CN116396461A - 一种异氰酸酯封端预聚物及其应用、利用该预聚物制备的聚氨酯粘合剂 - Google Patents
一种异氰酸酯封端预聚物及其应用、利用该预聚物制备的聚氨酯粘合剂 Download PDFInfo
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- CN116396461A CN116396461A CN202310368153.0A CN202310368153A CN116396461A CN 116396461 A CN116396461 A CN 116396461A CN 202310368153 A CN202310368153 A CN 202310368153A CN 116396461 A CN116396461 A CN 116396461A
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- acid
- isocyanate
- sodium
- chain extender
- terminated prepolymer
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Abstract
本申请涉及粘合剂的技术领域,具体公开了一种异氰酸酯封端预聚物及其应用、利用该预聚物制备的聚氨酯粘合剂。本申请提供的异氰酸酯封端预聚物,包括双官能度多元醇、多官能度多元醇和异氰酸酯、亲水扩链剂;其中,所述亲水扩链剂选自羧酸型亲水扩链剂、磺酸型亲水扩链剂中的一种或多种;所述异氰酸酯封端预聚物中所述亲水扩链剂的含量为1‑15wt%。本申请还提供了该异氰酸酯封端预聚物的应用,利用该异氰酸酯封端预聚物和水溶性胺类固化剂,获得了固化时间短的聚氨酯粘合剂,且该聚氨酯粘合剂具有亲水性好、组织表面浸润性好、湿粘合力高的优势。
Description
技术领域
本申请涉及粘合剂的技术领域,具体涉及一种异氰酸酯封端预聚物及其应用、利用该预聚物制备的聚氨酯粘合剂。
背景技术
目前,合成聚合物类粘合剂具有明确的分子结构,可进行大规模重复批量生产,且在化学和机械性能方面表现出高度的可调节性,因此在医用组织粘合剂中的研究越来越多。这类组织粘合剂主要包括氰基丙烯酸酯类、聚乙二醇类、聚氨酯类。其中氰基丙烯酸酯类组织粘合剂的毒性在很大程度上限制了其在临床中的应用;且其还具有脆性,固化后容易破裂,因此仅限于在低张力区域使用,不适合长切口。聚乙二醇类粘合剂聚合后为柔软或粘稠凝胶,临床中出现明显的粘连肿胀,本体机械强度和粘合力学均很差。尽管以上诸多种类医用粘合剂均有上市产品,但均存在或多或少的问题使其在组织快速修复上得不到较为广泛的应用。
而聚氨酯由于其高弹性、与生物组织之间高强度的共价键粘附作用和较低的溶胀率,在医用组织粘合剂中的研究与应用越来越广泛。异氰酸根可与组织蛋白质的氨基反应形成脲键,从而与组织牢固结合在一起。
聚氨酯类主要问题在于固化时间较长,降解速率较慢,及降解产物可能存在毒性和致癌性。典型产品为TissuGlu,该产品为以异氰酸酯封端的超支化预聚物,可用于减少死腔中的液体积累,消除手术引流需求。但该产品固化时间较长,约30min左右,不能完全满足生物组织间快速粘附的临床需求,且已退市。
现阶段芳香族异氰酸酯可实现快速固化,但与组织中的水反应生成聚氨酯泡沫,降低粘合剂本体的机械强度,同时会造成组织液渗出等不良影响。叔胺催化剂一般对脂肪族异氰酸酯无效,发泡反应发生概率较低,固化时间较长。依赖于封端的脂肪族异氰酸酯中的-NCO基团会出现与组织中活泼氢反应过慢的情况。
为解决固化慢的难题,专利CN202110383105.X中通过加入端羟基扩链剂,获得一种固化时长可控聚氨酯医用粘合剂,但其采用有机溶剂,后期需对溶剂进行去除,制备过程复杂。
为解决水下粘附的难题,专利CN202111615211.2在聚氨酯体系中引入邻苯二酚基团,但该基团不稳定易氧化,保存条件苛刻,且在固化过程中通常采用强氧化剂NaIO4固化,不适用于临床要求。
因聚氨酯材料本身具有较高的交联度,吸水率和溶胀率均较小,因此近年来对聚氨酯医用粘合剂的研究主要集中在克服水界面的屏障。第一,增强聚氨酯医用组织粘合剂的亲水性,使水分子更容易在表面聚集形成水化层,通过排水或吸水机制克服界面水化层的影响,促进与组织之间的粘附。第二,调节聚氨酯医用组织粘合剂的黏度,增强材料在组织表面的浸润性,使聚氨酯分子渗透扩散至组织表面,与其形成拓扑纠缠的二次互锁网络结构,实现与组织之间的粘附。
发明内容
为了克服聚氨酯粘合剂与组织之间的水界面屏障,增强聚氨酯分子在组织表面的浸润性,实现一种超亲水、粘度低、快速固化,可在血液与组织液中使用,可满足临床实际需求的医用聚氨酯粘合剂,本申请提供一种异氰酸酯封端预聚物及其应用、利用该预聚物制备的聚氨酯粘合剂。
第一方面,本申请提供一种异氰酸酯封端预聚物,包括双官能度多元醇、多官能度多元醇和异氰酸酯、亲水扩链剂;
其中,所述亲水扩链剂选自羧酸型亲水扩链剂、磺酸型亲水扩链剂中的一种或多种;所述异氰酸酯封端预聚物中所述亲水扩链剂的含量为1-15wt%;
按官能团摩尔量计,总-NCO与总-OH的官能团比值为1.1-3,所述双官能度多元醇中-OH与所述多官能度多元醇中-OH的官能团比值为0.2-3。
本申请的发明人首先利用双官能度多元醇、多官能度多元醇和异氰酸酯形成聚氨酯中间产物,并加入羟基酸型或者磺酸型等亲水扩链剂最终形成分子量适中的异氰酸酯封端预聚物。该预聚物与水溶性胺类固化剂反应,可以形成一种高亲水、低粘度、浸润性好、快速固化、生物相容性良好的聚氨酯组织粘合剂。
本申请利用羧酸型亲水扩链剂和磺酸型亲水扩链剂制备异氰酸酯封端预聚物,将羧基、磺酸基的亲水基团引入聚氨酯链段中,增强聚氨酯分子在组织表面的浸润性,克服医用粘合剂与组织表面的水界面屏障。
利用本申请提供的配方原料获得的异氰酸酯封端预聚物具有较低的黏度,有利于降低与胺类固化剂混合初期的黏度,在组织表面有较好的流动性,可扩散渗透至组织内部,形成拓扑纠缠的二次互锁网络结构,促进组织间的粘附。
优选地,所述异氰酸酯封端预聚物中所述亲水扩链剂的含量为5-10wt%。
在一个具体的实施方案中,所述异氰酸酯封端预聚物中所述亲水扩链剂的含量可以为1wt%、5wt%、7.4wt%、10wt%、15wt%。
在一些具体的实施方案中,所述异氰酸酯封端预聚物中所述亲水扩链剂的含量还可以为1-5wt%、1-8wt%、1-10wt%、5-8wt%、5-10wt%、8-10wt%、8-15wt%、10-15wt%。
经过试验分析可知,当亲水扩链剂的含量低于1wt%或者高于15wt%时,制备的异氰酸酯封端预聚物的黏度较大,使得聚氨酯组织粘合剂的浸润性较差,因此,本申请将亲水扩链剂的含量控制为1-15wt%;进一步地,本申请将亲水扩链剂的含量控制为5-10wt%。
优选地,所述羧酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1且羧基官能度≥1,包括但不限于2,2-二羟甲基丙酸、甘油酸、2,2-双羟甲基丁酸、3-羟基丙酸、3-羟基异丁酸、乳酸、柠檬酸、苹果酸、酒石酸、乙醇酸、水杨酸、葡萄糖二酸、粘液酸、氨基酸类、2-氨基丁酸、3-氨基丁酸、2,4-二氨基丁酸、2-氨基己二酸、2-氨基庚二酸、甘氨酸-DL-苯丙氨酸、8-氨基辛酸、5-羟基色氨酸、L-羟基脯氨酸中的一种或多种;
所述磺酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1,且含磺酸基团,包含但不限于牛磺酸、氨基磺酸、tris乙磺酸、氨基磺酸钠、2,4-二氨基苯磺酸钠、己二胺基乙磺酸钠、己二胺基己磺酸钠、靛蓝二磺酸钠、羟乙基磺酸钠、对氨基苯磺酸钠、3-氨基丙磺酸钠、3-羟基-1-丙磺酸钠、4-羟基丁烷磺酸钠、4-氨基苯磺酸钠中的一种或多种。
优选地,所述双官能度多元醇选自分子量为250-10000的聚四氢呋喃、分子量为200-10000的聚乙二醇、分子量为530-10000的聚己内酯二醇、分子量为10000的聚己内酯-聚四氢呋喃-聚己内酯嵌段共聚物、分子量为400-10000的聚己内酯-聚乙二醇嵌段共聚物、分子量为500-10000的聚乳酸-聚己内酯嵌段共聚物、聚乳酸二醇、聚对二氧环己酮二醇、聚羟基烷酸酯二醇、聚乙醇酸二醇、聚L-丙交酯-己内酯二醇中的一种或多种;所述多官能度多元醇选自300-2500的聚乙烯醇、葡萄糖、甘油、蓖麻油、分子量为550-10000的聚己内酯三醇、分子量为800-1000的壳聚糖、聚乳酸三醇、聚对二氧环己酮三醇、聚羟基烷酸酯三醇、聚乙醇酸三醇、聚L-丙交酯-己内酯三醇中的一种或多种。
优选地,所述异氰酸酯封端预聚物还包括催化剂;所述催化剂的用量为反应体系原料总质量的0-0.3wt%。
优选地,所述催化剂选自三乙醇胺、三乙胺、三乙烯二胺、二月桂酸二丁基锡、异辛酸锡、2-乙基己酸铋、2-乙基己酸锌中的一种或多种。
本申请提供的异氰酸酯封端预聚物未加入溶剂,在制备过程中采用无溶剂法,无后续脱除纯化流程,制备方法简单。
第二方面,本申请提供了上述异氰酸酯封端预聚物在医用材料或粘合剂材料中的应用。
本申请所使用的原料均为生物材料,安全无毒,生物相容性良好,能够用于医用材料中。同时,本申请提供的异氰酸酯封端预聚物具有较多的反应位点,具有较优异的粘结性能,可以作为粘合剂材料。
第三方面,本申请提供了一种聚氨酯粘合剂,包含A组分和B组分;所述A组分为上述任一项所述的异氰酸酯封端预聚物,所述B组分为水溶性胺类固化剂。
本申请利用异氰酸酯封端预聚物与水溶性胺类固化剂生成聚脲结构,与所需粘结组织中的活泼氢可以形成氢键结构,进一步加强组织粘附。水溶性胺类固化剂与聚氨酯预聚物生成聚脲结构,胺类固化剂的亲水性能进一步调节聚氨酯医用粘合剂的亲水性,通过排水或吸水机制克服界面水化层的影响,促进组织粘附。
另外,本申请异氰酸根封端预聚物与胺类固化剂反应较快,可实现快速固化,可缩短临床手术时间,且形成的聚氨酯胶体柔韧性较好,适应软组织自体机械性能。
优选地,所述水溶性胺类固化剂包括聚天门冬氨酸酯。
优选地,所述水溶性胺类固化剂还包括PEG氨基衍生物、聚乙烯亚胺、壳聚糖、聚赖氨酸、甘油、聚乙二醇、聚乙烯醇、聚醚胺、水中的一种或多种。
进一步地,所述水溶性胺类固化剂中所述聚天门冬氨酸酯的含量为5-100wt%。
进一步地,所述聚天门冬氨酸酯的制备方法为:按官能团摩尔量计,将脂肪族胺与不饱和烯按照-NH2:-C=C-=(0.8-1.5):1的比例进行反应获得;
其中,所述脂肪族胺包含聚醚胺、辛二胺、1,6-己二胺、2,6-二氨基-1-己醇、1,5-二氨基-2-甲基戊烷、1,5-二氨基戊烷、1,4-戊二胺、1,4-丁二胺、精胺、丁胺、丙胺中的一种或多种;所述不饱和烯包含丙烯酸、丙烯酸酯、丙烯酸羟酯中的一种或多种。
第四方面,本申请提供了上述聚氨酯粘合剂的使用方法,使用时,将A组分、B组分按官能团摩尔量之比-NCO:-NH=(1.05-1.15):1混合均匀涂覆到所需粘结组织表面即可。
综上所述,本申请的技术方案具有以下效果:
本申请提供的异氰酸酯封端预聚物未加入溶剂,在制备过程中采用无溶剂法,无后续脱除纯化流程,制备方法简单;且所用原料生物相容性好,安全无毒,无潜在细胞毒性,满足临床要求。
本申请将羧基、磺酸基的亲水基团引入聚氨酯链段中,增强聚氨酯分子在组织表面的浸润性,克服医用粘合剂与组织表面的水界面屏。
本申请将水溶性胺类固化剂与异氰酸酯封端预聚物生成聚脲结构,胺类固化剂的亲水性能进一步调节聚氨酯医用粘合剂的亲水性,通过排水或吸水机制克服界面水化层的影响,促进组织粘附;且水溶性胺类固化剂与异氰酸酯封端预聚物组分混合后黏度较低,在组织表面有较好的流动性,可扩散渗透至组织内部,形成拓扑纠缠的二次互锁网络结构,促进组织间的粘附;异氰酸根封端预聚物与胺类固化剂反应较快,可实现快速固化,可缩短临床手术时间,且形成的聚氨酯胶体柔韧性较好,适应软组织自体机械性能。
具体实施方式
第一方面,本申请提供一种异氰酸酯封端预聚物,包括双官能度多元醇、多官能度多元醇和异氰酸酯、亲水扩链剂;亲水扩链剂选自羧酸型亲水扩链剂、磺酸型亲水扩链剂中的一种或多种;异氰酸酯封端预聚物中亲水扩链剂的含量为1-15wt%;按官能团摩尔量计,总-NCO与总-OH的官能团比值为1.1-3,双官能度多元醇中-OH与多官能度多元醇中-OH的官能团比值为0.2-3。
具体地,羧酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1且羧基官能度≥1,包括但不限于2,2-二羟甲基丙酸、甘油酸、2,2-双羟甲基丁酸、3-羟基丙酸、3-羟基异丁酸、乳酸、柠檬酸、苹果酸、酒石酸、乙醇酸、水杨酸、葡萄糖二酸、粘液酸、氨基酸类、2-氨基丁酸、3-氨基丁酸、2,4-二氨基丁酸、2-氨基己二酸、2-氨基庚二酸、甘氨酸-DL-苯丙氨酸、8-氨基辛酸、5-羟基色氨酸、L-羟基脯氨酸中的一种或多种;
磺酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1,且含磺酸基团,包含但不限于牛磺酸、氨基磺酸、tris乙磺酸、氨基磺酸钠、2,4-二氨基苯磺酸钠、己二胺基乙磺酸钠、己二胺基己磺酸钠、靛蓝二磺酸钠、羟乙基磺酸钠、对氨基苯磺酸钠、3-氨基丙磺酸钠、3-羟基-1-丙磺酸钠、4-羟基丁烷磺酸钠、4-氨基苯磺酸钠中的一种或多种。
双官能度多元醇选自分子量为250-10000的聚四氢呋喃、分子量为200-10000的聚乙二醇、分子量为530-10000的聚己内酯二醇、分子量为10000的聚己内酯-聚四氢呋喃-聚己内酯嵌段共聚物、分子量为400-10000的聚己内酯-聚乙二醇嵌段共聚物、分子量为500-10000的聚乳酸-聚己内酯嵌段共聚物、聚乳酸二醇、聚对二氧环己酮二醇、聚羟基烷酸酯二醇、聚乙醇酸二醇、聚L-丙交酯-己内酯二醇中的一种或多种;所述多官能度多元醇选自300-2500的聚乙烯醇、葡萄糖、甘油、蓖麻油、分子量为550-10000的聚己内酯三醇、分子量为800-1000的壳聚糖、聚乳酸三醇、聚对二氧环己酮三醇、聚羟基烷酸酯三醇、聚乙醇酸三醇、聚L-丙交酯-己内酯三醇中的一种或多种。
异氰酸酯封端预聚物还包括催化剂;催化剂的用量为反应体系原料总质量的0-0.3wt%;催化剂选自三乙醇胺、三乙胺、三乙烯二胺、二月桂酸二丁基锡、异辛酸锡、2-乙基己酸铋、2-乙基己酸锌中的一种或多种。
第二方面,本申请提供了上述异氰酸酯封端预聚物在医用材料或粘合剂材料中的应用。
第三方面,本申请提供了一种聚氨酯粘合剂,包含A组分和B组分;A组分为上述异氰酸酯封端预聚物,B组分为水溶性胺类固化剂。
具体地,水溶性胺类固化剂包括含量为5-100wt%的聚天门冬氨酸酯。
水溶性胺类固化剂还包括PEG氨基衍生物、聚乙烯亚胺、壳聚糖、聚赖氨酸、甘油、聚乙二醇、聚乙烯醇、聚醚胺、水中的一种或多种。
聚天门冬氨酸酯的制备方法为:按官能团摩尔量计,将脂肪族胺与不饱和烯按照-NH2:-C=C-=(0.8-1.5):1的比例进行反应获得;
其中,脂肪族胺包含聚醚胺、辛二胺、1,6-己二胺、2,6-二氨基-1-己醇、1,5-二氨基-2-甲基戊烷、1,5-二氨基戊烷、1,4-戊二胺、1,4-丁二胺、精胺、丁胺、丙胺中的一种或多种;不饱和烯包含丙烯酸、丙烯酸酯、丙烯酸羟酯中的一种或多种。
第四方面,本申请提供了上述聚氨酯粘合剂的使用方法,使用时,将A组分、B组分按官能团摩尔量之比-NCO:-NH=(1.05-1.15):1混合均匀涂覆到所需粘结组织表面即可。
以下结合实施例、对比例以及性能检测试验对本申请作进一步详细描述,这些实施例不能理解为限制本申请所要求保护的范围。
实施例
实施例1
本实施例提供了一种聚氨酯粘合剂。
本实施例中聚氨酯粘合剂的制备方法,具体包括以下步骤:
S1:异氰酸酯封端预聚物的制备
在密封、加热温度为80℃、搅拌转速为300r/min的三口烧瓶中,依依次加入10g L-赖氨酸二异氰酸酯、7.080g PEG1000,0.904g聚己内酯二醇,6.110g蓖麻油,0.2434g 2,2-双羟基丙酸(用量为1wt%),0.026g 2-乙基己酸锌,反应至-OH被完全消耗,得到异氰酸酯封端预聚物作为组分A。
S2:水溶性胺类固化剂的制备
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加13g甲基丙烯酸羟乙酯,调节温度至80℃,反应24h,制得水溶性聚天门冬氨酸酯F1作为组分B。
S3:聚氨酯粘合剂的使用
使用时,将A、B组分按-NCO与-NH官能团摩尔比为1.2:1混合均匀,置于所需粘结组织表面。
实施例2
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例1的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为1.268g(用量为5wt%)。其余步骤与原料均与实施例1相同。
实施例3
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例1的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为2.095g(用量为8wt%)。其余步骤与原料均与实施例1相同。
实施例4
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例1的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为2.677g(用量为10wt%)。其余步骤与原料均与实施例1相同。
实施例5
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例1的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为4.252g(用量为15wt%)。其余步骤与原料均与实施例1相同。
实施例6
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:以2.095g的2,2-双羟基丁酸代替2.095g的2,2-双羟基丙酸。其余步骤与原料均与实施例3相同。
实施例7
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:以2.095g的乳酸代替2.095g的2,2-双羟基丙酸。其余步骤与原料均与实施例3相同。
实施例8
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:以2.095g的3-氨基丁酸代替2.095g的2,2-双羟基丙酸。其余步骤与原料均与实施例3相同。
实施例9
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:以2.095g的牛磺酸代替2.095g的2,2-双羟基丙酸。其余步骤与原料均与实施例3相同。
实施例10
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:以2.095g的tirs乙磺酸代替2.095g的2,2-双羟基丙酸。其余步骤与原料均与实施例3相同。
实施例11
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:S2:水溶性胺类固化剂的制备方法不同,具体为:
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加13g甲基丙烯酸羟乙酯,调节温度至80℃,反应24h,制得水溶性聚天门冬氨酸酯F1。
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入3.05g 1,5-二氨基-2-甲基戊烷,然后在1h内滴加完8.61g富马酸二乙酯,调节温度至80℃,反应24h,制得非水溶性聚天门冬氨酸酯F2。
按照质量比9:1将F1与F2进行混合制得水溶性胺类固化剂作为组分B。
实施例12
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:S2:水溶性胺类固化剂的制备方法不同,具体为:
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加13g甲基丙烯酸羟乙酯,调节温度至80℃,反应24h,制得水溶性聚天门冬氨酸酯F1。按照质量比9:1将F1与水进行混合制得水溶性胺类固化剂作为组分B。
实施例13
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:S2:水溶性胺类固化剂的制备方法不同,具体为:
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加13g甲基丙烯酸羟乙酯,调节温度至80℃,反应24h,制得水溶性聚天门冬氨酸酯F1。按照质量比1:9将F1与水进行混合制得水溶性胺类固化剂作为组分B。
实施例14
本实施例提供了一种聚氨酯粘合剂。
本实施例与实施例3的区别之处为:S2:水溶性胺类固化剂的制备方法不同,具体为:
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加13g甲基丙烯酸羟乙酯,调节温度至80℃,反应24h,制得水溶性聚天门冬氨酸酯F1。按照质量比9:1将F1与甘油进行混合制得水溶性胺类固化剂作为组分B。
对比例
对比例1
本对比例提供了一种聚氨酯粘合剂。
本对比例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为0.1943g(用量为0.8wt%)。其余步骤与原料均与实施例2相同。
对比例2
本对比例提供了一种聚氨酯粘合剂。
本对比例与实施例3的区别之处为:步骤S1的异氰酸酯封端预聚物的制备方法不同,具体为:2,2-双羟基丙酸的用量为4.935g(用量为17wt%)。其余步骤与原料均与实施例2相同。
对比例3
本对比例提供了一种聚氨酯粘合剂。
本对比例与实施例3的区别之处为:S2:胺类固化剂的制备方法不同,具体为:
在密封、加热温度为40℃、搅拌转速为300r/min的三口烧瓶中,加入5.80g 1,6-己二胺,然后在1h内向反应体系中滴加8.61g富马酸二乙酯,调节温度至80℃,反应24h,制得非水溶性聚天门冬氨酸酯F2作为组分B。
性能检测试验以实施例1-14与对比例1-3的聚氨酯粘合剂为检测对象,测定聚氨酯粘合剂的固化时间、粘合力、爆破压力以及质量损失。
(1)黏度
采用NDJ-8S旋转粘度计对实施例1-14与对比例1-3中的组分A的黏度进行测量。
(2)固化时间
参考GB/T 13477.5-2002《建筑密封材料试验方法第5部分:表干时间的测定》,将制备好的组织粘合剂在室温下静置一段时间,然后用无水乙醇擦净手指端部,轻轻接触粘合剂上三个不同部位,每10s间隔重复上述操作,直至无粘合剂粘在手指上为止,记录时间。
(3)爆破压力
根据ASTM F2392-04的测试方法,利用新鲜猪皮模拟生物体组织,在组织上造成直径1cm的缺口,使用直径为3cm的湿润补片进行粘接,粘接部分为1cm的圆环;将A、B组分按-NCO与-NH官能团摩尔比为1.05:1,混合均匀,置于所需粘结组织表面,5min后测定聚氨酯粘合剂的爆破压力,平行试验测定5次。
(4)搭接剪切力
根据YY/T 0729.1-2009《组织粘合剂粘接性能试验方法第1部分搭接-剪切拉伸承载强度》的测试方法,利用猪小肠模拟生物体组织,采用502胶水将其粘在80mm*10mm的亚克力板上,将A、B组分按-NCO与-NH官能团摩尔比为1.05:1,混合均匀,置于猪小肠组织表面,粘接面积为10mm*10mm,5min后测试聚氨酯粘合剂的搭接剪切力,平行试验测定5次。
(5)水接触角
采用DSA10动态滴张力仪(KRüSS,德国)在室温下进行测量聚氨酯粘合剂的水接触角。
检测结果:如表1所示。
表1实施例1-14以及对比例1-3中A组分的黏度、聚氨酯粘合剂的性能检测结果
结合表1,通过对比实施例1-14与对比例1-3的检测结果,可知,本申请利用双官能度多元醇、多官能度多元醇和异氰酸酯反应,并加入羟基酸型或者磺酸型等亲水扩链剂可以形成黏度为1500-2100cP的异氰酸酯封端预聚物,然后与水溶性胺类固化剂反应,可以形成一种聚氨酯组织粘合剂。该聚氨酯组织粘合剂在330s内可完成固化,搭接剪切力为5-12N/cm2,水接触角为35-70°,上述结果表明利用本申请提供的原料和配方制备得到的聚氨酯粘合剂具有高亲水、低粘度、浸润性好、快速固化、生物相容性良好的优势。
通过对比实施例1-5与对比例1-2的检测结果,可知在制备异氰酸酯封端预聚物的过程中,当亲水扩链剂的含量低于1wt%时,异氰酸酯封端预聚物的黏度较小、进而使得制备的聚氨酯粘合剂固化时间较长,且粘合剂的水接触角较大,即聚氨酯粘合剂的亲水性较差;当亲水扩链剂的含量高于15wt%时,异氰酸酯封端预聚物的黏度过大,不利于与水溶性胺类固化剂之间的流动性,进而使得制备的聚氨酯粘合剂在组织表面的浸润性较差,不利于促进组织间的粘附。因此本申请将亲水扩链剂的含量控制为1-15wt%的范围内。
通过对比实施例3与实施例6-10的检测结果,可知本申请选择2,2-双羟基丙酸、2,2-双羟基丁酸、乳酸、3-氨基丁酸、牛磺酸、tirs乙磺酸作为亲水扩链剂,均可以获得黏度较低的异氰酸酯封端预聚物,进而与水溶性胺类固化剂形成浸润性较好的聚氨酯粘合剂。
通过对比实施例3与对比例3的检测结果,可知在聚天门冬氨酸酯的制备方法中,当利用不饱和羰基化合物富马酸二乙酯作为原料与脂肪族胺反应时,得到的聚天门冬氨酸酯作为胺类固化剂的水溶性较差,使得聚氨酯粘合剂的亲水性较差。而本申请利用不饱和烯作为原料与脂肪族胺反应,得到的聚天门冬氨酸酯的水溶性较好,可以获得亲水性较优异的聚氨酯粘合剂。
通过对比实施例3与实施例11-14的检测结果,可知当将聚天门冬氨酸酯与其他如甘油和水的亲水性物资组合作为水溶性胺类固化剂时,制备得到的聚氨酯粘合剂的亲水性得到提高,但是固化时间加长。因此,在选择水溶性胺类固化剂的组分时,需要考虑亲水性和固化时间两方面的效果。
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种异氰酸酯封端预聚物,其特征在于,包括双官能度多元醇、多官能度多元醇和异氰酸酯、亲水扩链剂;
其中,所述亲水扩链剂选自羧酸型亲水扩链剂、磺酸型亲水扩链剂中的一种或多种;所述异氰酸酯封端预聚物中所述亲水扩链剂的含量为1-15wt%;
按官能团摩尔量计,总-NCO与总-OH的官能团比值为1.1-3,所述双官能度多元醇中-OH与所述多官能度多元醇中-OH的官能团比值为0.2-3。
2.根据权利要求1所述的异氰酸酯封端预聚物,其特征在于,所述羧酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1且羧基官能度≥1,包括但不限于2,2-二羟甲基丙酸、甘油酸、2,2-双羟甲基丁酸、3-羟基丙酸、3-羟基异丁酸、乳酸、柠檬酸、苹果酸、酒石酸、乙醇酸、水杨酸、葡萄糖二酸、粘液酸、氨基酸类、2-氨基丁酸、3-氨基丁酸、2,4-二氨基丁酸、2-氨基己二酸、2-氨基庚二酸、甘氨酸-DL-苯丙氨酸、8-氨基辛酸、5-羟基色氨酸、L-羟基脯氨酸中的一种或多种;
所述磺酸型亲水扩链剂中羟基官能度≥1或氨基官能度≥1,且含磺酸基团,包含但不限于牛磺酸、氨基磺酸、tris乙磺酸、氨基磺酸钠、2,4-二氨基苯磺酸钠、己二胺基乙磺酸钠、己二胺基己磺酸钠、靛蓝二磺酸钠、羟乙基磺酸钠、对氨基苯磺酸钠、3-氨基丙磺酸钠、3-羟基-1-丙磺酸钠、4-羟基丁烷磺酸钠、4-氨基苯磺酸钠中的一种或多种。
3.根据权利要求1所述的异氰酸酯封端预聚物,其特征在于,所述双官能度多元醇选自分子量为250-10000的聚四氢呋喃、分子量为200-10000的聚乙二醇、分子量为530-10000的聚己内酯二醇、分子量为10000的聚己内酯-聚四氢呋喃-聚己内酯嵌段共聚物、分子量为400-10000的聚己内酯-聚乙二醇嵌段共聚物、分子量为500-10000的聚乳酸-聚己内酯嵌段共聚物、聚乳酸二醇、聚对二氧环己酮二醇、聚羟基烷酸酯二醇、聚乙醇酸二醇、聚L-丙交酯-己内酯二醇中的一种或多种;所述多官能度多元醇选自300-2500的聚乙烯醇、葡萄糖、甘油、蓖麻油、分子量为550-10000的聚己内酯三醇、分子量为800-1000的壳聚糖、聚乳酸三醇、聚对二氧环己酮三醇、聚羟基烷酸酯三醇、聚乙醇酸三醇、聚L-丙交酯-己内酯三醇中的一种或多种。
4.如权利要求1-3中任一项所述的异氰酸酯封端预聚物在医用材料或粘合剂材料中的应用。
5.一种聚氨酯粘合剂,其特征在于,包含A组分和B组分;所述A组分为权利要求1-3中任一项所述的异氰酸酯封端预聚物,所述B组分为水溶性胺类固化剂。
6.根据权利要求5所述的聚氨酯粘合剂,其特征在于,所述水溶性胺类固化剂包括聚天门冬氨酸酯。
7.根据权利要求6所述的聚氨酯粘合剂,其特征在于,所述水溶性胺类固化剂还包括PEG氨基衍生物、聚乙烯亚胺、壳聚糖、聚赖氨酸、甘油、聚乙二醇、聚乙烯醇、聚醚胺、水中的一种或多种。
8.根据权利要求7所述的聚氨酯粘合剂,其特征在于,所述水溶性胺类固化剂中所述聚天门冬氨酸酯的含量为5-100wt%。
9.根据权利要求6-8任一项所述的聚氨酯粘合剂,其特征在于,所述聚天门冬氨酸酯的制备方法为:按官能团摩尔量计,将脂肪族胺与不饱和烯按照-NH2:-C=C- =(0.8-1.5):1的比例进行反应获得;
其中,所述脂肪族胺包含聚醚胺、辛二胺、1,6-己二胺、2,6-二氨基-1-己醇、1,5-二氨基-2-甲基戊烷、1,5-二氨基戊烷、1,4-戊二胺、1,4-丁二胺、精胺、丁胺、丙胺中的一种或多种;
所述不饱和烯包含丙烯酸、丙烯酸酯、丙烯酸羟酯中的一种或多种。
10.如权利要求5-9中任一项所述的聚氨酯粘合剂的使用方法,其特征在于,使用时,将A组分、B组分按官能团摩尔量之比-NCO:-NH=(1.05-1.15):1混合均匀涂覆到所需粘结组织表面即可。
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