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WO2019014959A1 - Élastomère de polyuréthane thermoplastique à moussage de faible densité et son procédé de préparation - Google Patents

Élastomère de polyuréthane thermoplastique à moussage de faible densité et son procédé de préparation Download PDF

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Publication number
WO2019014959A1
WO2019014959A1 PCT/CN2017/094636 CN2017094636W WO2019014959A1 WO 2019014959 A1 WO2019014959 A1 WO 2019014959A1 CN 2017094636 W CN2017094636 W CN 2017094636W WO 2019014959 A1 WO2019014959 A1 WO 2019014959A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic polyurethane
polyurethane elastomer
foamed thermoplastic
foaming
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/094636
Other languages
English (en)
Chinese (zh)
Inventor
王光阜
王仁鸿
张生
宋红玮
杨冲冲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Miracll Chemicals Co Ltd
Original Assignee
Miracll Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Miracll Chemicals Co Ltd filed Critical Miracll Chemicals Co Ltd
Publication of WO2019014959A1 publication Critical patent/WO2019014959A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08J9/14—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 organic
    • C08J9/141—Hydrocarbons
    • 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

Definitions

  • the invention relates to a method for preparing a foamed thermoplastic polyurethane elastomer, in particular to a method for preparing low-density foamed thermoplastic polyurethane elastomer particles, and belongs to the technical field of foam materials.
  • a plastic foam is used to fill a large amount of air bubbles inside the plastic by physical or chemical means to obtain a polymer foamed material.
  • Foam materials have the advantages of low density, thermal insulation, high specific strength, and cushioning. Therefore, they are widely used in the packaging industry, industry, agriculture, transportation, military industry, aerospace industry and daily necessities. Commonly used foam types are polyurethane (PU) soft and rigid foam, polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam and the like.
  • PS polystyrene
  • PE polyethylene
  • PP polypropylene
  • Styrofoam products are difficult to degrade and are prone to "white pollution” problems.
  • the UN Environment Organization has decided to stop using PS foam products.
  • Polyethylene foam is inexpensive, but it also has the problem of difficult degradation, and it is poor in wear resistance and elasticity. It is mainly used in low-end fields such as packaging materials.
  • Thermoplastic polyurethane elastomer has a wide range of hardness, excellent wear resistance, mechanical strength, water resistance, oil resistance, chemical resistance, mold resistance, environmental friendliness, and recycling.
  • the molded foamed article can be obtained by filling the foamed thermoplastic polyurethane particles into a mold and performing heat molding using steam.
  • the product has excellent resilience, shape diversity, and reduced density, and can be used over a wide temperature range.
  • TPU foaming materials have a very wide application prospect in many industrial fields (automotive industry, packaging materials) and daily life (shoe materials, pillows, mattresses). According to related materials It is reported that the bulk density of the foamed thermoplastic polyurethane elastomer material currently on the market is 120-300, and there is a problem of high density, which severely limits its application in the field of lightweight foaming materials.
  • the present invention provides a method for preparing low density foamed thermoplastic polyurethane elastomer particles in view of the deficiencies of the existing foamed thermoplastic polyurethane elastomer materials.
  • a method for preparing a low-density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • Primary foaming physical foaming of thermoplastic polyurethane elastomer particles having a Shore hardness of 70A-85D to obtain primary foamed thermoplastic polyurethane elastomer particles;
  • step 2) Re-foaming: the primary foamed thermoplastic polyurethane elastomer particles obtained in the step 1) are placed in a pressure-resistant container, pressurized to P1 by a gas, and kept under pressure; and then the primary foamed thermoplastic polyurethane elastomer is used using a gaseous heat medium. The pellets were heated to re-foam; the operation of step 2) was carried out N times, N ⁇ 1, to obtain low-density foamed thermoplastic polyurethane elastomer particles.
  • the low density foamed thermoplastic new polyurethane elastomer particles have a bulk density of less than 120 g/L, preferably less than 100 g/L, particularly preferably less than 60 g/L.
  • thermoplastic polyurethane elastomer particles in step 1) have a Shore hardness of from 70 A to 85 D, preferably from 85 A to 80 D, most preferably from 90 A to 75 D, which is obtained according to ASTM D2240.
  • P1 in the step 2) is 0.1 to 1.0 MPa, preferably 0.2 to 0.8 MPa, and most preferably 0.3 to 0.8 MPa.
  • the pressurized gas used in the step 2) is any one or a mixture of air, nitrogen, carbon dioxide, oxygen, and argon.
  • gaseous heat medium described in the step 2) is any one of air and water vapor, preferably water vapor.
  • the temperature of the gaseous heat medium used in the step 2) is 50 to 150 °C.
  • the heating time in the step 2) is from 5 to 60 s, preferably from 5 to 30 s, and most preferably from 8 to 20 s.
  • the time for holding the pressure in the step 2) is not less than 1 h, preferably 6-20 h, and most preferably 8-16 h.
  • thermoplastic polyurethane elastomer particles in the step 1) have a rheological softening point of from 100 to 210 ° C, preferably from 110 to 180 ° C, most preferably from 110 to 160 ° C, which is obtained by a constant pressure capillary rheometer test.
  • thermoplastic polyurethane elastomer particles 100 parts by weight of thermoplastic polyurethane elastomer particles, 10-60 parts by weight of physical gas blowing agent, 100-500 parts by weight of water are added to the autoclave, the pressure in the autoclave is maintained at 1-20 MPa, and the temperature is raised to thermoplastic polyurethane elasticity.
  • the rheological softening point of the body particles, the holding pressure is 1-300 min, and the material in the autoclave is discharged into the receiving tank to obtain a primary physical foaming thermoplastic polyurethane elastomer material, and the holding time is preferably maintained in the above step 1) 10-200min, particularly preferably 30-100min;
  • thermoplastic polyurethane elastomer particles 100 parts by weight of thermoplastic polyurethane elastomer particles, 10-60 parts by weight of physical gas foaming agent are put into the extruder, the control head pressure is 0.2-30MPa, the head temperature is 100-200 ° C, and the melt is orally After the foaming of the mold, underwater pelletizing, a primary physical foaming thermoplastic polyurethane elastomer material is obtained.
  • the physical gas blowing agent is preferably added in an amount of 10 to 50 parts by weight, particularly preferably 20 to 40 parts by weight;
  • the physical gas blowing agent is a mixture of one or more of carbon dioxide, nitrogen, propane, n-butane, isobutane, n-pentane, isopentane.
  • thermoplastic polyurethane particles used in the present invention have a high hard segment content, exhibit good plasticity and rapid setting ability, and impart the ability of the primary foamed particles to be further expanded and expanded.
  • thermoplastic polyurethane elastomer particles have a high density and a serious shrinkage.
  • the density of the foamed thermoplastic polyurethane elastomer particles prepared by the method of the invention is less than 120 g/L, It should be emphasized that the technical solution still has more excellent physical properties, including resilience, tensile strength, compressive modulus and the like, after reducing the density of the foamed thermoplastic polyurethane elastomer particles.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer particles obtained above were filled in a mold having a length of 300 mm ⁇ a width of 250 mm ⁇ a thickness of 50 mm. The water was compressed by 10% in the thickness direction of the mold to bond the particles, and finally a foamed thermoplastic polyurethane molded foamed article was obtained, and the properties thereof were evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm ⁇ a width of 250 mm and a thickness of 50 mm. The water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm. Using water vapor to compress 10% in the thickness direction of the mold to bond the particles Molding, finally obtaining a foamed thermoplastic polyurethane molded foam article. The performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer particles obtained in the step 2) were subjected to secondary foaming according to the process conditions and operation of the step 2) to obtain a secondary foamed thermoplastic polyurethane elastomer material having a density of 75 g/L.
  • the secondary foamed thermoplastic polyurethane elastomer particles obtained above were subjected to tertiary foaming according to the process conditions and operation of the step 2) to obtain final foamed thermoplastic polyurethane elastomer particles having a density of 30 g/L.
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • a method for preparing a low density foamed thermoplastic polyurethane elastomer comprising the steps of:
  • the foamed thermoplastic polyurethane elastomer material obtained above was filled in a mold having a length of 300 mm, a width of 250 mm, and a thickness of 50 mm.
  • the water is compressed by 10% in the thickness direction of the mold to bond the particles to form a foamed thermoplastic polyurethane molded foam product.
  • the performance was evaluated as shown in Table 1.
  • the bulk density test standard is ISO3944
  • the rebound test standard is ISO8307
  • the tensile strength test standard is ISO1798
  • the compression modulus test standard is ISO844.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne un élastomère de polyuréthane thermoplastique à moussage de faible densité et son procédé de préparation. Le procédé de préparation comprend le moussage physique primaire et le moussage de qualité N (N≥1) sous l'effet de chauffage d'un milieu chauffant. La densité de particules de l'élastomère de polyuréthane thermoplastique moussant, préparé par le procédé de la présente invention, est inférieure à 120 g/L, et un article de celui-ci présente de meilleures propriétés physiques, y compris une résilience de rebondissement, une résistance à la traction, un module de compression, etc.
PCT/CN2017/094636 2017-07-17 2017-07-27 Élastomère de polyuréthane thermoplastique à moussage de faible densité et son procédé de préparation Ceased WO2019014959A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710580224.8A CN107325317A (zh) 2017-07-17 2017-07-17 一种低密度发泡热塑性聚氨酯弹性体及其制备方法
CN201710580224.8 2017-07-17

Publications (1)

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WO2019014959A1 true WO2019014959A1 (fr) 2019-01-24

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WO (1) WO2019014959A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109293973A (zh) * 2018-08-22 2019-02-01 宁波格林美孚新材料科技有限公司 一种高分子微发泡材料及其成型工艺
CN110922555B (zh) * 2018-09-20 2022-05-03 大东树脂化学股份有限公司 热塑性聚氨酯及其弹性体粒子和它们的制备方法
CN109836604B (zh) * 2019-03-07 2021-04-02 无锡道石新材料有限公司 一种低密度发泡tpu的快速制备方法
CN111718514A (zh) * 2020-05-14 2020-09-29 福建兴迅新材料科技有限公司 一种超轻热塑性弹性体发泡材料的制备工艺
CN116376095B (zh) * 2022-12-31 2025-01-21 万卓（江苏）新材料有限公司 一种聚苯乙烯发泡材料的发泡方法

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CN104974370A (zh) * 2015-01-19 2015-10-14 常州市顺祥新材料科技有限公司 一种热塑性聚氨酯珠粒的制备方法及该珠粒成型工艺
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CN103709726B (zh) * 2013-12-17 2016-04-20 美瑞新材料股份有限公司 挤出发泡热塑性聚氨酯弹性体珠粒及其制备方法
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CN104130439A (zh) * 2014-08-11 2014-11-05 邓婷 一种热塑性聚氨酯弹性体发泡珠粒及其制备方法
CN104974370A (zh) * 2015-01-19 2015-10-14 常州市顺祥新材料科技有限公司 一种热塑性聚氨酯珠粒的制备方法及该珠粒成型工艺
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