CN116903827A - 一种亲水性聚氨酯泡沫材料 - Google Patents

一种亲水性聚氨酯泡沫材料 Download PDF

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CN116903827A
CN116903827A CN202310367743.1A CN202310367743A CN116903827A CN 116903827 A CN116903827 A CN 116903827A CN 202310367743 A CN202310367743 A CN 202310367743A CN 116903827 A CN116903827 A CN 116903827A
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李满霞
姜志国
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Beijing University of Chemical Technology
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Abstract

本发明属于新材料领域，提供一种能够替代聚乙烯醇缩甲醛泡沫在医用泡沫鼻腔棉及清洁棉方面的亲水性聚氨酯泡沫及其制备方法。该亲水性聚氨酯泡沫包括：聚合物多元醇、异氰酸酯、发泡剂、催化剂、匀泡剂、开孔剂；聚合物多元醇重量百分数为49％～67％，异氰酸酯重量百分数为30％～47％，发泡剂重量百分数为1.0％～1.5％，催化剂重量百分数为0.2％～0.3％，匀泡剂重量百分数为0.4％～1.0％，开孔剂重量百分数为1.0％～2.0％；亲水填料占聚合物多元醇总量的0～25％，不参与反应物用量的计算，聚合物多元醇包括聚醚多元醇和聚酯多元醇其中两种或三种的混合物。本发明中聚氨酯泡沫具有柔软多孔，亲水性好，制备简单，降解速率可调控等特点。

Description

一种亲水性聚氨酯泡沫材料
技术领域
本发明属于新材料技术领域，尤其涉及一种亲水性聚氨酯泡沫及其制备方法。
背景技术
现有聚乙烯醇缩甲醛泡沫具有以下缺点：1)不环保，在制备过程中采用淀粉为制孔剂，生产工程中浪费大量水(1m2泡沫产生8～12m2含淀粉的废水，处理费用高，处理不及时会氧化、发臭)；2)有毒，聚乙烯醇缩甲醛是由聚乙烯醇水溶液和过量甲醛缩合反应制得，生产过程及产品中会含未参加反应的甲醛，危害人们的健康；3)效率低，传统制备工艺，反应聚合时间5～10h，浇注成型工艺，热固型的废料处理成本较高。
因此研制了一步法制备亲水性聚氨酯泡沫替代聚乙烯醇缩甲醛泡沫。本发明中的聚氨酯泡沫自由发密度为50～120kg/m3；反应时间8～25min，与反应温度正相关；常温后固化7～10h。而且本发明中的鼻腔止血棉可以根据需要通过控制其降解速率调控泡沫体的强度。
鉴于上述亲水性聚氨酯泡沫的优点，提出本发明。
发明内容
本发明提供一种亲水性聚氨酯泡沫及其制备方法，用以解决现有聚乙烯醇缩甲醛泡沫在制备过程中废水量大、效率低、不环保、含有有毒气体等缺陷。
本发明中采用水为发泡剂，聚氨酯泡沫生产过程中没有废水的排放；解决了聚乙烯醇缩甲醛泡沫用淀粉做制孔剂，带来的生产过程中产生大量废水的缺陷。本发明中H2O与-NCO生成氨基甲酸(-NHCOOH)，-NHCOOH基团不稳定，化学键断裂分解为-NH2和CO2。反应开始后气体总量不断升高，当气体浓度增加到超过一平衡饱和浓度后，溶液中即开始形成微细的气泡，该过程通常称为核化过程；当核化进行至不再生成微泡时，溶液中气体通过扩散作用逸至已形成的圆球状微泡中去，此时溶液中气体浓度逐渐降低；当其减少至不再有气体发生时，溶液中的气体气体达到平衡饱和浓度阶段，此阶段以后，不再产生新的气泡，只通过气体扩散，小泡的气体并入大泡，形成并泡或由于气泡中气体受热而膨胀，泡沫体积变大，物料的液相变得更薄。随着液相变薄，气泡逐渐失去其圆球形，发展为多面体结构，最后在表面张力作用下，相互连接成网络结构的开放式微孔。本发明采用聚合物多元醇与二异氰酸酯发生扩链反应，形成氨基甲酸酯聚合大分子，与二氧化碳共同作用形成了具有三维网络结构的亲水性聚氨酯泡沫，来提供泡沫使用过程中所需要的强度。
上述反应方程式如下：
反应(1)，聚合物多元醇与异氰酸酯发生扩链反应，形成氨基甲酸酯聚合大分子；反应(2)，H2O与-NCO生成氨基甲酸(-NHCOOH)，-NHCOOH基团不稳定，化学键断裂分解为-NH2和CO2；反应(3)，反应(2)中的端基伯胺反应活性较高，可与-NCO基团反应生成脲基甲酸酯键。
本专利中的简单易制是指亲水性聚氨酯泡沫的制备为一步法制备，反应时间较短，8～25min。常温后固化7-10h之后从模具中取出裁割成所需的形状及大小即可。
本发明中亲水性聚氨酯泡沫的亲水性是指泡沫体在遇水时具有的吸水性能。
本发明中的亲水性能通过在聚氨酯主链上引入亲水基团醚键与酯基和加入亲水填料来实现，饱和吸水率最高能达到18g/g。而且采用聚丙烯酸钠和海藻酸钠做亲水填料的聚氨酯泡沫遇水之后表面会形成一层凝胶层，此凝胶层能够防止鼻腔内新生的组织肉芽向泡沫体内生长，防止泡沫取出时对人体造成的二次伤害。
本发明中的可降解速率是指亲水性聚氨酯泡沫在作为鼻腔棉时，为了避免取出时对病人造成的二次伤害，而需要在3-7天时表现出的力学性能崩溃的现象。
本发明中降解速率的控制则是通过调控聚合物多元醇的种类和用量的不同而实现的。其他条件不变的情况下，聚乳酸多元醇基聚氨酯泡沫降解速率＞多元醇聚酯多元醇基聚氨酯泡沫＞聚醚多元醇基聚氨酯泡沫。通过复配聚合物多元醇的种类及用量来使亲水性聚氨酯泡沫的降解速率达到使用需求。
本发明中亲水性聚氨酯泡沫能够在21天时，全部变成长度小于1mm的碎屑，已经没有完整的圆形泡孔结构，力学性能完全溃散。
本发明中提到的鼻腔棉需满足以下条件：柔软性好，便于塞取，减少在使用时病人的不适感；具有一定的压缩强度，能够实现压迫止血，帮助病人创伤处及时止血；吸液性好，能够将伤口处的血液和组织液完全吸纳；泡沫表面要能够阻止新生组织肉芽生长进入泡沫体，防止取出时的拖拽带来的二次伤害。本发明在鼻腔棉上的创新点是：泡沫体表面产生光滑柔软的凝胶层来代替聚乙烯醇缩甲醛鼻腔止血棉表面的疏水涂层，透气性好，摩擦系数小；泡沫体的力学性能在第三天左右会发生溃散，力学性能大大降低，取出时由一个整体变成几部分大块泡沫，减少了泡沫体与皮肤的接触面积，减轻病人的不适感。
本发明中的提到的清洁棉需要满足以下条件：泡孔孔径足够小，能够依靠其内部纳米毛细管开孔结构达到物理去污的效果；吸液性好，能够清除清洁地所不需的水分等；回弹性能好，多次挤压之后仍然能够回复到原来的状态，延长使用寿命，降低消费者成本；湿态吸液性能好，能够重复多次吸水，便于海绵自清洁和对污秽处的清理。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将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作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。
实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
本发明中接触角(浮法玻璃)的测试方法参照GB/T 2013-2010中接触角测试方法；
本发明中鼻腔棉吸水率的测试方法参照GB/T 1034-2008中吸水率的测试方法；
本发明中清洁棉吸水率的测试方法参照QBT 4318-2012中吸水率测试方法；
本发明中清洁棉疲劳测试参照QBT 4318-2012中吸水率测试方法。
本发明实施例中制备聚氨酯泡沫材料的原料来源见下表1。
表1
实施例1亲水性聚氨酯泡沫
一种亲水性聚氨酯泡沫的制备方法，其步骤如下：
(1)原料准备工序。
(1.1)脱水处理
将聚醚多元醇倒入三口烧瓶中，三口烧瓶的三个口分别连接搅拌装置，温度计和循环水式多用真空泵。三口烧瓶置于加热套中，在低于-0.095MPa的压力下将温度从80℃按5℃/10min的速率缓慢升温至110℃，并在110℃时控温2.5h，去掉真空泵；后5℃/10min的速率缓慢降温至80℃，关闭加热套，待聚醚多元醇冷却至室温后装瓶密封待用。
将聚醚多元醇倒入三口烧瓶中，三口烧瓶的三个口分别连接搅拌装置，温度计和循环水式多用真空泵。三口烧瓶置于加热套中，在低于-0.095MPa的压力下将温度从80℃按5℃/10min的速率缓慢升温至140℃，并在140℃时控温1h，去掉真空泵；后5℃/10min的速率缓慢降温至80℃，关闭加热套，待聚醚多元醇冷却至室温后装瓶密封待用。
将聚乳酸多元醇倒入三口烧瓶中，三口烧瓶的三个口分别连接搅拌装置，温度计和循环水式多用真空泵。三口烧瓶置于加热套中，在低于-0.095MPa的压力下将温度从80℃按5℃/10min的速率缓慢升温至110℃，并在110℃时控温2.5h，去掉真空泵；后5℃/10min的速率缓慢降温至80℃，关闭加热套，待聚乳酸多元醇冷却至室温后装瓶密封待用。
(1.2)预热处理
在进行试验之前，先将二异氰酸酯、聚醚多元醇、聚酯多元醇、聚乳酸多元醇、聚丙烯酸钠盐置于电热鼓风干燥箱中，控制温度为80℃，加热40min待用。
(2)亲水性聚氨酯泡沫的制备
依将称量好的聚醚多元醇、聚酯多元醇、聚乳酸多元醇、H2O、A-33、A-1、T9、匀泡剂、开孔剂和亲水填料加入到纸杯中，后用增力电动搅拌器采用反式四叶桨在一定转速下高速搅拌一定时间，使其各原料混合均匀，得到A组分，并保持其一定的温度；后加入称量好的二异氰酸酯(即B组分)，高速搅拌,待物料发白时，将A、B组分混合物倒入预先准备好的容器中，常温下静置发泡，后常温固化，进行裁样和性能测试。
具体的实施例见下表2，亲水性聚氨酯泡沫的性能见表3。
表2亲水性聚氨酯泡沫的实施例
表3亲水性聚氨酯泡沫的性能
实施例1所制备的亲水性聚氨酯为替代聚乙烯醇缩甲醛鼻腔止血棉的泡沫最优配方。结果表明，泡沫体的自由发密度在80kg/m3，泡沫体柔软、回弹性良好；在浸水3s时，泡沫体表面开始出凝胶层，6h时凝胶层基本达到最厚，为3mm，而且只要不是人为的破坏，凝胶层在浸水72h内不会发生太明显地变化；在浸水3d时泡沫体破裂，已经不能通过万能试验机来测试其拉伸强度和压缩模量，力学性能溃散；浸水21d时泡沫体分解成长度小于1mm的细小碎屑，此时不能再对泡沫体进行质量的称量，可以认定此时质量损失率达到了100％。由上述现象可知，此亲水性聚氨酯泡沫能够满足鼻腔止血棉材料的性能，而且因其凝胶现象，能够阻止新生组织肉芽进入泡沫体；在浸水3d时力学性能溃散，也可以保证在取出时减少与皮肤表面的接触面积，减少病人的不适感。
实施例2所制备的亲水性聚氨酯泡沫为替代聚乙烯醇缩甲醛清洁棉的最优配方。结果表明，接触角59°，亲水材料；自由发密度57kg/m3，，且泡孔细小而均匀，能够实现物理去污；泡沫体湿态吸水率、干态吸水率和疲劳测试都能达到行业推荐性标准。
实施例3所制备的亲水性聚氨酯泡沫与实施例1相比，将原料中的聚乳酸多元醇全部替换为亲水性EP3602，没有添加亲水填料。结果表明，吸水率接近实施例1的1/2；浸水后泡沫体的力学性能保持的比实施例1要好，不容易发生溃散；接触角减小，EP3602的亲水性比PLA2015要好；无凝胶层。实施例3所制备的亲水性聚氨酯泡沫与实施例2相比，EP3602和PEG2000的用量之比变小。结果表明，断裂伸长率有所下降，接触角有所提升，吸水率变小，浸水后的力学性能损失增大，这些都是由于EP3602与PEG2000比，亲水性弱，分子量变大，官能度大，交联点增多而造成的。
实施例4所制备的亲水性聚氨酯泡沫与实施例1相比，将原料中的聚乳酸多元醇部分替换为亲水性EP3602，增加发泡剂的用量，减少亲水填料添加量。结果表明，吸水率减小；浸水后泡沫体的力学性能保持的比实施例1要好，但在第三天时的拉伸强度已经减半，证明已经有了力学性能的溃散产生；接触角减小，EP3602的亲水性比PLA2015要好；凝胶层薄，凝胶层厚度的变化与泡沫体孔径的大小和聚丙烯酸钠的添加量有关。实施例4所制备的亲水性聚氨酯泡沫与实施例3相比，将部分EP3602替换为PLA2015，增加发泡剂的用量。结果表明，拉伸强度和断裂伸长率均稍有所下降，压缩模量明显增大，接触角有所提升，吸水率变大，浸水后的力学性能损失增大，疲劳测试变差；产生这些变化的原因是由实验原料的改变引起的：发泡剂用量增大，亲水性变强，交联点增多，压缩模量变大；EP3602与PLA2015比，亲水性强，分子量变大，官能度大，交联点增多，降解性能变弱而造成的。
实施例5所制备的亲水性聚氨酯泡沫与实施例4相比，将配方中部分EP3602替换为PLA2015，减少发泡剂的用量，增加聚丙烯酸钠用量。结果表明，泡沫体的拉伸强度和断裂伸长率均下降，压缩模量减小，凝胶层厚度变厚，接触角有所提升，吸水率变小，浸水后的力学性能损失严重，疲劳测试变差；产生这些变化的原因是由实验原料的改变引起的：EP3602和发泡剂用量减小，化学交联点变少，力学性能减弱；EP3602的亲水性比PLA2015好，接触角变大；聚丙烯酸钠用量增大，凝胶层厚度增大；PLA2015降解性能优于EP3602，进水后力学性能损失变大，疲劳测试效果差。
以上所描述的实施例仅仅是示意性的，其中所述作为组分可以是或者也可以不是单独添加或者混合添加。可以根据实际的需要选择其中的部分或者全部组分来实现本实施例方案的目的。本领域普通技术人员在不付出创造性的劳动的情况下，即可以理解并实施。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明的各实施例技术方案的精神和范围。

Claims (10)

1.一种能够替代聚乙烯醇缩甲醛泡沫在医用泡沫及清洁棉方面的亲水性聚氨酯泡沫，其特征在于，包括：聚合物多元醇、异氰酸酯、发泡剂、催化剂、匀泡剂、开孔剂；聚合物多元醇重量百分数为49％～67％，异氰酸酯重量百分数为30％～47％，发泡剂重量百分数为1.0％～1.5％，催化剂重量百分数为0.2％～0.3％，匀泡剂重量百分数为0.4％～1.0％，开孔剂重量百分数为1.0％～2.0％；所述聚合物多元醇为聚醚多元醇、聚酯多元醇中的两种或三种。
2.权利要求1所述的亲水性聚氨酯泡沫，其特征在于，所聚合物多元醇为聚乙二醇、聚丙二醇、1，4-丁二醇、聚乙烯醇、聚己内酯二醇，聚乳酸多元醇、聚乳酸-羟基乙酸共聚物，亲水聚醚中的两种或三种；
优选地，聚乙二醇2000和亲水聚醚3602的混合物，用于清洁棉的制备；
优选地，聚乙二醇2000、聚乳酸2015和亲水聚醚3602的混合物，用于可降解鼻腔棉的制备。
3.权利要求1～2中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述异氰酸酯包括二苯基甲烷二异氰酸酯和氢化二苯基甲烷二异氰酸酯；
优选为2,4’-二苯基甲烷二异氰酸酯和氢化二苯基甲烷二异氰酸酯的混合物。
4.权利要求1～3中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述发泡剂为水；所述聚合物多元醇与发泡剂的质量比为100：(1.65～4.15)。
5.权利要求1～4中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述催化剂为胺类催化剂和有机锡类催化剂中的一种及以上；所述聚合物多元醇与催化剂的质量比为100：(0.4～1.2)。
优选地，所述催化剂为北京北化工程技术有限公司的A-1；
优选地，所述催化剂为北京北化工程技术有限公司的A-33；
优选地，所述催化剂为山东振威新材料有限公司的T-9。
6.权利要求1～5中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述匀泡剂为有机硅化合物；所述聚合物多元醇与匀泡剂的质量比为100：(0.6～2.5)
优选地，所述匀泡剂为江苏美思德化学股份有限公司的M-7771LF2。
7.权利要求1～6中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述开孔剂为表面活性剂；
优选地，所述开孔剂为江苏美思德化学股份有限公司的M-9955。
8.权利要求1～7中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述亲水填料为壳聚糖、壳寡糖、羟甲基淀粉、海藻酸钠、聚丙烯酸钠；
优选地，聚丙烯酸钠作为亲水填料加入到鼻腔止血棉中。
9.权利要求1～8中任一项所述的亲水性聚氨酯泡沫的制备方法，其特征在于，包括：
将聚合物多元醇、异氰酸酯进行加热，温度在35～50℃；
将聚合物多元醇、发泡剂、催化剂、匀泡剂、开孔剂按比例混合，得到A组分；
按R值为0.8～1.2的比例将二异氰酸酯称量好，得到B组分；
将所述A组分和B组分在28～45℃的温度范围内混合，高速搅拌，静置，得到亲水性聚氨酯泡沫。
10.权利要求1～9中任一项所述的亲水性聚氨酯泡沫，其特征在于，所述降解速率的调控在于通过加入聚合物多元醇的种类和用量，来改变其降解速率，应用包括：替代现有的聚乙烯醇缩甲醛鼻腔止血海绵；替代聚乙烯醇缩甲醛清洁棉。
优选地，所述鼻腔止血海绵能够调控其降解速率。
CN202310367743.1A 2023-04-07 2023-04-07 一种亲水性聚氨酯泡沫材料 Pending CN116903827A (zh)

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