CN115181237A - 一种抗冲击发泡材料及其制备方法与应用 - Google Patents
一种抗冲击发泡材料及其制备方法与应用 Download PDFInfo
- Publication number
- CN115181237A CN115181237A CN202210755732.6A CN202210755732A CN115181237A CN 115181237 A CN115181237 A CN 115181237A CN 202210755732 A CN202210755732 A CN 202210755732A CN 115181237 A CN115181237 A CN 115181237A
- Authority
- CN
- China
- Prior art keywords
- parts
- impact
- weight
- polyol
- component
- 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
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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/28—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
-
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- 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
- 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
- C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
- C08J9/148—Halogen containing compounds containing carbon and halogen atoms only perfluorinated
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- 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
- C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
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)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种抗冲击发泡材料及其制备方法与应用,属于冲击防护材料技术领域。所述的抗冲击发泡材料,包括A组分和B组分;A组分包括如下重量份组分:多元醇85~92份、刷状扩链剂5~10份、发泡剂0.3~1份、催化剂1~4.5份;B组分包括如下重量份组分:多异氰酸酯90~95份、助剂5~10份。本发明在聚氨酯合成中引入一类具有长支链的刷状扩链剂,在材料受到冲击时交联网络中的高分子链运动摩擦,消耗大量能量,从而提高材料的抗冲击性能该材料具有轻质、高强、高能量耗散、高抗冲击等特性,可应用于包装运输、运动防护、防暴防弹、航天航海滤波与吸能、医疗减震等多种防护领域。
Description
技术领域
本发明属于冲击防护材料技术领域,涉及一种抗冲击发泡材料及其制备方法与应用。
背景技术
发泡结构材料为一种经发泡后形成的具有一定力学强度和结构稳定性的泡沫材料,已逐渐应用包装运输、运动防护、防暴防弹、航天航海滤波与吸能、医疗减震等领域。常用的冲击防护缓冲材料有泡棉、EVA、橡胶、EPS等,但是泡棉强度太低,EVA热稳定性差,橡胶笨重且不透气,EPS易被破坏。因此市场上已有的一些缓冲材料尚存在不足,难以同时具备轻质、高强、高能量耗散的性能,只能适用于各自特定的缓冲防护场景。
发明内容
本发明的首要目的在于克服现有技术的缺点与不足,提供一种抗冲击发泡材料。本发明的抗冲击发泡材料具有轻质、高强、高能量耗散的特点,能够在常温下短时间内成型熟化。
本发明的另一个目的在于提供上述抗冲击发泡材料的制备方法。
本发明的再一目的在于提供上述抗冲击发泡材料的应用。
本发明的目的通过下述技术方案实现:
一种抗冲击发泡材料,包括A组分和B组分;
其中,A组分包括如下重量份的各组分:
所述的刷状扩链剂的制备方法优选包括如下步骤:将酯类化合物、3-巯基-1,2-丙二醇、偶氮二异丁腈和四氢呋喃混匀,除水除氧后在氮气氛围中进行聚合反应,得到混合物;将混合物用有机溶剂沉淀,去除溶剂,即得刷状扩链剂。
所述的酯类化合物优选包括但不限于丙烯酸三异丙基硅酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸异辛酯、乙酸烯丙酯、丙烯酸正丙酯、1,3-丙二醇单丙烯酸酯、4-丙烯酰氧基二苯甲酮和甲基丙烯酸苄酯中的至少一种。
所述的酯类化合物与3-巯基-1,2-丙二醇优选按质量比26~29:1.8~4计算。
所述的酯类化合物与偶氮二异丁腈优选按质量比26~29:0.013~3计算。
所述的酯类化合物与四氢呋喃优选按质量比26~29:70计算。
所述的聚合反应的条件优选为:60~80℃聚合11~13h;更优选为:70℃聚合12h。
所述的有机溶剂优选包括但不限于正己烷。
所述的去除溶剂的方法优选为烘干法;所述的烘干法的烘干温度优选为:30~50℃;更优选为40℃。
所述的多元醇包括聚醚多元醇、聚酯多元醇和植物油基改性多元醇中的至少一种。
所述的聚醚多元醇优选包括甘油聚醚多元醇、三羟甲基丙烷聚醚多元醇、季戊四醇聚醚多元醇、山梨醇聚醚多元醇、甘露醇聚醚多元醇、蔗糖聚醚多元醇和蔗糖-甘油聚醚多元醇中的至少一种。
所述的聚醚多元醇的羟值优选为350~650mg KOH/g。
所述的聚酯多元醇优选为苯酐聚酯多元醇。
所述的植物油基改性多元醇优选为蓖麻油多元醇、大豆油多元醇、桐油多元醇、棕榈油多元醇、玉米油多元醇和芝麻油多元醇中的至少一种。
所述的竞争性反应物优选为3,3’-二氯-4,4’-二氨基二苯甲烷、聚四亚甲基醚二醇双(对氨基苯甲酸)酯、聚天冬氨酸、N,N,N',N'-四(2-羟基丙基)乙二胺、聚醚胺D230、聚醚胺D400、聚醚胺D2000、聚醚胺T403和聚醚胺T5000中的至少一种。
所述的发泡剂优选为去离子水、一氟二氯乙烷、三氟二氯乙烷、三氟三氯乙烷、五氟丙烷、五氟丁烷、环戊烷、正戊烷和全氟庚烷中的至少一种。
所述的催化剂优选包括有机金属类催化剂和叔胺类催化剂。
所述的有机金属类催化剂优选为辛酸亚锡、二月桂酸二丁基锡、异辛酸铋和新葵酸铋中的至少一种。
所述的叔胺类催化剂优选为三乙烯二胺、N,N-二甲基环己胺、三乙醇胺、N,N,N’,N’-四甲基-1,6-己二胺、N,N-二甲基氨基乙醇、N,N,N’,N’,N’-五甲基二乙烯三胺和N,N,N’,N’-四甲基亚甲二胺中的至少一种。
B组分包括如下重量份的各组分:
多异氰酸酯 90~95份;
助剂 5~10份。
所述的多异氰酸酯优选为多苯基多亚甲基多异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、1,1-异亚丙基亚(环己基异氰酸酯-4)、甲基环己烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和聚六亚甲基二异氰酸酯中的至少一种。
所述的助剂优选为聚二甲基硅氧烷、环甲基硅氧烷、磺化蓖麻醇酸钠盐、聚氧乙烯山梨醇酐单油酸酯、聚甲基苯基硅氧烷、聚醚聚硅氧烷共聚物和环聚二甲基硅氧烷中的至少一种。
所述的抗冲击发泡材料的制备方法,包括如下步骤:将A组分和B组分按照重量比100:80~120混匀,得到抗冲击发泡材料。
所述的抗冲击发泡材料在冲击防护领域中的应用。
本发明相对于现有技术具有如下的优点及效果:
(1)常规的聚氨酯发泡材料表面硬度低、脆性高、抗冲击性能较弱、使用寿命短,通常也采用外加无机填料的方式改性,调料难以分散均匀、改性效果不稳定的困难难以避免。本发明通过合成一类具有长刷状支链的刷状扩链剂,向交联网络中以化学方法添加“聚合物刷”;在材料受到冲击时,“聚合物刷”的运动和相互摩擦、缠结会消耗大量的能量,因此该发泡材料具有良好的抗冲击性能。
(2)本发明充分利用叔胺类催化剂与有机金属催化剂复配对聚氨酯泡沫凝胶反应速度及发泡反应速度进行调控,使得材料发泡正常,不出现塌泡、顶裂、收缩等缺陷;且将起发时间控制在20~40s,数分钟之内即完成发泡。
(3)与橡胶、EVA等缓冲材料相比,本发明所述的缓冲减震泡沫材料具有多孔结构,达到相同体积使用的原材料更少,成本更低,轻质、高强,更为环保。
(4)本发明通过化学方法在高分子网络中引入“聚合物刷”,其结构稳定,不会受外部影响而改变,具有良好的耐候性及可重复使用性。本发明的抗冲击发泡材料通过分布在材料网络中的长支链“聚合物刷”(即刷状扩链剂)运动、相互缠结和摩擦耗散能量,实现抗冲击的目的,能够应用于各种冲击条件下的防护。
(5)本发明在聚氨酯合成中引入一类具有长支链的刷状扩链剂,在材料受到冲击时交联网络中的高分子链运动摩擦,消耗大量能量,从而提高材料的抗冲击性能该材料具有轻质、高强、高能量耗散、高抗冲击等特性,可应用于包装运输、运动防护、防暴防弹、航天航海滤波与吸能、医疗减震等多种防护领域。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
如非特殊说明,实施例中用到的试剂均可通过市售得到。
实施例1
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将28重量份丙烯酸三异丙基硅酯、2重量份3-巯基-1,2-丙二醇加入反应器,加入0.014重量份偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将48.2重量份的甘油聚醚多元醇(购于山东万华聚氨酯有限公司,羟值415mgKOH/g)、30重量份苯酐聚酯多元醇(CAS号:32472-85-8,购于青岛瑞诺化工有限公司;下同)、10重量份的大豆油多元醇(购于广州市海珥玛植物油脂有限公司)、10重量份刷状扩链剂、0.1重量份去离子水、0.2重量份一氟二氯乙烷、2重量份辛酸亚锡、1重量份N,N-二甲基环己胺混合均匀得到A组分;
(3)将50重量份苯二亚甲基二异氰酸酯(CAS:25854-16-4)、40重量份异佛尔酮二异氰酸酯、6重量份环甲基硅氧烷(CAS:1627-99-2)、4重量份磺化蓖麻醇酸钠盐(购于湖北科沃德化工有限公司)混合均匀得到B组分;
(4)使用时将A组分、B组分按100:80的重量比搅拌混合均匀后置于常温下自由发泡,得到抗冲击发泡材料。
实施例2
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将13重量份甲基丙烯酸甲酯、13重量份甲基丙烯酸丁酯与4重量份3-巯基-1,2-丙二醇加入反应器,加入0.013重量份的偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将38.6重量份的三羟甲基丙烷聚醚多元醇(购于上海晔兴实业有限公司,羟值600mgKOH/g)、40重量份苯酐聚酯多元醇、10重量份蓖麻油多元醇(购于武汉曙尔生物科技有限公司)、7重量份刷状扩链剂、0.2重量份去离子水、0.2重量份三氟二氯乙烷、2重量份新葵酸铋、1重量份N,N’-二甲基环己胺、1重量份三乙烯二胺混合均匀得到A组分;
(3)将76重量份甲苯-2,4-二异氰酸酯、19重量份甲苯-2,6-二异氰酸酯、5重量份聚甲基苯基硅氧烷(CAS:9005-12-3)混合均匀得到B组分;
(4)使用时将A组分、B组分按100:80的重量比搅拌混合均匀后于常温下自由发泡,得到抗冲击发泡材料。
实施例3
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将19重量份丙烯酸异辛酯、8重量份乙酸烯丙酯与3重量份3-巯基-1,2-丙二醇加入反应器,加入3重量份的偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将56.2重量份的山梨醇聚醚多元醇(购于山东万华聚氨酯有限公司,羟值450mgKOH/g)、30重量份苯酐聚酯多元醇、5重量份大豆油多元醇(购于广州市海珥玛植物油脂有限公司)、5重量份刷状扩链剂、0.6重量份去离子水、0.2重量份三氟三氯乙烷、2重量份二月桂酸二丁基锡、1重量份N,N,N’,N’-四甲基亚甲二胺(CAS号:51-80-9)混合均匀得到A组分;
(3)50重量份甲基环己烷二异氰酸酯、45重量份1,1-异亚丙基亚(环己基异氰酸酯-4)(CAS号:26189-89-9)、3重量份环甲基硅氧烷(CAS号:1627-99-2)、2重量份磺化蓖麻醇酸钠盐(购于湖北科沃德化工有限公司)混合均匀得到B组分;
(4)使用时将A组分、B组分按100:100的重量比搅拌混合均匀后于常温下自由发泡,得到抗冲击发泡材料。
实施例4
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将16重量份丙烯酸正丙酯、10重量份1,3-丙二醇单丙烯酸酯与4重量份3-巯基-1,2-丙二醇加入反应器,加入0.013重量份的偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将45重量份的蔗糖聚醚多元醇(购于山东万华聚氨酯有限公司,羟值470mgKOH/g)、20重量份蔗糖-甘油聚醚多元醇(购于山东万华聚氨酯有限公司,羟值430mgKOH/g)、10重量份苯酐聚酯多元醇、10重量份棕榈油多元醇(购于Maskimi多元醇公司)、10重量份刷状扩链剂、0.25重量份五氟丙烷、0.25重量份五氟丁烷、3重量份异辛酸铋、1.5重量份N,N,N’,N’,N’-五甲基二乙烯三胺混合均匀得到A组分;
(3)将95重量份二苯基甲烷二异氰酸酯、5重量份环聚二甲基硅氧烷(CAS号:69430-24-6)混合均匀得到B组分;
(4)使用时将A组分、B组分按100:120的重量比搅拌混合均匀后于常温下自由发泡,得到抗冲击发泡材料。
实施例5
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将28.2重量份4-丙烯酰氧基二苯甲酮与1.8重量份3-巯基-1,2-丙二醇加入反应器,加入0.0141重量份的偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将75.6重量份的蔗糖聚醚多元醇(购于山东万华聚氨酯有限公司,羟值470mgKOH/g)、10重量份的甘油聚醚多元醇(购于山东万华聚氨酯有限公司,羟值415mgKOH/g)、5重量份蓖麻油多元醇(购于武汉曙尔生物科技有限公司)、6重量份刷状扩链剂、0.2重量份去离子水、0.2重量份全氟庚烷、2重量份二月桂酸二丁基锡、1重量份三乙醇胺均匀得到A组分;
(3)将95重量份多苯基多亚甲基多异氰酸酯、3重量份环甲基硅氧烷、2重量份聚氧乙烯山梨醇酐单油酸酯(CAS号:9005-65-6)混合均匀得到B组分;
(4)使用时将A组分、B组分按100:110的重量比搅拌混合均匀后于常温下自由发泡,得到抗冲击发泡材料。
实施例6
一种抗冲击发泡材料的制备方法,包括如下步骤:
(1)将27.6重量份甲基丙烯酸苄酯与2.4重量份3-巯基-1,2-丙二醇加入反应器,加入0.0138重量份的偶氮二异丁腈以及70重量份的四氢呋喃混合均匀,除水除氧后在氮气氛围中70℃聚合12小时,在正己烷中沉淀两次后于40℃下烘去溶剂,获得刷状扩链剂;
(2)将60重量份的山梨醇聚醚多元醇(购于山东万华聚氨酯有限公司,羟值450mgKOH/g)、10份的苯酐聚酯多元醇、20份蓖麻油多元醇(购于武汉曙尔生物科技有限公司)、5份刷状扩链剂、1份去离子水、2份异辛酸铋、2份三乙醇胺混合均匀得到A组分;
(3)将42份碳化二亚胺改性二苯基甲烷二异氰酸酯(购于山东万华聚氨酯有限公司)、50份聚六亚甲基二异氰酸酯(CAS号:28182-81-2)、8份环聚二甲基硅氧烷混合均匀得到B组分;
(4)使用时将A组分、B组分按100:120的重量比搅拌混合均匀后于常温下自由发泡,得到抗冲击发泡材料。
性能测定:
测定实施例1~6任一所述的抗冲击发泡材料的以下性能:
其中,
表干时间通过GB/T 13477.5-2002测定;
抗冲击强度通过GB/T 11548-1989测定;
抗压强度通过GB/T 8813-2020测定。
表1:
注:抗压强度(40min)为材料起发后于常温下熟化40分钟下测得的抗压强度。
从表1可以看出,该抗冲击发泡材料具有合适的可操作时间,能够在短时间内成型固化,而且在相应的发泡倍率下具有较高的抗压强度和抗冲击强度,具有轻质、高强、高抗冲击等特性,可应用于包装运输、运动防护、防暴防弹、航天航海滤波与吸能、医疗减震等多种防护领域。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的刷状扩链剂的制备方法包括如下步骤:将酯类化合物、3-巯基-1,2-丙二醇、偶氮二异丁腈和四氢呋喃混匀,除水除氧后在氮气氛围中进行聚合反应,得到混合物;将混合物用有机溶剂沉淀,去除溶剂,即得刷状扩链剂。
3.根据权利要求2所述的抗冲击发泡材料,其特征在于,
所述的酯类化合物包括但不限于丙烯酸三异丙基硅酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸异辛酯、乙酸烯丙酯、丙烯酸正丙酯、1,3-丙二醇单丙烯酸酯、4-丙烯酰氧基二苯甲酮和甲基丙烯酸苄酯中的至少一种;
所述的酯类化合物与3-巯基-1,2-丙二醇按质量比26~29:1.8~4计算;
所述的酯类化合物与偶氮二异丁腈按质量比26~29:0.013~3计算;
所述的酯类化合物与四氢呋喃按质量比26~29:70计算;
所述的聚合反应的条件为:60~80℃聚合11~13h。
4.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的多元醇包括聚醚多元醇、聚酯多元醇和植物油基改性多元醇中的至少一种;
所述的聚醚多元醇包括甘油聚醚多元醇、三羟甲基丙烷聚醚多元醇、季戊四醇聚醚多元醇、山梨醇聚醚多元醇、甘露醇聚醚多元醇、蔗糖聚醚多元醇和蔗糖-甘油聚醚多元醇中的至少一种;
所述的聚醚多元醇的羟值为350~650mg KOH/g;
所述的聚酯多元醇为苯酐聚酯多元醇;
所述的植物油基改性多元醇为蓖麻油多元醇、大豆油多元醇、桐油多元醇、棕榈油多元醇、玉米油多元醇和芝麻油多元醇中的至少一种。
5.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的竞争性反应物为3,3’-二氯-4,4’-二氨基二苯甲烷、聚四亚甲基醚二醇双(对氨基苯甲酸)酯、聚天冬氨酸、N,N,N',N'-四(2-羟基丙基)乙二胺、聚醚胺D230、聚醚胺D400、聚醚胺D2000、聚醚胺T403和聚醚胺T5000中的至少一种。
6.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的发泡剂为去离子水、一氟二氯乙烷、三氟二氯乙烷、三氟三氯乙烷、五氟丙烷、五氟丁烷、环戊烷、正戊烷和全氟庚烷中的至少一种;
所述的催化剂包括有机金属类催化剂和叔胺类催化剂;
所述的有机金属类催化剂为辛酸亚锡、二月桂酸二丁基锡、异辛酸铋和新葵酸铋中的至少一种;
所述的叔胺类催化剂为三乙烯二胺、N,N-二甲基环己胺、三乙醇胺、N,N,N’,N’-四甲基-1,6-己二胺、N,N-二甲基氨基乙醇、N,N,N’,N’,N’-五甲基二乙烯三胺和N,N,N’,N’-四甲基亚甲二胺中的至少一种。
7.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的多异氰酸酯为多苯基多亚甲基多异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、1,1-异亚丙基亚(环己基异氰酸酯-4)、甲基环己烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和聚六亚甲基二异氰酸酯中的至少一种。
8.根据权利要求1所述的抗冲击发泡材料,其特征在于,
所述的助剂为聚二甲基硅氧烷、环甲基硅氧烷、磺化蓖麻醇酸钠盐、聚氧乙烯山梨醇酐单油酸酯、聚甲基苯基硅氧烷、聚醚聚硅氧烷共聚物和环聚二甲基硅氧烷中的至少一种。
9.权利要求1~8任一所述的抗冲击发泡材料的制备方法,其特征在于,包括如下步骤:将A组分和B组分按照重量比100:80~120混匀,得到抗冲击发泡材料。
10.权利要求1~8任一所述的抗冲击发泡材料在冲击防护领域中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210755732.6A CN115181237A (zh) | 2022-06-30 | 2022-06-30 | 一种抗冲击发泡材料及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210755732.6A CN115181237A (zh) | 2022-06-30 | 2022-06-30 | 一种抗冲击发泡材料及其制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115181237A true CN115181237A (zh) | 2022-10-14 |
Family
ID=83514449
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210755732.6A Pending CN115181237A (zh) | 2022-06-30 | 2022-06-30 | 一种抗冲击发泡材料及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115181237A (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003062297A1 (en) * | 2002-01-25 | 2003-07-31 | Perstorp Specialty Chemicals Ab | Polyurethane foam composition comprising chain extended dendritic polyether |
CN102174163A (zh) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | 一种侧链功能化两亲性聚氨酯及其制备方法与应用 |
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 |
CN104341579A (zh) * | 2014-10-27 | 2015-02-11 | 中国科学院长春应用化学研究所 | 一种低形变聚氨酯减震缓冲块的制备方法 |
CN109651591A (zh) * | 2018-12-21 | 2019-04-19 | 山东诺威聚氨酯股份有限公司 | 低voc高性能植物油基聚氨酯座椅组合料及其制备方法 |
CN114933687A (zh) * | 2022-06-30 | 2022-08-23 | 华南理工大学 | 一种高强度可控发泡材料及其制备方法与应用 |
-
2022
- 2022-06-30 CN CN202210755732.6A patent/CN115181237A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003062297A1 (en) * | 2002-01-25 | 2003-07-31 | Perstorp Specialty Chemicals Ab | Polyurethane foam composition comprising chain extended dendritic polyether |
CN102174163A (zh) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | 一种侧链功能化两亲性聚氨酯及其制备方法与应用 |
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 |
CN104341579A (zh) * | 2014-10-27 | 2015-02-11 | 中国科学院长春应用化学研究所 | 一种低形变聚氨酯减震缓冲块的制备方法 |
CN109651591A (zh) * | 2018-12-21 | 2019-04-19 | 山东诺威聚氨酯股份有限公司 | 低voc高性能植物油基聚氨酯座椅组合料及其制备方法 |
CN114933687A (zh) * | 2022-06-30 | 2022-08-23 | 华南理工大学 | 一种高强度可控发泡材料及其制备方法与应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100975452B1 (ko) | 개선된 내수성, 긴 가사시간 및 짧은 이형 시간을 가진신택틱 발포체 | |
CN109851750B (zh) | 一种分子链硬段阻燃聚氨酯泡沫的制备方法 | |
WO2013091271A1 (zh) | 动态性能优异的微孔聚氨酯弹性体组合物及其制备方法 | |
CN115181413A (zh) | 基于聚硼硅氧烷改性聚氨酯的应变速率敏感冲击防护材料及其制备方法与应用 | |
CN1186364C (zh) | 一种聚氨酯泡沫材料及其制备方法 | |
CN105440243A (zh) | 用于汽车天窗缓冲垫块的聚氨酯组合物及其制备方法 | |
CN104151518A (zh) | 聚氨酯运动护膝组合物及其制备方法 | |
CN114933687B (zh) | 一种高强度可控发泡材料及其制备方法与应用 | |
CN112934206A (zh) | 一种改性木质素聚氨酯吸附剂及其制备方法 | |
CN110903454B (zh) | 一种改性聚氨酯发泡材料及其制备方法和应用 | |
CN112375182A (zh) | 一种端羟基聚丁二烯型水性聚氨酯/丙烯酸酯材料及其制备方法和应用 | |
CN115181237A (zh) | 一种抗冲击发泡材料及其制备方法与应用 | |
CN109942774B (zh) | 一种分子链硬段阻燃聚氨酯泡沫 | |
CN113174028A (zh) | 一种全水发泡聚氨酯泡沫及其制备方法和用途 | |
WO2017038863A1 (ja) | ブロックイソシアネート組成物、プレポリマー組成物及びそれらの製造方法、並びに、ブロックイソシアネート組成物の熱解離性ブロック剤 | |
KR102211997B1 (ko) | 폴리우레탄 폼 제조용 폴리올 조성물 및 이를 포함하는 폴리우레탄 폼 | |
CN110982039A (zh) | 一种半硬质聚氨酯泡沫以及制备方法和在汽车车顶中的应用 | |
CN110105537A (zh) | 一种聚氨酯硬泡材料及其制备方法 | |
CN114015227B (zh) | 一种快速固化慢回弹丙烯酸泡棉及其制备方法和应用 | |
CN113896860B (zh) | 一种全水聚氨酯硬泡材料及制备方法及应用 | |
CN113621128B (zh) | 安全型酚醛树脂改性聚氨酯功能材料及其制备方法 | |
CN113248681B (zh) | 一种低密度高强度的聚氨酯泡沫及其制备方法和用途 | |
CN112266461B (zh) | 一种能够低温环境下使用的缓冲材料及其制备方法与应用 | |
CN109880058B (zh) | 一种分子链软段阻燃聚氨酯泡沫的制备方法 | |
CN110922565A (zh) | 1,5-萘二异氰酸酯基微孔弹性体的制备方法 |
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 |