CN111057208A - Polyolefin polyol modified thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Polyolefin polyol modified thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN111057208A CN111057208A CN201911304503.7A CN201911304503A CN111057208A CN 111057208 A CN111057208 A CN 111057208A CN 201911304503 A CN201911304503 A CN 201911304503A CN 111057208 A CN111057208 A CN 111057208A
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- thermoplastic polyurethane
- polyurethane elastomer
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- polyolefin polyol
- polyol
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention discloses a polyolefin polyol modified thermoplastic polyurethane elastomer which comprises the following components in parts by weight: 20-30 parts of polyolefin polyol; 30-40 parts of polyester/polyether polyol; 20-40 parts of diisocyanate; and 5-20 parts of a chain extender. The invention also discloses a preparation method of the composition. The material disclosed by the invention has the advantages of excellent wear resistance, high hardness, high elasticity, good mechanical strength, excellent oil resistance and excellent oxygen resistance of the thermoplastic polyurethane elastomer, and has the characteristics of excellent low-temperature performance, excellent hydrolysis resistance and small dynamic heat generation of polyolefin rubber.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyolefin polyol modified thermoplastic polyurethane elastomer and a preparation method thereof.
Background
The thermoplastic polyurethane elastomer has the advantages of firmness, wear resistance, corrosion resistance, aging resistance, small pollution and the like, and is a widely applied high polymer material. The polyolefin polyol is a telechelic liquid polymer with low molecular weight, and has the advantages of low glass transition temperature, good transparency, low viscosity, difficult volatilization, oil resistance, aging resistance, low temperature, good processability and the like, so the polyolefin polyol has wide application in the military and civil fields.
However, the conventional polyester/ether type thermoplastic polyurethane elastomer has disadvantages of high permeability to moisture, low hydrolytic stability, and large dynamic heat generation.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a polyolefin polyol modified thermoplastic polyurethane elastomer.
The second object of the present invention is a process for preparing the polyolefin polyol-modified thermoplastic polyurethane elastomer.
In order to realize one of the purposes of the invention, the adopted technical scheme is as follows:
the polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following components in parts by weight:
20-30 parts of polyolefin polyol;
30-40 parts of polyester/polyether polyol;
20-40 parts of diisocyanate;
5-20 parts of a chain extender;
the polyolefin polyol is one or more of polyisoprene polyol, polybutadiene polyol, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated styrene-butadiene liquid rubber or hydrogenated hydroxyl-terminated polybutadiene;
the diisocyanate is any one or more of diphenylmethane diisocyanate, hydrogenated phenylalkyl diisocyanate or hexamethylene diisocyanate;
the chain extender is any one or more of ethylene glycol, butanediol or hexanediol.
In a preferred embodiment of the present invention, the polyolefin polyol has a molecular weight in the range of 1000 to 3000 and a functionality of 2.
In order to realize the second purpose of the invention, the technical scheme is as follows:
a preparation method of a polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following steps:
the method comprises the following steps: uniformly mixing the pre-dried polyolefin polyol and the pre-dried polyester/polyether polyol, adding the mixture and the diisocyanate into a reaction vessel, stirring, heating and vacuumizing;
step two: and (3) removing the vacuum, adding the chain extender, quickly stirring until the temperature of the material is raised and the viscosity is increased, stopping stirring, curing, cooling and crushing to obtain the polyolefin polyol modified thermoplastic polyurethane elastomer.
In a preferred embodiment of the invention, the temperature of the stirring temperature rise is 60-90 ℃.
In a preferred embodiment of the present invention, the reaction time in the first step is 2 to 4 hours.
In a preferred embodiment of the present invention, the curing in the second step is performed by pouring into a teflon plate for curing, wherein the curing temperature is 110-.
The invention has the beneficial effects that:
the polyolefin type thermoplastic polyurethane elastomer is prepared by utilizing polyolefin polyol and polyester/polyether polyol, and a polyolefin polyol structure is introduced into a molecular structure, so that the dynamic mechanical property of the polyurethane material can be improved, the internal heat generation of the polyurethane material can be reduced, and the low temperature resistance, hydrolysis resistance and other properties of the material are improved to a certain extent.
Detailed Description
The main principle of the invention is as follows:
by introducing a polyolefin polyol structure into a molecular structure, the structural characteristics and excellent characteristics of polyolefin are utilized, the dynamic mechanical property of the material is improved, the internal heat generation is reduced, and meanwhile, the hydrolysis resistance of the material can be improved to a certain extent due to the hydrophobic characteristic of the polyolefin structure.
Comparative example 1
The preparation method of the polyether type thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 60 parts by weight of pre-dried polytetrahydrofuran polyol with the molecular weight of about 1000g/mol, uniformly mixing and stirring, adding the mixture and 33.4 parts of diphenylmethane diisocyanate into a reaction vessel, heating to 80 ℃ under continuous stirring, and carrying out vacuum pumping reaction; (2) and (3) removing vacuum, adding 6.6 parts of pre-dried butanediol, quickly stirring, gradually raising the temperature of the material to 120 ℃, obviously increasing the viscosity, stopping stirring, pouring the mixture into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
Comparative example 2
The preparation method of the polyester type thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 60 parts by weight of pre-dried polyester polyol with the molecular weight of about 2000g/mol, uniformly mixing and stirring, adding the polyester polyol and 33.9 parts by weight of hydrogenated phenylalkyl diisocyanate into a reaction container, heating to 80 ℃ under continuous stirring, and carrying out vacuum pumping reaction; (2) and (3) removing vacuum, adding 6.1 parts of predried ethylene glycol, quickly stirring, gradually raising the temperature of the material to 120 ℃, obviously increasing the viscosity, stopping stirring, pouring the mixture into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
Example 1
A preparation method of a polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 20 parts by weight of pre-dried polybutadiene polyol with the molecular weight of about 1000 and 40 parts by weight of pre-dried polytetrahydrofuran polyol with the molecular weight of about 1000g/mol, uniformly mixing and stirring, adding the mixture and 33.4 parts of diphenylmethane diisocyanate into a reaction vessel, heating to 80 ℃ under continuous stirring, and carrying out vacuum pumping reaction; (2) and (3) removing vacuum, adding 6.6 parts of pre-dried butanediol, quickly stirring, gradually raising the temperature of the material to 120 ℃, obviously increasing the viscosity, stopping stirring, pouring the mixture into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
Example 2
A preparation method of a polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 30 parts by weight of predried hydroxyl-terminated polybutadiene-acrylonitrile with molecular weight of 2000 and 30 parts by weight of predried polyester polyol with molecular weight of about 2000g/mol, uniformly mixing and stirring, adding 33.9 parts of hydrogenated phenylalkyl diisocyanate into a reaction container, heating to 80 ℃ under continuous stirring, and vacuumizing for reaction; (2) and (3) removing vacuum, adding 6.1 parts of predried ethylene glycol, quickly stirring, gradually raising the temperature of the material to 120 ℃, obviously increasing the viscosity, stopping stirring, pouring the mixture into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
Example 3
A preparation method of a polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 25 parts by weight of predried hydroxyl-terminated styrene-butadiene liquid rubber with the molecular weight of 3000 and 25 parts by weight of predried polyester polyol with the molecular weight of about 2000g/mol, uniformly mixing and stirring, adding 21.7 parts of hexamethylene diisocyanate into a reaction vessel, heating to 75 ℃ under continuous stirring, and vacuumizing for reaction; (2) and (3) removing vacuum, adding 13.1 parts of pre-dried hexanediol, quickly stirring, gradually raising the temperature of the material to 115 ℃, obviously increasing the viscosity, stopping stirring, pouring into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
Example 4
A preparation method of a polyolefin polyol modified thermoplastic polyurethane elastomer comprises the following steps: (1) weighing 20 parts by weight of predried hydrogenated hydroxyl-terminated polybutadiene with the molecular weight of 2000 and 30 parts by weight of predried polyester polyol with the molecular weight of about 2000g/mol, uniformly mixing and stirring, adding 22 parts of diphenylmethane diisocyanate and 31.4 parts of diphenylmethane diisocyanate into a reaction vessel, heating to 85 ℃ under continuous stirring, and carrying out vacuum pumping reaction; (2) and (3) removing vacuum, adding 8.6 parts of pre-dried butanediol, quickly stirring, gradually raising the temperature of the material to 120 ℃, obviously increasing the viscosity, stopping stirring, pouring the mixture into a polytetrafluoroethylene disc, curing, cooling and crushing to obtain the modified thermoplastic polyurethane elastomer.
The compression fatigue test is the most intuitive way to describe the heat build-up in a material, with elastomers having less heat build-up under alternating stress, and having a lower temperature rise and a shorter retention time at the highest temperature. In the comparative tests, the test was carried out at 80 ℃.
Some of the performance data for the above comparative and examples are given in table 1 below:
TABLE 1
The foregoing is merely illustrative of the principles of the present invention and the foregoing description of the embodiments is presented to enable a person skilled in the art to make and use the invention. The invention is not limited to the embodiments described, and any equivalent changes or simple modifications made by the embodiments and the conception of the invention by those skilled in the art should fall within the scope of the invention.
Claims (6)
1. The polyolefin polyol modified thermoplastic polyurethane elastomer is characterized by comprising the following components in parts by weight:
20-30 parts of polyolefin polyol;
30-40 parts of polyester/polyether polyol;
20-40 parts of diisocyanate;
5-20 parts of a chain extender;
the polyolefin polyol is one or more of polyisoprene polyol, polybutadiene polyol, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated styrene-butadiene liquid rubber or hydrogenated hydroxyl-terminated polybutadiene;
the diisocyanate is any one or more of diphenylmethane diisocyanate, hydrogenated phenylalkyl diisocyanate or hexamethylene diisocyanate;
the chain extender is any one or more of ethylene glycol, butanediol or hexanediol.
2. The polyolefin polyol modified thermoplastic polyurethane elastomer is characterized in that the molecular weight range of the polyolefin polyol is 1000-3000, and the functionality is 2.
3. The process for producing a polyolefin polyol-modified thermoplastic polyurethane elastomer according to claim 1 or 2, comprising the steps of:
the method comprises the following steps: uniformly mixing the pre-dried polyolefin polyol and the pre-dried polyester/polyether polyol, adding the mixture and the diisocyanate into a reaction vessel, stirring, heating and vacuumizing;
step two: and (3) removing the vacuum, adding the chain extender, quickly stirring until the temperature of the material is raised and the viscosity is increased, stopping stirring, curing, cooling and crushing to obtain the polyolefin polyol modified thermoplastic polyurethane elastomer.
4. The process for preparing a polyolefin polyol-modified thermoplastic polyurethane elastomer according to claim 3, wherein the temperature for raising the temperature by stirring is 60 to 90 ℃.
5. The method for preparing a polyolefin polyol-modified thermoplastic polyurethane elastomer as claimed in claim 3, wherein the reaction time in the first step is 1-4 h.
6. The method for preparing polyolefin polyol modified thermoplastic polyurethane elastomer as claimed in claim 3, wherein the curing in the second step is performed by pouring into a polytetrafluoroethylene plate, and the curing temperature is 110-140 ℃ and the curing time is 9-13 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911304503.7A CN111057208A (en) | 2019-12-17 | 2019-12-17 | Polyolefin polyol modified thermoplastic polyurethane elastomer and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112646355A (en) * | 2021-01-14 | 2021-04-13 | 江苏威久科技发展有限公司 | High-strength wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN113583432A (en) * | 2021-08-19 | 2021-11-02 | 山东一诺威聚氨酯股份有限公司 | High-wear-resistance low-internal-heat-generation TPU material and preparation method thereof |
| CN113912813A (en) * | 2021-10-29 | 2022-01-11 | 山东一诺威聚氨酯股份有限公司 | Plasticizer-free high-hydrolysis-resistance TPU and preparation method thereof |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646355A (en) * | 2021-01-14 | 2021-04-13 | 江苏威久科技发展有限公司 | High-strength wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
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| CN113912813A (en) * | 2021-10-29 | 2022-01-11 | 山东一诺威聚氨酯股份有限公司 | Plasticizer-free high-hydrolysis-resistance TPU and preparation method thereof |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
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Application publication date: 20200424 |