaction and slip out extra alcohol in 30Pa.
8. the preparation method of room temperature liquid polyesters according to claim 7, which is characterized in that the liquid polyesters are averaged
Degree of functionality is 2-3, and hydroxyl value 25-400, acid value is less than 10.
9. the preparation method of room temperature liquid polyesters according to claim 8, which is characterized in that the acid value of the liquid polyesters
For 0.2-0.9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910428654.7A CN110092893A (en) | 2019-05-22 | 2019-05-22 | A kind of room temperature liquid polyesters and preparation method thereof |
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| US4778830A (en) * | 1986-12-13 | 1988-10-18 | Basf Aktiengesellschaft | Polyester polyols liquid at room temperature and their preparation and use in preparing plastics by polyisocyanate addition polymerization |
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| CN107868235A (en) * | 2017-10-30 | 2018-04-03 | 广州擎天材料科技有限公司 | A kind of powdery paints difunctional polyester resin and preparation method thereof |
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| CN109180915A (en) * | 2018-08-03 | 2019-01-11 | 山东诺威聚氨酯股份有限公司 | Polyurethane coating liquid polyesters polyalcohol and its preparation method and application |
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| US4778830A (en) * | 1986-12-13 | 1988-10-18 | Basf Aktiengesellschaft | Polyester polyols liquid at room temperature and their preparation and use in preparing plastics by polyisocyanate addition polymerization |
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