CN107383327A - 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法 - Google Patents

硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法 Download PDF

Info

Publication number
CN107383327A
CN107383327A CN201710212121.6A CN201710212121A CN107383327A CN 107383327 A CN107383327 A CN 107383327A CN 201710212121 A CN201710212121 A CN 201710212121A CN 107383327 A CN107383327 A CN 107383327A
Authority
CN
China
Prior art keywords
composition
polyurethane foam
rigid polyurethane
polyol
weight
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
CN201710212121.6A
Other languages
English (en)
Inventor
吉川悠人翔
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.)
Seif Vichy Co., Ltd.
Original Assignee
Toyo Tire and Rubber 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 Toyo Tire and Rubber Co Ltd filed Critical Toyo Tire and Rubber Co Ltd
Publication of CN107383327A publication Critical patent/CN107383327A/zh
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/161Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20Heterocyclic amines; Salts thereof
    • C08G18/2009Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2027Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/222Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/225Catalysts containing metal compounds of alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/227Catalysts containing metal compounds of antimony, bismuth or arsenic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/26Catalysts containing metal compounds of lead
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • C08J9/08Working-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 chemical blowing agent developing carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0025Foam properties rigid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/10Water or water-releasing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/18Binary blends of expanding agents
    • C08J2203/184Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/10Rigid foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/04Aerosol, e.g. polyurethane foam spray
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

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)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明提供即使是含有金属催化剂且使用HFO‑1233zd作为发泡剂的情况下原液保存稳定性也良好的硬质聚氨酯泡沫用多元醇组合物。一种硬质聚氨酯泡沫用多元醇组合物,其是至少含有多元醇化合物、发泡剂及金属催化剂、且与包含聚异氰酸酯化合物的异氰酸酯成分混合并使其发泡固化而形成硬质聚氨酯泡沫的硬质聚氨酯泡沫用多元醇组合物,上述发泡剂含有1‑氯‑3,3,3‑三氟丙烯,上述多元醇组合物含有辛酸钙。

Description

硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造 方法
技术领域
本发明涉及作为发泡剂成分含有作为必须成分的1-氯-3,3,3-三氟丙烯(以下,也记载为HFO-1233zd)的硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法、更具体而言喷雾发泡硬质聚氨酯泡沫用多元醇组合物及喷雾发泡硬质聚氨酯泡沫的制造方法。
背景技术
硬质聚氨酯泡沫为作为绝热材料、轻量结构材料等公知的材料。所述硬质聚氨酯泡沫通过将含有多元醇化合物、发泡剂作为必须成分的多元醇组合物与异氰酸酯成分混合并使其发泡、固化而形成。作为硬质聚氨酯泡沫的制造方法之一,有喷雾发泡法(例如专利文献1及2)。
作为上述发泡剂,以往使用CFC-11等氟利昂化合物,但该CFC-11由于会引起臭氧层的破坏所以被禁止使用,替换成HCFC-141b,进而从2004年开始进行向臭氧层破坏系数为零的HFC-245fa或HFC-365mfc的替换,但该HFC-245fa或HFC-365mfc具有GWP(地球温暖化系数)大的问题。因此,正在进行臭氧层破坏系数和地球温暖化系数低且没有可燃性的HFO-1233zd的作为发泡剂的开发。
例如,含有HFO-1233zd的多元醇组合物由于原液保存稳定性差,所以正在进行改善含有HFO-1233zd的多元醇组合物的原液保存稳定性的尝试(例如专利文献3~6)。
现有技术文献
专利文献
专利文献1:日本特开2006-328172号公报
专利文献2:日本特开2009-114288号公报
专利文献3:日本特表2011-500891号公报
专利文献4:日本特表2011-500892号公报
专利文献5:日本特表2011-500893号公报
专利文献6:日本特表2013-501844号公报
发明内容
发明所要解决的课题
在利用喷雾发泡法的硬质聚氨酯泡沫的制造中,由于要求聚异氰酸酯化合物与多元醇化合物的迅速的反应,所以为了提高聚异氰酸酯化合物与多元醇化合物的反应速度,有时使用活性高的金属催化剂。
但是,获知含有金属催化剂及HFO-1233zd的多元醇组合物的原液保存稳定性差,有时在保存中作为喷雾发泡用所期望的金属催化剂的活性消失。由于若作为喷雾发泡用所期望的金属催化剂的活性消失,则聚异氰酸酯化合物与多元醇化合物的反应速度降低,所以有时利用喷雾发泡法的硬质聚氨酯泡沫的制造变得困难。
本发明提供即使含有金属催化剂及HFO-1233zd,原液保存稳定性也良好的硬质聚氨酯泡沫用多元醇组合物。
用于解决课题的方案
本发明的硬质聚氨酯泡沫用多元醇组合物是至少含有多元醇化合物、发泡剂及金属催化剂、且与包含聚异氰酸酯化合物的异氰酸酯成分混合并使其发泡固化而形成硬质聚氨酯泡沫的硬质聚氨酯泡沫用多元醇组合物,上述发泡剂含有HFO-1233zd,上述多元醇组合物含有辛酸钙。
发明效果
根据本发明,能够提供即使含有金属催化剂及HFO-1233zd,原液保存稳定性也良好的硬质聚氨酯泡沫用多元醇组合物。
具体实施方式
<硬质聚氨酯泡沫用多元醇组合物>
本实施方式的硬质聚氨酯泡沫用多元醇组合物(以下,也简称为多元醇组合物)是至少含有多元醇化合物、发泡剂及金属催化剂、且与包含聚异氰酸酯化合物的异氰酸酯成分混合并使其发泡固化而形成硬质聚氨酯泡沫的硬质聚氨酯泡沫用多元醇组合物,上述发泡剂含有HFO-1233zd,上述多元醇组合物含有辛酸钙。
根据本实施方式的多元醇组合物,能够提供即使含有金属催化剂及HFO-1233zd,原液保存稳定性也良好的硬质聚氨酯泡沫用多元醇组合物。本实施方式的多元醇组合物发挥这样的效果的理由并不确定,但如下考虑。
认为金属催化剂与原液保存中的HFO-1233zd来源的氟反应而变成氟化金属物,将催化性能失活,但由于辛酸钙与氟的反应性高,氟与金属催化剂相比优先与辛酸钙来源的钙反应,能够防止保存中的金属催化剂的失活,所以能够提供即使含有金属催化剂及HFO-1233zd,原液保存稳定性也良好的硬质聚氨酯泡沫用多元醇组合物。
〔多元醇化合物〕
作为多元醇化合物,可以没有限定地使用公知的硬质聚氨酯泡沫用多元醇化合物。作为所述多元醇化合物,可例示出含叔氨基的多元醇化合物、脂肪族多元醇化合物、芳香族多元醇化合物等。
含叔氨基的多元醇化合物是以伯胺或仲胺作为引发剂使环氧烷烃、具体而言环氧丙烷(PO)、环氧乙烷(EO)、环氧苯乙烷(SO)、四氢呋喃等1种以上进行开环加聚而得到的多官能性的多元醇化合物。
作为含叔氨基的多元醇化合物的引发剂即伯胺或仲胺引发剂,可例示出氨、甲基胺、乙基胺等脂肪族伯或仲单胺类、乙二胺、六亚甲基二胺、N,N’-二甲基乙二胺等脂肪族伯或仲多胺类、苯胺、二苯基胺、甲苯二胺、二苯基甲烷二胺、N-甲基苯胺等芳香族伯或仲的单或多胺类、单乙醇胺、二乙醇胺等链烷醇胺类。含叔氨基的多元醇化合物的含量在多元醇化合物中,优选为10~60重量%,更优选为20~50重量%。含叔氨基的多元醇化合物对于反应性的上升、物性的体现是有效的,若少于10重量%则经常见不到反应性的上升,若超过60重量%则由于反应性变得过高,有时成为泡沫的烧伤、裂纹的产生原因。
脂肪族多元醇化合物是在作为多元醇引发剂的脂肪族或脂环族多官能性活泼氢化合物上开环加聚环氧烷烃、具体而言环氧丙烷(PO)、环氧乙烷(EO)、环氧苯乙烷(SO)、四氢呋喃等环状醚的1种以上、优选PO或PO和EO而得到的多官能性的低聚物。
作为脂肪族多元醇化合物的多元醇引发剂,可例示出乙二醇、丙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、新戊二醇等二醇类、三羟甲基丙烷、甘油等三元醇类、季戊四醇等4官能醇类、山梨糖醇、蔗糖等多官能醇类、水等。
芳香族多元醇化合物可例示出通过在分子内具有芳香环的多官能性的活泼氢化合物上加成上述的环氧烷烃的方法而得到的多元醇化合物、芳香族聚羧酸与多官能醇的酯多元醇化合物等。
作为在多官能性的活泼氢化合物上加成上述的环氧烷烃而得到的多元醇化合物,具体地可例示出在氢醌、双酚A、曼尼希等上开环加成PO、EO、SO中的至少1种、优选PO或PO和EO而得到的化合物。
作为芳香族聚羧酸与多官能醇的酯多元醇化合物,具体地可例示出使对苯二甲酸、邻苯二甲酸、间苯二甲酸等与乙二醇、二乙二醇等的羟基末端醇反应而得到的酯多元醇化合物。
上述多元醇化合物优选羟值为50~1500mgKOH/g。这些多元醇化合物中,若使用含叔氨基的多元醇化合物、脂肪族多元醇化合物,则可以得到使多元醇组合物的粘度下降的效果。
上述多元醇化合物也可以包含乙二醇(EG)、三乙二醇、二乙二醇(DEG)、1,4-丁二醇、1,6-己二醇(1,6-HD)、新戊二醇、二乙二醇、二丙二醇(DPG)等二醇、甘油、三羟甲基丙烷等三元醇等。
〔发泡剂〕
上述发泡剂含有臭氧层破坏系数和地球温暖化系数低且没有可燃性的HFO-1233zd。
上述发泡剂优选进一步含有水。通过水的添加,能够使多元醇组合物的蒸气压下降。水的含量相对于多元醇化合物的总计100重量份优选为0.5~5重量份。
上述发泡剂也可以进一步含有硬质聚氨酯泡沫用的公知的发泡剂。
上述发泡剂的含量相对于多元醇化合物总计100重量份优选为5~50重量份,更优选为10~40重量份。
〔金属催化剂〕
作为上述金属催化剂,可以没有特别限定地使用促进氨基甲酸酯化及脲化反应的公知的金属催化剂。作为上述金属催化剂中包含的金属,可例示出锡、钛、铅、铋、钴、钾等。
作为金属催化剂的更具体的例子,可列举出二月桂酸二丁基锡、马来酸二辛基锡、辛酸锡、二丁基氧化锡等锡化合物、钛酸四丁酯等钛化合物、环烷酸铅、辛酸铅等铅化合物、新癸酸铋、辛酸铋等铋化合物、环烷酸钴、辛酸钴等钴化合物、辛酸钾、乙酸钾、甲酸钾等钾化合物等。这些金属催化剂可以单独或混合使用。
关于上述多元醇组合物中的金属催化剂的量,从得到喷雾发泡法中所期望的反应速度的观点出发,相对于多元醇化合物100重量份以有效成分(除稀释成分以外的金属盐成分)计优选为0.05重量%以上,更优选为0.1重量%以上。但是,由于若反应速度过高,则有时因混合装置堵塞等而损害操作性,所以上述多元醇组合物中的金属催化剂的量相对于多元醇化合物100重量份优选为10重量%以下,更优选为5重量%以下,进一步优选为4重量%以下。
〔辛酸钙〕
关于上述多元醇组合物中的辛酸钙的量,从原液保存稳定性的观点出发,相对于多元醇化合物100重量份以有效成分(除稀释成分以外的辛酸钙成分)计优选为0.05重量份以上,更优选为0.1重量份以上,进一步优选为0.2重量份以上。但是,由于若在上述多元醇组合物中包含大量辛酸钙,则有时其他金属催化剂的活性降低,所以上述多元醇组合物中的辛酸钙的量相对于多元醇化合物100重量份以有效成分(除稀释成分以外的辛酸钙成分)计优选为2重量份以下,更优选为1重量份以下。
〔其他成分〕
上述多元醇组合物也可以含有硬质聚氨酯泡沫用的除上述金属催化剂以外的公知的催化剂、整泡剂、阻燃剂、相容剂、增塑剂、着色剂、抗氧化剂等。
作为除上述金属催化剂以外的公知的催化剂,可例示出N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基六亚甲基二胺(Kao.No.1)、N,N,N’,N’,N”-五甲基二亚乙基三胺(Kao.No.3)等N-烷基聚亚烷基多胺类、1-异丁基-2-甲基咪唑、1-甲基咪唑、1,2-二甲基咪唑等、二氮杂二环十一碳烯(DBU)、N,N-二甲基环己基胺(Polycat-8)、三乙二胺、N-甲基吗啉、双(2-二甲基-氨乙基)醚(NIAX-A-1)等叔胺类作为氨基甲酸酯化反应催化剂。
作为上述整泡剂,可以没有限定地使用硬质聚氨酯泡沫用的公知的整泡剂。作为整泡剂,通常使用聚二甲基硅氧烷以及聚二甲基硅氧烷与聚环氧烷烃的接枝共聚物或嵌段共聚物。作为聚环氧烷烃,使用平均分子量为5000~8000的聚环氧乙烷、聚环氧丙烷、环氧乙烷与环氧丙烷的无规共聚物或嵌段共聚物。
作为上述阻燃剂,可例示出含卤素的化合物、有机磷酸酯类、三氧化锑、氢氧化铝等金属化合物。关于这些阻燃剂,例如若过量地添加有机磷酸酯,则有时所得到的硬质聚氨酯泡沫的物性下降,此外若过量地添加三氧化锑等金属化合物粉末,则有时会产生对泡沫的发泡行为显出影响等问题,其添加量被限制为不产生所述问题的范围。
作为上述增塑剂,可列举出磷酸的卤代烷基酯、烷基磷酸酯或芳基磷酸酯、膦酸酯等,具体而言可例示出三(2-氯乙基)磷酸酯(CLP、大八化学社制)、三(β-氯丙基)磷酸酯(TMCPP、大八化学社制)、三丁氧基乙基磷酸酯(TBEP、Rhodia公司制)、磷酸三丁基酯、磷酸三乙基酯、磷酸甲苯基苯基酯、膦酸二甲基甲基酯等,可以使用它们中的1种以上。增塑剂的添加量相对于多元醇组合物100重量份优选为5~40重量份。若超过该范围,则无法充分得到增塑效果,有时产生泡沫的物性下降等问题。
<硬质聚氨酯泡沫的制造方法>
本实施方式的硬质聚氨酯泡沫的制造方法为将上述多元醇组合物与聚异氰酸酯化合物通过喷雾装置混合并使其反应而制成硬质聚氨酯泡沫的硬质聚氨酯泡沫的制造方法。
在本实施方式的硬质聚氨酯泡沫的制造方法中,由于使用即使含有金属催化剂及HFO-1233zd原液保存稳定性也良好的上述多元醇组合物,所以即使是保存后的多元醇组合物也能够通过喷雾发泡法来制造硬质聚氨酯泡沫。
作为上述异氰酸酯成分,从处理的容易性、反应的速度、所得到的硬质聚氨酯泡沫的物性优异、低成本等出发,使用液状MDI。作为液状MDI,使用未加工(粗制)MDI(c-MDI)(44V-10,44V-20L等(Sumika Covestro Urethane Co.,Ltd.制))、含脲酮亚胺的MDI(Millionate MTL;Nippon Polyurethane Industry Co.,Ltd.制)等。这些聚异氰酸酯化合物中,从所形成的硬质聚氨酯泡沫的机械强度等物性优异、并且为低价格的方面考虑,特别优选使用未加工(粗制)MDI。
除了液状MDI以外,也可以并用其他的异氰酸酯成分。在聚氨酯的技术领域中公知的二异氰酸酯化合物或聚异氰酸酯化合物可以没有限定地使用。
在上述硬质聚氨酯泡沫的制造方法中,上述多元醇组合物与异氰酸酯成分的混合中的异氰酸酯基/活泼氢基当量比(NCO指数)优选为1.0~2.2,更优选为1.1~2.1,进一步优选为1.2~2.0。
在本实施方式的制造方法中,适当使用一般公知的聚氨酯用喷雾发泡·成形装置,成形为与用途相应的形状。
[实施例]
以下,对具体地表示本发明的构成和效果的实施例等进行说明。
<评价方法>
〔初期凝胶时间〕
将温度调整为15℃的多元醇组合物和异氰酸酯成分用搅拌叶片以3000转/分钟旋转的搅拌机搅拌混合4秒钟,测定已发泡形成的聚氨酯泡沫的凝胶时间。凝胶时间设定为在发泡中的泡沫顶端部中插入玻璃棒时泡沫开始拔丝的时间。
〔在40℃下保管30天后凝胶时间〕
将多元醇组合物以密闭在塑料容器内的状态在设定为40℃的烘箱内培养30天后,将温度调整为15℃的培养后的多元醇组合物和异氰酸酯成分用搅拌叶片以3000转/分钟旋转的搅拌机搅拌混合4秒钟,测定已发泡形成的聚氨酯泡沫的凝胶时间。
〔凝胶时间延迟〕
由上述在40℃下保管30天后凝胶时间的值减去上述初期凝胶时间的值而求出凝胶时间延迟的时间(凝胶时间延迟)。凝胶时间延迟越少,意味着保存稳定性越好。
<实施例1~8、比较例1~3>
使用表1中记载的原料,以表2及表3中记载的组成制备多元醇组合物,将该多元醇组合物和表1中记载的聚异氰酸酯按照成为表2及表3中记载的重量比的方式投入发泡用容器中,通过上述方法求出初期凝胶时间、在40℃下保管30天后凝胶时间及凝胶时间延迟。将测定结果示于表2及表3中。
[表1]
[表2]
※凝胶时间延迟秒数越短,保存稳定性越好。
[表3]
※凝胶时间延迟秒数越短,保存稳定性越好。
如由上述表2及表3判断的那样,在多元醇组合物中含有辛酸钙的组合物由于凝胶时间延迟少,所以判断多元醇组合物的保存稳定性提高。另一方面,辛酸锌没有效果。

Claims (6)

1.一种硬质聚氨酯泡沫用多元醇组合物,其是至少含有多元醇化合物、发泡剂及金属催化剂、且与包含聚异氰酸酯化合物的异氰酸酯成分混合并使其发泡固化而形成硬质聚氨酯泡沫的硬质聚氨酯泡沫用多元醇组合物,其中,
所述发泡剂含有HFO-1233zd,
所述多元醇组合物含有辛酸钙。
2.根据权利要求1所述的硬质聚氨酯泡沫用多元醇组合物,其中,
所述金属催化剂为选自由二月桂酸二丁基锡、马来酸二辛基锡、辛酸锡、二丁基氧化锡、钛酸四丁酯、环烷酸铅、辛酸铅、新癸酸铋、辛酸铋、环烷酸钴、辛酸钴、乙酰丙酮铁、新癸酸铋、辛酸钾、乙酸钾及甲酸钾组成的组中的1种以上。
3.根据权利要求1或2所述的硬质聚氨酯泡沫用多元醇组合物,其中,
所述多元醇组合物中的所述金属催化剂的量相对于所述多元醇化合物100重量份为0.05重量%以上且10重量%以下。
4.根据权利要求1~3中任一项所述的硬质聚氨酯泡沫用多元醇组合物,其中,
所述多元醇组合物中的所述辛酸钙的量相对于多元醇化合物100重量份为0.05重量份以上且2重量份以下。
5.根据权利要求1~4中任一项所述的硬质聚氨酯泡沫用多元醇组合物,其用于利用喷雾发泡法的硬质聚氨酯泡沫的制造。
6.一种硬质聚氨酯泡沫的制造方法,其将权利要求1~5中任一项所述的硬质聚氨酯泡沫用多元醇组合物与聚异氰酸酯化合物通过喷雾装置混合并使其反应而制成硬质聚氨酯泡沫。
CN201710212121.6A 2016-05-16 2017-04-01 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法 Pending CN107383327A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016098050A JP6951012B2 (ja) 2016-05-16 2016-05-16 硬質ポリウレタンフォーム用ポリオール組成物、及び硬質ポリウレタンフォームの製造方法
JP2016-098050 2016-05-16

Publications (1)

Publication Number Publication Date
CN107383327A true CN107383327A (zh) 2017-11-24

Family

ID=60338312

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710212121.6A Pending CN107383327A (zh) 2016-05-16 2017-04-01 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法

Country Status (3)

Country Link
JP (1) JP6951012B2 (zh)
KR (1) KR20170129047A (zh)
CN (1) CN107383327A (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT3837296T (pt) * 2018-08-16 2022-10-31 Basf Se Sistemas de espuma de pulverização de poliuretano respeitadores do ambiente
JP2020063178A (ja) * 2018-10-18 2020-04-23 株式会社プラスラボ 酸化カルシウムを含む焼成物の分散液
KR20230030293A (ko) 2021-08-25 2023-03-06 투원테크주식회사 스프레이용 이액형 폴리우레탄 폼 조성물

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076459A (zh) * 1992-02-14 1993-09-22 大金工业株式会社 制备硬质聚氨酯泡沫体的方法
CN101544778A (zh) * 2009-04-07 2009-09-30 广东格兰仕集团有限公司 一种用于制作硬质聚氨酯泡沫塑料的发泡剂组合物及其应用
CN103415548A (zh) * 2011-04-15 2013-11-27 阿科玛股份有限公司 包含卤代烯烃发泡剂的聚氨酯多元醇共混物的改善的稳定性
CN103619955A (zh) * 2011-02-21 2014-03-05 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混料和由其制得的泡沫
CN103619893A (zh) * 2011-02-21 2014-03-05 霍尼韦尔国际公司 用于含有卤代烯烃发泡剂的聚氨酯泡沫多元醇预混合料的催化剂
CN103703042A (zh) * 2011-06-08 2014-04-02 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混料和由其制得的泡沫
CN103819651A (zh) * 2014-02-28 2014-05-28 北京东方雨虹防水技术股份有限公司 一种硬质聚氨酯泡沫材料及其制备方法
CN104685021A (zh) * 2012-09-24 2015-06-03 阿科玛股份有限公司 包含卤代烯烃发泡剂的聚氨酯多元醇共混物的改善的稳定性
CN104755518A (zh) * 2012-10-24 2015-07-01 气体产品与化学公司 改善具有含卤素发泡剂的聚氨酯体系的稳定性的胺催化剂
CN105579484A (zh) * 2013-02-26 2016-05-11 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混物和由其制造的泡沫

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4217247A (en) * 1979-03-07 1980-08-12 Mobay Chemical Corporation Catalyst system for polyurethane foams
CA2829486C (en) * 2011-03-11 2019-03-26 Arkema Inc. Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent
KR102082103B1 (ko) * 2012-02-02 2020-02-28 알케마 인코포레이티드 활성 성분의 캡슐화에 의한 할로겐화 올레핀을 함유하는 폴리올 배합물의 저장 수명의 개선
EP3004226A4 (en) * 2013-05-28 2017-02-01 Arkema, Inc. Stabilized polyurethane polyol blends containing halogenated olefin blowing agent
JP6809685B2 (ja) * 2014-10-08 2021-01-06 積水ソフランウイズ株式会社 硬質ポリウレタンフォーム用ポリオール組成物、及び硬質ポリウレタンフォームの製造方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076459A (zh) * 1992-02-14 1993-09-22 大金工业株式会社 制备硬质聚氨酯泡沫体的方法
CN101544778A (zh) * 2009-04-07 2009-09-30 广东格兰仕集团有限公司 一种用于制作硬质聚氨酯泡沫塑料的发泡剂组合物及其应用
CN103619955A (zh) * 2011-02-21 2014-03-05 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混料和由其制得的泡沫
CN103619893A (zh) * 2011-02-21 2014-03-05 霍尼韦尔国际公司 用于含有卤代烯烃发泡剂的聚氨酯泡沫多元醇预混合料的催化剂
CN103415548A (zh) * 2011-04-15 2013-11-27 阿科玛股份有限公司 包含卤代烯烃发泡剂的聚氨酯多元醇共混物的改善的稳定性
US20140051776A1 (en) * 2011-04-15 2014-02-20 Benjamin Bin Chen Improved stability of polyurethane polyol blends containing halogenated olefin blowing agents
CN103703042A (zh) * 2011-06-08 2014-04-02 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混料和由其制得的泡沫
CN104685021A (zh) * 2012-09-24 2015-06-03 阿科玛股份有限公司 包含卤代烯烃发泡剂的聚氨酯多元醇共混物的改善的稳定性
CN104755518A (zh) * 2012-10-24 2015-07-01 气体产品与化学公司 改善具有含卤素发泡剂的聚氨酯体系的稳定性的胺催化剂
CN105579484A (zh) * 2013-02-26 2016-05-11 霍尼韦尔国际公司 含有卤代烯烃发泡剂的聚氨酯泡沫预混物和由其制造的泡沫
CN103819651A (zh) * 2014-02-28 2014-05-28 北京东方雨虹防水技术股份有限公司 一种硬质聚氨酯泡沫材料及其制备方法

Also Published As

Publication number Publication date
KR20170129047A (ko) 2017-11-24
JP6951012B2 (ja) 2021-10-20
JP2017206584A (ja) 2017-11-24

Similar Documents

Publication Publication Date Title
EP0202732B1 (en) Method for the preparation of semi-rigid polyurethane modified polyurea foam compositions
JP7509950B2 (ja) 2液型プレミックス組成物、及び裏込め注入用硬質ポリイソシアヌレートフォーム
CN106750482A (zh) 包含卤代烯烃发泡剂的聚氨酯多元醇共混物的改善的稳定性
CN107383327A (zh) 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法
JPS6245609A (ja) 焼け及び変色安定化難燃化可撓性ポリウレタンフオ−ムの製造方法
CN106687491B (zh) 硬质聚氨酯泡沫用多元醇组合物、及硬质聚氨酯泡沫的制造方法
CN110139884A (zh) 具有含硫聚酯多元醇的聚氨酯产品
CN106687490A (zh) 硬质聚氨酯泡沫用多元醇组合物、及硬质聚氨酯泡沫的制造方法
CN104955863A (zh) 阻燃剂发泡体配制品
CN106715506A (zh) 硬质聚氨酯泡沫用多元醇组合物、及硬质聚氨酯泡沫的制造方法
JP2002293868A (ja) 硬質ポリウレタンフォームおよびその製造方法
US10793665B2 (en) Polyurethane foam from high functionality polyisocyanate
JP5866839B2 (ja) 硬質ポリウレタンフォーム組成物
JP5723951B2 (ja) アミンアルキレンオキサイド付加物の製造方法
US12110361B2 (en) Hybrid foam formulations
CN109963900A (zh) 可燃性降低的柔性聚氨酯泡沫
JP2019077815A (ja) ポリウレタン樹脂製造用プレミックス液およびポリウレタン樹脂の製造方法
WO2021016295A1 (en) Formulated polyol compositions
JP4252856B2 (ja) 硬質ポリウレタンフォーム用ポリオール組成物及び硬質ポリウレタンフォームの製造方法
JP2023100568A (ja) ポリウレタンフォーム及び緩衝材

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
TA01 Transfer of patent application right

Effective date of registration: 20180917

Address after: Japan's Osaka Prefecture, Osaka City North District hall Island, 5 Ding 30

Applicant after: Seif Vichy Co., Ltd.

Address before: Hyogo City, Hyogo Prefecture, Japan

Applicant before: Toyo Tire Rubber

TA01 Transfer of patent application right
CB02 Change of applicant information

Address after: No.4, 4-4, 2-D, xitianman, Shibei District, Osaka, Osaka, Japan

Applicant after: Seif Vichy Co., Ltd.

Address before: Japan's Osaka Prefecture, Osaka City North District hall Island, 5 Ding 30

Applicant before: Seif Vichy Co., Ltd.

CB02 Change of applicant information
RJ01 Rejection of invention patent application after publication

Application publication date: 20171124

RJ01 Rejection of invention patent application after publication