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WO2018036013A1 - Plastique expansé souple de polyuréthanne réticulé de type polyester, et procédé de préparation associé - Google Patents

Plastique expansé souple de polyuréthanne réticulé de type polyester, et procédé de préparation associé Download PDF

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Publication number
WO2018036013A1
WO2018036013A1 PCT/CN2016/107697 CN2016107697W WO2018036013A1 WO 2018036013 A1 WO2018036013 A1 WO 2018036013A1 CN 2016107697 W CN2016107697 W CN 2016107697W WO 2018036013 A1 WO2018036013 A1 WO 2018036013A1
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WO
WIPO (PCT)
Prior art keywords
foam
polyester
reticulated
preparing
foaming
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/CN2016/107697
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English (en)
Chinese (zh)
Inventor
崔爱华
林永飞
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.)
Jiangsu Lvyuan New Materials Co ltd
Original Assignee
Jiangsu Lvyuan New Materials Co ltd
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Filing date
Publication date
Application filed by Jiangsu Lvyuan New Materials Co ltd filed Critical Jiangsu Lvyuan New Materials Co ltd
Publication of WO2018036013A1 publication Critical patent/WO2018036013A1/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
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • 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
    • 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
    • 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
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • 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

Definitions

  • the present invention relates to a polyester type mesh polyurethane flexible foam and a preparation method thereof.
  • Polyether sponge is formed by polymerizing and foaming polyether and isocyanate under various additives. Based on the polarity of polyether, it can form a very stable lubricant film with high adsorption and load carrying capacity under almost all lubrication conditions, with low friction coefficient and strong shear resistance. And its biggest feature is that it can be easily split.
  • the polyester sponge also has special properties such as oil resistance, water resistance, abrasion resistance, corrosion resistance, high temperature resistance and strong stretchability, and the product has uniform cells and good gloss, and is viscous with the fabric. Strong knot rate and other characteristics. Therefore, polyester sponges are widely used in more advanced vehicle interiors, air conditioner filters, train oil pillows, aircraft fuel tank fillers and the like.
  • Reticulated polyurethane foam is a high-porosity flexible polyurethane foam with special functions, which has a high porosity; its softness, gas permeability, sound absorption, mechanical strength, etc. are better than ordinary polyurethane. Good foam, good filtration and processing properties. Due to its low density and porous foam structure, the wall shell has a three-dimensional skeleton structure, and thus has been widely used in filter materials and filling materials.
  • Reticulated foam as a filter material has the advantages of large voids in the foam, low resistance to the medium, easy washing, and the foam can be repeatedly used, and is suitable for use in various air purifying equipments; as a tank filling medium, It is also widely used in tanks and reticulated foams for a wide range of flammable fluid storage tanks; reticulated foams can also be used for sound insulation materials, material carriers, etc.
  • An object of the present invention is to provide a polyester mesh flexible polyurethane foam having uniform cells and a smooth cell network and a preparation method thereof.
  • a polyester type reticulated flexible polyurethane foam characterized by: mixing foaming with at least one polyester polyol as a raw material and an isocyanate component and a catalyst, a foaming agent, and a foam stabilizer Polymerized polyurethane foam, which is obtained by reticulating and has a meshing foam with a pupil ratio of 99% or more.
  • a method for preparing a polyester mesh flexible polyurethane foam characterized in that: mixing at least one polyester polyol as a raw material with an isocyanate component and a catalyst, a foaming agent, and a foam stabilizer The foaming polymerization produces a polyurethane flexible foam and is reticulated.
  • the preparation method of the polyester mesh flexible polyurethane foam comprises the following steps: (1) pressing a polyester polyol, a catalyst, a foaming agent, a foam stabilizer and an isocyanate component through a metering pump The fixed proportion is sent to the foaming machine head, and after high-speed stirring, it is evenly distributed on the kraft paper of the continuous foaming production line; (2) It is matured in the process of conveying in the continuous foaming production line, and is solidified to obtain polyurethane flexible foam, and then online. Cut into the specified size; (3) Reticulate the cut polyurethane soft foam.
  • the polyester polyol is a phthalic anhydride polyester polyol, wherein the average functionality is 2-3, the hydroxyl value is 10-200 m gKOH/g, the preferred functionality is 2.0-2.5, and the hydroxyl value is 50-150 mgKOH/ Between g; the isocyanate component is one or more of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polyisocyanate; the mass ratio of polyester polyol to isocyanate component is 100: 40 -60.
  • the catalyst is an amine and/or metal salt catalyst; the blowing agent is a physical and/or chemical blowing agent, respectively.
  • the amine catalyst in the amine and / or metal salt catalyst is a tertiary amine catalyst, which is pentamethyldiethylenetriamine, hydrazine, hydrazine-dimethylcyclohexylamine, triethylenediamine, At least one of triethylamine and didimethylaminoethyl ether;
  • the metal salt catalyst is potassium isooctoate, quaternary ammonium formate, potassium acetate, dibutyltin dilaurate, stannous octoate and potassium oleate At least one of them.
  • the physical foaming agent is water; the chemical foaming agent is 1,1-dichloro-1-fluoroethane (HCFC-141B), 1,1, 1,3,3-five At least one of fluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365) One.
  • HCFC-141B 1,1-dichloro-1-fluoroethane
  • HFC-245fa 1,1, 1,3,3-five At least one of fluoropropane
  • HFC-365 1,1,1,3,3-pentafluorobutane
  • the reticulation treatment method is an alkali immersion method, an explosion method, a steam hydrolysis method or a hot air method.
  • the explosion method is to detonate by using a plurality of explosive gas mixtures to reach the required explosion limit, and to break the membrane wall by using instantaneous explosive energy and high-temperature flame, thereby causing the polyurethane foam cell membrane wall to melt and adhere to the foam meridian, thereby To achieve the purpose of networking.
  • the specific method is to put the cut polyurethane soft foam into the blasting box, and according to the external temperature, fill the corresponding proportion of the gas required to reach the gas explosion equilibrium point and then detonate to obtain the pupil sponge reticular foam.
  • the gas is acetylene, oxygen or nitrogen.
  • the invention utilizes the polyester sponge to have special properties such as oil resistance, water resistance, wear resistance, corrosion resistance, high temperature resistance, strong stretchability, and more importantly, the characteristics of uniform cells and good luster, and meshing thereof. Treatment, the obtained mesh foam with uniform pupil and smooth cell network.
  • the high-temperature porous ceramics fired by the reticulated foam can be used as a filter material in the metallurgical industry, and its durability and economy are unmatched advantages of other products.
  • the preparation method of the polyester mesh flexible polyurethane foam comprises the following steps: (1) a polyester polyol, a catalyst, a foaming agent, a foam stabilizer and an isocyanate component; The components listed in 2 were transported to the foaming machine head by the metering pump according to the weight ratio in Table 2, and after high-speed stirring, uniformly distributed on the kraft paper of the continuous foaming production line to produce a semi-finished foam material of 2.4 m length. These foams are prepared using a line mixing foaming step known to those of ordinary skill in the art to determine foam properties after the foam has been cured.
  • polyester polyols are used as a main raw material. If you want to adjust the foaming speed, you can adjust the amount of catalyst; if you want to adjust the foam density, you can adjust the amount of water and physical foaming agent.
  • the cooked polyurethane soft sponge foam is cut into a blasting box, and according to the external temperature, the corresponding proportion of the required gas, such as acetylene, oxygen, nitrogen, etc., is reached, and the gas explosion equilibrium point is detonated, and the pupil is obtained. Sponge reticulated foam.
  • the foam properties after blasting are shown in Table 4 below.
  • the reticulated foam can be adjusted according to the raw materials to obtain foams of different properties.
  • the physical properties of the foam before and after the net treatment are shown in Table 4. Compared with the foam before the net treatment, the tensile strength and elongation of the reticulated foam increased, while the hardness and density of the indentation decreased slightly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un plastique expansé souple de polyuréthanne réticulé de type polyester, et un procédé de préparation associé. Un plastique expansé souple de polyuréthanne est produit par utilisation d'au moins un polyester polyol en tant que matière première, mélange, expansion et polymérisation de ce dernier à l'aide d'un constituant isocyanate sous l'action d'un catalyseur, d'un agent d'expansion et d'un agent stabilisant de mousse, ce dernier étant soumis à un traitement de réticulation de façon à préparer une mousse réticulée présentant une porosité ouverte de 99 % ou plus. Dans la présente invention, on utilise les propriétés spéciales, telles que la résistance à l'huile, la résistance à l'eau, la résistance à l'abrasion, la résistance à la corrosion, la résistance aux hautes températures, et une forte étirabilité, et, ce qui est plus important, les caractéristiques telles que des alvéoles uniformes et un bon brillant, d'une éponge de polyester; et, grâce à la mise en œuvre d'un traitement de réticulation sur la mousse de polyester, on obtient une mousse réticulée ayant une porosité uniforme et un réseau d'alvéoles lisses. Une céramique réticulée poreuse résistante aux hautes températures, cuite à partir de la mousse réticulée, peut être utilisée en tant que matériau filtrant dans l'industrie métallurgique. Par comparaison avec d'autres produits, sa durabilité et son efficacité économique présentent en outre un avantage incomparable.
PCT/CN2016/107697 2016-08-23 2016-11-29 Plastique expansé souple de polyuréthanne réticulé de type polyester, et procédé de préparation associé Ceased WO2018036013A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610707747.XA CN106243322A (zh) 2016-08-23 2016-08-23 聚酯型网状聚氨酯软质泡沫塑料及其制备方法
CN201610707747.X 2016-08-23

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WO2018036013A1 true WO2018036013A1 (fr) 2018-03-01

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WO (1) WO2018036013A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111875766A (zh) * 2020-08-19 2020-11-03 东莞市永迪泡绵有限公司 聚氨酯打磨盘聚酯海绵及其制作工艺

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CN109679325A (zh) * 2017-10-18 2019-04-26 江西鸿司远特种泡沫材料有限公司 多孔陶瓷用有机泡沫体及其制备方法
CN109384901A (zh) * 2018-11-08 2019-02-26 湖北世丰汽车内饰有限公司 一种用于陶瓷过滤片的聚酯型粗孔过滤海绵及其制备方法
CN111205629A (zh) * 2020-03-10 2020-05-29 重庆永迪高分子材料有限公司 一种聚氨酯软质聚酯海绵及其制备方法
CN111925503A (zh) * 2020-08-19 2020-11-13 东莞市永迪泡绵有限公司 聚氨酯口罩绵聚酯软质海绵及其制作工艺
CN114133614A (zh) * 2021-12-27 2022-03-04 温州创源环境科技有限公司 一种网化聚氨酯泡沫塑料的制备方法
CN115403826A (zh) * 2022-09-30 2022-11-29 佛山市顺德区品睡海绵有限公司 一种硅胶海绵及其制备方法
CN118546427A (zh) * 2024-06-06 2024-08-27 深圳市国志汇富高分子材料股份有限公司 一种油箱罐用聚醚型大孔径网状聚氨酯抑爆材料及其制作工艺方法

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CN1313347A (zh) * 2001-03-21 2001-09-19 杨卫 聚氨酯网状泡沫塑料及其制备方法
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