WO2021129486A1 - 硬质聚氨酯泡沫及其制造方法 - Google Patents

硬质聚氨酯泡沫及其制造方法 Download PDF

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Publication number
WO2021129486A1
WO2021129486A1 PCT/CN2020/136828 CN2020136828W WO2021129486A1 WO 2021129486 A1 WO2021129486 A1 WO 2021129486A1 CN 2020136828 W CN2020136828 W CN 2020136828W WO 2021129486 A1 WO2021129486 A1 WO 2021129486A1
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polyurethane foam
rigid polyurethane
foam
inorganic particles
hollow inorganic
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French (fr)
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上田勉
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Qingdao Haier Refrigerator Co Ltd
Haier Smart Home Co Ltd
Aqua Co Ltd
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Qingdao Haier Refrigerator Co Ltd
Haier Smart Home Co Ltd
Aqua Co Ltd
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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
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to rigid polyurethane foams with reduced thermal conductivity.
  • Rigid polyurethane foam is generally used as heat insulation material for refrigerators and freezers.
  • the thermal conductivity of cyclopentane is higher than that of CFC-11, and the rigid polyurethane foam has poor thermal insulation performance when used as a blowing agent.
  • the boiling point of cyclopentane blowing agent is as high as 49.2°C. In low temperature areas such as refrigerators, the gas in the polyurethane foam cells is in a liquefied state, and the physical properties of the foam are also poor.
  • Patent Document 1 provides a rigid polyurethane foam, by dispersing a styrene-based or vinylidene chloride-based vacuum small-diameter body in the polyurethane foam, and the dispersion surface is covered with a vinylidene chloride resin, thereby achieving excellent insulation. Thermal.
  • Patent Document 1 JP Patent Laid-Open No. 8-3360.
  • hollow particles are organic particles whose shells are formed of organic substances, the fluidity and moldability of the mixture before foaming may be reduced.
  • the hollow organic particles have low strength and heat resistance, and are easily damaged and deformed.
  • the addition amount of the hollow organic particles must be limited to a low level, so that the thermal conductivity of the rigid polyurethane foam cannot be sufficiently reduced.
  • the content of hollow organic particles increases to a level where the thermal conductivity increases, the foam physical properties of the rigid polyurethane foam deteriorate.
  • the present invention is used to solve the above-mentioned common problems, and aims to provide a rigid polyurethane foam with reduced thermal conductivity and excellent foam physical properties.
  • foam physical properties include foaming density, dimensional stability and compressive strength under high temperature and low temperature environments.
  • the rigid polyurethane foam provided by the present invention includes a polyurethane resin matrix and a large number of closed cells, and has a density of 30.0-33.0kg/m 3.
  • the polyurethane resin matrix is a reaction product of polyisocyanate and polyol, and the closed cells are made of The foaming agent and 3-30% by weight of hollow inorganic particles are dispersed in the aforementioned polyurethane resin matrix.
  • the content of the hollow inorganic particles relative to the polyurethane resin is 5-15% by weight.
  • the hollow inorganic particles have a particle size of 1200-9300 nm.
  • the hollow inorganic particles are at least one selected from aluminum silicate particles and silica ceramic particles.
  • the blowing agent is cyclopentane.
  • the present invention also provides a method for manufacturing rigid polyurethane foam with a density of 30.0-33.0 kg/m 3, which includes the following steps:
  • hollow inorganic particles and foaming agent are added to obtain a second polyol mixture.
  • the added amount of the hollow inorganic particles is relative to the polyurethane resin 3-30% by weight;
  • the polyisocyanate is added to the second polyol mixture to react.
  • the hollow inorganic particles when added to the first polyol mixture, they are in a state of a dispersion uniformly dispersed in the foaming agent.
  • a rigid polyurethane foam with reduced thermal conductivity and excellent foam physical properties is provided.
  • the rigid polyurethane foam of the present invention can be widely used as a heat insulating material such as refrigerators and freezers.
  • Polyisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, and Its modified products, such as urethane modified products or urea modified products that react with polyols or polyamines, carbodiimide modified products or uretonimine modified products that react in the presence of a catalyst or under heating Products, etc., or mixtures thereof.
  • modified products such as urethane modified products or urea modified products that react with polyols or polyamines, carbodiimide modified products or uretonimine modified products that react in the presence of a catalyst or under heating Products, etc., or mixtures thereof.
  • Polyols include sucrose, sorbitol, pentaerythritol, glycerol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and other polyols, ammonia, ethylenediamine, diethylenetriamine, triethylene Diamine, trimethyldiethylene triamine, polyether polyamine, toluene diamine, diphenylmethane diamine, xylene diamine and other polyamines, to diethanolamine, triethanolamine and other alkanolamines or In the mixture, with or without water, a polyether polyol obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides is added.
  • hollow inorganic particles examples include particles in which the material constituting the outer shell is aluminum silicate, silica ceramics, silica, and the like. Among them, from the viewpoint of maintaining good fluidity, aluminum silicate hollow particles and silica ceramic hollow particles are preferred. Hollow inorganic particles have excellent strength and can withstand the shearing force and stress generated in the process of manufacturing composite materials. In addition, in terms of physical properties, its high stability can improve the physical properties of composite materials.
  • the average particle diameter of the hollow inorganic particles is generally 1200 to 9300 nm, and from the viewpoint of reducing the thermal conductivity of the resulting rigid polyurethane foam, it is preferably 1600 to 7600 nm, and more preferably 3000 to 5000 nm.
  • the average particle diameter of the hollow inorganic particles is less than 1200 nm, the fluidity and moldability of the mixture before foaming decrease, and when the average particle diameter is greater than 9300 nm, the particles are likely to aggregate.
  • a laser diffraction type particle size distribution measuring device can be used to measure the average particle size of the hollow inorganic particles by the laser diffraction/scattering method (micro-diameter method).
  • a specific example of a laser diffraction particle size distribution measuring device can include the "MT3000II" (trade name) series manufactured by Microtrack Bell.
  • the void ratio of the hollow inorganic particles is greater than or equal to 25%. When the void ratio of the hollow inorganic particles is less than 25%, the thermal conductivity of the resulting rigid polyurethane foam is not sufficiently reduced.
  • the void ratio of the hollow inorganic particles is preferably 30 to 70%, more preferably 40 to 60%.
  • the content of the hollow inorganic particles is 3 to 30% by weight relative to the polyurethane resin.
  • the content of hollow inorganic particles relative to the polyurethane resin is less than 3% by weight, the thermal conductivity of the resulting rigid polyurethane foam is not sufficiently reduced.
  • the content exceeds 30% by weight the fluidity and moldability of the mixture before foaming decrease, and the foam Physical properties deteriorate.
  • the above-mentioned content of the hollow inorganic particles is preferably 5 to 20% by weight, more preferably 10 to 15%.
  • the hollow inorganic particles are preferably used in the state of a dispersion dispersed in a foaming agent.
  • a dispersion of hollow inorganic particles By using a dispersion of hollow inorganic particles, the aggregation of particles during foaming can be suppressed, so that the fluidity and moldability of the mixture before foaming are not easily reduced.
  • blowing agent cyclopentane, water, etc.
  • the amount is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, relative to the polyol.
  • auxiliary agents such as catalysts, foam stabilizers, flame retardants, plasticizers, fillers, stabilizers, and colorants are used as needed.
  • the catalysts include pentamethyldiethylenetriamine, N,N'-dimethylaminoethyl ether, dimethylcyclohexylamine, tetramethylhexamethylenediamine, tetramethylethylenediamine and other tertiary Organic metal compounds such as amine, tin acetate, tin octoate, tin laurate dichloride, dibutyl tin dilaurate, dibutyl tin diacetate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.
  • the amount of the catalyst used is 0.0001 to 10% by weight relative to the polyol.
  • Foam stabilizers are surfactants of organosilicon compounds, such as L-501, L-520, L-532, L-540, L-544, L-3550, L-5302, L-5305, L-501, L-520, L-532, L-540, L-544, L-3550, L-5302, L-5305, L-5320, L-5340, L-5410, L-5420, L-5710, L-5720, etc., SH-190, SH-192, SH-193, SH-194, SH-195, etc. produced by Torre Silicone SH-200, SRX-253, etc., F-114, F-121, F-122, F-220, F-230, F-258, F-260B, F-305, F-306, etc. produced by Shinetsu Silicone F-317, F-341, etc., TFA-4200, TFA-4202, etc. produced by Toshiba Silicone Corporation. Regarding the amount of foam stabilizer, it is 0.1 to 10% by weight relative to the polyol.
  • the rigid polyurethane foam of the present invention is manufactured by the following method: uniformly mixing polyols, catalysts, foam stabilizers and other auxiliary agents to obtain a first polyol mixture; adding hair to the first polyol mixture
  • the foaming agent and the hollow inorganic particles are uniformly mixed to obtain the second polyol mixture; when preparing the second polyol mixture, it is preferable to add the hollow inorganic particles and the foaming agent to the first polyol mixture at the same time, more preferably ,
  • the hollow inorganic particles are uniformly mixed with the foaming agent in advance to make them into a state of dispersion, and then the obtained dispersion is added to the first polyol mixture.
  • the polyisocyanate is continuously mixed into the second polyol mixture in an equivalent ratio of 0.5 to 5.0. Then, the obtained foam stock solution is injected into the void or mold, and the foam stock solution is foamed and cured, thereby manufacturing a rigid polyurethane foam.
  • the unit of the addition amount is based on the weight basis of "parts”.
  • the polyol mixture (a mixture of polyol, catalyst, foam stabilizer, and water) is 100 parts, add a predetermined amount of aluminum silicate hollow particles to 14 parts of cyclopentane as the blowing agent, and stir at 2000 rpm for 2 Minutes, a dispersion of hollow particles is obtained.
  • the first polyol mixture, the hollow particle dispersion, and 124 parts of diphenylmethane diisocyanate were continuously mixed, and rapidly stirred at a speed of 4000 rpm for 4 seconds to obtain a foam stock solution.
  • the foam stock solution was poured into a 600mm ⁇ 400mm ⁇ 50mm vertical aluminum box coated with a paraffin-based release agent and heated to 40°C to make it foam freely. After the foam overflowed from the aluminum box was removed, the foam weight was measured. Increase the weight of the foam stock solution by 20%, and pour it into an aluminum box with a cover of the same size for sealing and foaming to obtain a rigid polyurethane foam.
  • the foam sample was cut into 75 ⁇ 75 ⁇ 25 mm, and the surface layer was cut to expose the core (Core) part. Measure the dimensions in each direction, and then calculate the dimensional stability under the following conditions according to the following formula.
  • the foam sample into 50 ⁇ 50 ⁇ 25mm, and then cut off the surface layer to expose the core.
  • a tensile tester to measure the compressive strength.
  • the test conditions are tensile 5mm/min, deformation 10%, and the compressive strength value at this time is calculated by the following formula.
  • the compression direction is referred to as the thickness direction.
  • the polyol mixture (a mixture of polyol, catalyst, foam stabilizer, and water) is 100 parts, continuously add the polyol mixture, 14 parts of cyclopentane as a blowing agent, 14 parts, and 124 parts of diphenylmethane diisocyanate , Stir quickly at 4000 rpm for 4 seconds to obtain foam stock solution.
  • Polyol produced by Sumika Cobestro Urethane Company.
  • Hollow particles “E-SPHERES” produced by Pacific Cement; average particle size: 1.6 ⁇ m, 3.8 ⁇ m (measured with the laser diffraction particle size distribution measuring device "MT3000II” (trade name) produced by Microtrac Bell); void ratio : 40%.

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  • 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)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

提供一种热导率降低、泡沫物理性能也优异的硬质聚氨酯泡沫。该硬质聚氨酯泡沫的密度为30.0～33.0kg/m 3，其包括聚氨酯树脂基体及大量闭孔，所述聚氨酯树脂基体是多异氰酸酯与多元醇的反应产物，所述闭孔由发泡剂及3～30％重量的中空颗粒分散在该聚氨酯树脂基体中而形成。

Description

硬质聚氨酯泡沫及其制造方法 技术领域
本发明涉及热导率降低的硬质聚氨酯泡沫。硬质聚氨酯泡沫一般被用作冰箱、冰柜的隔热材料。
背景技术
近年来，限制臭氧层破坏物质使用的法规越来越严格，已经禁止使用CFC-11作为硬质聚氨酯泡沫的发泡剂。当前的替代发泡剂是使用环戊烷作为非氟烃发泡剂。
但是，环戊烷的热导率比CFC-11高，用作发泡剂时硬质聚氨酯泡沫的隔热性能差。此外，环戊烷发泡剂的沸点高达49.2℃，在诸如冰箱中的低温区域，聚氨酯泡沫孔内的气体处于液化状态，并且泡沫的物理性能也较差。
在专利文献1中提供了一种硬质聚氨酯泡沫，通过将苯乙烯系或偏二氯乙烯系真空小径体分散在聚氨酯泡沫中，且分散表面被偏二氯乙烯树脂覆盖，从而实现优异的隔热性。
现有技术文献
专利文献
专利文献1：JP特开平8-3360号公报。
发明内容
发明要解决的问题
本领域技术人员已经尝试了将中空颗粒结合到硬质聚氨酯泡沫，来改善聚氨酯泡沫的隔热性。但是，当中空颗粒是外壳由有机物质形成的有机颗粒时，会出现发泡前混合物的流动性及成型性降低的问题。此外，还存在中空有机颗粒的强度和耐热性低，从而容易破损、变形的问题。
即，如果希望维持硬质聚氨酯泡沫的泡沫物理性能，则必须将中空有机颗粒的添加量限制在低水平，这样就无法充分降低硬质聚氨酯泡沫的热导率。相反，当中空有机颗粒的含量增加到热导率提高的水平时，硬质聚氨酯泡沫的泡沫物理性能变差。
本发明用于解决上述常见问题，目的是提供一种热导率降低、泡沫物理性能优异的硬质聚氨酯泡沫。泡沫物理性能的具体示例可列举发泡密度、高温环境及低温环境下的尺寸稳定性及抗压强度等。
用于解决问题的方案
本发明提供的硬质聚氨酯泡沫，包括聚氨酯树脂基体及大量闭孔，且密度为30.0～33.0kg/m 3，所述聚氨酯树脂基体是多异氰酸酯与多元醇的反应产物，所述闭孔是由发泡剂和3～30％重量的中空无机颗粒分散在上述聚氨酯树脂基体中而形成。
在一个实施方式中，所述中空无机颗粒相对于聚氨酯树脂的含量为5～15％重量。
在一个实施方式中，所述中空无机颗粒的粒径为1200～9300nm。
在一个实施方式中，所述中空无机颗粒是选自硅酸铝颗粒及二氧化硅陶瓷颗粒中的至少一种。
在一个实施方式中，所述发泡剂是环戊烷。
此外，本发明还提供密度为30.0～33.0kg/m 3的硬质聚氨酯泡沫的制造方法，包括如下工序：
向包含多元醇、催化剂及泡沫稳定剂的第一多元醇混合物中，添加中空无机颗粒及发泡剂，从而获得第二多元醇混合物，上述中空无机颗粒对添加量是相对于聚氨酯树脂为3～30％重量；及
向第二多元醇混合物中添加多异氰酸酯进行反应。
在一个实施方式中，向第一多元醇混合物中添加所述中空无机颗粒时，其处于均匀分散在发泡剂中的分散体的状态。
【发明效果】
根据本发明，提供热导率降低、泡沫物理性能也优异的硬质聚氨酯泡沫。本发明的硬质聚氨酯泡沫可广泛用作诸如冰箱及冰柜的隔热材料。
多异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、聚亚甲基多苯基多异氰酸酯、亚二甲苯基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、萘二异氰酸酯、及其改性产物、例如与多元醇或多元胺反应的氨基甲酸酯改性产物或脲改性产物、在催化剂存在下或加热下反应的碳二亚胺改性产物或脲酮亚胺改性产物等、或其混合物。
多元醇包括蔗糖、山梨糖醇、季戊四醇、甘油、三羟甲基丙烷、乙二醇、丙二醇、二甘醇、二丙二醇等多元醇、氨、乙二胺、二亚乙基三胺、三亚乙基二胺、三甲基二亚乙基三胺、聚醚多胺、甲苯二胺、二苯基甲烷二胺、二甲苯二胺等多元胺、向二乙醇胺、三乙醇胺等烷醇胺或其混合物中，加水或不加水，加成聚合环氧乙烷、环氧丙烷、环氧丁烷等环氧烷而获得的聚醚多元醇。
作为中空无机颗粒，例如可列举构成外壳的材料是硅酸铝、二氧化硅陶瓷、二氧化硅等的颗粒。其中，从维持良好的流动性的观点出发，优选硅酸铝中空颗粒及二氧化硅陶瓷中空颗粒。中空无机颗粒具有优异的强度，可以承受在制造复合材料的过程中产生的剪切力和应力。此外，就物理性能方面而言，其稳定性高，可以改善复合材料料的物理性能。
中空无机颗粒的平均粒径一般是1200～9300nm，从降低所得的硬质聚氨酯泡沫的热导率的观点出发，优选为1600～7600nm，更优选为3000～5000nm。当中空无机颗粒的平均粒径小于1200nm时，发泡前混合物的流动性及成型性降低，若平均粒径大于9300nm，则颗粒容易发生聚集。
例如，可以使用激光衍射式粒径分布测量装置，以激光衍射/散射法(微径法)，测量中空无机颗粒的平均粒径。激光衍射式粒径分布测量装置的具体示例可列举Microtrack Bell公司制造的“MT3000II”(商品名)系列。
中空无机颗粒的空隙率大于等于25％。当中空无机颗粒的空隙率小于25％时，所得硬质聚氨酯泡沫的热导率并未充分降低。中空无机颗粒的空隙率优选为30～70％，更优选为40～60％。
中空无机颗粒的含量相对于聚氨酯树脂为3～30％重量。当中空无机颗粒相对于聚氨酯树脂 的含量小于3％重量时，所得硬质聚氨酯泡沫的热导率未充分降低，当含量超过30％重量时，发泡前混合物的流动性及成型性降低，泡沫物理性能变差。中空无机颗粒的上述含量优选为5～20％重量，更优选为10～15％。
中空无机颗粒优选以分散在发泡剂中的分散体的状态使用。通过使用中空无机颗粒的分散液，可抑制发泡时颗粒之间的聚集，使得发泡前混合物的流动性及成型性不易降低。
作为发泡剂可使用环戊烷、水等。其用量相对于多元醇为0.1～10％重量，优选为0.5～5％重量。
作为其它成分，根据需要使用催化剂、泡沫稳定剂、阻燃剂、增塑剂、填充剂、稳定剂、着色剂等助剂。
催化剂有五甲基二亚乙基三胺、N，N′-二甲基氨基乙基醚、二甲基环己胺、四甲基六亚甲基二胺、四甲基乙二胺等叔胺、乙酸锡、辛酸锡、月桂酸二氯化锡、二月桂酸二丁基锡、二乙酸二丁锡、辛酸铅、环烷酸铅、环烷酸镍、环烷酸钴等有机金属化合物等。关于催化剂的用量，相对于多元醇为0.0001～10％重量。
泡沫稳定剂是有机硅化合物的表面活性剂，例如日本Unicar公司生产的L-501、L-520、L-532、L-540、L-544、L-3550、L-5302、L-5305、L-5320、L-5340、L-5410、L-5420、L-5710、L-5720等，Torre Silicone公司生产的SH-190、SH-192、SH-193、SH-194、SH-195、SH-200、SRX-253等，Shinetsu Silicone公司生产的F-114、F-121、F-122、F-220、F-230、F-258、F-260B、F-305、F-306、F-317、F-341等，东芝有机硅公司生产的TFA-4200、TFA-4202等。关于泡沫稳定剂的用量，相对于多元醇为0.1～10％重量。
例如，本发明的硬质聚氨酯泡沫是通过如下方法制造的：将多元醇、催化剂、泡沫稳定剂及其它助剂均匀混合，得到第一多元醇混合物；向第一多元醇混合物中添加发泡剂及中空无机颗粒并均匀混合，得到第二多元醇混合物；制备第二多元醇混合物时，优选将中空无机颗粒与发泡剂同时添加到第一多元醇混合物中，更优选为，将中空无机颗粒预先与发泡剂均匀混合使其变成分散体的状态，然后将得到的分散体添加到第一多元醇混合物中。
以当量比0.5～5.0的方式，向第二多元醇混合物中连续混合多异氰酸酯。然后，将得到的泡沫原液注入空隙或模具，泡沫原液发泡并固化，从而制造硬质聚氨酯泡沫。
具体实施方式
以下将通过实施例更具体地说明本发明，但本发明并不限定于此。实施例中，除非另有说明，否则添加量的单位使用的是“份”这一重量基准。
【实施例】
＜实施例1～3、比较例＞
多元醇混合物(多元醇、催化剂、泡沫稳定剂及水的混合物)为100份时，向14份作为发泡剂的环戊烷中添加既定量的硅酸铝中空颗粒，以2000rpm的速度搅拌2分钟，得到中空颗粒分散体。将第一多元醇混合物、中空颗粒分散体、及124份二苯基甲烷二异氰酸酯连续混合，以4000rpm 的速度快速搅拌4秒钟，得到泡沫原液。
将该泡沫原液注入到涂有石蜡基脱模剂并加热到40℃的600mm×400mm×50mm的垂直铝箱中，使其自由发泡，将从铝箱溢出的泡沫除去后，测量泡沫重量。将泡沫原液的重量增加20％，注入同样大小的带盖铝箱进行密封发泡，得到硬质聚氨酯泡沫。
按照以下所示的物理性能测量方法，测量该泡沫的芯部的发泡密度、热导率、低温尺寸稳定性、高温尺寸稳定性、及抗压强度，并目视评价气泡破裂。结果示于表1。
＜物理性能测量方法＞发泡密度
将泡沫样品切成70×70×t mm，然后切去表层使其露出芯(Core：芯)部。使用化学天平和卡尺测量芯样品的重量和体积，并按照下式计算密度。
密度(kg/m 3)＝样品重量/样品体积。
热导率
将泡沫样品切成200×200×25mm，然后切去表层露出芯部。将芯样品温度调节至24℃，使用Hidehiro Seiki公司生产的热导仪“FOX200”(商品名)，测量热导率(mW/m·k)。
尺寸稳定性
将泡沫样品切成75×75×25mm，切去表层露出芯(Core：芯)部。测量各个方向的尺寸，然后按照下式计算下述条件下的尺寸稳定性。
耐热性：70℃×48小时；
耐寒性：-30℃×48小时；
尺寸稳定性(％)＝{(试验前尺寸－试验后尺寸)/试验前尺寸}×100。
抗压强度
将泡沫样品切成50×50×25mm，然后切去表层露出芯部。使用拉伸测试仪来测量抗压强度。试验条件是拉伸5mm/分钟，变形10％，按下式计算此时的抗压强度值。另外，压缩方向设为厚度方向。
10％变形时的抗压强度(kgf/cm 2)＝10％变形时负载/样品压缩前的受压面积。
＜比较例2＞
多元醇混合物(多元醇、催化剂、泡沫稳定剂及水的混合物)为100份时，连续添加多元醇混合物、14份作为发泡剂的环戊烷14部、及124份二苯基甲烷二异氰酸酯，以4000rpm的速度快速搅拌4秒钟，得到泡沫原液。
除了使用此次得到的泡沫原液外，按照与上述实施例相同的方式制作硬质聚氨酯泡沫，并进行评价。结果示于表1。
[表1]
Figure PCTCN2020136828-appb-000001
Figure PCTCN2020136828-appb-000002
另外，实施例及比较例中使用的多元醇、中空颗粒的种类如下。
多元醇：Sumika Cobestro Urethane公司生产。
中空颗粒：Pacific Cement公司生产的“E-SPHERES”；平均粒径：1.6μm、3.8μm(用Microtrac Bell公司生产的激光衍射式粒径分布测量器“MT3000II”(商品名)测量)；空隙率：40％。

Claims (7)

  1. 一种硬质聚氨酯泡沫，其特征在于，密度为30.0～33.0kg/m 3，包括聚氨酯树脂基体及大量闭孔，所述聚氨酯树脂基体是多异氰酸酯与多元醇的反应产物，所述闭孔由发泡剂及3～30％重量的中空无机颗粒分散在该聚氨酯树脂基体中而形成。
  2. 根据权利要求1所述的硬质聚氨酯泡沫，其特征在于，所述中空无机颗粒相对于聚氨酯树脂的含量为5～15％重量。
  3. 根据权利要求1所述的硬质聚氨酯泡沫，其特征在于，所述中空无机颗粒的粒径为1200～9300nm。
  4. 根据权利要求1所述的硬质聚氨酯泡沫，其特征在于，所述中空无机颗粒是选自硅酸铝颗粒及二氧化硅陶瓷颗粒中的至少一种。
  5. 根据权利要求1所述的硬质聚氨酯泡沫，其特征在于，所述发泡剂是环戊烷。
  6. 一种硬质聚氨酯泡沫的制造方法，其特征在于，包括以下工序：
    向包含多元醇、催化剂及泡沫稳定剂的第一多元醇混合物中，添加中空无机颗粒及发泡剂，得到第二多元醇混合物，添加量为相对于聚氨酯树脂为3～30％重量；及
    向第二多元醇混合物中添加多异氰酸酯进行反应；得到密度30.0～33.0kg/m 3的硬质聚氨酯泡沫。
  7. 根据权利要求6所述的硬质聚氨酯泡沫的制造方法，其特征在于，所述中空无机颗粒是以均匀分散在发泡剂中的分散体的状态，添加至第一多元醇混合物。
PCT/CN2020/136828 2019-12-24 2020-12-16 硬质聚氨酯泡沫及其制造方法 Ceased WO2021129486A1 (zh)

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