CN109415528A - 阻燃半硬质聚氨酯泡沫 - Google Patents

阻燃半硬质聚氨酯泡沫 Download PDF

Info

Publication number
CN109415528A
CN109415528A CN201780042984.1A CN201780042984A CN109415528A CN 109415528 A CN109415528 A CN 109415528A CN 201780042984 A CN201780042984 A CN 201780042984A CN 109415528 A CN109415528 A CN 109415528A
Authority
CN
China
Prior art keywords
bis
foam
method described
polyurethane foam
flame
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.)
Pending
Application number
CN201780042984.1A
Other languages
English (en)
Inventor
G·圭代蒂
S·弗雷格尼
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CN109415528A publication Critical patent/CN109415528A/zh
Pending legal-status Critical Current

Links

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
    • C08G18/28—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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • 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
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/125—Water, e.g. hydrated salts
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2330/00—Thermal insulation material
    • 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
    • C08G2350/00—Acoustic or vibration damping material
    • 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
    • C08J2203/10—Water or water-releasing compounds
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/08—Semi-flexible foams
    • 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
    • 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
    • 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
    • C08J2375/08—Polyurethanes from polyethers

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)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

公开了一种用于生产开孔低密度半硬质聚氨酯泡沫的方法，所述聚氨酯泡沫一般适用作热绝缘材料和/或声学应用。所述方法包含一种生产整体密度为5至30kg/m2的阻燃开孔半硬质聚氨酯泡沫的方法，所述聚氨酯泡沫是通过使(a)多异氰酸酯和(b)分子量为100至10,000的多元醇在(c)2,2‑双(氯甲基)‑三亚甲基双(双(2‑氯乙基)磷酸酯、(d)发泡剂和(e)任选的附加组分存在下反应来生产。

Description

阻燃半硬质聚氨酯泡沫
技术领域
本发明涉及一种用于阻燃半硬质聚氨酯泡沫的组合物，所述阻燃半硬质聚氨酯泡沫可用于需要隔音和振动管理的车辆应用，特别是用于薄壁应用。
背景技术
噪音和振动管理对于汽车制造商来说是一个重要问题，因为在汽车乘客舒适体验中车厢噪音是一个主要因素。因此，噪音和振动消减措施通常被纳入机动车辆中。这些消减措施通常使用软质聚氨酯泡沫。然而，这种泡沫通常被要求执行一个或多个功能目的，其不会以噪声和振动吸收为代价而受到损害，例如，在引擎罩下应用需要高度的阻燃性以满足原始设备制造商(OEM)的技术要求。
在聚氨酯泡沫中使用阻燃剂是众所周知的。赋予阻燃性的方法也是已知的，其将碳酸钙、氢氧化铵或另一种这样的无机化合物、卤代磷酸化合物、三聚氰胺或另一种这样的化合物与多元醇组合。然而，必须加入大量这样的化合物以赋予阻燃性，经常导致与性能、可模塑性、经济性等有关的相当大的问题。
制备阻燃软质聚氨酯泡沫的方法还可包括将卤代磷酸酯作为阻燃剂添加到聚酯基聚氨酯泡沫的组合物中，并使用向多羟基化合物或有机多异氰酸酯中添加磷或卤素原子的反应性阻燃剂，所述多羟基化合物或有机多异氰酸酯是聚氨酯泡沫的原料。然而，通过这些方法获得的氨基甲酸酯泡沫随着时间的推移而变色，泡沫本身劣化，并且由于阻燃剂挥发，因此在长时间内不能保持足够的阻燃性。
由于最近的环境和市场趋势，已经寻求非卤化阻燃剂解决方案。例如，USP6,765,034公开了一种用于隔音和振动应用的阻燃软质聚氨酯组合物，其不包含阻燃剂并且依赖于特定异氰酸酯混合物和多元醇的选择。
美国专利公开20030130365描述了由硬质聚氨酯泡沫制备软质聚氨酯泡沫的方法，所述硬质聚氨酯泡沫包含有机磷酸酯阻燃剂与可膨胀石墨的组合。然而，所述方法是需要破碎步骤和加热步骤的多步骤方法。
USP 6,552,098公开了一种半硬质聚氨酯泡沫，其包含剥离石墨和任选的一种或多种附加阻燃添加剂。然而，所述方法没有公开在薄壁应用中具有改进的阻燃性能的半硬质聚氨酯泡沫。
对于满足OEM要求的隔音和振动应用的阻燃半硬质聚氨酯泡沫组合物存在未满足的需求，特别是在薄壁应用中和制备所述泡沫的方法，这是成本有效的，不需要多于常规方法的附加多工艺步骤，并且不需要复杂的阻燃剂混合物和/或高水平的阻燃剂。
发明内容
根据本发明，提供了一种用于生产整体密度为5至30kg/m3的阻燃开孔半硬质聚氨酯泡沫的方法，所述方法是通过使(a)多异氰酸酯(优选多亚甲基多亚苯基多异氰酸酯或其异构体)和(b)多元醇(优选聚醚多元醇或聚酯多元醇，其平均分子量为100至10,000并且平均官能度为2至6)在2,2-双(氯甲基)-三亚甲基双(双(2-氯乙基)磷酸酯(优选泡沫的2至25重量％)、(d)发泡剂和(e)一种或多种任选的附加组分(优选剥离石墨，其量等于或大于泡沫的2重量％且等于或小于泡沫的20重量％)存在下反应来进行，条件是，在所得阻燃开孔半硬质聚氨酯泡沫中不存在除了(c)之外的其它含磷阻燃添加剂。
在另一个实施例中，本发明的方法在制备这类泡沫中使用水作为基本上唯一的发泡剂，优选以每100重量份多元醇5至25重量份的量添加。
在另一个实施例中，本发明的方法使用水和卤烃的组合作为发泡剂。
另外，根据本发明，通过上文所述方法生产半硬质低密度开孔泡沫。
令人惊讶地发现，在生产半软质泡沫中使用2,2-双(氯甲基)-三亚甲基双(双(2-氯乙基)磷酸酯作为唯一的含磷阻燃剂可以生产低密度泡沫，其具有增强的阻燃性能，特别是对于较薄的泡沫尺寸。
具体实施方式
应用于泡沫的术语半硬质是本领域中使用的标准术语。通常，这类泡沫的玻璃化转变温度(Tg)在硬质和软质泡沫之间。低密度泡沫是指泡沫的密度为5至30kg/m3，优选10至20kg/m3，更优选密度为10至15kg/m3。开孔泡沫意味着泡沫中50％或更多的泡孔具有开放结构。优选地，对于在声学应用中使用，泡沫具有大于90％的开放泡孔。
可用于制备聚氨酯的多异氰酸酯包括脂肪族和脂环族和优选芳香族多异氰酸酯或其组合，每个分子有利地具有平均2至3.5，并且优选2至3.2个异氰酸酯基团。本发明实践中还可以使用粗多异氰酸酯，如通过使甲苯二胺的混合物光气化而获得的粗二异氰酸甲苯酯，或通过使粗亚甲基二苯胺光气化而获得的粗二苯基甲烷二异氰酸酯。优选的多异氰酸酯是芳香族多异氰酸酯，如USP3,215,652中所公开的，其全文以引用的方式并入本文。
特别优选用于本发明的多异氰酸酯是多亚甲基多亚苯基多异氰酸酯(MDI)。如本文中所使用，MDI是指选自以下的多异氰酸酯：二苯基甲烷二异氰酸酯异构体、多苯基多亚甲基多异氰酸酯以及其带有至少两个异氰酸酯基团的衍生物。除异氰酸酯基团外，这类化合物还可含有碳二亚胺基团、脲酮亚胺基团、异氰脲酸酯基团、氨基甲酸酯基团、脲基甲酸酯基团、脲基团或缩二脲基团。MDI可通过将苯胺与甲醛缩合，然后进行光气化来获得，该过程产生所谓的粗MDI。通过分馏粗MDI，可以获得聚合和纯MDI。粗MDI、聚合MDI或纯MDI可以与多元醇或多元胺反应，以得到改性的MDI。MDI宜具有每个分子平均2到3.5，并且优选2到3.2个异氰酸酯基团。特别优选的是亚甲基桥连的多苯基多异氰酸酯及其与粗二苯基甲烷二异氰酸酯的混合物，因为它们能够交联聚氨酯。
用于制备聚氨酯泡沫的多异氰酸酯的总量应足以提供通常25至300的异氰酸酯反应指数。优选地，指数为95至110。异氰酸酯指数为100对应于如水和多元醇组合物中存在的每个异氰酸酯反应性氢原子一个异氰酸酯基团。
可用于制备基于多异氰酸酯的多孔聚合物的多元醇包括具有两个或多个含有能够与异氰酸酯反应的活性氢原子的基团的那些材料。这类化合物中优选的是每分子具有至少两个羟基或伯胺或仲胺、羧酸或硫醇基的材料。每分子具有至少两个羟基的化合物是特别优选的，这归因于其与多异氰酸酯的所需反应性。通常，适用于制备硬质聚氨酯的多元醇包括平均分子量为100至10,000并且优选200至7,000的那些。这类多元醇还有利地具有每分子至少2个，优选3个和至多8个活性氢原子的官能度。对于生产半硬质泡沫，优选地使用羟基数是30至500mg KOH/g的三官能多元醇。代表性多元醇包括聚醚多元醇、聚酯多元醇、多羟基封端的缩醛树脂、羟基封端的胺以及多元胺。这些和其它合适异氰酸酯反应性材料的实例更充分地描述于USP 4,394,491中，所述专利全文以引用的方式并入本文。优选的是通过以下制备的多元醇：将环氧烷如环氧乙烷、环氧丙烷、环氧丁烷或其组合添加到具有2至8，优选3至6个活性氢原子的引发剂中。
在优选的实施例中，多元醇是用于制备“软质”泡沫的聚醚或聚酯多元醇和用于制备“硬质”泡沫的多元醇的混合物。软质多元醇通常具有25至75的羟值和2至3的官能度。用于硬质泡沫的多元醇通常具有150至800的羟值和2至8的官能度。当使用这类共混物时，共混物具有如上所述的平均分子量和平均官能度。
在优选的实施例中，聚醚醇是100％环氧丙烷基，官能度为4.5至6.5，羟值为460至500mg KOH/g。
优选的是，发泡剂基本上由水作为基本上唯一的发泡剂组成。水与反应混合物中的异氰酸酯反应形成二氧化碳气体，从而使泡沫制剂阀泡。添加的水量通常在每100重量份多元醇5至25重量份范围内。优选地，添加在每100份多元醇5至15份，更优选8至12份范围内的水。
如果需要，可以使用挥发性液体，如卤代烃或低沸点烃(常压下沸点为-10℃至+70℃)，如戊烷和/或其异构体或异丁烷和/或异构体，作为补充发泡剂。尽管不是优选的，但卤烃可用作补充发泡剂。卤烃包括完全和部分卤代的脂肪族烃，例如碳氟化合物、氯碳化合物和氯氟碳。碳氟化合物的实例包括氟甲烷、全氟甲烷、氟乙烷、1,1-二氟乙烷、1,1,1-三氟乙烷(HFC-143a)、1,1,1,2-四氟乙烷(HFC-134a)、五氟乙烷、二氟甲烷、全氟乙烷、2,2-二氟丙烷、1,1,1-三氟丙烷、全氟丙烷、二氯丙烷、二氟丙烷、全氟丁烷、全氟环丁烷。
用于本发明的部分卤代的碳氯化合物和氯氟碳包括氯甲烷、二氯甲烷、氯乙烷、1,1,1-三氯乙烷、1,1-二氯-1-氟乙烷(FCFC-141b)、1-氯-1,1-二氟乙烷(HCFC-142b)、1,1-二氯-2,2,2-三氟乙烷(HCHC-123)和1-氯-1,2,2,2-四氟乙烷(HCFC-124)。
完全卤代的氯氟碳包括三氯单氟甲烷(CFC-11)二氯二氟甲烷(CFC-12)、三氯三氟乙烷(CFC-113)、1,1,1-三氟乙烷、五氟乙烷、二氯四氟乙烷(CFC-114)、氯七氟丙烷和二氯六氟丙烷。
本发明的半硬质聚氨酯泡沫组合物含有含磷阻燃剂。我们已经发现了一种特定氯化的含磷化合物，与其它含磷阻燃化合物相比，其提供了改进的可燃性能，特别是在较薄的泡沫中。可用于本发明的所述化合物含磷化合物是2,2-双(氯甲基)三亚甲基双(双(2-氯乙基)磷酸酯。
在泡沫中用于提供所需阻燃性能而使用的2,2-双(氯甲基)三亚甲基双(双(2-氯乙基)磷酸酯的量等于或小于泡沫的35重量％，等于或小于泡沫的30重量％，更优选小于或等于泡沫的25重量％。优选地，2,2-双(氯甲基)三亚甲基双(双(2-氯乙基)磷酸酯的量等于或大于泡沫的2重量％，优选等于或大于泡沫的5重量％，更优选等于或大于泡沫的7重量％，更优选等于或大于泡沫的10重量％。
在本发明的优选实施例中，本发明的半硬质聚氨酯泡沫组合物中仅有的含磷阻燃化合物是2,2-双(氯甲基)-三亚甲基双(双(2-氯乙基)磷酸酯。换句话说，本发明的半硬质聚氨酯泡沫组合物不能含有除2,2-双(氯甲基)-三亚甲基双(双(2-氯乙基)磷酸酯以外的含磷阻燃化合物。
在一个实施例中，本发明的半硬质聚氨酯泡沫组合物除2,2-双(氯甲基)三亚甲基以外可包含一种或多种阻燃添加剂，只要它不是含磷化合物，例如附加的阻燃添加剂包括但不限于剥离石墨、多磷酸铵、含卤素化合物、锑氧化物、含硼化合物、水合氧化铝等。通常，当存在时，附加阻燃剂的添加量为最终泡沫的5至20重量。
当存在时，附加阻燃添加剂优选是剥离石墨。剥离石墨是含有一种或多种剥离剂的石墨，使得在暴露于热时发生相当大的膨胀。通过本领域已知的程序制备剥离石墨。通常首先用氧化剂(如硝酸盐、铬酸盐、过氧化物)或通过电解来改性石墨以打开晶体层，然后将硝酸盐或硫酸盐嵌入石墨中。
如果存在，泡沫中用于提供所需物理性质而使用的剥离石墨的量通常小于泡沫的20重量％。优选地，石墨的量为泡沫的15重量％或更少。优选地，石墨的量为最终泡沫中石墨的2重量％或更多。优选地，石墨的量为泡沫的4重量％或更多。
除前述关键组分以外，在制备多孔聚合物中使用某些其它成分常常合乎需要。这些附加组分包括催化剂、表面活性剂、防腐剂、着色剂、抗氧化剂、增强剂、稳定剂和填料。在制备聚氨基甲酸酯泡沫中，一般非常优选地使用少量的表面活性剂以稳定发泡反应混合物直到其固化。这类表面活性剂宜包含液体或固体有机硅酮表面活性剂。其它较不优选的表面活性剂包括长链醇的聚乙二醇醚，长链烷基酸硫酸酯、烷基磺酸酯和烷基芳基磺酸的叔胺或烷醇胺盐。这类表面活性剂以足以使发泡的反应混合物稳定，防止坍塌和形成较大不均匀泡孔的量采用。通常，出于此目的，每100重量份总多元醇0.2到5份的表面活性剂足够。
有利地使用多元醇(和水，如果存在的话)与多异氰酸酯反应的一种或多种催化剂。可以使用任何合适的氨基甲酸酯催化剂，包括叔胺化合物以及有机金属化合物。示例性叔胺化合物包括三亚乙基二胺、N-甲基吗啉、N,N-二甲基环己胺、五甲基二亚乙基三胺、四甲基乙二胺、1-甲基-4-二甲基氨基乙基哌嗪、3-甲氧基-N-二甲基丙胺、N-乙基吗啉、二乙基乙醇胺、N-共-吗啉、N,N-二甲基-N',N'-二甲基异丙基丙二胺、N,N-二乙基-3-二乙基氨基丙胺和二甲基苄胺。示例性有机金属催化剂包括有机汞、有机铅、有机铁和有机锡催化剂，其中优选有机锡催化剂。合适的锡催化剂包括氯化亚锡、羧酸的锡盐(如二-2乙基己酸二丁基锡)以及如USP2,846,408中所公开的其它有机金属化合物，所述专利全文以引用的方式并入本文。在本文中还可以任选地采用用于三聚化多异氰酸酯、产生多异氰脲酸酯的催化剂，如碱金属醇盐。这类催化剂的用量可以显著提高聚氨酯或多异氰脲酸酯的形成速率。典型的量是每100重量份多元醇0.001至2份催化剂。
在制备聚氨酯泡沫体时，多元醇、多异氰酸酯和包括含磷化合物和任选的剥离石墨的其它组分接触、充分混合并允许膨胀和固化成多孔聚合物。在多异氰酸酯和含活性氢的组分反应之前预混合某些原料通常是方便的，但不是必需的。例如，将多元醇、发泡剂、表面活性剂、催化剂和除多异氰酸酯之外的其它组分混合，然后使该混合物与多异氰酸酯接触通常是有用的。在优选的实施例中，含磷化合物和任选的剥离石墨均匀分散在多元醇组分中。替代地，可以将所有组分单独引入混合区，在该混合区中多异氰酸酯和多元醇接触。在这类方法中，含磷化合物和任选的剥离石墨在多元醇中的分散体可以作为浓缩物通过单独的管线添加到多元醇中进入混合区。还可以在不存在水的情况下使全部或部分多元醇与多异氰酸酯预反应以形成预聚物。替代地，含磷化合物均匀分散在异氰酸酯组分中。
在一个实施例中，根据本发明生产的半硬质泡沫是通过板坯技术生产的。它可以是连续的板坯生产，但最优选的是不连续的生产。在生产聚氨酯泡沫块之后，根据最终应用将泡沫切割成具有不同尺寸的片材，通常为10至50mm。
根据本发明生产的半硬质泡沫在国内部门中使用，例如提供吸声、作为镶板元件，和在汽车行业中，作为结构传播隔音材料和墙壁和屋顶的热绝缘。
以下实例用以说明本发明并且不应解释为以任何方式限制本发明。除非另外说明，否则所有份和百分比按重量给出。
实例
比较例A和B以及实例1至4包含与聚合MDI反应制备板坯半硬质聚氨酯泡沫的配制的多元醇共混物。聚合MDI的异氰酸酯含量为约32重量％。多元醇共混物和聚合MDI在聚氨酯分配机中混合。该分配机是市场上可获得的标准机器，例如来自像OMS、Henneke和Cannon等设备供应商。分配机能够以给定的比例混合系统。该比率由泵/马达尺寸控制。该材料的分配温度在75至95℉范围内，并且对于两侧而言优选在85℉。
以下组分用于比较例A至D和实例1至4，量以基于表1中异氰酸酯方面或多元醇方面的总重量的重量％给出：
“多元醇-1”是标称6000Mw EO封端的三醇，其OH值为29mg KOH/g，可以SPECFLEX TMNC 138Polyol购自陶氏化学公司(The Dow Chemical Company)；
“多元醇-2”是标称4800Mw EO封端的三醇，OH值为34mg KOH/g，可以VORANOLTM4711Polyol购自陶氏化学公司；
“多元醇-3”是标称700Mw均聚物，6官能蔗糖/甘油引发的聚醚多元醇，OH值为477KOH/g，可以VORANOL RN 482Polyol购自陶氏化学公司；
“抗氧化剂”是用作聚氨酯泡沫的焦化抑制剂的抗氧化剂的共混物；
“硅酮”是用于硬质聚氨酯泡沫的聚硅酮表面活性剂的共混物；
“FR-1”是合成的异丙基化三芳基磷酸酯，可在各种树脂中作为阻燃添加剂使用，可以REOFOSTM 50购自Great lakes solutions；
“FR-2”是用于软质聚氨酯泡沫的烷基磷酸酯低聚物阻燃添加剂，可以FYROLTM PNX购自ICL工业产品(ICL Industrial Products)；
“FR-3”是磷酸三乙酯，一种可购自Quimidroga的阻燃添加剂；
“FR-4”是2,2-双(氯甲基)三亚甲基双(双(2-氯乙基)磷酸酯)是高分子量磷酸酯，可以CEL TECHTM 60购自Cellular Technology Europe；
“异氰酸酯”是基于35％的聚合MDI、65％的单体MDI的多亚甲基多亚苯基多异氰酸酯，并且可以SPECFLEX TM NE 449Isocyanate购自陶氏化学公司。
以下测试方法用于表征表2中的比较例A至D和实例1至4：
应用密度根据DIN 53420/ISO 845测定；
40％压缩时的刚度根据DIN EN ISO 3386测定；
拉伸强度根据DIN EN ISO 1798测定；
断裂伸长率根据DIN EN ISO 1798测定；
声学评价是混响室中吸声系数
Alpha Cabin测试根据DIN 52212/ISO 354 2003测定；
可燃性在20和/或13mm处测定。测试试样的尺寸至少为(230×200)mm。火焰暴露测试分为短时火焰暴露15秒和长期火焰暴露10分钟。用于火焰测试设备的提取系统可以提取产生的废气但不得损害燃烧器火焰或防止在试样上形成火焰或有助于
试样上的火焰增大或扩散。除非另有说明，否则在表面火焰暴露期间，试样的两侧都会发生火焰。火焰高度为100mm的炽热黄色火焰设置在燃烧器竖直位置。没有空气进入燃烧管。
水平测试
夹紧的试样水平固定在支架上；燃烧器位于试样下方，使得火焰在对角线相交的点(试样表面的中心)处撞击试样表面。燃烧器顶部与试样表面之间的距离为90mm。
竖直测试
将试样竖直固定在支架上，然后将燃烧器置于试样边缘下方的竖直位置，使得火焰到达待测边缘。燃烧器喷嘴顶部与试样底边缘之间的距离为30mm。
短期火焰暴露：
在15秒的火焰暴露期后，关闭气体供应并根据测试报告评估第一个样品。
长期火焰暴露：
在10分钟的火焰暴露后，关闭气体供应并根据测试报告评估第二个样品。
评估-通过样品必须符合以下标准：
自熄灭：除去点火火焰后，试样上的火焰必须在5秒内熄灭。任何受损区域的尺寸不得超过150mm(竖直试样布置：150mm长度，水平试样布置：直径150mm)。
重新点火：使用吹风机吹风时，试样不得重新点燃。受损区域的尺寸不得超过150mm。
材料滴落：不允许滴落燃烧物质。滴落材料不得点燃位于试样下方棉花球。
在泡沫生产过程中主观确定气味为可接受的(额定“合格”)或不可接受的。
表1
表2

Claims (12)

1.一种用于生产整体密度为10至20kg/m3的阻燃开孔半硬质聚氨酯泡沫的方法，所述方法是通过使(a)多异氰酸酯和(b)平均分子量为100至10,000并且平均官能度为2至8的多元醇在(c)2,2-双(氯甲基)-三亚甲基双(双(2-氯乙基)磷酸酯、(d)发泡剂和(e)一种或多种任选的附加组分存在下反应来进行，条件是，在所述所得阻燃开孔半硬质聚氨酯泡沫中不存在除了(c)之外的其它含磷阻燃添加剂。
2.根据权利要求1所述的方法，其中所述多元醇是聚醚多元醇。
3.根据权利要求1所述的方法，其中所述多元醇是聚酯多元醇。
4.根据前述权利要求中任一项所述的方法，其中所述发泡剂是水。
5.根据权利要求4所述的方法，其中所述水的添加量为每100重量份多元醇5至25重量份。
6.根据权利要求1所述的方法，其中所述发泡剂是水和沸点为-10℃至+70℃的烃的组合。
7.根据权利要求1所述的方法，其中所述发泡剂是水和卤烃的组合。
8.根据权利要求1所述的方法，其中所述2,2-二(氯甲基)三亚甲基双(双(2-氯乙基)磷酸酯的添加量等于或大于所述最终泡沫的2重量％且等于或小于所述最终泡沫的25重量％。
9.根据权利要求1所述的方法，其中所述多异氰酸酯是多亚甲基多亚苯基多异氰酸酯或其异构体。
10.根据权利要求1所述的方法，其中所述任选的附加组分包括附加阻燃剂。
11.根据权利要求10所述的方法，其中所述任选的附加辅助物质是剥离石墨。
12.一种泡沫，其通过根据权利要求1所述的方法生产。
CN201780042984.1A 2016-05-30 2017-05-23 阻燃半硬质聚氨酯泡沫 Pending CN109415528A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT102016000055347 2016-05-30
ITUA20163911 2016-05-30
PCT/US2017/034016 WO2017210022A1 (en) 2016-05-30 2017-05-23 Flame retardant semi-rigid polyurethane foam

Publications (1)

Publication Number Publication Date
CN109415528A true CN109415528A (zh) 2019-03-01

Family

ID=56940292

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780042984.1A Pending CN109415528A (zh) 2016-05-30 2017-05-23 阻燃半硬质聚氨酯泡沫

Country Status (6)

Country Link
US (1) US20200325268A1 (zh)
JP (1) JP2019517600A (zh)
KR (1) KR20190014522A (zh)
CN (1) CN109415528A (zh)
BR (1) BR112018074443A2 (zh)
WO (1) WO2017210022A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114206965A (zh) * 2019-08-13 2022-03-18 陶氏环球技术有限责任公司 聚氨酯泡沫

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3151709C (en) 2018-02-16 2023-10-10 H.B. Fuller Company Electric cell potting compound and method of making

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951822A (en) * 1974-11-18 1976-04-20 Monsanto Company Fire retardant composition for urethane polymers
US4246360A (en) * 1977-07-22 1981-01-20 Monsanto Company Fire retardant, non-dripping flexible polyurethane foam
CN1343227A (zh) * 1999-02-02 2002-04-03 陶氏化学公司 具有片状脱落石墨的开孔半硬质泡沫塑料
US20030134922A1 (en) * 1998-12-11 2003-07-17 Inna Dolgopolsky Isocyanate-based polymer foam and process for production thereof
US20110184079A1 (en) * 2010-01-27 2011-07-28 Intellectual Property Holdings, Llc Fire-retardant polyurethane foam and process for preparing the same
WO2011127028A1 (en) * 2010-04-09 2011-10-13 Albemarle Corporation Liquid flame retardant formulation useful for flame lamination applications
CN104845352A (zh) * 2014-02-19 2015-08-19 东曹株式会社 阻燃性聚氨酯泡沫体及其制造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846408A (en) 1954-01-19 1958-08-05 Bayer Ag Cellular polyurethane plastics of improved pore structure and process for preparing same
US3215652A (en) 1962-09-24 1965-11-02 Allied Chem Process for producing a rigid polyether-polyurethane foam
US4394491A (en) 1980-10-08 1983-07-19 The Dow Chemical Company Addition polymerizable adduct of a polymeric monoahl and an unsaturated isocyanate
CZ20012011A3 (cs) * 1998-12-18 2001-11-14 The Dow Chemical Company Polyurethanová pěna obsahující odlupovací grafit a způsob její výroby
WO2001025324A1 (en) 1999-10-07 2001-04-12 Huntsman International Llc Process for making rigid and flexible polyurethane foams containing a fire-retardant
JP3546033B2 (ja) 2001-09-27 2004-07-21 東海ゴム工業株式会社 車両用難燃性防音・防振材及びその製造方法
AU2010221725A1 (en) * 2009-03-05 2011-10-06 Dow Global Technologies Inc. Polyols from HPPO and polyurethane products made therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951822A (en) * 1974-11-18 1976-04-20 Monsanto Company Fire retardant composition for urethane polymers
US4246360A (en) * 1977-07-22 1981-01-20 Monsanto Company Fire retardant, non-dripping flexible polyurethane foam
US20030134922A1 (en) * 1998-12-11 2003-07-17 Inna Dolgopolsky Isocyanate-based polymer foam and process for production thereof
CN1343227A (zh) * 1999-02-02 2002-04-03 陶氏化学公司 具有片状脱落石墨的开孔半硬质泡沫塑料
US20110184079A1 (en) * 2010-01-27 2011-07-28 Intellectual Property Holdings, Llc Fire-retardant polyurethane foam and process for preparing the same
WO2011127028A1 (en) * 2010-04-09 2011-10-13 Albemarle Corporation Liquid flame retardant formulation useful for flame lamination applications
CN104845352A (zh) * 2014-02-19 2015-08-19 东曹株式会社 阻燃性聚氨酯泡沫体及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
蒋弘: "《实用小化工项目400项》", 31 July 2002, 科学技术文献出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114206965A (zh) * 2019-08-13 2022-03-18 陶氏环球技术有限责任公司 聚氨酯泡沫

Also Published As

Publication number Publication date
BR112018074443A2 (pt) 2019-03-06
WO2017210022A1 (en) 2017-12-07
JP2019517600A (ja) 2019-06-24
US20200325268A1 (en) 2020-10-15
KR20190014522A (ko) 2019-02-12

Similar Documents

Publication Publication Date Title
US10941237B2 (en) Storage stable foamable compositions containing 1,1,1,4,4,4-hexafluoro-2-butene
EP2464684B1 (en) Foams and foamable compositions containing halogenated olefin blowing agents
US9701782B2 (en) Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd)
JP2017197768A (ja) 発泡体、およびｈｃｆｏまたはｈｆｏ発泡剤を含む発泡体から作られる物品
ES2714250T3 (es) Uso de fosfato de trialquilo como supresor de humo en espuma de poliuretano
WO2002000752A1 (en) Process for making rigid polyurethane foams having high adhesion
AU3696100A (en) Open-celled semi-rigid foams with exfoliating graphite
JP2010184974A (ja) 耐火断熱被覆材
CN109415528A (zh) 阻燃半硬质聚氨酯泡沫
US11655328B2 (en) Dimensionally stable closed-cell and rigid foams produced with methylal blowing agent
JP6768631B2 (ja) 難燃性ポリイソシアヌレートフォーム
EP0742237B1 (en) Foamed thermal insulating material and insulated structure
EP3464434B1 (en) Flame retardant semi-rigid polyurethane foam
JP2022048708A (ja) 難燃性ウレタン樹脂組成物
JPH07133368A (ja) 硬質ポリウレタンフォームの製造方法
JP2022038409A (ja) ポリウレタン発泡体
JPH07133369A (ja) 硬質ポリウレタンフォームの製造方法
JP2003201330A (ja) ウレタン変性ポリイソシアヌレート発泡体
MXPA01007813A (en) Open-celled polyurethane foams containing graphite which exhibit low thermal conductivity
JP2001261878A (ja) 複合発泡体の製造方法
MXPA01007817A (en) Open-celled semi-rigid foams with exfoliating graphite

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190301

WD01 Invention patent application deemed withdrawn after publication