CN112457462A - 一种非离子型水性聚氨酯及其制备方法和应用 - Google Patents
一种非离子型水性聚氨酯及其制备方法和应用 Download PDFInfo
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- CN112457462A CN112457462A CN201911172395.2A CN201911172395A CN112457462A CN 112457462 A CN112457462 A CN 112457462A CN 201911172395 A CN201911172395 A CN 201911172395A CN 112457462 A CN112457462 A CN 112457462A
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- parts
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- nonionic
- prepolymer
- silicone oil
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Classifications
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Abstract
本发明提供了一种非离子型水性聚氨酯及其制备方法和应用,属于聚氨酯技术领域。本发明提供的非离子型水性聚氨酯,由包括以下重量份的组分制备得到:聚多元醇120~185份;二异氰酸酯30~40份;抗氧剂0.3~0.6份;有机金属催化剂0.1~0.5份;分子内交联剂1~3份;硅油4~6份;助剂2.1~5.5份;扩链剂1~2份;水600~750份;所述聚多元醇包括聚醚二元醇和聚酯二元醇;所述助剂包括润湿剂、流平剂和消泡剂。本发明提供的非离子型水性聚氨酯耐水性能、机械性能和相容性优异,且未添加任何有机溶剂,不产生二次污染,对环境友好。
Description
技术领域
本发明涉及聚氨酯技术领域,具体涉及一种非离子型水性聚氨酯及其制备方法和应用。
背景技术
水性聚氨酯以水为溶剂,具有安全可靠、机械性能好、易于改性等优点,已逐步取代溶剂型聚氨酯,成为聚氨酯工业发展的重要方向。水性聚氨酯可广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂等领域。
水性聚氨酯依亲水性基团的电荷性质可分为三大类:阴离子型、阳离子型和非离子型。其中,非离子型聚氨酯涂膜的耐酸和耐电介质性能好,且生物相容性好,在皮革涂饰剂等方面有着很大的应用发展空间。但是现有的非离子型水性聚氨酯在乳化阶段完全靠其内部亲水性基团的作用,与阴离子型聚氨酯相比其耐水性较差,限制了其应用。而且,现有的非离子型水性聚氨酯合成过程中,为了提高聚氨酯的分散性能和满足其使用需要,通常需添加少量的有机溶剂,例如酮等,然而添加的有机溶剂在使用时会以气态分子的形式挥发至空气中,不仅造成了环境污染,同时也对人体健康构成了威胁。
发明内容
鉴于此,本发明的目的在于提供一种非离子型水性聚氨酯及其制备方法和应用,本发明提供的非离子型水性聚氨酯耐水性能、机械性能和相容性优异,且未添加有机溶剂,对环境友好。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种非离子型水性聚氨酯,由包括以下重量份的组分制备得到:
聚多元醇120~185份;
二异氰酸酯30~40份;
抗氧剂0.3~0.6份;
有机金属催化剂0.1~0.5份;
分子内交联剂1~3份;
硅油4~6份;
助剂2.1~5.5份;
扩链剂1~2份;
水600~750份;
所述聚多元醇包括聚醚二元醇和聚酯二元醇;
所述助剂包括润湿剂、流平剂和消泡剂。
优选地,所述聚醚二元醇包括聚乙二醇、聚氧化丙烯二醇、聚四氢呋喃醚二醇、环氧乙烷聚醚、非离子二元醇、线性聚乙烯乙二醇双功能甲醚和聚乙二醇单甲醚中的至少两种。
聚酯二元醇包括聚碳酸酯二元醇、聚己内酯多元醇和聚己二酸丁二醇的至少一种。
优选地,所述聚醚二元醇和聚酯二元醇的质量比为(110~155):(10~30)。
优选地,所述二异氰酸酯包括异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯和六亚甲基二异氰酸酯中的至少一种。
优选地,所述硅油为含羟基硅油和/或含氨基硅油。
优选地,所述抗氧剂包括受阻酚类抗氧剂和/或亚磷酸酯抗氧剂;
所述有机金属催化剂包括有机银催化剂、有机铋催化剂和有机锌催化剂中的至少一种;
所述分子内交联剂包括三羟甲基丙烷和/或三羟甲基乙烷;
所述扩链剂包括乙二胺、羟乙基乙二胺和异佛尔酮二胺中的至少一种。
优选地,所述润湿剂、流平剂和消泡剂的质量比为(1~3):(1~2):(0.1~0.5)。
本发明提供了上述技术方案所述非离子型水性聚氨酯的制备方法,包括以下步骤:
将聚多元醇、抗氧剂、二异氰酸酯和有机金属催化剂混合,进行第一聚合反应,得到第一预聚物;
将所述第一预聚体和分子内交联剂混合,进行交联反应,得到第二预聚物;
将所述第二预聚体和硅油混合,进行第二聚合反应,得到第三预聚物;
将所述第三预聚物、助剂、扩链剂和水混合,进行扩链反应,得到非离子型水性聚氨酯;
所述助剂包括润湿剂、流平剂和消泡剂。
优选地,所述第一聚合反应的温度为60~75℃,时间为0.5~0.6h;
所述交联反应的温度为75~85℃,时间为1.0~1.5h;
所述第二聚合反应的温度为85~90℃,时间为1.5~2.0h。
所述扩链反应的温度为10~20℃,时间为0.5~1.0h。
本发明还提供了上述技术方案所述非离子型水性聚氨酯或上述技术方案所述制备方法制备的非离子型水性聚氨酯在皮革涂饰剂、玻璃纤维和纺织助剂中的应用。
本发明提供了一种非离子型水性聚氨酯,由包括以下重量份的组分制备得到:聚多元醇120~185份;二异氰酸酯30~40份;抗氧剂0.3~0.6份;有机金属催化剂0.1~0.5份;分子内交联剂1~3份;硅油4~6份;助剂2.1~5.5份;扩链剂1~2份;水600~750份;所述聚多元醇包括聚醚二元醇和聚酯二元醇;所述助剂包括润湿剂、流平剂和消泡剂。本发明提供的非离子型水性聚氨酯以聚多元醇和二异氰酸酯为主体,配合使用硅油作为功能单体,并添加润湿剂、流平剂和消泡剂,在抗氧剂、有机金属催化剂、分子内交联剂和扩链剂的共同作用下,得到的非离子型水性聚氨酯的耐水性能、机械性能和相容性优异,且未添加任何有机溶剂,不产生二次污染,对环境友好。
本发明提供了所述非离子型水性聚氨酯的制备方法,操作简单,适宜规模化生产。
具体实施方式
本发明提供了一种非离子型水性聚氨酯,由包括以下重量份的组分制备得到:
聚多元醇120~185份;
二异氰酸酯30~40份;
抗氧剂0.3~0.6份;
有机金属催化剂0.1~0.5份;
分子内交联剂1~3份;
硅油4~6份;
助剂2.1~5.5份;
扩链剂1~2份;
水600~750份;
所述聚多元醇包括聚醚二元醇和聚酯二元醇;
所述助剂包括润湿剂、流平剂和消泡剂。
在本发明中,若无特殊说明,所有的原料组分均为本领域技术人员熟知的市售商品。
在本发明中,按重量份数计,制备所述非离子型水性聚氨酯的原料包括聚多元醇120~185份,优选为125~170份,更优选为130~160份,最优选为135~150份。在本发明中,所述所有聚多元醇的分子量优选1900~2100,更优选为2000。在本发明中,所述聚醚二元醇优选包括聚乙二醇、聚氧化丙烯二醇、聚四氢呋喃醚二醇、环氧乙烷聚醚、非离子二元醇、线性聚乙烯乙二醇双功能甲醚和聚乙二醇单甲醚中的至少两种,更优选包括聚乙二醇、聚氧化丙烯二醇、聚四氢呋喃醚二醇、环氧乙烷聚醚、非离子二元醇中至少一种,以及线性聚乙烯乙二醇双功能甲醚和聚乙二醇单甲醚中的至少一种;所述聚酯二元醇优选包括聚碳酸酯二元醇、聚己内酯多元醇和聚己二酸丁二醇中的至少一种,更优选包括聚碳酸酯二元醇、聚己内酯多元醇或聚己二酸丁二醇。在本发明中,所述聚醚二元醇和聚酯二元醇的质量比优选为(110~155):(10~30),更优选为(115~145):(15~30),最优选为(120~135):(15~25)。本发明采用上述两种聚多元醇,具有良好的低温柔软性、耐候、耐水性、力学性能及热稳定性等,进而提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括二异氰酸酯30~40份,优选为32~40份,更优选为35~40份。在本发明中,所述二异氰酸酯优选包括异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯和六亚甲基二异氰酸酯中的至少一种,更优选包括二异氰酸酯包括异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯。在本发明中,所述二异氰酸酯是脂肪族二异氰酸酯,合成的聚氨酯具有优异的力学性能,光稳定性和耐化学药品性等。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括抗氧剂0.3~0.6份,优选为0.4~0.6份,更优选为0.5份。在本发明中,所述抗氧剂优选包括受阻酚类抗氧剂和/或亚磷酸酯抗氧剂。本发明采用上述抗氧剂,能够避免其他原料被氧化,提高了非离子型水性聚氨酯的抗氧化性能、机械性能和耐水性能,延长了其使用寿命。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括有机金属催化剂0.1~0.5份,更优选为0.2~0.4份,更优选为0.2~0.3份。在本发明中,所述有机金属催化剂优选包括有机银催化剂、有机铋催化剂和有机锌催化剂中的至少一种,更优选包括有机银催化剂、有机铋催化剂或有机锌催化剂。本发明对于所述有机银催化剂、有机铋催化剂和有机锌催化剂的具体种类和型号没有特殊的限定,采用本领域技术人员熟知的市售商品即可,具体如催化剂ESCAT 100Ag-18KM(韩国世好公司)、AC-83(美国凡特鲁斯公司)或优美科1910(东莞市领先环保材料有限公司)。本发明采用上述有机金属催化剂,环保安全,催化活性温和,还是非常有效的后期交联促进剂,可复合使用,提高了非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括分子内交联剂1~3份,优选为38~48份,更优选为35~45份,最优选为40份。在本发明中,所述分子内交联剂优选包括三羟甲基丙烷和/或三羟甲基乙烷,更优选包括三羟甲基丙烷或三羟甲基乙烷。本发明采用的分子内交联剂的交联度高,能够使得聚多元醇和二异氰酸酯充分交联,进而提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括硅油4~6份,优选为4.5~5.5份,更优选为4.5~5份。在本发明中,所述硅油优选为含羟基硅油和/或含氨基硅油。在本发明中,所述含羟基硅油的羟基含量优选为8~12wt%;所述含氨基硅油的氨基含量优选为0.9~1.1%。含羟基硅油和含氨基硅油具有具有低表面能、疏水性好、耐候性好等优点,将其作为功能单体,能够将亲水性链段和耐水性链段引入到聚氨酯分子中,提高非离子型水性聚氨酯的耐水性能、机械性能和相容性,延长其使用寿命。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括助剂2.1~5.5份,优选为2.5~5份,更优选为3~4.5份;所述助剂包括润湿剂、流平剂和消泡剂。在本发明中,所述润湿剂、流平剂和消泡剂的质量比优选为(1~3):(1~2):(0.1~0.5),更优选为(1.5~3):(1.2~2):(0.1~0.4),最优选为(1.5~2.5):(1.5~2):(0.2~0.3)。
在本发明中,所述润湿剂优选包括有机硅类润湿剂和/或醇醚类润湿剂,更优选为有机硅类润湿剂或醇醚类润湿剂。本发明对于所述有机硅类润湿剂和醇醚类润湿剂的具体种类和型号没有特殊的限定,采用本领域技术人员熟知的市售商品即可,具体如DOW OFX-5211(美国道康宁公司)。在本发明中,所述润湿剂能够促使所述非离子型水性聚氨酯制备过程中的润湿流平性,有利于提高快速润湿底材,增进流平性,提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,所述流平剂优选为有机硅类流平剂。本发明对于所述有机硅类流平剂的具体种类和型号没有特殊的限定,采用本领域技术人员熟知的市售商品即可,具体如TEGO 450(德国TEGO迪高助剂)。在本发明中,所述润湿剂能够促使所述非离子型水性聚氨酯制备过程中的高相容性、良好的重涂性、改善耐刮性和防针孔等,有利于提高所述非离子型水性聚氨酯的成膜平整致密,提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,所述消泡剂优选包括聚硅氧烷消泡剂、矿物油消泡剂和聚醚消泡剂中的至少一种,更优选包括聚硅氧烷消泡剂、矿物油消泡剂或聚醚消泡剂。本发明对于所述聚硅氧烷消泡剂、矿物油消泡剂和聚醚消泡剂的具体种类和型号没有特殊的限定,采用本领域技术人员熟知的市售商品即可,具体如TEGO Foamex 810(德国TEGO迪高助剂)或ACP-1500(美国道康宁公司)。在本发明中,所述消泡剂能够消除非离子型水性聚氨酯生产及施工过程中产生的泡沫,有利于提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括扩链剂1~2份,优选为1.1~1.8份,更优选为1.2~1.5份。在本发明中,所述扩链剂优选包括乙二胺、羟乙基乙二胺和异佛尔酮二胺中的至少一种,更优选包括乙二胺、羟乙基乙二胺或异佛尔酮二胺。本发明采用上述扩链剂,能够使水性聚氨酯乳液粒径变小,粘度变大,进而提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,以所述聚多元醇的重量份数为基准,制备所述非离子型水性聚氨酯的原料包括水600~750份,优选为620~400份,更优选为650份。本发明对于所述水没有特殊限定,采用本领域熟知的水即可,具体如去离子水或蒸馏水。在本发明中,所述水能够调节非离子型水性聚氨酯的黏度,有利于提高非离子型水性聚氨酯使用时的施工和易性,同时本发明以水为溶剂,且未添加有机溶剂,不产生二次污染,绿色环保。
本发明提供的非离子型水性聚氨酯以聚多元醇和二异氰酸酯为主体,配合使用硅油作为功能单体,并添加抗氧剂、润湿剂、流平剂和消泡剂,在分子内交联剂、有机金属催化剂和扩链剂的共同作用下,得到的非离子型水性聚氨酯耐水性优异。
本发明提供了上述技术方案所述非离子型水性聚氨酯的制备方法,包括以下步骤:
将聚多元醇、抗氧剂、二异氰酸酯和有机金属催化剂混合,进行第一聚合反应,得到第一预聚物;
将所述第一预聚体和分子内交联剂混合,进行交联反应,得到第二预聚物;
将所述第二预聚体和硅油混合,进行第二聚合反应,得到第三预聚物;
将所述第三预聚物、助剂、扩链剂和水混合,进行扩链反应,得到非离子型水性聚氨酯;
所述助剂包括润湿剂、流平剂和消泡剂。
本发明将聚多元醇、抗氧剂、二异氰酸酯和有机金属催化剂混合,进行第一聚合反应,得到第一预聚物。
在本发明中,聚多元醇、抗氧剂、二异氰酸酯和有机金属催化剂混合的顺序优选为将聚多元醇和抗氧剂进行第一混合后脱水,然后在所得体系中加入二异氰酸酯和有机金属催化剂进行第二混合。在本发明中,所述脱水的方式优选为真空脱水;所述真空脱水的温度优选为75~85℃,时间优选为0.5~0.8h,真空度优选为-0.08~-0.1MPa;脱水后的聚多元醇的含水率优选≤0.05%,防止水分影响反应。在本发明中,所述第二混合的温度优选为60~65℃。在本发明中,所述第一混合和第二混合的方式优选为搅拌混合,本发明对于所述第一混合和第二混合的速度和时间没有特殊限定,能够保证原料混合均匀即可。
在本发明中,所述第一聚合反应的温度优选为60~75℃,更优选为65~75℃,时间优选为0.5~0.6h。
得到第一预聚物后,本发明将所述第一预聚体和分子内交联剂混合,进行交联反应,得到第二预聚物。
在本发明中,所述交联反应的温度优选为75~85℃,时间优选为1.0~1.5h;所述交联反应能够提高聚氨酯的分子交联密度,进而提高其耐水性能、机械性能和相容性。
得到第二预聚物后,本发明将所述第二预聚体和硅油混合,进行第二聚合反应,得到第三预聚物。
在本发明中,所述第二聚合反应的温度优选为85~90℃,时间优选为1.5~2.0h;所述第二聚合反应过程中,聚氨酯分子链中引入了功能性(即耐水性)单体硅油,提高了非离子型水性聚氨酯的耐水性能。
完所述第二聚合反应后,本发明优选测定反应体系中的NCO含量达到理论值后,将体系的温度降至55~60℃,然后进行后续的扩链反应。在本发明中,所述NCO含量优选参照HG-T 2409-1992《聚氨酯预聚体中异氰酸酯基含量的测定》进行测定。在本发明中,所述NCO含量的理论值优选为1.8~2.5。
得到第三预聚物后,本发明将所述第三预聚物、助剂、扩链剂和水混合,进行扩链反应,得到非离子型水性聚氨酯;所述助剂包括润湿剂、流平剂和消泡剂。
在本发明中,所述第三预聚物、助剂、扩链剂和水混合的方式优选为将水、助剂进行第三混合,在所得体系中加入第三预聚物和扩链剂进行第四混合。在本发明中,所述第三混合和第四混合的温度独立地优选≤12℃,更优选为10~12℃。
在本发明中,所述扩链反应的温度优选为10~20℃,更优选为10~15℃,时间优选为0.5~1.0h,更优选为0.6~0.8h。在本发明中,所述扩链反应过程中,小分子二元胺与异氰酸酯反应生成内聚能高的脲基,能赋予聚氨酯聚合物很好的物理机械性能,提高非离子型水性聚氨酯的耐水性能、机械性能和相容性。
在本发明中,所述第三混合和第四混合和扩链反应优选在分散釜中进行。
本发明提供的制备方法操作简单,适宜工业化生产,将亲水性聚醚二元醇中亲水性链段引入到分子中,同步引入硅油作为耐水性反应单体,经自乳化合成耐水性能、机械性能和相容性优异的非离子型水性聚氨酯;而且制备过程中未加入有机溶剂,不产生二次污,环境友好。
本发明还提供了上述技术方案所述非离子型水性聚氨酯或上述技术方案所述制备方法制备的非离子型水性聚氨酯在皮革涂饰剂、玻璃纤维和纺织助剂中的应用。
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
按重量份数计,在反应釜中加入80kg分子量为2000的聚氧化丙烯二醇、15kg分子量为2000的聚己内酯二醇、40kg亲水性聚醚二元醇和0.5kg抗氧剂1010,在搅拌条件下升温至75℃,在真空度为-0.08MPa条件下抽真空0.8h,使所得混合物的含水率<0.05%;将体系升温至60℃,加入35kg异佛尔酮二异氰酸酯和0.2kg有机锌催化剂优美科1910,在65℃条件下反应0.6h,得到第一预聚物;
第一预聚物和0.9kg三羟甲基丙烷(即分子内交联剂占除去离子水以外的其它原料总质量的0.5%)在75℃条件下反应1.5h;升温至85℃后加入4.8kg含羟基硅油,反应2.0h,参照HG-T 2409-1992《聚氨酯预聚体中异氰酸酯基含量的测定》,检测体系中NCO含量达到1.8~2.0后降温至55℃,得到第二预聚物;
在分散釜中加入650kg去离子水,降温至10℃,加入1.5kg有机硅润湿剂OFX-5211、2kg有机硅流平剂TEGO 450和0.2kg有机硅消泡剂WA-560混合均匀,在所得体系中加入第二预聚物混合均匀,然后滴加1.0kg异佛尔酮二胺,反应1.0h,得到非离子型水性聚氨酯。
实施例2
按照实施例1的方法制备非离子型水性聚氨酯,与实施例1的区别在于,三羟甲基丙烷的用量为1.8kg,即分子内交联剂占除去离子水外原料总质量的1.0%。
实施例3
按照实施例1的方法制备非离子型水性聚氨酯,与实施例1的区别在于,三羟甲基丙烷的用量为2.7kg,即分子内交联剂占除去离子水外原料总质量的1.5%。
实施例4
按重量份数计,在反应釜中加入85kg分子量为2000的聚氧化丙烯二醇、25kg分子量为2000的聚己内酯二醇、38kg非离子二元醇和0.5kg抗氧剂1010,在搅拌条件下升温至85℃,在真空度为-0.1MPa条件下抽真空0.7h,使聚多元醇的含水率<0.05%;将体系升温至65℃,加入40kg异佛尔酮二异氰酸酯和0.2kg有机铋催化剂AC-83,在75℃条件下反应0.5h,得到第一预聚物;
第一预聚物和1.5kg三羟甲基乙烷在85℃条件下反应1.0h;升温至90后加入2.4kg含羟基硅油(即含羟基硅油占除去离子水外原料总质量的1.2%),反应1.5h,参照HG-T2409-1992《聚氨酯预聚体中异氰酸酯基含量的测定》,检测体系中NCO含量达到2.2~2.5后降温至60℃,得到第二预聚物;
在分散釜中加入650kg去离子水,降温至8℃,加入1.5kg有机硅润湿剂OFX-5211、2kg有机硅流平剂TEGO 450和0.2kg有机硅消泡剂WA-560混合均匀,在所得体系中加入第二预聚物混合均匀,然后滴加1.2kg乙二胺,反应0.8h,得到非离子型水性聚氨酯。
实施例5
按照实施例2的方法制备非离子型水性聚氨酯,与实施例2的区别在于,含羟基硅油的质量为4.8kg,即含羟基硅油占除去离子水外原料总质量的2.4%。
实施例6
按照实施例2的方法制备非离子型水性聚氨酯,与实施例2的区别在于,含羟基硅油的质量为7.2kg,即含羟基硅油占除去离子水外原料总质量的3.6%,用量控制在一个合适的范围内。
对比例1
按照实施例1的方法制备非离子型水性聚氨酯,与实施例1的区别在于,不添加三羟甲基丙烷。
对比例2
按照实施例2的方法制备非离子型水性聚氨酯,与实施例2的区别在于,不添加含羟基硅油。
测试例1
分别测试实施例1~6和对比例1~2制备的非离子型水性聚氨酯乳液的乳液粒径和乳液粘度,测试结果如表1~2所示。
分别精确称量10g实施例1~6和对比例1~2制备的非离子型水性聚氨酯乳液置于φ9cm表面皿中,使乳液于皿底部形成一层均匀的薄膜,放置于72℃的干燥箱内干燥12h,取出冷却至室温后小心揭下,得到非离子型水性聚氨酯膜,将所得非离子型水性聚氨酯膜裁成2cm×2cm的试样并且称重g1,室温条件下,将胶膜浸泡在去离子水中24h后,取出并迅速吸干表面的水分,称重g2,非离子型水性聚氨酯膜的吸收率计算公式为:x(%)=(g2-g1)/g1×100%,测试结果如表1~2所示。
表1分子内交联剂对非离子型水性聚氨酯的影响
表1中,分子内交联剂的质量分数表示分子内交联剂的质量占除水外所有原料质量总和百分数。由表1可知,一定范围内,乳液的粒径和粘度随着分子内交联用量增加而增大,而吸水率降低,表明本发明提供的非离子型水性聚氨酯具有良好的耐水性能。
表2含羟基硅油对非离子型水性聚氨酯的影响
表2中,含羟基硅油的质量分数表示含羟基硅油的质量占除水外所有原料质量总和的百分数。由表2可知,一定范围内,乳液的粒径和粘度随着含羟基硅油用量增加而增大,而吸水率降低,表明,本发明提供的非离子型水性聚氨酯具有良好的耐水性能。
测试例2
力学性能测试:
将样品膜在烘箱中真空干燥24小时,再用模具将试样制成哑铃型样条。将制成的样条在烘箱中放置半小时,以消除试样在压制过程中所产生的应力。使用CMT6014型电子万能(拉力)试验机测试。在室温条件下,采用通用橡胶拉伸模式在100mm/min的速率下测定其力学性能。
表3分子内交联剂对非离子型水性聚氨酯力学性能的影响
表3是分子内交联剂是对聚氨酯薄膜力学性能的影响。由表3可得随着分子内交联剂比例的增加,薄膜的拉伸强度增大,而断裂伸长率则逐下降。
表4含羟基硅油对非离子型水性聚氨酯力学性能的影响
表4是含羟基硅油对非离子型水性聚氨酯力学性能的影响。由表4可得随着含羟基硅油用量的增加,薄膜的拉伸强度下降,而断裂伸长率则逐升高。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种非离子型水性聚氨酯,其特征在于,由包括以下重量份的组分制备得到:
聚多元醇120~185份;
二异氰酸酯30~40份;
抗氧剂0.3~0.6份;
有机金属催化剂0.1~0.5份;
分子内交联剂1~3份;
硅油4~6份;
助剂2.1~5.5份;
扩链剂1~2份;
水600~750份;
所述聚多元醇包括聚醚二元醇和聚酯二元醇;
所述助剂包括润湿剂、流平剂和消泡剂。
2.根据权利要求1所述的非离子型水性聚氨酯,其特征在于,所述聚醚二元醇包括聚乙二醇、聚氧化丙烯二醇、聚四氢呋喃醚二醇、环氧乙烷聚醚、非离子二元醇、线性聚乙烯乙二醇双功能甲醚和聚乙二醇单甲醚中的至少两种。
聚酯二元醇包括聚碳酸酯二元醇、聚己内酯多元醇和聚己二酸丁二醇中的至少一种。
3.根据权利要求1或2所述的非离子型水性聚氨酯,其特征在于,所述聚醚二元醇和聚酯二元醇的质量比为(110~155):(10~30)。
4.根据权利要求1所述的非离子型水性聚氨酯,其特征在于,所述二异氰酸酯包括异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯和六亚甲基二异氰酸酯中的至少一种。
5.根据权利要求1所述的非离子型水性聚氨酯,其特征在于,所述硅油包括含羟基硅油和/或含氨基硅油。
6.根据权利要求1所述的非离子型水性聚氨酯,其特征在于,所述抗氧剂包括受阻酚类抗氧剂和/或亚磷酸酯抗氧剂;
所述有机金属催化剂包括有机银催化剂、有机铋催化剂和有机锌催化剂中的至少一种;
所述分子内交联剂包括三羟甲基丙烷和/或三羟甲基乙烷;
所述扩链剂包括乙二胺、羟乙基乙二胺和异佛尔酮二胺中的至少一种。
7.根据权利要求1所述的非离子型水性聚氨酯,其特征在于,所述润湿剂、流平剂和消泡剂的质量比为(1~3):(1~2):(0.1~0.5)。
8.权利要求1~7任一项所述非离子型水性聚氨酯的制备方法,其特征在于,包括以下步骤:
将聚多元醇、抗氧剂、二异氰酸酯和有机金属催化剂混合,进行第一聚合反应,得到第一预聚物;
将所述第一预聚体和分子内交联剂混合,进行交联反应,得到第二预聚物;
将所述第二预聚体和硅油混合,进行第二聚合反应,得到第三预聚物;
将所述第三预聚物、助剂、扩链剂和水混合,进行扩链反应,得到非离子型水性聚氨酯;
所述助剂包括润湿剂、流平剂和消泡剂。
9.根据权利要求8所述的制备方法,其特征在于,所述第一聚合反应的温度为60~75℃,时间为0.5~0.6h;
所述交联反应的温度为75~85℃,时间为1.0~1.5h;
所述第二聚合反应的温度为85~90℃,时间为1.5~2.0h。
所述扩链反应的温度10~20℃,时间为0.5~1.0h。
10.权利要求1~7任一项所述非离子型水性聚氨酯或权利要求8~9任一项所述制备方法制备的非离子型水性聚氨酯在皮革涂饰剂、玻璃纤维和纺织助剂中的应用。
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