CN105153393B - 亲水及生物安全的聚合物泡沫、其制备方法和应用 - Google Patents
亲水及生物安全的聚合物泡沫、其制备方法和应用 Download PDFInfo
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Abstract
提供了用于制备亲水性聚合物泡沫的方法,包括提供异氰酸酯官能化预聚物(A)的步骤和使预聚物(A)发泡并固化的步骤。预聚物(A)通过二异氰酸酯(A1)和聚醚多元醇(A2)反应获得,二异氰酸酯(A1)选自1,4‑丁二异氰酸酯(BDI)、赖氨酸二异氰酸酯(LDI),1,5‑戊二异氰酸酯(PDI)中的任意一种及它们的组合;聚醚多元醇(A2)是环氧乙烷(EO)与环氧丙烷(PO)和/或环氧丁烷(BO)的共聚物;环氧乙烷在聚醚多元醇中的重量百分含量在约50%到约100%之间,且具有3‑6的OH官能度,羟基值为约168mgKOH/g‑约21mgKOH/g,具有约1000g/mol到约8000g/mol的数均分子量;预聚物(A)中的NCO含量为1‑10%。
Description
技术领域
本发明涉及亲水性聚合物泡沫,特别是具有生物安全性的亲水性聚氨酯泡沫的制备方法、由该方法制得的产品及该产品的应用。
背景技术
异氰酸酯是合成聚氨酯的主要原料,大致可分脂肪族和芳香族两类。虽然文献中介绍的异氰酸酯的种类较多,但只有上述获得了实际应用。目前聚氨酯敷料主要有两种类型,一种是以芳香族异氰酸酯为原料,例如甲苯二异氰酸酯(TDI)和二苯甲烷二异氰酸酯(MDI);另一种是和以脂肪族异氰酸酯为原料,例如己二异氰酸酯(HDI),二环己基甲烷二异氰酸酯(HMDI)和异佛尔酮二异氰酸酯(IPDI)。
美国专利US7,777,091中提出一种以甲苯二异氰酸酯(TDI)和异佛尔酮二异氰酸酯(IPDI)为主的聚氨酯体系,其中聚醚组份是以高环氧乙烷(EO)含量的环氧乙烷(EO)/环氧丙烷(PO)三官能共聚体。但是这种材料用于医用敷料在降解过程中会产生甲苯二胺(TDA),二苯基甲烷二胺(MDA)等芳香族二胺,经大量毒理实验证实,TDA,MDA是强烈致癌、可诱导基因突变的物质。因此,以芳香族异氰酸酯为原料的聚氨酯并不是理想的安全材料。
美国专利申请公开US 20110184080(申请号US13,003,205)主要以六亚甲基二异氰酸酯(HDI)与高EO含量的聚醚制备预聚体,以三官能度HDI三聚体与单官能度聚氧乙烯醇合成所谓亲水性异氰酸酯,两者的混合物在水,催化剂,表面活性剂的共同作用下反应生成亲水性的聚氨酯发泡材料。其主体异氰酸酯为脂肪族异氰酸酯如HDI。这种聚氨酯材料的降解产物中存在六亚甲基二胺(HDA),虽然这类物质不是至癌的芳香族二胺,但它仍然不是人体中存在的物质,安全性仍有待验证。同时在材料制备过程中需要加入催化剂及其它金属盐作为发泡助剂,否则无法获得理想的泡沫材料,泡沫在发泡后会遭受所期望的强烈收缩。
发明内容
为了解决现有的聚氨酯泡沫材料存在的降解产物安全性差的问题,本发明人发现用这里公开的方法,以赖氨酸二异氰酸酯(LDI),1,4-丁二异氰酸酯(BDI)或1,5-戊二异氰酸酯(PDI)中的任意一种或它们的组合作为异氰酸酯原料制备出的聚氨酯泡沫材料能够提供生物安全性高的医用卫生产品。
本发明人还吃惊地发现:以LDI,BDI,PDI中的任意一种或它们的组合作为异氰酸酯原料制备聚氨酯泡沫材料的过程中,即使不额外添加催化剂或其它各种金属盐类,也可以获得亲水性聚氨酯泡沫材料,且孔隙率大、质轻、吸水率高,特别适合作为伤口敷料、失禁产品和美容产品,且所制得的聚氨酯泡沫材料具有很好的人体接触安全性, 其安全性远高于现有市场产品及现有专利中的描述。
本发明一方面提供了用于制备亲水性聚氨酯泡沫的方法,包括提供异氰酸酯官能化预聚物(A)的步骤和使预聚物(A)发泡并固化的步骤。预聚物(A)通过二异氰酸酯(A1)和聚醚多元醇(A2)反应获得,二异氰酸酯(A1)选自1,4-丁二异氰酸酯(BDI)、赖氨酸二异氰酸酯(LDI),1,5-戊二异氰酸酯(PDI)中的任意一种及它们的组合;聚醚多元醇(A2)是环氧乙烷(EO)与环氧丙烷(PO)和/或环氧丁烷(BO)的共聚物;环氧乙烷在聚醚多元醇中的重量百分含量在约50%到约100%之间,且具有3-6的OH官能度,羟基值为约168mgKOH/g-约21mgKOH/g,具有约1000g/mol到约8000g/mol的数均分子量;预聚物(A)中的NCO含量为1-10%。
本发明另一方面提供了制备亲水性聚氨酯泡沫的方法,在提供异氰酸官能的预聚物(A)的步骤后还包括至少部分地除去未反应的二异氰酸酯(A1)的步骤。
本发明再一方面提供了制备亲水性聚氨酯泡沫的方法,在发泡并固化的步骤前还包括使预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)混合的步骤。
本发明再一方面提供了制备亲水性聚氨酯泡沫的方法,在发泡并固化的步骤前还包括使预聚物(A)与改性多官能异氰酸酯(C)混合的步骤,该改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为200到2000g/mol的单官能聚氧化乙烯(C2)的聚合物。
本发明再一方面提供了制备亲水性聚氨酯泡沫的方法,在发泡并固化的步骤前还包括使预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)和改性多官能异氰酸酯(C)和混合的步骤,该改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为200到2000g/mol的单官能聚氧化乙烯(C2)的聚合物。
本发明又一方面提供了制备亲水性聚氨酯泡沫的方法,在该方法中不使用催化剂。
本发明另一方面提供了制备亲水性聚氨酯泡沫的方法,在该方法中不使用金属盐类添加剂。
附图说明
图1是以BDI体系发泡得到的泡沫的电镜照片(实施例3的泡沫)。
图2是以LDI体系发泡得到的泡沫的电镜照片(实施例4的泡沫)。
图3是以LDI加LTI体系发泡得到的泡沫的电镜照片(实施例5的泡沫)。
图4是以BDI体系发泡得到的泡沫的应力-应变曲线(实施例3的泡沫的应力-应变曲线)。
图5是以LDI体系发泡得到的泡沫的应力-应变曲线(实施例4的泡沫的应力-应变曲线)。
具体实施方式
以下对本发明的实施进行详细描述,以更好地理解、说明和实现 本发明。
异氰酸酯预聚物(A)
异氰酸酯预聚物(A)是由过量的二异氰酸酯(A1)和聚醚多元醇(A2)反应来制备。
二异氰酸酯(A1)
二异氰酸酯(A1)可以为1,4-丁二异氰酸酯(BDI)、赖氨酸二异氰酸酯(LDI),1,5-戊二异氰酸酯(PDI)中的任意一种及它们的组合。
以赖氨酸二异氰酸酯(LDI)为异氰酸酯原料制备出的聚氨酯泡沫材料,其降解产物是人体内的一种氨基酸——赖氨酸,不会导致炎症发生,与细胞界面友好,非生物特异作用小等。
以1,4-丁二异氰酸酯(BDI)为异氰酸酯原料制备的聚氨酯材料,其降解产物是1,4-丁二胺,可以被人体吸收。1,4-丁二胺又名腐胺,是生物活体或尸体中蛋白质的氨基酸降解产物。腐胺的分子式为NH2(CH2)4NH2。在生物体内,鸟氨酸脱羧酶的作用下鸟氨酸脱羧能降解,产生少量的腐胺。多胺类化合物(腐胺是其中具有最简单结构的一种),是细胞***过程中所必须的一类生长因子。腐胺作为生物体的正常成分而广泛存在着,它在每一个细胞中都可以找到。人们认为这种化合物通过升高或降低它的含量水平来控制细胞的pH值。
以1,5-戊二异氰酸酯(PDI)为异氰酸酯原料制备的聚氨酯材料, 其降解产物是1,5-戊二胺,又名尸胺,结构式NH2(CH2)5NH2,是蛋白质腐败时赖氨酸在脱羧酶的作用下发生脱羧反应生成,是广泛存在于生物体中的正常成分。尸胺是一种在动物身体组织腐烂时由蛋白质水解产生的具有腐臭气味的化合物,常温下为浆状液体,深度冷冻可凝固结晶。其实,这种二胺并不是只与腐败作用有关,生物活体在生命代谢中也会产生少量的尸胺。它是造成尿液与***的特殊气味的部分原因。
聚醚多元醇(A2)
聚醚多元醇(A2)可以是是环氧乙烷(EO)与环氧丙烷(PO)和/或环氧丁烷(BO)的共聚物,优选为环氧乙烷(EO)与环氧丙烷(PO)的共聚物。并且,环氧乙烷在聚醚多元醇(A2)中的重量百分含量在约50%到约100%之间,优选大于80%,小于100%。。
聚醚多元醇(A2)的数均分子量典型地是在约1000g/mol-约8000g/mol范围内,优选是在约3000-约5000g/mol范围内。
聚醚多元醇(A2)具有3-6的OH官能度,优选具有3-4的OH官能度,羟基值为约168g/mol-约21g/mol,优选为约56mgKOH/g到约33mgKOH/g。
聚醚多元醇(A2)以多元醇或胺作为起始剂形成的共聚物。适合的起始剂例如可以是甘油、三羟甲基丙烷(TMP)、山梨糖醇、季戊四醇、三乙醇胺、氨或乙二胺。优选甘油和三羟甲基丙烷(TMP),进一步优选甘油。
异氰酸酯(A1)与聚醚多元醇(A2)的摩尔比一般为1-20:1, 优选1-10:1,更优选4-7:1。
异氰酸酯官能化预聚物(A)中的NCO含量为1-10%,优选为3-9%,更优选为4-8%。NCO含量的数值是根据GB/T 12009.4-1989“多亚甲基多苯基异氰酸酯中异氰酸根含量测定方法”测定得出。
预聚物(A)中未反应掉的过量的二异氰酸酯例如可以通过薄膜蒸发等方法除去,从而使异氰酸酯官能化预聚物(A)中的NCO含量降低到3%以下,更进一步降低到2%以下。
预聚物(A)具有约1000g/mol到约8000g/mol的数均分子量,优选具有约3000g/mol到约5000g/mol的数均分子量。
二异氰酸酯(A1)和聚醚多元醇(A2)的反应一般是在约50-约100℃,优选在约70-约90℃下进行。
二异氰酸酯(A1)和聚醚多元醇(A2)的反应即使在不使用常规的氨酯化催化剂如锡化合物、锌化合物、胺、胍或脒的存在下,也能够进行,并达到经济的生产效率。
可以向反应体系中加入稳定剂来增加二异氰酸酯单体的稳定性。例如,可以添加酸性或烷基化稳定剂,如苯甲酰氯、间苯二酰氯、甲苯磺酸甲基酯、氯丙酸、盐酸或抗氧化剂,如二叔丁基甲苯酚或生育酚。
在发泡并固化的步骤前还包括使预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)混合的步骤。预聚物(A)的定义如上所述。预聚物(A)优选为赖氨酸二异氰酸酯(LDI)与聚醚多元醇(A2)反应形成的预聚物。预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)的重量比例为 约10:1-约40:1,优选为约20:1-约25:1。
在发泡并固化的步骤前也可以包括使预聚物(A)与改性多官能异氰酸酯(C)混合的步骤。改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为约200g/mol到约2000g/mol的单官能聚氧化乙烯(C2)反应形成的预聚物,且赖氨酸三异氰酸酯(LTI)(B)和单官能聚氧化乙烯(C2)的摩尔比例为约1:1-约10:1。预聚物(A)与改性多官能异氰酸酯(C)的重量比例为约1:1-约50:1,优选为约1:1-约10:1。
在发泡并固化的步骤前也可以包括使预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)及改性多官能异氰酸酯(C)混合的步骤。改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为约200g/mol到约2000g/mol的单官能聚氧化乙烯(C2)的聚合物,且赖氨酸三异氰酸酯(LTI)(B)和单官能聚氧化乙烯(C2)的摩尔比例为约1:1-约10:1。预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)及改性多官能异氰酸酯(C)的添加量大约为:100重量份预聚物A,赖氨酸三异氰酸酯(LTI)(B)加入量为0-10重量份,改性多官能异氰酸酯(C)的加入量约为0-20重量份。
发泡剂(D)
发泡剂可以选择水、一氟二氯乙烷(CFC-141b)等,优选以水作为发泡剂。
交联剂(E)
交联剂可以选择官能度在两个以上的多羟基化合物,包括但不限于:甘油、三羟甲基丙烷、季戊四醇、山梨糖醇等,及它们的任意混合物;优选官能度大于2的多元醇作为交联剂,进一步优选甘油作为交联剂。
催化剂(F)
在发泡过程中,可以使用催化剂,也可以不使用催化剂。当采用催化剂时,可以加速脲烷的形成。催化剂典型的是聚氨酯合成技术领域中已知的化合物。优选的是选自催化活性金属、胺、脒和胍的化合物。例如辛酸锡、乙酸锡、辛酸锌、二月桂酸二丁锡(DBTL)、1,8-二氮杂二环十一碳-7-烯(DBU)、1,5-二氮杂双环[4.3.0]壬烯-5(DBN)、1,4-二氮杂双环[3.3.0]辛烯-4(DBO)、N-乙基吗啉(NEM)、三亚乙基二胺(DABCO)、五甲基胍(PMG)、四甲基胍(TMG)、环四甲基胍(TMGC)、正癸基四甲基胍(TMGD)、正十二烷基四甲基胍(TMGDO)、二甲基氨基乙基四甲基胍(TMGN)、1,1,4,4,5,5-六甲基异双胍(HMIB)、苯基四甲基胍(TMGP)和六亚甲基八甲基胍(HOBG)。
进一步优选的催化剂是胺、眯、胍或它们的混合物。本发明特别优选的是不加入任何催化剂。
表面活性剂(G)
为了能够对泡沫的形成、稳定性或其性能加以改进,可以添加表面活性剂。表面活性剂可以是阴离子、阳离子、两性或非离子型表面活性剂以及它们的混合物。例如,可以选用聚醚改性硅油,例如赢创B8715赢创B8870赢创O-501,赢创B8871赢创B8409 赢创B8948赢创B8738赢创B8460等。
在一些实施方式中,组分(A)-(G)可以典型地以下列用量使用:
100重量份的异氰酸酯官能化预聚物(A)
0-100重量份的水(D)
0-40重量份的交联剂(E)
0-1重量份的催化剂(F)
0-3重量份的表面活性剂(G)
上述物质用量更优选的范围是:
100重量份的异氰酸酯官能化预聚物(A)
10-60重量份的水(D)
0-20重量份的交联剂(E)
0重量份的催化剂(F)
1-2重量份的表面活性剂(G)
在另一些实施方式中,组分(A)-(G)可以典型地以下列用量使用:
100重量份的异氰酸酯官能化预聚物(A)
0-10重量份的赖氨酸三异氰酸酯(LTI)(B)
0-100重量份的水(D)
0-40重量份的交联剂(E)
0-1重量份的催化剂(F)
0-2重量份的表面活性剂(G)
上述物质用量更优选的范围是:
100重量份的异氰酸酯官能化预聚物(A)
1-5重量份的赖氨酸三异氰酸酯(LTI)(B)
10-50重量份的水(D)
0-20重量份的交联剂(E)
0重量份的催化剂(F)
0-1.5重量份的表面活性剂(G)
在又一些实施方式中,组分(A)-(G)可以典型地以下列用量使用:
100重量份的异氰酸酯官能化预聚物(A)
0-100重量份的改性多官能异氰酸酯(C)
0-100重量份的水(D)
0-40重量份的交联剂(E)
0-1重量份的催化剂(F)
0-2重量份的表面活性剂(G)
上述物质用量更优选的范围是:
100重量份的异氰酸酯官能化预聚物(A)
10-80重量份的改性多官能异氰酸酯(C)
10-50重量份的水(D)
0-20重量份的交联剂(E)
0重量份的催化剂(F)
0-1重量份的表面活性剂(G)
在又一些实施方式中,组分(A)-(G)可以典型地以下列用量使用:
100重量份的异氰酸酯官能化预聚物(A)
0-10重量份的赖氨酸三异氰酸酯(LTI)(B)
0-100重量份的改性多官能异氰酸酯(C)
0-100重量份的水(D)
0-40重量份的交联剂(E)
0-1重量份的催化剂(F)
0-2重量份的表面活性剂(G)
上述物质用量更优选的范围是:
100重量份的异氰酸酯官能化预聚物(A)
2-8重量份的赖氨酸三异氰酸酯(LTI)(B)
0-80重量份的改性多官能异氰酸酯(C)
10-50重量份的水(D)
0-20重量份的交联剂(E)
0重量份的催化剂(F)
0-1重量份的表面活性剂(G)
这里公开的制备聚氨酯泡沫的方法中,是将组分(A)、(D)(E)(G)与任选的组分(B)、(C)、(F)和按照任意顺序混合,将混合物发泡,然后固化。
由该方法得到的聚氨酯泡沫具有柔性,可用作伤口敷料、失禁用品或化妆品等用途,特别是在人或动物皮肤上直接接触伤口和皮肤。
该聚氨酯泡沫具有较低的密度,密度为约0.01-约0.50g/cm3,优选为约0.10-约0.20g/cm3(根据GB/T 6343-2009方法测定)。
该聚氨酯泡沫的生理盐水吸收率典型是在约100-约3000%范围内,优选在约500-约2000%范围内,优选为约1000%-约1300%范围内,最优选在大于800-1500%范围,(根据GB/T 8810-2005方法测定)。
该聚氨酯泡沫具有良好的舒适性压缩曲线(见图3和4)。
异氰酸酯官能化预聚物(A)的制备
实施例1:预聚体1的制备
将40克1,4-丁二异氰酸酯BDI,200克聚醚多元醇ZS-3602,其具有3个OH官能度,EO%=80,羟基值为35mg KOH/g,数均分子量4800,加入到三口烧瓶,在70℃加热并搅拌7小时,到NCO达到理论值7%时停止反应,冷却备用。NCO测定根据国家标准GB/T 12009.4-1989测定。
实施例2:预聚体2的制备
将50克赖氨酸二异氰酸酯(LDI),150克聚醚多元醇(ZS-3602,其具有3个OH官能度,EO%=80,羟基值为35mg KOH/g,数均分子量4800,加入到三口烧瓶,在70℃加热并搅拌7小时,到NCO达到理论值7%时停止反应,冷却备用。NCO测定根据国家标准GB/T 12009.4-1989测定。
实施例3:聚氨酯泡沫1的制备
将24g预聚体1,10g水,5g甘油,0.07g表面活性剂B8460,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
所得到的聚氨酯泡沫具有以下特性:
样品密度:0.18g/cm3(根据GB/T 6343-2009方法测定)
吸水率1200%(根据GB/T 8810-2005方法测定)
如图1所示,泡孔直径在400到600μm的范围内,泡孔壁上有100到200μm的开放微孔。这样的结构一方面有利于液体的吸收,另一方面开放的微孔有效的防止发泡过程中泡沫的塌陷。
如图3的应力应变曲线所示,该聚氨酯泡沫具有良好的舒适性压缩性能。
实施例4:聚氨酯泡沫2的制备
将24g预聚体2,10g水,5g甘油,0.07g表面活性剂B8460,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
所得到的聚氨酯泡沫具有以下特性:
样品密度:0.17g/cm3(根据GB/T 6343-2009方法测定)
吸水率1100%(根据GB/T 8810-2005方法测定)
如图2所示,泡孔直径在200到400μm,泡孔壁上有50到100μm的开放微孔,一方面有利于液体的吸收,另一方面开放的微孔有效的防止发泡过程中泡沫的塌陷。如图4的应力应变曲线所示,该聚氨酯泡沫具有良好的舒适性压缩性能。
实施例5:聚氨酯泡沫3的制备
将22g预聚体2,1.5g三官能的L-赖氨酸三异氰酸酯(LTI),10g 水,5g甘油,0.07g表面活性剂B8460,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
所得到的聚氨酯泡沫具有以下特性:
样品密度:0.15g/cm3(根据GB/T 6343-2009方法测定)
吸水率1100%(根据GB/T 8810-2005方法测定)
由图3可以看出,泡孔直径在200到400μm,泡孔壁上有50到100μm的开放微孔,一方面有利于液体的吸收,另一方面开放的微孔有效的防止发泡过程中泡沫的塌陷。
对比例1:聚氨酯泡沫4的制备
将24g预聚体1,10g水,5g甘油,0.07g表面活性剂B8460,0.05g催化剂DBU混合,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
样品无法正常成型。
对比例2:聚氨酯泡沫5的制备
将24g预聚体2,10g水,5g甘油,0.07g表面活性剂B8460,0.05g催化剂DBU混合,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
样品无法正常成型。
对比例3:聚氨酯泡沫6的制备
将22g预聚体2,1.5g三官能的L-赖氨酸三异氰酸酯,10g水,5g甘油,0.07g表面活性剂B8460,0.05g催化剂DBU混合,在4000rmp转速下搅拌10秒钟,然后迅速倒入烧杯钟,40℃下自由发泡。
样品无法正常成型。
Claims (11)
1.用于制备亲水性聚合物泡沫的方法,包括以下步骤:
提供异氰酸酯预聚物(A)的步骤,
所述预聚物(A)通过二异氰酸酯(A1)和聚醚多元醇(A2)反应获得,其中
所述二异氰酸酯(A1)选自1,4-丁二异氰酸酯(BDI)、赖氨酸二异氰酸酯(LDI)、1,5-戊二异氰酸酯(PDI)中的任意一种及它们的组合;所述聚醚多元醇(A2)是环氧乙烷(EO)与环氧丙烷(PO)和/或环氧丁烷(BO)的共聚物;环氧乙烷在聚醚多元醇中的重量百分含量在50%到100%之间,且具有3-6的OH官能度,羟基值为168mgKOH/g-21mgKOH/g,具有1000g/mol到8000g/mol的数均分子量;
所述预聚物(A)中的NCO含量为1-10%;
使所述预聚物(A)与改性多官能异氰酸酯(C)混合的步骤,其中
所述改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为200g/mol到2000g/mol的单官能聚氧化乙烯(C2)的聚合物;
使所述预聚物(A)及改性多官能异氰酸酯(C)组合发泡并固化的步骤。
2.权利要求1的制备亲水性聚合物泡沫的方法,其中,在所述提供异氰酸官能的预聚物(A)的步骤后还包括至少部分地除去未反应的二异氰酸酯(A1)的步骤。
3.权利要求1的制备亲水性聚合物泡沫的方法,其中,所述聚醚多元醇(A2)以多元醇或多元胺起始,所述聚醚多元醇(A2)中的环氧乙烷的重量百分含量大于80%,小于100%。
4.权利要求1的制备亲水性聚合物泡沫的方法,其中,所述聚醚多元醇(A2)的数均分子量为3000g/mol到6000g/mol,羟基值为56mgKOH/g到28mgKOH/g。
5.用于制备亲水性聚合物泡沫的方法,包括以下步骤:
提供异氰酸酯预聚物(A)的步骤,
所述预聚物(A)通过二异氰酸酯(A1)和聚醚多元醇(A2)反应获得,其中
所述二异氰酸酯(A1)选自1,4-丁二异氰酸酯(BDI)、赖氨酸二异氰酸酯(LDI)、1,5-戊二异氰酸酯(PDI)中的任意一种及它们的组合;所述聚醚多元醇(A2)是环氧乙烷(EO)与环氧丙烷(PO)和/或环氧丁烷(BO)的共聚物;环氧乙烷在聚醚多元醇中的重量百分含量在50%到100%之间,且具有3-6的OH官能度,羟基值为168mgKOH/g-21mgKOH/g,具有1000g/mol到8000g/mol的数均分子量;
所述预聚物(A)中的NCO含量为1-10%;
使所述预聚物(A)与赖氨酸三异氰酸酯(LTI)(B)及改性多官能异氰酸酯(C)混合的步骤,其中
所述改性多官能异氰酸酯(C)含有赖氨酸三异氰酸酯(LTI)(B)和数均分子量为200g/mol到2000g/mol的单官能聚氧化乙烯(C2)的聚合物;
使所述预聚物(A)与所述赖氨酸三异氰酸酯(LTI)(B)及所述改性多官能异氰酸酯(C)组合发泡并固化的步骤。
6.权利要求5的制备亲水性聚合物泡沫的方法,其中,在所述提供异氰酸官能的预聚物(A)的步骤后还包括至少部分地除去未反应的二异氰酸酯(A1)的步骤。
7.权利要求5的制备亲水性聚合物泡沫的方法,其中,所述聚醚多元醇(A2)以多元醇或多元胺起始,所述聚醚多元醇(A2)中的环氧乙烷的重量百分含量大于80%,小于100%。
8.权利要求5的制备亲水性聚合物泡沫的方法,其中,所述聚醚多元醇(A2)的数均分子量为3000g/mol到6000g/mol,羟基值为56mgKOH/g到28mgKOH/g。
9.由权利要求1-8中任一项所述的方法获得的亲水性聚合物泡沫。
10.权利要求9的亲水性聚合物泡沫,其密度为0.01-0.50g/cm3;吸水率为100%-3000%。
11.权利要求9的亲水性聚合物泡沫,其用做伤口敷料、失禁产品或美容产品。
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KR1020187003827A KR20180036980A (ko) | 2015-08-04 | 2016-08-02 | 친수성 및 생물안전성 폴리머 발포체, 그의 제조방법과 응용 |
EP16832298.0A EP3333206A4 (en) | 2015-08-04 | 2016-08-02 | HYDROPHILIC AND BIOLOGICALLY SAFE POLYMER FOAM, AND METHOD FOR PREPARING THE SAME, AND USE THEREOF |
JP2018526288A JP2018526523A (ja) | 2015-08-04 | 2016-08-02 | 生物安全性を有する親水性ポリマーフォーム、その製造方法及び応用 |
PCT/CN2016/092823 WO2017020810A1 (zh) | 2015-08-04 | 2016-08-02 | 亲水及生物安全的聚合物泡沫、其制备方法和应用 |
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CN110036063A (zh) * | 2016-11-14 | 2019-07-19 | 科思创聚合物(中国)有限公司 | 用于化妆施用的聚氨酯泡沫 |
CN107185030A (zh) * | 2017-04-25 | 2017-09-22 | 哈尔滨工程大学 | 一种高吸附性泡沫敷料及其制备方法 |
CN109276749A (zh) * | 2017-07-20 | 2019-01-29 | 泰陞国际科技股份有限公司 | 抗沾粘敷料及其制造方法 |
CN109276739A (zh) * | 2017-07-20 | 2019-01-29 | 泰陞国际科技股份有限公司 | 吸收性敷料及其制造方法 |
CN109276746A (zh) * | 2017-07-20 | 2019-01-29 | 泰陞国际科技股份有限公司 | 除疤贴片及其制造方法 |
WO2019051341A2 (en) * | 2017-09-08 | 2019-03-14 | Maple Ridge, Llc | OIL COPOLYMERS FOR TISSUE FASTENERS |
WO2019137882A1 (de) * | 2018-01-12 | 2019-07-18 | Covestro Deutschland Ag | Verfahren zur herstellung elastischer und reissfester polyurethanschäume sowie deren anwendungen |
CN108976775B (zh) * | 2018-07-05 | 2021-02-09 | 江苏钟山化工有限公司 | 水中可沉降的聚氨酯软泡材料的制备方法及其应用 |
MX2022009817A (es) * | 2020-02-17 | 2022-09-05 | Dow Global Technologies Llc | Espuma rigida de poliuretano. |
US20210317332A1 (en) * | 2020-04-09 | 2021-10-14 | Acushnet Company | Method of making golf ball and resulting golf ball |
CN113713163A (zh) * | 2021-09-09 | 2021-11-30 | 武汉理工大学 | 亲水性聚氨酯敷料及其制备方法 |
CN114452434A (zh) * | 2022-01-26 | 2022-05-10 | 武汉理工大学 | 一种广谱抗菌聚氨酯泡沫敷料及其制备方法和应用 |
CN114632182B (zh) * | 2022-03-30 | 2022-12-27 | 云南清逸堂实业有限公司 | 一种聚氨酯泡沫吸收芯体 |
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