CN110922564A - Polyether ester type thermoplastic polyurethane elastomer foaming bead and preparation method thereof - Google Patents
Polyether ester type thermoplastic polyurethane elastomer foaming bead and preparation method thereof Download PDFInfo
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to polyether ester type thermoplastic polyurethane elastomer foam beads and a preparation method thereof. The polyether ester type thermoplastic polyurethane elastomer foaming bead is prepared by taking polyether polyol, diisocyanate, a chain extender, an antioxidant, a cell stabilizer and a catalyst as raw materials, and is further prepared by a kettle pressure foaming process. According to the invention, polyether polyol with low molecular weight is used for replacing micromolecular dihydric alcohol to react with adipic acid, and a polyether chain segment structure is introduced into a main chain of the polyester polyol through an advanced alcohol acid condensation process to synthesize brand-new polyether polyol; the product has the characteristics of high tensile strength and good wear resistance of the polyester ETPU, and also has the advantages of good hydrolysis resistance and good resilience of the polyether ETPU, thereby greatly expanding the application range of the ETPU.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to polyether ester type thermoplastic polyurethane elastomer foam beads and a preparation method thereof.
Background
Thermoplastic polyurethane elastomers (TPU) are a special polymer material with properties and processing technology between those of plastics and rubber, excellent properties and wide application range.
The foaming material prepared by taking TPU as a matrix is widely applied to various industries due to the advantages of light weight, air permeability, environmental protection, high resilience and the like. At present, most of foaming TPU is foamed by a chemical foaming agent, and the foaming agent causes environmental pollution and does not decompose for a long time. The supercritical physical foaming technology has become an international research hotspot due to the advantages of environmental protection, high efficiency and the like. Foamed particles (ETPU) prepared by the kettle pressure industry and the supercritical foaming technology have low density, high specific strength and excellent heat insulation performance, and are widely applied to the fields of packaging, industry, agriculture, transportation industry, daily necessities and the like.
At present, ETPU in the market is mainly classified into polyester type and polyether type according to raw materials, the polyester type has high strength, wear resistance and low cost, but the performances of hydrolysis resistance, cold resistance, mould resistance and the like are poor, and the application field is narrow; however, the polyether type is resistant to hydrolysis and low temperature, but has poor strength, poor wear resistance and high cost, and the application field of the polyether type cannot be further expanded. Therefore, developing an ETPU having both polyester and polyether characteristics becomes a research hotspot in the industry.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method is characterized in that polyether polyol with low molecular weight is used for replacing micromolecular dihydric alcohol to react with adipic acid from the design of a polyol structure, a novel efficient composite catalyst is preferably selected, and a polyether chain segment structure is introduced into a main chain of polyester polyol through an advanced alcohol acid condensation process to synthesize brand-new polyether polyol; meanwhile, the structural composition of the polyether ester polyol is effectively regulated and controlled, so that the industrialization of the polyether ester polyol with a series of molecular weights (Mn range of 600-4000) is realized.
The polyether ester type thermoplastic polyurethane elastomer foaming bead is prepared from the following raw materials in parts by weight:
the polyether polyol has the number average molecular weight of 600-4000, preferably 1000-3000, and is preferably PEM polyether polyol produced by Shandong-Nowei polyurethane GmbH.
The diisocyanate is one of aromatic isocyanate or aliphatic isocyanate. Aromatic diisocyanates such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI) and the like are preferred.
The chain extender is a micromolecular chain extender and is one or a mixture of any two of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or glycerol.
The antioxidant is one or a mixture of more of ester antioxidants, amine antioxidants or phenol antioxidants. Such as antioxidant 126 (bis [2, 4-di-tert-butylphenol ] pentaerythritol ester) and a phosphite ester complex.
The foam stabilizer is one or a mixture of more of tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyether modified silicone oil, amino modified silicone oil or hydroxyl modified silicone oil.
The catalyst is one of organic tin catalysts or bismuth catalysts, preferably bismuth catalysts, such as bismuth octyldecanoate or bismuth isooctanoate.
The preparation method of the polyether ester type thermoplastic polyurethane elastomer foaming bead comprises the following steps of preparing the polyether ester type thermoplastic polyurethane elastomer from the raw materials, and further preparing the polyether ester type thermoplastic polyurethane elastomer foaming bead by a kettle pressure foaming process:
(1) injecting polyether ester polyol, diisocyanate, a chain extender, an antioxidant, a foam stabilizer and a catalyst into a double-screw extruder through a casting machine, setting the temperature of a screw temperature zone, uniformly mixing a melt and a small molecular auxiliary agent to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a neck mold, and dehydrating and drying through a vibrating screen to obtain polyether type thermoplastic polyurethane elastomer transparent particles;
(2) and (2) adding the polyether type thermoplastic polyurethane elastomer transparent particles obtained in the step (1) into a supercritical reaction kettle, introducing a cooling medium and supercritical gas, heating, maintaining pressure, and rapidly releasing pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
The double-screw extruder in the step (1) is divided into ten temperature zones, the temperature is 100-; the water temperature in the underwater pelletizing is 20-45 ℃, and the rotating speed of the adopted pelletizer is 200-3500 r/min.
The cooling medium in the step (2) is water or glycerol, preferably water, and the introduction amount is 30-300L.
The supercritical gas in the step (2) is one or two of carbon dioxide and nitrogen, and the introduction amount is 3-13MPa, preferably 4-10 MPa.
The pressure maintaining after the temperature rise in the step (2) is performed after the temperature rise to 150 ℃ and the pressure maintaining for 0.5 to 5 hours, and preferably performed after the temperature rise to 140 ℃ and the pressure maintaining for 2 to 4 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyether ester ETPU prepared by the invention has the characteristics of high tensile strength and good wear resistance of the polyester ETPU, and also has the advantages of hydrolysis resistance and good resilience of the polyether ETPU, overcomes the disadvantage of high cost of the polyether ETPU, and greatly expands the application range of the ETPU.
2. The invention starts from the structural design of polyol, polyether polyol with low molecular weight is used for replacing micromolecular dihydric alcohol to react with adipic acid, a novel efficient composite catalyst is preferably selected, and a polyether chain segment structure is introduced into the main chain of the polyester polyol through an advanced alcohol acid condensation process to synthesize brand-new polyether polyol; meanwhile, the structural composition of the polyether ester polyol is effectively regulated and controlled, so that the industrialization of the polyether ester polyol with a series of molecular weights (Mn range of 600-4000) is realized.
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials used in the examples are all commercially available unless otherwise specified.
Example 1
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 1000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical autoclave, and introducing 100L of cooling water and 4MPa of CO2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Example 2
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 1000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical autoclave, and introducing 100L of cooling water and 4MPa of N2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Example 3
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 1000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5Mpa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical high-pressure kettle, and introducing 100L of cooling water and 2MPa of CO2And 2MPa of N2And (3) heating to 130 ℃, keeping the pressure for 4 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Example 4
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 2000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical autoclave, and introducing 100L of cooling water and 4MPa of CO2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Example 5
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 2000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical autoclave, and introducing 100L of cooling water and 4MPa of N2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Example 6
1. Accurately metering 50 parts by mass of polyether ester polyol (PEM-molecular weight 2000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octyldecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical high-pressure kettle, and introducing 100L of cooling water and 2MPa of CO2And 2MPa of N2And (3) heating to 130 ℃, keeping the pressure for 4 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Comparative example 1
1. Accurately metering 50 parts by mass of polyether polyol (polytetrahydrofuran glycol-molecular weight is 1000), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octodecanoate, injecting the mixture into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliary agent to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a die, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. accurately metering the prepared particles, adding the particles into a supercritical autoclave, and introducing 100L of cooling water and 4MPa of CO2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Comparative example 2
1. The preparation method comprises the steps of accurately metering 50 parts by mass of polyester polyol (polybutylene adipate glycol (PBA) -1000 in molecular weight), 30 parts by mass of MDI, 10 parts by mass of 1, 4-butanediol, 1 part by mass of antioxidant 126, 0.5 part by mass of cell regulator polytetrafluoroethylene and 0.1 part by mass of catalyst bismuth octodecanoate, injecting the metered materials into a double-screw extruder through a casting machine, controlling the temperature of a screw temperature zone to uniformly mix TPU polymer melt and small molecular auxiliaries to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a neck mold, and dehydrating and drying the melt through a vibrating screen to obtain transparent particles. Wherein the temperature of a mouth mold of the double-screw extruder is 190 ℃, the pressure of a melt pump is 5MPa, the water temperature is 30 ℃, and the rotating speed of a granulator is 3000 r/min;
2. adding the prepared particles into the mixture after the particles are accurately measuredIntroducing 100L of cooling water and 4MPa of CO into the autoclave2And (3) heating to 120 ℃, keeping the pressure for 2 hours, and finally quickly relieving the pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
Performance testing
The polyether ester type thermoplastic polyurethane elastomer expanded beads prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to a performance test, and the test data are shown in Table 1.
TABLE 1 Performance data for examples 1-6 and comparative examples 1-2
As can be seen from the performance data in the table 1, compared with the comparative example 2, the polyether ester ETPU in the embodiment 1 and the comparative example 1 has the advantages of high tensile strength and good wear resistance of the polyester ETPU, good hydrolysis resistance and good rebound of the polyether ETPU, overcomes the disadvantage of high cost of the polyether ETPU, and greatly expands the application range of the ETPU.
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 (10)
1. A polyether ester type thermoplastic polyurethane elastomer foaming bead is characterized in that: the feed is prepared from the following raw materials in parts by mass:
2. the polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the polyether polyol has the number average molecular weight of 600-4000.
3. The polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the diisocyanate is one of aromatic isocyanate or aliphatic isocyanate.
4. The polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the chain extender is one or a mixture of any two of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or glycerol.
5. The polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the antioxidant is one or a mixture of more of ester antioxidants, amine antioxidants or phenol antioxidants.
6. The polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the foam stabilizer is one or a mixture of more of tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyether modified silicone oil, amino modified silicone oil or hydroxyl modified silicone oil.
7. The polyether ester type thermoplastic polyurethane elastomer expanded bead as claimed in claim 1, wherein: the catalyst is one of organic tin catalysts or bismuth catalysts.
8. A method for producing the polyether ester type thermoplastic polyurethane elastomer expanded beads as claimed in any one of claims 1 to 7, wherein: the method comprises the following steps:
(1) injecting polyether ester polyol, diisocyanate, a chain extender, an antioxidant, a foam stabilizer and a catalyst into a double-screw extruder, setting the temperature of a screw temperature zone, uniformly mixing a melt and a small molecular auxiliary agent to obtain a homogeneous system, carrying out underwater granulation on the melt after passing through a neck mold, and dehydrating and drying through a vibrating screen to obtain polyether type thermoplastic polyurethane elastomer transparent particles;
(2) and (2) adding the polyether type thermoplastic polyurethane elastomer transparent particles obtained in the step (1) into a supercritical reaction kettle, introducing a cooling medium and supercritical gas, heating, maintaining pressure, and rapidly releasing pressure to obtain the polyether ester type thermoplastic polyurethane elastomer foaming beads.
9. The method for producing polyether ester type thermoplastic polyurethane elastomer expanded beads according to claim 8, wherein: the double-screw extruder in the step (1) is divided into ten temperature zones, the temperature is 100-210 ℃, the neck mold temperature of the double-screw extruder is 170-200 ℃, and the pressure is 1-15 MPa; the water temperature in the underwater pelletizing is 20-45 ℃, and the rotating speed of the adopted pelletizer is 200-3500 r/min.
10. The method for producing polyether ester type thermoplastic polyurethane elastomer expanded beads according to claim 8, wherein: the cooling medium in the step (2) is water or glycerol; the supercritical gas is one or two of carbon dioxide or nitrogen, and the input amount is 3-13 MPa; the pressure maintaining after the temperature rise is that the pressure is maintained for 0.5 to 5 hours after the temperature rises to 100 ℃ and 150 ℃.
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| CN113736048A (en) * | 2020-05-27 | 2021-12-03 | 潍坊誉博新材料有限公司 | Method and device for continuously preparing foamed thermoplastic polyurethane elastomer beads |
| CN115160766A (en) * | 2022-08-30 | 2022-10-11 | 江苏中科聚合新材料产业技术研究院有限公司 | High-resilience low-shrinkage polyurethane foaming bead and preparation method thereof |
| CN115160765A (en) * | 2022-08-30 | 2022-10-11 | 江苏中科聚合新材料产业技术研究院有限公司 | Polyurethane foaming bead and preparation method thereof |
| CN115260450A (en) * | 2022-08-25 | 2022-11-01 | 佛山市立大立塑新材料有限公司 | High-light-transmittance aromatic elastic polyurethane film and preparation method thereof |
| CN116589657A (en) * | 2023-05-19 | 2023-08-15 | 沃德丰汽车用品(南通)有限公司 | Breathable water-permeable washable slow rebound sponge |
| CN113736048B (en) * | 2020-05-27 | 2024-04-26 | 潍坊誉博新材料有限公司 | Method and device for continuously preparing foaming thermoplastic polyurethane elastomer beads |
-
2019
- 2019-12-10 CN CN201911258186.XA patent/CN110922564A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736048A (en) * | 2020-05-27 | 2021-12-03 | 潍坊誉博新材料有限公司 | Method and device for continuously preparing foamed thermoplastic polyurethane elastomer beads |
| CN113736048B (en) * | 2020-05-27 | 2024-04-26 | 潍坊誉博新材料有限公司 | Method and device for continuously preparing foaming thermoplastic polyurethane elastomer beads |
| CN113307942A (en) * | 2021-05-21 | 2021-08-27 | 东莞市吉鑫高分子科技有限公司 | E-TPU (ethylene-thermoplastic polyurethane) elastomer material and preparation method thereof |
| CN113307942B (en) * | 2021-05-21 | 2022-11-15 | 东莞市吉鑫高分子科技有限公司 | E-TPU (ethylene-thermoplastic polyurethane) elastomer material and preparation method thereof |
| CN115260450A (en) * | 2022-08-25 | 2022-11-01 | 佛山市立大立塑新材料有限公司 | High-light-transmittance aromatic elastic polyurethane film and preparation method thereof |
| CN115260450B (en) * | 2022-08-25 | 2023-10-20 | 佛山市立大立塑新材料有限公司 | High-light-transmittance aromatic elastic polyurethane film and preparation method thereof |
| CN115160766A (en) * | 2022-08-30 | 2022-10-11 | 江苏中科聚合新材料产业技术研究院有限公司 | High-resilience low-shrinkage polyurethane foaming bead and preparation method thereof |
| CN115160765A (en) * | 2022-08-30 | 2022-10-11 | 江苏中科聚合新材料产业技术研究院有限公司 | Polyurethane foaming bead and preparation method thereof |
| CN116589657A (en) * | 2023-05-19 | 2023-08-15 | 沃德丰汽车用品(南通)有限公司 | Breathable water-permeable washable slow rebound sponge |
| CN116589657B (en) * | 2023-05-19 | 2023-12-19 | 沃德丰汽车用品(南通)有限公司 | Breathable water-permeable washable slow rebound sponge |
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