CN116333250A - 聚氨酯软质泡沫塑料、制备方法及其应用 - Google Patents
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Abstract
本发明涉及一种聚氨酯软质泡沫塑料、制备方法及其应用,主要解决现有技术中存在聚醚型聚氨酯软质泡沫抗撕裂性能差、聚酯型聚氨酯软质泡沫生产条件苛刻的问题,本发明通过采用一种新的聚氨酯软质泡沫塑料,以重量份数计,包括以下组分:聚醚多元醇70~90份、聚酯醚多元醇10~30份、发泡剂1~4份、胺类催化剂0.1~1份、有机金属催化剂0.1~0.5份、泡沫稳定剂0.5~3份、异氰酸酯30~60份及其制备方法的技术方案,较好地解决了该问题,可在软体家具、体育用品或汽车配饰行业应用。
Description
技术领域
本发明涉及一种聚氨酯软质泡沫塑料、制备方法及其应用。
背景技术
聚氨酯软质泡沫,简称聚氨酯普通软泡,俗称海绵,是一种兼具优异的弹性和柔软性能的聚氨酯泡沫塑料。因其具有密度低、弹性好、吸音、保温、透气等性能,主要用作家具垫材、交通工具座椅垫材、各种软性衬垫层压复合材料,工业和民用上也把软泡用作过滤材料、隔音材料、防震材料、装饰材料、包装材料及隔热保温材料等。
现有技术中,大多数的聚氨酯软质泡沫为聚醚型软质泡沫塑料,存在使用后易出现破损问题,主要原因在于软质泡沫塑料的抗撕裂性能差,在日常使用中反复拉伸、弯折后出现撕裂现象。现有技术通常采用的方法为将含有酯基结构的多元醇直接做为发泡原料或与异氰酸酯进行反应后形成改性异氰酸酯进行使用来提高软质泡沫塑料性能。比如中国专利CN103261257A公开了一种制备软质聚氨酯软质泡沫塑料的方法,使用蓖麻油酸与多元醇进行反应,得到了一种蓖麻油酸酯,再与异氰酸酯反应得到异氰酸酯预聚物,使用该材料发泡制得的软质泡沫塑料具有较好的抗撕裂性能。在聚醚型软质泡沫塑料配方中添加聚酯多元醇会导致相容性问题,且聚酯多元醇粘度普遍较高,以现有聚醚型泡沫塑料生产设备的条件难以大量使用。
中国专利CN113527616A提供一种聚氨酯普通软泡,制备原料包括辅助提高聚氨酯撕裂和压缩永久形变性能的聚醚多元醇;但该专利制备得到的聚氨酯普通软泡的密度为32kg/m3时,拉伸强度为191.34Kpa、断裂伸长率为215.32%、撕裂强度为290.10N/m。
发明内容
本发明所要解决的技术问题之一是,现有技术中存在聚醚型聚氨酯软质泡沫抗撕裂性能差、聚酯型聚氨酯软质泡沫生产条件苛刻的问题,提供一种新的聚氨酯软质泡沫塑料,该聚氨酯软质泡沫塑料具有高拉伸强度、高压陷硬度的优点;本发明所要解决的技术问题之二是提供一种与所要解决的技术问题之一相对应的聚氨酯软质泡沫的制备方法;本发明所要解决的技术问题之三是提供一种与所要解决的技术问题之一相对应的聚氨酯软质泡沫的应用。
为解决上述技术问题之一,本发明采用的技术方案如下:一种聚氨酯软质泡沫塑料,以重量份数计,包括以下组分:聚醚多元醇70~90份、聚酯醚多元醇10~30份、发泡剂1~4份、胺类催化剂0.1~1份、有机金属催化剂0.1~0.5份、泡沫稳定剂0.5~3份、异氰酸酯30~60份。
上述技术方案中,优选地,所述的聚醚多元醇的羟值为28~340mgKOH/g、官能度为2~4;所述的发泡剂为水;所述的胺类催化剂选自三亚乙基二胺、双(2-二甲基氨基乙基)醚、N,N,N′,N′-四甲基己二胺或五甲基二亚丙基三胺中的至少一种;所述有机金属催化剂选自辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯或新癸酸铋中的至少一种;所述泡沫稳定剂为聚硅氧烷-氧化烯烃共聚物;所述的异氰酸酯选自甲苯二异氰酸酯、二苯甲基二异氰酸酯或改性二苯甲基二异氰酸酯中的至少一种。
上述技术方案中,优选地,所述的泡沫稳定剂选自Tegostab B-8716或NiaxL-580中的一种。
上述技术方案中,优选地,所述的聚酯醚多元醇的羟值为42~108mgKOH/g、官能度为2~4、粘度为1000~2500mps·s。
上述技术方案中,优选地,所述的聚酯醚多元醇的制备方法包括以下步骤:
(1)将多官能度聚醚多元醇、二元酸酐投入反应釜中,用氮气多次置换掉反应釜中的空气,使釜内压力保持在0.01~0.4Mpa,升温,控制釜内反应温度为125~135℃,反应时间为2~4小时;
(2)将反应釜内温度降至70~90℃;向反应釜中添加质量为多官能度聚醚多元醇0.2~0.5%的液碱水溶液;
(3)在负压-0.1~-0.01Mpa下,向反应釜中通过环氧丙烷;然后控制反应温度为110~120℃;反应压力为0.01~0.4Mpa;反应时间为5~8小时;得到聚酯醚多元醇的粗醚;
(4)将釜内温度降至80~85℃,在搅拌条件下加入硅酸镁复配吸附剂;搅拌40~90分钟后,将釜内温度升至110~120℃,进行脱水2~4小时后,得到最终产品聚酯醚多元醇。
上述技术方案中,优选地,所述的多官能度聚醚多元醇由丙二醇、二乙二醇、1,4-丁二醇、甘油、山梨醇、季戊四醇中的至少一种为起始剂制备得到,分子量为200~2000;二元酸酐选自邻苯二甲酸酐、间苯二甲酸酐、马来酸酐中的至少一种;多官能度聚醚多元醇与二酸酐的摩尔比为1:1~2;多官能度聚醚多元醇与环氧丙烷的摩尔比为1:2~5。
上述技术方案中,优选地,所述的异氰酸酯指数为80-120;所述异氰酸酯指数是表征-NCO基团与-OH基团的摩尔数比例,计算方法为:异氰酸酯指数=NCO基团摩尔数/OH基团摩尔数*100。
上述技术方案中,优选地,所述的聚氨酯软质泡沫塑料的密度为25~80kg/m3、拉伸强度≥120Kpa、40%压陷硬度≥130N。
为解决上述技术问题之二,本发明采用的技术方案如下:
一种前述的聚氨酯软质泡沫塑料的制备方法,包括以下步骤:
准备组分A:以重量份数计,将聚醚多元醇70~90份、聚酯醚多元醇10~30份、发泡剂1~4份、胺类催化剂0.1~1份、有机金属催化剂0.1~0.5份、泡沫稳定剂0.5~3份混合均匀,控制混合物温度为22~24℃;
准备组分B:以重量份数计,准备好异氰酸酯30~60份;
将组分A、组分B混合搅拌,搅拌速度为2000~3000rpm/s,搅拌5~10s后倒入铺有聚乙烯薄膜的木质方形模具中并熟化24~72小时,取出切割即得到所述的聚氨酯软质泡沫塑料。
为解决上述技术问题之三,本发明采用的技术方案如下:
一种前述的聚氨酯软质泡沫塑料在软体家具、体育用品或汽车配饰行业应用。
本发明提供一种新的聚氨酯软质泡沫塑料、制备方法及其应用,通过采用一种含有脂肪族改性的聚酯醚多元醇,该聚酯醚多元醇具有较低的粘度且与聚醚多元醇相容性好,并且,用该聚酯醚多元醇制备的聚氨酯软质泡沫塑料具有较好的拉伸强度(≥120Kpa)和高压陷硬度(40%压陷硬度≥130N),取得了较好地技术效果。
具体实施方式
原料清单:
聚醚多元醇1:CHE-330N,羟值为35mgKOH/g的聚醚多元醇,官能度为3,厂家:长华化学科技有限公司;
聚醚多元醇2:CHE-350D,羟值为33mgKOH/g的聚醚多元醇,官能度4,厂家:长华化学科技有限公司;
聚醚多元醇3:CHE-5602,羟值为56mgKOH/g的聚醚多元醇,官能度2,厂家:长华化学科技有限公司;
聚醚多元醇4:CHE-210,羟值为112mgKOH/g的聚醚多元醇,官能度2,厂家:长华化学科技股份有限公司;
聚酯多元醇:XCP-2000M,羟值为5656mgKOH/g,粘度:4499mpa·s,厂家:旭川化学公司。
胺类催化剂1:三亚乙基二胺的醇溶液,商品名A-33
胺类催化剂2:双(2-二甲基氨基乙基)醚,商品名A-1
有机金属催化剂3:辛酸亚锡,商品名T-9
泡沫稳定剂1:聚硅氧烷-氧化烯烃共聚物,牌号Tegostab B-8716,Evonik公司
泡沫稳定剂2:聚硅氧烷-氧化烯烃共聚物,牌号Niax L-580,Momentive公司
异氰酸酯:甲苯二异氰酸酯TDI
聚酯醚多元醇-1的制备:
向装有搅拌装置的反应釜中加入1000g CHE-210,196g邻苯二甲酸酐,用氮气置换釜内空气,保持釜内真空状态,升温至130℃反应3个小时。降温至85℃,补加2.1g质量百分浓度为50%的氢氧化钾水溶液,然后在负压-0.05Mpa条件下,向釜中通入116g PO,在115℃条件下反应6个小时,出料。将料置于带有搅拌装置的三口烧瓶中,在85℃条件下搅拌并加入7.9g硅酸镁复配吸附剂,其中,硅酸镁复配吸附剂为硅酸镁A与硅酸镁B的混合物,硅酸镁A 2.0g,硅酸镁B 5.9g;硅酸镁A的粒径为45μm,比表面积100m2/g,孔容0.06cm3/g;硅酸镁B的粒径大小110μm,比表面积为32m2/g,孔容0.68cm3/g;一小时后逐渐将温度升至115℃,脱水3小时,过滤得到聚酯醚多元醇,羟值86mgKOH/g,粘度1260mpa·s。
【实施例1】
准备组分A:以重量份数计,将聚醚多元醇CHE-330N 74份、CHE-350D 6份、聚酯醚多元醇20份、水2.71份、A33 0.06份、A-1 0.26份、T-9 0.12份、B-8716 0.62份、L-580 0.28份;混合均匀,控制混合物温度为22~24℃;
准备组分B:以重量份数计,准备好TDI 34.85份;
将组分A、组分B混合搅拌,搅拌速度为2000~3000rpm/s,搅拌5~10s后倒入铺有聚乙烯薄膜的木质方形模具中并熟化24~72小时,取出切割即得到所述的聚氨酯软质泡沫塑料。所得到的聚氨酯软质泡沫塑料的物理性能检测数据见表2。
【实施例2-3】及【比较例1-2】
实施例2-3及比较例1-2按照实施例1的各个步骤进行,唯一的区别是反应原料、原料配比等不同,具体见表1,制备得到的聚氨酯软质泡沫塑料的物理性能检测数据如表2所示。
表1实施例1-3以及比较例1-2中原料重量份数配比
实施例1 | 实施例2 | 实施例3 | 比较例1 | 比较例2 | |
CHE-330N | 74 | 70 | 81 | 73 | 81 |
CHE-350D | 6 | 8 | 5 | 5 | 4 |
CHE-5602 | 22 | 15 | |||
XCP-2000M | |||||
聚酯醚多元醇-1 | 20 | 22 | 14 | ||
H2O | 2.71 | 2.44 | 2.36 | 2.60 | 2.35 |
A-33 | 0.06 | 0.06 | 0.08 | 0.06 | 0.07 |
A-1 | 0.26 | 0.27 | 0.31 | 0.28 | 0.30 |
T-9 | 0.12 | 0.11 | 0.11 | 0.15 | 0.13 |
Tegostab B-8716 | 0.62 | 0.71 | 0.80 | 0.88 | 0.79 |
Niax L-580 | 0.28 | 0.19 | 0.12 | 0.26 | 0.21 |
TDI | 34.85 | 32.24 | 30.84 | 33.02 | 30.24 |
异氰酸酯指数 | 105 | 105 | 105 | 105 | 105 |
表2实施例1至实施例3以及比较例1至比较例2的聚氨酯软质泡沫检测数据
【实施例4-6】以及【比较例3-4】
实施例4-5及比较例3-4按照实施例1的各个步骤进行,唯一的区别是反应原料、原料配比等不同,具体见表3,制备得到的聚氨酯软质泡沫塑料的物理性能检测数据如表4所示。
表3实施例4-6以及比较例3-4中原料重量份数配比
实施例4 | 实施例5 | 实施例6 | 比较例3 | 比较例4 | |
CHE-330N | 65 | 66 | 75 | 65 | 75 |
CHE-350D | 10 | 11 | 7 | 8 | 9 |
CHE-5602 | 27 | ||||
XCP-2000M | 16 | ||||
聚酯醚多元醇-1 | 25 | 23 | 18 | ||
H2O | 1.63 | 1.58 | 1.72 | 1.66 | 1.80 |
A-33 | 0.11 | 0.12 | 0.11 | 0.11 | 0.09 |
A-1 | 0.32 | 0.30 | 0.28 | 0.30 | 0.30 |
T-9 | 0.08 | 0.10 | 0.12 | 0.12 | 0.10 |
Tegostab B-8716 | 0.47 | 0.45 | 0.50 | 0.50 | 0.65 |
Niax L-580 | 0.29 | 0.31 | 0.33 | 0.30 | |
TDI | 21.88 | 21.29 | 22.26 | 21.34 | 22.29 |
异氰酸酯指数 | 95 | 95 | 95 | 95 | 95 |
表4实施例4至实施例6以及比较例3至比较例4的聚氨酯软质泡沫检测数据
通过表3和表4中实施例与比较例的比较,实施例体现出了较好的拉伸强度与撕裂强度,表明通过本发明中的方法制备的聚醚-聚酯多元醇对聚氨酯软质泡沫塑料的性能有提升,制备的聚氨酯软质泡沫塑料具有更好的拉伸、抗撕裂性能。
观察对比例4,原料混合物(除异氰酸酯)静止60min后观察到有明显分层现象。观察实施例1-6的原料混合物(除异氰酸酯),24h内未发现分层、析出、沉淀等相分离现象。
Claims (9)
1.一种聚氨酯软质泡沫塑料,以重量份数计,包括以下组分:聚醚多元醇70~90份、聚酯醚多元醇10~30份、发泡剂1~4份、胺类催化剂0.1~1份、有机金属催化剂0.1~0.5份、泡沫稳定剂0.5~3份、异氰酸酯30~60份。
2.根据权利要求1所述的聚氨酯软质泡沫塑料,其特征在于,所述的聚醚多元醇的羟值为28~340mgKOH/g、官能度为2~4;所述的发泡剂为水;所述的胺类催化剂选自三亚乙基二胺、双(2-二甲基氨基乙基)醚、N,N,N′,N′-四甲基己二胺或五甲基二亚丙基三胺中的至少一种;所述有机金属催化剂选自辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯或新癸酸铋中的至少一种;所述泡沫稳定剂为聚硅氧烷-氧化烯烃共聚物;所述的异氰酸酯选自甲苯二异氰酸酯、二苯甲基二异氰酸酯或改性二苯甲基二异氰酸酯中的至少一种。
3.根据权利要求2所述的聚氨酯软质泡沫塑料,其特征在于,所述的泡沫稳定剂选自Tegostab B-8716或NiaxL-580中的一种。
4.根据权利要求1所述的聚氨酯软质泡沫塑料,其特征在于,所述的聚酯醚多元醇的羟值为42~108mgKOH/g、官能度为2~4、粘度为1000~2500mps·s。
5.根据权利要求4所述的聚氨酯软质泡沫塑料,其特征在于,所述的聚酯醚多元醇的制备方法包括以下步骤:
(1)将多官能度聚醚多元醇、二元酸酐投入反应釜中,用氮气多次置换掉反应釜中的空气,使釜内压力保持在0.01~0.4Mpa,升温,控制釜内反应温度为125~135℃,反应时间为2~4小时;
(2)将反应釜内温度降至70~90℃;向反应釜中添加质量为多官能度聚醚多元醇0.2~0.5%的液碱水溶液;
(3)在负压-0.1~-0.01Mpa下,向反应釜中通过环氧丙烷;然后控制反应温度为110~120℃;反应压力为0.01~0.4Mpa;反应时间为5~8小时;得到聚酯醚多元醇的粗醚;
(4)将釜内温度降至80~85℃,在搅拌条件下加入硅酸镁复配吸附剂;搅拌40~90分钟后,将釜内温度升至110~120℃,进行脱水2~4小时后,得到最终产品聚酯醚多元醇。
6.根据权利要求1所述的聚氨酯软质泡沫塑料,其特征在于,所述的异氰酸酯指数为80-120;所述异氰酸酯指数是表征-NCO基团与-OH基团的摩尔数比例,计算方法为:异氰酸酯指数=NCO基团摩尔数/OH基团摩尔数*100。
7.根据权利要求1所述的聚氨酯软质泡沫塑料,其特征在于,所述的聚氨酯软质泡沫塑料的密度为25~80kg/m3、拉伸强度≥120Kpa、40%压陷硬度≥130N。
8.一种权利要求1所述的聚氨酯软质泡沫塑料的制备方法,包括以下步骤:
(1)准备组分A:以重量份数计,将聚醚多元醇70~90份、聚酯醚多元醇10~30份、发泡剂1~4份、胺类催化剂0.1~1份、有机金属催化剂0.1~0.5份、泡沫稳定剂0.5~3份混合均匀,控制混合物温度为22~24℃;
(2)准备组分B:以重量份数计,准备好异氰酸酯30~60份;
(3)将组分A、组分B混合搅拌,搅拌速度为2000~3000rpm/s,搅拌5~10s后倒入铺有聚乙烯薄膜的木质方形模具中并熟化24~72小时,取出切割即得到所述的聚氨酯软质泡沫塑料。
9.一种权利要求1所述的聚氨酯软质泡沫塑料在软体家具、体育用品或汽车配饰行业应用。
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CN117659334A (zh) * | 2023-12-09 | 2024-03-08 | 无锡市伟友汽摩配件有限公司 | 一种聚醚酯型聚氨酯高强度抗撕裂靠背及其制备方法 |
CN117659334B (zh) * | 2023-12-09 | 2024-05-28 | 无锡市伟友汽摩配件有限公司 | 一种聚醚酯型聚氨酯高强度抗撕裂靠背及其制备方法 |
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