CN111269377A - High-hardness polyurethane elastomer and preparation method thereof - Google Patents
High-hardness polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN111269377A CN111269377A CN202010139841.6A CN202010139841A CN111269377A CN 111269377 A CN111269377 A CN 111269377A CN 202010139841 A CN202010139841 A CN 202010139841A CN 111269377 A CN111269377 A CN 111269377A
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
-
- 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
- C08G18/44—Polycarbonates
-
- 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
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G9/00—Installations of electric cables or lines in or on the ground or water
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G9/00—Installations of electric cables or lines in or on the ground or water
- H02G9/06—Installations of electric cables or lines in or on the ground or water in underground tubes or conduits; Tubes or conduits therefor
Abstract
The invention discloses a high-hardness polyurethane elastomer and a preparation method thereof, belonging to the technical field of materials. According to the invention, polycarbonate polyol and polyether polyol are used as the soft segment part of the polyurethane elastomer, diphenylmethane diisocyanate is used as the hard segment component of the high-hardness polyurethane elastomer, the high-hardness polyurethane elastomer prepared from the elastomer material has the advantages of high impact resistance, high tensile strength, higher hydrolysis resistance, high bacteria resistance and the like, the strength can reach 85D (Shore) hardness, and the polyurethane elastomer is produced by using the formula and the process, so that the problem of high price required by import is solved; in the present invention, the ratio of polycarbonate polyol and polyether polyol is changed and liquid MDI is used to achieve 85D hardness, and the tensile strength and abrasion are greatly improved.
Description
Technical Field
The invention relates to a high-hardness polyurethane elastomer and a preparation method thereof, belonging to the technical field of materials.
Background
A submarine cable protection sleeve, namely a bending limiter, is a polyurethane material which is applied to a submarine cable shell protection device and has the hardness of 85D Shore. The cable is mainly limited by the excellent mechanical properties of high hardness, high tensile strength, ultrahigh impact resistance and the like of the material to bend the submarine cable and damage the submarine cable by the severe submarine environment, so that the cable is protected. On one hand, the raw materials have polycarbonate-based branched chains, so the material has excellent hydrolysis resistance; on the other hand, it is ultra-hard to withstand the environmental impact of the sea floor.
In the prior art, polyurethane elastomers with high hardness applied to a submarine protection device are not produced in the market, the process is not mature, and products with specific requirements cannot be produced.
Disclosure of Invention
In order to solve the above problems, the present invention provides a high hardness polyurethane elastomer and a method for preparing the same, wherein the hardness of the polyurethane elastomer is 85D by changing the ratio of polycarbonate polyol to polyether polyol and using liquid MDI, and the tensile strength and abrasion of the prepared polyurethane elastomer are greatly improved.
The first object of the present invention is to provide a method for preparing a high hardness polyurethane elastomer, comprising the steps of:
s1, preparation of the component A: dehydrating and vacuumizing polycarbonate polyol and polyether polyol at the temperature of 110-115 ℃, cooling to 50-60 ℃, adding liquid isocyanate, freely heating, and then carrying out heat preservation reaction for 2-3 hours to obtain a component A;
s2, preparation of a component B: heating polycarbonate polyol, a chain extender, color paste, a defoaming agent, a catalyst and a toughening agent to 110-115 ℃, dehydrating, vacuumizing, and cooling to 65-70 ℃ to obtain a component B;
s3, preparation of high-hardness polyurethane elastomer: controlling the temperature of the component A and the component B to be 60-70 ℃; adjusting the ratio of the component A to the component B to ensure that the ratio of the mole number of isocyanate groups in the component A to the mole number of active hydrogen in the component B is 1.0: 1.0-1.1; quickly mixing the component A and the component B at the speed of 3000-;
the component A and the component B respectively comprise the following components in parts by weight:
the component A comprises: liquid isocyanate: 100 to 200 parts of
Polycarbonate polyol: 50-100 parts of
Polyether polyol: 50-100 parts;
and B component: polycarbonate polyol: 50-100 parts of
Chain extender: 60 to 80 portions of
And (3) defoaming agent: 0.2 to 0.5 portion
Color paste: 0.2 to 1 portion
Catalyst: 0.2 to 0.5 portion
A toughening agent: 0.1 to 0.2 portion.
Further, the isocyanate is diphenylmethane diisocyanate.
Further, the diphenylmethane diisocyanate was liquid MDI50, i.e., 50% 2, 4-diphenylmethane diisocyanate and 50% 2, 2-diphenylmethane diisocyanate.
Further, the polyether polyol is polytetrahydrofuran polyol, and the molecular weight of the polyether polyol is 350-450.
Furthermore, the molecular weight of the polycarbonate polyol is 900-1200.
Further, the catalyst is an organic tin catalyst.
Further, the defoaming agent is an organosilicon surfactant.
Further, in the step S1 or the step S2, the dehydration vacuum pumping time is 30 to 40 minutes, and the vacuum degree is 0.098 to 0.10 MPa.
The second purpose of the invention is to provide a high-hardness polyurethane elastomer prepared by the method.
The third purpose of the invention is to provide the application of the high-hardness polyurethane elastomer in preparing the submarine cable protective sleeve.
The invention has the beneficial effects that:
(1) according to the invention, polycarbonate polyol and polyether polyol are used as the soft segment part of the polyurethane elastomer, diphenylmethane diisocyanate is used as the hard segment component of the high-hardness polyurethane elastomer, the high-hardness polyurethane elastomer prepared from the elastomer material has the advantages of high impact resistance, high tensile strength, higher hydrolysis resistance, high bacteria resistance and the like, the strength can reach 85D (Shore) hardness, and the polyurethane elastomer is produced by using the formula and the process, so that the problem of high price required by import is solved; (2) in the present invention, the ratio of polycarbonate polyol and polyether polyol is changed and liquid MDI is used to achieve 85D hardness, and the tensile strength and abrasion are greatly improved.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1:
the component A is a prepolymer component and comprises the following components in parts by weight:
liquid MID 50: 150 portions of
Polycarbonate polyol: 80 portions
Polytetrahydrofuran polyol: 80 parts of a mixture;
the component B is a polyol component and comprises the following components in parts by weight:
polycarbonate polyol: 80 portions
Chain extender MOCA: 70 portions of
Silicone surfactant: 0.3 part
Color paste: 0.5 portion
Organotin catalyst: 0.3 part
A toughening agent: 0.1 part.
The preparation steps of the high-hardness polyurethane elastomer comprise the following steps:
(1) preparation of component A: placing polycarbonate polyol and polytetrahydrofuran polyol into a reaction kettle, dehydrating and vacuumizing for 30 minutes at 115 ℃, cooling to 55 ℃, adding liquid MID50, freely heating, then carrying out heat preservation reaction for 2-3 hours, controlling the-NCO content to be about 20% of that of the component B, discharging, and sealing and storing for later use;
(2) preparation of the component B: adding polycarbonate polyol, MOCA, color paste, a defoaming agent, an organic silicon surfactant, an organic tin catalyst, a toughening agent and the like into a reaction kettle at one time, heating to 115 ℃, dehydrating, vacuumizing for 30 minutes, cooling to 65 ℃, and sealing for storage for later use;
(3) molding and forming of high-hardness polyurethane elastomer: controlling the temperature of the component A and the component B to be 65 ℃; adjusting the proportion of the two components to ensure that the ratio of the mole number of-NCO in the component A to the mole number of active hydrogen in the component B is 1: 1.05; the two components are quickly mixed at the speed of 5000 r/min, injected into a mold at the temperature of 100 ℃, pre-vulcanized at the temperature of 120 ℃ for 20min, and then demoulded, and post-vulcanized at the temperature of 90 ℃ for 6h after demoulding, so that the high-hardness polyurethane elastomer is prepared.
Example 2:
the component A is a prepolymer component and comprises the following components in parts by weight:
liquid MID 50: 100 portions of
Polycarbonate polyol: 50 portions of
Polytetrahydrofuran polyol: 50 parts of a mixture;
the component B is a polyol component and comprises the following components in parts by weight:
polycarbonate polyol: 50 portions of
Chain extender MOCA: 60 portions of
Silicone surfactant: 0.2 part
Color paste: 0.2 part
Organotin catalyst: 0.2 part
A toughening agent: 0.1 part.
The preparation steps of the high-hardness polyurethane elastomer comprise the following steps:
(1) preparation of component A: placing polycarbonate polyol and polytetrahydrofuran polyol into a reaction kettle, dehydrating and vacuumizing for 40 minutes at 110 ℃, cooling to 50 ℃, adding liquid MID50, freely heating, then preserving heat for reaction for 2-3 hours, controlling the-NCO content to be about 20% of that of the component B, discharging, and sealing and storing for later use;
(2) preparation of the component B: adding polycarbonate polyol, MOCA, color paste, a defoaming agent, an organic silicon surfactant, an organic tin catalyst, a toughening agent and the like into a reaction kettle at one time, heating to 110 ℃, dehydrating, vacuumizing for 40 minutes, cooling to 70 ℃, and sealing for storage for later use;
(3) molding and forming of high-hardness polyurethane elastomer: controlling the temperature of the component A and the component B to be 70 ℃; adjusting the proportion of the two components to ensure that the ratio of the mole number of-NCO in the component A to the mole number of active hydrogen in the component B is 1: 1.05; the two components are quickly mixed at the speed of 3000 r/min, then injected into a mold at the temperature of 100 ℃, pre-vulcanized at the temperature of 120 ℃ for 20min, then the mold is removed, and after demolding, post-vulcanization is carried out at the temperature of 90 ℃ for 6h, thus preparing the high-hardness polyurethane elastomer.
Example 3:
the component A is a prepolymer component and comprises the following components in parts by weight:
liquid MID 50: 200 portions of
Polycarbonate polyol: 100 portions of
Polytetrahydrofuran polyol: 100 parts of (A);
the component B is a polyol component and comprises the following components in parts by weight:
polycarbonate polyol: 100 portions of
Chain extender MOCA: 80 portions
Silicone surfactant: 0.5 portion
Color paste: 1 part of
Organotin catalyst: 0.5 portion
A toughening agent: 0.2 part.
The preparation steps of the high-hardness polyurethane elastomer comprise the following steps:
(1) preparation of component A: placing polycarbonate polyol and polytetrahydrofuran polyol into a reaction kettle, dehydrating and vacuumizing for 40 minutes at 115 ℃, cooling to 60 ℃, adding liquid MID50, freely heating, then preserving heat for reaction for 2-3 hours, controlling the-NCO content to be about 20% of that of the component B, discharging, and sealing and storing for later use;
(2) preparation of the component B: adding polycarbonate polyol, MOCA, color paste, a defoaming agent, an organic silicon surfactant, an organic tin catalyst, a toughening agent and the like into a reaction kettle at one time, heating to 115 ℃, dehydrating, vacuumizing for 40 minutes, cooling to 70 ℃, and sealing for storage for later use;
(3) molding and forming of high-hardness polyurethane elastomer: controlling the temperature of the component A and the component B to be 70 ℃; adjusting the proportion of the two components to ensure that the ratio of the mole number of-NCO in the component A to the mole number of active hydrogen in the component B is 1: 1.05; the two components are quickly mixed at the speed of 6000 r/min, injected into a mold at the temperature of 100 ℃, pre-vulcanized at the temperature of 120 ℃ for 20min, and then demoulded, and post-vulcanized at the temperature of 90 ℃ for 6h after demoulding, so that the high-hardness polyurethane elastomer is prepared.
Comparative example 1:
the basic steps and parameters are consistent with those of example 1, except that the MID is in a solid state in step (1) of the comparison document 1.
Comparative example 2:
the component A is a prepolymer component and comprises the following components in parts by weight:
liquid MID 50: 150 portions of
Polycarbonate polyol: 100 portions of
Polytetrahydrofuran polyol: 60 parts;
the component B is a polyol component and comprises the following components in parts by weight:
polycarbonate polyol: 80 portions
Chain extender MOCA: 70 portions of
Silicone surfactant: 0.3 part
Color paste: 0.5 portion
Organotin catalyst: 0.3 part
A toughening agent: 0.1 part.
The preparation procedure was as in example 1 to give a polyurethane elastomer.
Comparative example 3:
the component A is a prepolymer component and comprises the following components in parts by weight:
liquid MID 50: 150 portions of
Polycarbonate polyol: 60 portions of
Polytetrahydrofuran polyol: 100 parts of (A);
the component B is a polyol component and comprises the following components in parts by weight:
polycarbonate polyol: 80 portions
Chain extender MOCA: 70 portions of
Silicone surfactant: 0.3 part
Color paste: 0.5 portion
Organotin catalyst: 0.3 part
A toughening agent: 0.1 part.
The preparation procedure was as in example 1 to give a polyurethane elastomer.
The polyurethane elastomers obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, and the results are shown in table 1.
TABLE 1
From the results of table 1, the hardness of the polyurethane elastomer prepared by the method of the present invention can reach 85D (shore), and the properties such as tensile strength, etc. are greatly improved. The cable bending limiter prepared by the polyurethane elastomer has the advantages of high impact resistance, high tensile strength, higher hydrolysis resistance, high bacteria resistance and the like.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a high-hardness polyurethane elastomer is characterized by comprising the following steps:
s1, preparation of the component A: dehydrating and vacuumizing polycarbonate polyol and polyether polyol at the temperature of 110-115 ℃, cooling to 50-60 ℃, adding liquid isocyanate, freely heating, and then carrying out heat preservation reaction for 2-3 hours to obtain a component A;
s2, preparation of a component B: heating polycarbonate polyol, a chain extender, color paste, a defoaming agent, a catalyst and a toughening agent to 110-115 ℃, dehydrating, vacuumizing, and cooling to 65-70 ℃ to obtain a component B;
s3, preparation of high-hardness polyurethane elastomer: controlling the temperature of the component A and the component B to be 60-70 ℃; adjusting the ratio of the component A to the component B to ensure that the ratio of the mole number of isocyanate groups in the component A to the mole number of active hydrogen in the component B is 1.0: 1.0-1.1; quickly mixing the component A and the component B at the speed of 3000-;
the component A and the component B respectively comprise the following components in parts by weight:
the component A comprises: liquid isocyanate: 100 to 200 parts of
Polycarbonate polyol: 50-100 parts of
Polyether polyol: 50-100 parts;
and B component: polycarbonate polyol: 50-100 parts of
Chain extender: 60 to 80 portions of
And (3) defoaming agent: 0.2 to 0.5 portion
Color paste: 0.2 to 1 portion
Catalyst: 0.2 to 0.5 portion
A toughening agent: 0.1 to 0.2 portion.
2. The method of claim 1, wherein the isocyanate is diphenylmethane diisocyanate.
3. The method of claim 2, wherein the diphenylmethane diisocyanate is liquid MDI50, and 50% of the liquid MDI50 is 2, 4-diphenylmethane diisocyanate and 50% is 2, 2-diphenylmethane diisocyanate.
4. The method according to claim 1, wherein the polyether polyol is polytetrahydrofuran polyol and has a molecular weight of 350-450.
5. The method according to claim 1, wherein the polycarbonate polyol has a molecular weight of 900 to 1200.
6. The method of claim 1, wherein the catalyst is an organotin catalyst.
7. The method of claim 1 wherein said defoamer is a silicone surfactant.
8. The method as claimed in claim 1, wherein the dehydrating evacuation time is 30 to 40 minutes and the vacuum degree is 0.098 to 0.10MPa in the step of S1 or S2.
9. A high-hardness polyurethane elastomer prepared by the method according to any one of claims 1 to 8.
10. Use of the high durometer polyurethane elastomer of claim 9 in the manufacture of a sea cable protective sleeve.
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| CN202010139841.6A CN111269377A (en) | 2020-03-03 | 2020-03-03 | High-hardness polyurethane elastomer and preparation method thereof |
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| CN202010139841.6A CN111269377A (en) | 2020-03-03 | 2020-03-03 | High-hardness polyurethane elastomer and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574968A (en) * | 2009-07-07 | 2012-07-11 | 拜尔材料科学股份公司 | Polyurethane and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574968A (en) * | 2009-07-07 | 2012-07-11 | 拜尔材料科学股份公司 | Polyurethane and use thereof |
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Application publication date: 20200612 |