CN110054744B - 改性环氧树脂增强聚氨酯组合料及其制备方法和应用 - Google Patents

改性环氧树脂增强聚氨酯组合料及其制备方法和应用 Download PDF

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CN110054744B
CN110054744B CN201910211345.4A CN201910211345A CN110054744B CN 110054744 B CN110054744 B CN 110054744B CN 201910211345 A CN201910211345 A CN 201910211345A CN 110054744 B CN110054744 B CN 110054744B
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epoxy resin
polyol
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isocyanate
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蔡武
赵叶宝
张学军
潘超凡
金美金
吴章兴
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Zhejiang Huafeng New Material Co ltd
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Abstract

本发明公开了一种改性环氧树脂增强聚氨酯组合料及其制备方法和应用，所述改性环氧树脂增强聚氨酯组合料，包含：含有改性环氧树脂的多元醇组分(A组分)和异氰酸根封端的预聚体组分(B组分)，所述的含有改性环氧树脂的多元醇组分(A组分)中羟基(‑OH)和异氰酸酯预聚体组分(B组分)中异氰酸基(‑NCO)的摩尔比为(0.95～1.05):1，可用于制备高性能聚氨酯弹性体。本发明填充颗粒的添加量范围宽，无需使用胶粘剂即可有效粘连高填充量的颗粒，制得的杂化材料弹性佳，密度和硬度可调范围宽，应用广。环氧树脂的加入，提升了杂化材料的耐热性能，使其可应用于高温环境。

Description

改性环氧树脂增强聚氨酯组合料及其制备方法和应用
技术领域
本发明涉及改性环氧树脂增强聚氨酯组合料及其制备方法和应用。
背景技术
聚氨酯是一类含有氨基甲酸酯重复结构单元的高分子材料，具有强度高、物性调节范围宽、工艺操作性好等优点，广泛应用于日常生活、工农业生产和医学等领域。在聚氨酯材料中填充其它材料或者与其它材料结合制备复合材料，可进一步提升聚氨酯的特定性能或降低生产成本，扩大聚氨酯复合材料的应用领域。如ZL201210562641.7公开聚氨酯原液A组分、B组分和废旧橡胶颗粒混合均匀生产聚氨酯鞋底，利用废旧橡胶颗粒提高鞋底的抗拉强度、耐磨性、耐撕裂强度等。WO 2008/087078公开了包含由聚氨酯组成的基体和包含在基体中的热塑性聚氨酯发泡颗粒的杂化材料。将异氰酸酯、具有对异氰酸酯有反应性的氢原子的化合物、扩链剂和/或交联剂、催化剂和其它添加剂制备异氰酸酯预聚物，然后将异氰酸酯预聚物与热塑性聚氨酯的发泡例子混合，并通过水的作用使复合材料固化。WO2014/023794公开包含由聚氨酯泡沫组成的基体和包含在基体中的热塑性聚氨酯发泡颗粒的组成泡沫，其中基体和颗粒各自由多元醇组分和多异氰酸酯组分组成，其中至少50重量％的用于形成基体和颗粒的多元醇组分的基本结构单元相同，且至少50重量％的用于形成基体和颗粒的多异氰酸酯组分的基体结构单元相同，其中基体完全开孔且基体中的发泡颗粒至少部分开孔。ZL 201110354028.1公开聚硅氧烷改性聚氨酯-环氧树脂聚合物材料，将干燥的亲水性二官能度或三官能度聚醚、双酚A型环氧树脂和二异氰酸酯加入反应釜生成聚氨酯-环氧树脂聚合物体系，再加入端羟基聚硅氧烷反应生成聚硅氧烷-聚氨酯-环氧树脂预聚物体系，反应结束前加入固化剂和催化剂，搅拌均匀后倒入模具固化成型，但环氧树脂中羟基-OH含量很低，与异氰酸酯反应困难。201210329012.X公开了一种将含端异氰酸酯基聚氨酯预聚体与环氧树脂混合，而后加入胺类固化剂对体系固化，制备环氧树脂-聚氨酯互穿网络材料的方法，但由于环氧树脂和聚氨酯的溶解性不同，在环氧树脂-聚氨酯共混体系中两组分会发生不同程度的分离且环氧树脂中羟基-OH含量很低，很难发生交联或者交联密度很低，实际难以充分发挥优势互补作用。201510748261.6专利申请文件公开一种有机酸改性环氧树脂聚氨酯材料，将双酚A型环氧树脂与有机酸在N,N-二甲基乙醇胺催化剂下反应生成有机酸改性环氧树脂，将有机酸改性环氧树脂与端羟基聚丁二烯按照羟基含量1:9混合均匀，再与聚氨酯预聚体按-NCO/-OH比为1.4混合均匀，注模固化成型，其中的有机酸为一元羧酸。有机酸的羧基与环氧树脂的环氧基发生开环加成反应，生成的仲羟基与异氰酸酯预聚体中的异氰酸酯基进一步反应，得到分散均匀、交联密度大、硬度高、耐热性和粘接性好的环氧树脂-端羟基聚丁二烯型聚氨酯材料。但该方法中聚氨酯预聚体制备时需要使用较大量的稀释剂。
发明内容
本发明的目的是提供一种改性环氧树脂增强聚氨酯组合料及其制备方法和应用，以解决现有技术存在的不足。
所述改性环氧树脂增强聚氨酯组合料，包含：含有改性环氧树脂的多元醇组分(A组分)和异氰酸根封端的预聚体组分(B组分)，所述的含有改性环氧树脂的多元醇组分(A组分)中羟基(-OH)和异氰酸酯预聚体组分(B组分)中异氰酸基(-NCO)的摩尔比为(0.95～1.05):1；
所述含有改性环氧树脂的多元醇组分(A组分)，各原料的重量份数为：
Figure BDA0002000627930000021
所述异氰酸根封端的预聚体组分(B组分)为过量异氰酸酯与低聚物多元醇B的反应产物，所述异氰酸酯预聚体组分(B组分)中NCO含量为0.1wt％～15.0wt％。优选的，所述异氰酸酯预聚体组分(B组分)中NCO含量为0.1wt％～10.0wt％。优选的在反应原料中加入占原料总质量0.002wt％～0.020wt％的磷酸。
所述改性环氧树脂为环氧树脂与有机酸开环反应制得，开环反应如“端羟基聚丁二烯型聚氨酯梯度材料的制备”，熊锃，中国优秀硕士学位论文全文数据库，工程科技Ⅰ辑，2013年第S2期，第28～30页。
优选的，所述改性环氧树脂为二聚酸改性环氧树脂，数均分子量为1000～3000。
所述低聚物多元醇A为聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇中的一种以上；
所述低聚物多元醇A的分子量为1000～10000，官能度为2～3；
所述低聚物多元醇B为聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇中的一种以上；
所述低聚物多元醇B的分子量为1000～10000，官能度为2～3；
所述低聚物多元醇B与低聚物多元醇A可以相同或不同。
所述聚酯多元醇由含2～14个碳原子的有机二羧酸与含2～14个碳原子的多元醇酯化反应制得；
所述有机二羧酸为己二酸、丁二酸、戊二酸、辛二酸、癸二酸、壬二酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、癸烷二羧酸、马来酸、富马酸中的一种以上；
所述多元醇为乙二醇、二乙二醇、1,2-或1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、甘油、三羟甲基丙烷中的一种以上；
所述聚醚多元醇为聚氧化丙烯多元醇、聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯共聚多元醇、聚四氢呋喃二醇、聚四氢呋喃共聚物二醇、聚三亚甲基醚二醇中的一种以上。
所述扩链剂为乙二醇、1,4-丁二醇、1,2-丙二醇、1,3-丙二醇、一缩二乙二醇、3,3’-二氯-4,4’-二苯基甲烷二胺(MOCA)、3,5-二乙基甲苯二胺(DETDA)、3,5-二甲硫基甲苯二胺(DMTDA)中的一种以上；
所述发泡剂为水和/或环戊烷；
所述匀泡剂为有机硅匀泡剂；
所述催化剂为三乙烯二胺的乙二醇和/或辛酸亚锡；
优选的，所述的多元醇混合物组分还包含抗氧剂、抗静电剂、耐磨剂，所述抗氧剂、抗静电剂和耐磨剂的用量为具有对异氰酸酯呈反应性集团的聚合物(B)质量的0.01wt％～3.0wt％；
所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、脲酮亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、亚甲基二(环己基二异氰酸酯)中的一种以上。
所述改性环氧树脂增强聚氨酯组合料的制备方法，包括如下步骤：
(1)将低聚物多元醇A、改性环氧树脂、扩链剂、发泡剂、匀泡剂、催化剂在(40～45)℃下混合(2.5～3.5)h，出料密封保存，得到改性环氧树脂增强聚氨酯组合料多元醇混合物组分，即A组分；
(2)将过量的异氰酸酯、低聚物多元醇B、磷酸在(75～85)℃下反应(2.0～3.0)h，得到异氰酸根封端的预聚体组分，即B组分。
所述的改性环氧树脂增强聚氨酯组合料，可用于制备高性能聚氨酯弹性体，应用方法如下：
维持A组分的温度为(20～40)℃，B组分的温度为(40～70)℃，按-OH与-NCO的摩尔比为(0.95～1.05):1，将A、B组分与填充颗粒均匀混合，注入(50～80)℃模具反应(3～8)min成型，脱模，熟化(45～50)h，即可获得所述的高性能聚氨酯弹性体，为一种改性环氧树脂增强聚氨酯杂化材料；
所述填充颗粒为热塑性聚氨酯发泡颗粒、CPU颗粒、橡胶颗粒、乙烯-醋酸乙烯共聚物(EVA)颗粒、聚氨酯发泡颗粒中的一种以上；
所述填充颗粒的添加量为杂化材料总质量的1wt％～90wt％。
所述填充颗粒的直径为0.1cm至10cm，且为球形或椭圆形。
所述填充颗粒为管状颗粒，长度为1mm至40mm，直径为1mm至40mm。
所述高性能聚酰胺-聚氨酯杂化材料密度为0.10g/cm3至1.20g/cm3。
所述改性环氧树脂增强聚氨酯杂化材料，可用于用于鞋底、单车鞍座、运动器材、儿童游乐场、室内装饰品、汽车内外饰、运动跑道的制备。
本发明的有益效果：
本发明的有益效果：体系起发时间长，改性环氧树脂增强的聚氨酯与填充颗粒的粘接性高，填充颗粒的添加量范围宽，无需使用胶粘剂即可有效粘连高填充量的颗粒，制得的杂化材料脱模时间短，弹性佳，密度和硬度可调范围宽，应用广。环氧树脂的加入，提升了杂化材料的耐热性能，使其可应用于高温环境。
具体实施方式
下面通过具体的实施例对本发明做进一步的阐述，但是需要说明的是本发明的实施例中所描述的具体的物料配比，工艺条件及结果仅用于说明本发明，并不能以此限制本发明的保护范围，凡是根据本发明的精神实质所做的等效变化或修饰，都应该涵盖在本发明的保护范围内。
按表1将环氧树脂、聚酯多元醇、聚醚多元醇、扩链剂、发泡剂、匀泡剂、催化剂、抗氧剂等混合，其中实施例1～3在40℃下混合3.5h，实施例4～5在在45℃下混合2.5h，出料密封保存，得到多元醇混合物组分，即A组分。
按表1将异氰酸酯、聚酯多元醇、聚醚多元醇、磷酸投入反应釜中，其中实施例1～2在75℃下反应3.0h，实施例3在80℃下反应2.5h，实施例4～5在85℃下反应2.0h，得到异氰酸根封端的预聚体组分，即B组分。
维持实施例1～2中的聚氨酯组合料中A组分的温度为20℃，B组分的温度为40℃，维持实施例3～5中的聚氨酯组合料中A组分的温度为40℃，B组分的温度为70℃，按表1将A组分、B组分与填充颗粒均匀混合，实施例1注入50℃模具反应3min成型，脱模，熟化46h，实施例2注入60℃模具反应4min成型，脱模，熟化45h，实施例3和实施例9注入70℃模具反应6min成型，脱模，熟化48h，实施例4～5注入80℃模具反应8min成型，脱模，熟化50h，皆得到高性能环氧树脂-聚氨酯杂化材料。
表1
Figure BDA0002000627930000051
Figure BDA0002000627930000061
按表2将环氧树脂、聚酯多元醇、聚醚多元醇、扩链剂、发泡剂、匀泡剂、催化剂、抗氧剂等混合，其中对比例1～3在40℃下混合3.5h，对比例4～5在在45℃下混合2.5h，出料密封保存，得到多元醇混合物组分，即A组分。
按表2将异氰酸酯，聚酯多元醇，聚醚多元醇，磷酸加入反应釜，其中对比例1～2在75℃下反应3.0h，对比例3在80℃下反应2.5h，对比例4～5在85℃下反应2.0h，得到异氰酸根封端的预聚体组分，即B组分。
维持对比例1～2中的聚氨酯组合料中A组分的温度为20℃，B组分的温度为40℃，维持对比例3～5中的聚氨酯组合料中A组分的温度为40℃，B组分的温度为70℃，按表1将A组分、B组分与填充颗粒均匀混合，对比例1注入50℃模具反应3min成型，脱模，熟化46h，对比例2注入60℃模具反应4min成型，脱模，熟化45h，对比例3注入70℃模具反应6min成型，脱模，熟化48h，对比例4～5注入80℃模具反应8min成型，脱模，熟化50h，皆得到聚氨酯杂化材料。
表2
Figure BDA0002000627930000071
Figure BDA0002000627930000081
应用实施例1～5和对比例1～5所制得的聚氨酯杂化材料的各项物性测试结果列于表3。其中：成型密度采用GB/T 1033.1-2008方法检测，成型硬度(邵A)采用GB/T 531.1-2008方法检测，TGA热失重率使用热重分析仪检测，抗拉强度(MPa)和伸长率(％)采用GB/T528-2009方法检测，撕裂强度(kN/m)采用GB/T 529-2008方法检测，起发时间采用HG/T4574-2014测定。
表3
Figure BDA0002000627930000091
由表3，可知，本发明的体系起发时间长，改性环氧树脂增强的聚氨酯与填充颗粒的粘接性高，填充颗粒的添加量范围宽，无需使用胶黏剂即可有效粘连填充颗粒，制成的杂化材料脱模时间短，弹性佳，密度和硬度可调范围宽，应用广。添加环氧树脂，提高了杂化材料的耐热性，使其可应用于高温环境。
尽管上述实施例已经对本发明的技术方案进行了详细地描述，但本发明的技术方案并不限于以上实施例，在不脱离本发明的思想和宗旨情况下，对本发明申请专利范围的内容所作的等效变化或修饰，都应为本发明的技术范畴。

Claims (10)

1.改性环氧树脂增强聚氨酯组合料，其特征在于，包含：含有改性环氧树脂的多元醇组分和异氰酸根封端的预聚体组分，所述的含有改性环氧树脂的多元醇组分中羟基（-OH）和异氰酸根封端的预聚体组分中异氰酸基（-NCO）的摩尔比为（0.95~1.05）:1；
所述改性环氧树脂为二聚酸改性环氧树脂，数均分子量为1000~3000；
所述含有改性环氧树脂的多元醇组分，各原料的重量份数为：
低聚物多元醇A 100份；
改性环氧树脂 15~30份；
扩链剂 0.01 ~6.5份；
发泡剂 1.0~10.0份；
匀泡剂 0.1~6.5份；
催化剂 1.0~4.0份；
所述低聚物多元醇A为聚醚多元醇和聚酯多元醇的混合物，所述低聚物多元醇A的分子量为1000~10000，官能度为2~3。
2.根据权利要求1所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述异氰酸根封端的预聚体组分为过量异氰酸酯与低聚物多元醇B的反应产物，所述异氰酸根封端的预聚体组分中NCO含量为0.1wt%~15.0wt%。
3.根据权利要求2所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述异氰酸根封端的预聚体组分中NCO含量为0.1 wt%~10.0 wt%，在反应原料中加入占原料总质量0.002wt%~0.020wt%的磷酸。
4.根据权利要求2所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述低聚物多元醇B为聚醚多元醇、聚酯多元醇中的一种以上，所述低聚物多元醇B的分子量为1000~10000，官能度为2~3；所述低聚物多元醇B与低聚物多元醇A相同或不同。
5.根据权利要求2所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述低聚物多元醇B为聚己内酯多元醇、聚碳酸酯多元醇中的一种以上，所述低聚物多元醇B的分子量为1000~10000，官能度为2~3；所述低聚物多元醇B与低聚物多元醇A相同或不同。
6.根据权利要求4所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述聚酯多元醇由含2~14个碳原子的有机二羧酸与含2~14个碳原子的多元醇酯化反应制得；
所述有机二羧酸为己二酸、丁二酸、戊二酸、辛二酸、癸二酸、壬二酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、癸烷二羧酸、马来酸、富马酸中的一种以上；
所述多元醇为乙二醇、二乙二醇、1,2-或1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、甘油、三羟甲基丙烷中的一种以上；
所述聚醚多元醇为聚氧化丙烯多元醇、聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯共聚多元醇、聚四氢呋喃二醇、聚三亚甲基醚二醇中的一种以上。
7.根据权利要求1所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述扩链剂为乙二醇、1,4-丁二醇、1,2-丙二醇、1,3-丙二醇、一缩二乙二醇、3,3’-二氯-4,4’-二苯基甲烷二胺、3,5-二乙基甲苯二胺、3,5-二甲硫基甲苯二胺中的一种以上；
所述发泡剂为水和/或环戊烷；
所述匀泡剂为有机硅匀泡剂；
所述催化剂为三乙烯二胺的乙二醇溶液和/或辛酸亚锡。
8.根据权利要求1所述的改性环氧树脂增强聚氨酯组合料，其特征在于，所述的含有改性环氧树脂的多元醇组分还包含抗氧剂、抗静电剂、耐磨剂，所述抗氧剂、抗静电剂和耐磨剂各自的用量为异氰酸根封端的预聚体组分质量的0.01wt%~3.0wt%；
所述异氰酸根封端的预聚体组分的反应原料异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、脲酮亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、亚甲基二（环己基二异氰酸酯）中的一种以上。
9.根据权利要求1-8任一项所述的改性环氧树脂增强聚氨酯组合料，其特征在于，包括如下步骤：
（1）将低聚物多元醇A、改性环氧树脂、扩链剂、发泡剂、匀泡剂、催化剂在（40~45）℃下混合（2.5~3.5）h，出料密封保存，得到改性环氧树脂增强聚氨酯组合料的含有改性环氧树脂的多元醇组分；
（2）将过量的异氰酸酯、低聚物多元醇B、磷酸在（75~85）℃下反应（2.0~3.0）h，得到异氰酸根封端的预聚体组分。
10.根据权利要求1-8任一项所述的改性环氧树脂增强聚氨酯组合料的应用，其特征在于，用于制备聚氨酯弹性体，应用方法如下：
维持含有改性环氧树脂的多元醇组分的温度为（20~40）℃， 异氰酸根封端的预聚体组分的温度为（40~70）℃，按-OH与-NCO的摩尔比为（0.95~1.05）:1，将含有改性环氧树脂的多元醇组分、异氰酸根封端的预聚体组分与填充颗粒均匀混合，注入（50~80）℃模具反应（3~8）min成型，脱模，熟化（45~50）h。
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