CN112679694A - Preparation method of high-performance polyurethane elastomer - Google Patents
Preparation method of high-performance polyurethane elastomer Download PDFInfo
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- CN112679694A CN112679694A CN202011581813.6A CN202011581813A CN112679694A CN 112679694 A CN112679694 A CN 112679694A CN 202011581813 A CN202011581813 A CN 202011581813A CN 112679694 A CN112679694 A CN 112679694A
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- polyurethane elastomer
- diisocyanate
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Abstract
The invention belongs to the technical field of polyurethane application, and particularly relates to a preparation method of a high-performance polyurethane elastomer, which comprises the following steps: (1) mixing polyol and isocyanate to prepare hydroxyl-terminated modified polyol; (2) the prepolymer with NCO content of 3.0-6.0% is prepared by mixing and reacting modified polyol and isocyanate; (3) and fully mixing the prepolymer component and the chain extender component, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the high-performance polyurethane elastomer. The invention adopts different isocyanate modified polyols, has the advantages of large isocyanate hard segment aggregation density, targeted control reaction and regular chain segment, can obviously improve the physical and mechanical properties of polyurethane, further improves the product forming process by adopting low-polymer amine or alcohol curing agents, and has excellent high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of polyurethane application, and particularly relates to a preparation method of a high-performance polyurethane elastomer.
Background
The polyurethane elastomer is a high molecular material containing a large amount of urethane groups on the main chain, and is a block copolymer with hard blocks and soft blocks which are alternately reacted by isocyanate and polyol (polyether and polyester). Generally, the soft segment is composed of a polyol, and the soft segment composed of a polyol has various conformations at normal temperature, and is called a soft segment. The rigid chain segment with aromatic group, carbamido group and urethane group is obtained by reacting micromolecule chain extender (cross linker) such as dihydric alcohol, diamine and the like with diisocyanate. The conformation of the rigid segment is not easily changed, and is called a hard segment.
The polyurethane has the characteristics of good mechanical property, high elasticity and large elongation at break, and has excellent wear resistance, chemical resistance, tearing resistance and good shock absorption performance. Due to the chemical structural characteristics of polyurethane, the polyurethane has poor heat resistance, is easy to soften and decompose under high temperature, has rapidly reduced mechanical property, generally has a long-term use temperature not exceeding 80 ℃ and a short-term use temperature not exceeding 120 ℃, and greatly limits the application range of the polyurethane.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the high-performance polyurethane elastomer overcomes the defects of the prior art, improves the prior polyurethane elastomer, and is excellent in mechanical property, high in tear strength and high in mechanical property retention rate under a high-temperature condition.
The preparation method of the polyurethane polishing gasket layer comprises the following steps:
(1) dehydrating the polyol until the water content is less than or equal to 0.03 percent, mixing the dehydrated polyol with diisocyanate, and reacting at 70-85 ℃ to obtain hydroxyl-terminated modified polyol;
(2) mixing and reacting modified polyol and diisocyanate to prepare a prepolymer with NCO content of 3.0-6.0%;
(3) and fully mixing the prepolymer component and the chain extender component, pouring the mixture into a mold, and opening the mold and vulcanizing to obtain the high-performance polyurethane elastomer.
Wherein:
the mass ratio of the polyol to the diisocyanate in the step (1) is 70-90: 10-20 parts of; the mass of the modified polyol and the diisocyanate in the step (2) is 70-90: 10-25.
The polyol in the step (1) is one or more of polyester polyols with the functionality of 2 and the number average molecular weight of 500-2000.
The diisocyanate is one or more of 2, 4-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, a mixture of 50% of 2, 4' -diphenylmethane diisocyanate and 50% of 4,4 '-diphenylmethane diisocyanate, liquefied MDI, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate.
The chain extender in the step (3) is one or more than one of 4-chloro-3, 5-diaminobenzoic acid isobutyl ester, 3' -dichloro-4, 4' -diaminodiphenylmethane, 4' -methylene-bis (3-chloro-2, 6-diethylaniline), 1, 4-butanediol, hydroquinone dihydroxyethyl ether or 1, 3-propanediol-bis (4-aminobenzoic acid) ester.
In the step (3), the mass ratio of the prepolymer to the chain extender is 100: 12-15.
The hardness of the high-performance polyurethane elastomer prepared in the step (3) is 40-55D.
Compared with the prior art, the invention has the following beneficial effects:
1. the isocyanate modified polyol is used in the synthesis of the prepolymer, and the prepolymer is prepared after the modified polyol and the isocyanate are mixed and reacted, so that the method has the advantages of target control reaction, high isocyanate hard segment aggregation density and regular chain segment, and can obviously improve the physical and mechanical properties of polyurethane.
2. The prepolymer synthesized by the method has the characteristics that the proportion of hard segments is larger than that of the hard segments of the prepolymers with the same content, and the tearing strength is high.
3. The curing agent chain extender adopts the curing agents such as oligomeric diamine chain extender 1, 3-propylene glycol-bis (4-aminobenzoic acid) ester, 4-chloro-3, 5-diaminobenzoic acid isobutyl ester, 4,4' -methylene-bis (3-chloro-2, 6-diethylaniline) and the like, and can obviously improve the temperature resistance of polyurethane.
4. The high-performance polyurethane elastomer prepared by the invention has longer service life.
Detailed Description
The present invention will be further described with reference to the following examples.
All the raw materials used in the examples are commercially available unless otherwise specified.
PE-4005 poly adipic acid polyester diol, number average molecular weight 500;
PE-4007 poly adipic acid polyester diol, number average molecular weight 700;
PE-4020 Polyadipate polyester diol, number average molecular weight 2000;
PE-2020 poly adipic acid polyester diol, number average molecular weight 2000;
PCL-1000 polycaprolactone diol, number average molecular weight 1000;
PCL-2000 polycaprolactone diol, number average molecular weight 2000;
XYlink 16044-chloro-3, 5-diaminobenzoic acid isobutyl ester
XYlink 740M 1, 3-propanediol-bis (4-aminobenzoic acid) ester;
MCDEA 4,4' -methylene-bis (3-chloro-2, 6-diethylaniline)
TDI-1002, 4-toluene diisocyanate;
MDI-1004, 4' -diphenylmethane diisocyanate;
MDI-502, 4 '-diphenylmethane diisocyanate in admixture with 4,4' -diphenylmethane diisocyanate;
MOCA 3,3 '-dichloro-4, 4' -diaminodiphenylmethane;
1,4-BDO 1, 4-butanediol;
HQEE hydroquinone bis hydroxyethyl ether.
Example 1
(1) Preparation of prepolymer component
81.2g of PE-4005 was dehydrated at 100 ℃ under a vacuum of 0.095MPa to a water content of 0.03%, and reacted with 18.8g of TDI-100 at 75 ℃ for 4.5 hours to obtain a hydroxyl-terminated modified polyol.
85.1g of modified polyol is dehydrated at the temperature of 100 ℃ and the vacuum degree of 0.095MPa until the water content is 0.03 percent, and is reacted with 14.9g of TDI-100 at the temperature of 75 ℃ for 4 hours to obtain a prepolymer with the NCO content of 3.0 percent.
(2) Preparation of polyurethane elastomers
Heating the prepolymer to 80 ℃, then melting MCDEA at 110 ℃, fully mixing the prepolymer/MCDEA in a ratio of 100/12.3, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polyurethane elastomer with the hardness of 45D.
Example 2
(1) Preparation of prepolymer component
89.6g of PCL-1000 is dehydrated at the temperature of 100 ℃ and the vacuum degree of 0.095MPa until the water content is 0.03 percent, and is reacted with 10.4g of TDI-100 at the temperature of 75 ℃ for 4.5h to obtain the hydroxyl-terminated modified polyol.
87.2g of modified polyol is dehydrated at the temperature of 100 ℃ and the vacuum degree of 0.095MPa until the water content is 0.03 percent, and is reacted with 12.8g of TDI-100 at the temperature of 75 ℃ for 4 hours to obtain a prepolymer with the NCO content of 4.0 percent.
(2) Preparation of polyurethane elastomers
Heating the prepolymer to 80 ℃, then melting XYlink 740M at 135 ℃, fully mixing the prepolymer/XYlink 740M in a ratio of 100/13.5, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polyurethane elastomer with the hardness of 49D.
Example 3
80.8g of PE-4007 was dehydrated at 100 ℃ and a vacuum degree of 0.095MPa to a water content of 0.03%, and reacted with 12.8g of MDI-100 at 75 ℃ for 4.5 hours to obtain a hydroxyl-terminated modified polyol.
76.3g of modified polyol is dehydrated at the temperature of 100 ℃ and the vacuum degree of 0.095MPa until the water content is 0.03 percent, and is reacted with 23.7g of MDI-100 at the temperature of 75 ℃ for 4 hours to obtain a prepolymer with the NCO content of 5.5 percent.
(2) Preparation of polyurethane elastomers
Heating the prepolymer to 90 ℃, then melting HQEE at 110 ℃, fully mixing the prepolymer/HQEE in a ratio of 100/12.4, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polyurethane elastomer with the hardness of 50D.
Comparative example 1
(1) Preparation of prepolymer component
86.3g of PE-4020 is dehydrated at 100 ℃ and under the vacuum degree of 0.095MPa until the water content is 0.03%, and reacted with 13.7g of TDI-100 at 75 ℃ for 4h to obtain a prepolymer with the NCO content of 3.0%.
(2) Preparation of polyurethane elastomers
Heating the prepolymer to 80 ℃, then melting MCDEA at 110 ℃, fully mixing the prepolymer/MCDEA in a ratio of 100/12.3, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polyurethane elastomer with the hardness of 44D.
Comparative example 2
(1) Preparation of prepolymer component
74.3g of PE-4020 is dehydrated at 100 ℃ and under the vacuum degree of 0.095MPa until the water content is 0.03%, and the dehydrated PE-4020 reacts with 25.7g of MDI-100 at 75 ℃ for 4 hours to obtain a prepolymer with the NCO content of 5.5%.
(2) Preparation of polyurethane elastomers
Heating the prepolymer to 90 ℃, then melting HQEE at 110 ℃, fully mixing the prepolymer/HQEE in a ratio of 100/12.4, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polyurethane elastomer with the hardness of 48D.
The polyurethane elastomers prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to performance tests in accordance with the existing national standards, and the test results are shown in table 1.
TABLE 1 Performance results for polyurethane elastomer articles of examples 1-3 and comparative examples 1-2
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (9)
1. A preparation method of a high-performance polyurethane elastomer is characterized by comprising the following steps: the method comprises the following steps:
(1) dehydrating polyol, mixing with diisocyanate, and reacting to obtain hydroxyl-terminated modified polyol;
(2) mixing and reacting modified polyol and diisocyanate to prepare a prepolymer with NCO content of 3.0-6.0%;
(3) and mixing the prepolymer component and the chain extender component, pouring the mixture into a mold, and opening the mold and vulcanizing to obtain the high-performance polyurethane elastomer.
2. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: in the step (1), the polyhydric alcohol is dehydrated until the water content is less than or equal to 0.03 percent, and the reaction temperature is 70-85 ℃.
3. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the mass ratio of the polyol to the diisocyanate in the step (1) is 70-90: 10-20.
4. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the polyol in the step (1) is one or more of polyester polyols with the functionality of 2 and the number average molecular weight of 500-2000.
5. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the diisocyanate is one or more of 2, 4-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, a mixture of 50% of 2, 4' -diphenylmethane diisocyanate and 50% of 4,4 '-diphenylmethane diisocyanate, liquefied MDI, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate.
6. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the mass of the modified polyol and the diisocyanate in the step (2) is 70-90: 10-25.
7. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the chain extender in the step (3) is one or more than one of 4-chloro-3, 5-diaminobenzoic acid isobutyl ester, 3' -dichloro-4, 4' -diaminodiphenylmethane, 4' -methylene-bis (3-chloro-2, 6-diethylaniline), 1, 4-butanediol, hydroquinone dihydroxyethyl ether or 1, 3-propanediol-bis (4-aminobenzoic acid) ester.
8. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: in the step (3), the mass ratio of the prepolymer to the chain extender is 100: 12-15.
9. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein: the hardness of the high-performance polyurethane elastomer prepared in the step (3) is 40-55D.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354941A (en) * | 2021-04-26 | 2021-09-07 | 广东鹏德橡塑有限公司 | Polyurethane rubber roller and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231222A (en) * | 2014-09-19 | 2014-12-24 | 黎明化工研究设计院有限责任公司 | High-wear-resistance polyurethane elastomer and preparation method thereof |
| CN111793186A (en) * | 2020-06-30 | 2020-10-20 | 山东一诺威聚氨酯股份有限公司 | Preparation method of polyurethane polishing pad layer |
| CN111848906A (en) * | 2020-06-30 | 2020-10-30 | 山东一诺威聚氨酯股份有限公司 | Polyurethane for CMP polishing pad and preparation method thereof |
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- 2020-12-28 CN CN202011581813.6A patent/CN112679694A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231222A (en) * | 2014-09-19 | 2014-12-24 | 黎明化工研究设计院有限责任公司 | High-wear-resistance polyurethane elastomer and preparation method thereof |
| CN111793186A (en) * | 2020-06-30 | 2020-10-20 | 山东一诺威聚氨酯股份有限公司 | Preparation method of polyurethane polishing pad layer |
| CN111848906A (en) * | 2020-06-30 | 2020-10-30 | 山东一诺威聚氨酯股份有限公司 | Polyurethane for CMP polishing pad and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354941A (en) * | 2021-04-26 | 2021-09-07 | 广东鹏德橡塑有限公司 | Polyurethane rubber roller and preparation method thereof |
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Application publication date: 20210420 |