CN111303618A - 有机硅改性tpu医用导管及其制备方法 - Google Patents
有机硅改性tpu医用导管及其制备方法 Download PDFInfo
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- CN111303618A CN111303618A CN201911324013.3A CN201911324013A CN111303618A CN 111303618 A CN111303618 A CN 111303618A CN 201911324013 A CN201911324013 A CN 201911324013A CN 111303618 A CN111303618 A CN 111303618A
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- organic silicon
- tpu
- medical catheter
- silicon modified
- polyol
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 42
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 30
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
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- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
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- -1 small molecule diol Chemical class 0.000 claims description 8
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- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 2
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical compound [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 claims description 2
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- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
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- 239000003518 caustics Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
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Abstract
本发明属于聚氨酯弹性体技术领域,具体涉及一种有机硅改性TPU医用导管及其制备方法。所述的有机硅改性TPU医用导管,包括TPU材料和聚乙烯吡咯烷酮涂层;所述TPU材料由以下质量份数的原料制成:有机硅改性多元醇49‑70份,二异氰酸酯23‑40份,扩链剂3‑12份,催化剂0.02‑0.04份,偶联剂0.1‑0.5份。本发明的有机硅改性TPU医用导管,具有优良的机械性能和生物相容性,较高的低温柔韧性、耐水性能、亲水润滑性,同时有机硅在初始原料合成中参与反应,避免了迁移的问题;本发明还提供其制备方法、工艺简单,操作简便。
Description
技术领域
本发明属于聚氨酯弹性体技术领域,具体涉及一种有机硅改性TPU医用导管及其制备方法。
背景技术
当前,在我国医用导管大多采用的原料是软质聚氯乙烯,但材料中残留的氯乙烯单体和添加在其中的增塑剂都会对人体造成很大的危害。TPU和其他医用材料如PE、PP、TPE、PVC和硅橡胶等相比生物相容性好、无致畸变作用、无过敏反应,血液相容性、抗血栓性能好,且不损伤血液成分,具有优良的稳定性以及力学和加工性能,且该材料不含增塑剂,易于焚化,不会释放出腐蚀性物质以及其他危险化学物质,在医疗行业得到广泛的应用。
医用导管对材料的耐低温性、机械性能和耐磨性等性能要求较高,并要求材料具有较好的亲水性,而传统TPU材料的耐低温性和机械性能还有待提高,而且TPU材料的亲水性也较差,在一定程度上限制了其在医用导管领域的应用。为了提高TPU材料的机械性能和耐低温性能,常采用的方法是在TPU体系中通过共混或者在合成过程中引入有机硅组分。
专利CN 109135293 A中公开了一种动态硫化硅橡胶/热塑性聚氨酯弹性体及其制备方法,采用硅橡胶与TPU进行动态硫化,分两步进行制备,高温捏炼造粒及动态硫化;其操作复杂,需要开发动态硫化专用设备、精确控制动态硫化工艺,容易出现橡胶不易剪切、破碎,形成微小的分散相颗粒,难以实现硅橡胶在TPU基体中的理想分散,导致制品的微观形态不够精细,力学性能和弹性较差,该共混改性方法只能改进表面性能,有机硅容易迁移,并且材料的疏水性及环保性能不适合用于医用介入导管。
专利CN201510740025X中公开了一种有机硅改性热塑性聚氨酯弹性体及其制备方法,采用大分子二元醇、端羟烷基封端聚二甲基硅氧烷、二异氰酸酯、小分子扩链剂、催化剂、抗氧化剂、紫外线吸收剂合成聚氨酯弹性体;其在TPU合成过程中直接加入有机硅,虽然增强了聚氨酯弹性体的耐高低温性能和机械性能,但是有机硅与其他组分相容性较差,在使用过程中容易迁移,且有机硅的加入进一步增强了TPU材料的疏水性,不适合用于医用介入导管。
发明内容
针对现有技术的不足,本发明的目的是提供一种有机硅改性TPU医用导管,具有优良的机械性能,较高的低温柔韧性和耐水性能,同时有机硅在初始原料合成中参与反应,避免了迁移的问题;通过PVP表面改性改善了制品的疏水性能,提高了生物相容性和亲水润滑性,本发明还提供其制备方法、工艺简单,操作简便。
本发明所述的有机硅改性TPU医用导管,包括TPU材料和聚乙烯吡咯烷酮(PVP)涂层;所述TPU材料由以下质量份数的原料制成:
有机硅改性多元醇为有机硅改性聚酯多元醇、有机硅改性聚己内酯多元醇、有机硅改性聚碳酸酯多元醇、有机硅改性聚丁二烯多元醇、有机硅改性聚四亚甲基醚二醇中的一种或多种,聚合物多元醇的数均分子量为1000-3000。
优选地,有机硅改性聚酯多元醇为有机硅改性聚己二酸乙二醇酯、有机硅改性聚己二酸丁二醇酯、有机硅改性聚己二酸乙二醇丁二醇酯、有机硅改性聚己二酸己二醇酯。
有机硅改性多元醇所用的有机硅改性剂为小分子羟基硅烷、氨基硅烷、环氧基硅烷、羧基硅烷、丙烯酰氧基硅烷中的一种或多种,其数均分子量为100-800。
二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种。
扩链剂为含有2-10个碳原子的小分子二醇。
催化剂为环保有机铋催化剂。
偶联剂为有机硅偶联剂。
本发明在带有活泼氢的多元醇合成过程中引入有机硅组分,得到有机硅改性的多元醇,以有机硅改性的多元醇为原料与二异氰酸酯、扩链剂反应得到有机硅改性热塑性聚氨酯弹性体材料,与共混改性方法只能改进表面性能以及在TPU合成过程中引入有机硅组分不同,可以提高聚氨酯材料的低温柔韧性、耐水性、耐撕拉等性能,同时避免了有机硅迁移的问题。
本发明所述的有机硅改性TPU医用导管的制备方法,包括以下步骤:
(1)多元醇聚合物合成过程中加入有机硅改性剂,氮气保护下搅拌升温,得到有机硅改性多元醇。
(2)将有机硅改性多元醇、偶联剂加入反应釜A中,在95-105℃温度下搅拌;将二异氰酸酯加入反应釜B中,在60-75℃温度下搅拌;将扩链剂加入反应釜中C,保持温度为40-60℃;通过灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
步骤(1)中有机硅改性剂的用量为有机硅改性多元醇原料总质量的10-30%。
步骤(2)中聚乙烯吡咯烷酮水溶液的浓度为0.1-0.5wt%。
步骤(2)中TPU原料组分体系的异氰酸酯指数为0.99-1.03。
本发明在TPU水下切粒过程中,用PVP水溶液代替纯水,TPU材料中的游离的异氰酸酯与水充分反应交联并与PVP产生物理缠结,同时借助TPU材料中硅烷偶联剂的作用,使PVP在TPU材料表面形成均匀的涂层,从而改善制品的疏水性能,提高有机硅改性TPU材料的生物相容性和亲水润滑性。
与现有技术相比,本发明具有以下有益效果:
(1)本发明在聚氨酯材料原位合成中引入有机硅组分,与共混改性方法只能改进表面性能以及在TPU合成过程中引入有机硅组分不同,可以提高聚氨酯材料的低温柔韧性、耐水性、耐撕拉等性能,同时避免了有机硅迁移的问题;
(2)本发明采用借助硅烷偶联剂进行表面处理,同时,在TPU水下切粒过程中,用PVP水溶液代替纯水,游离的异氰酸酯与水充分反应交联并与PVP产生物理缠结,在TPU材料表面制备一层聚乙烯吡咯烷酮(PVP)亲水涂层,提高了TPU材料的亲水润滑性,应用于医用介入导管,避免了在介入人体时对组织的摩擦力大,容易吸附细菌引起并发炎症的问题;
(3)本发明采用一步法反应挤出工艺,生成原位聚合的热塑性有机硅聚氨酯弹性体,操作简单,生产效率高。
具体实施方式
以下结合实施例对本发明做进一步说明,但本发明的保护范围不仅限于此,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
所述方法如无特别说明均为常规方法,所述原材料如无特别说明均能从公开商业途径而得。
实施例1
按照以下方法制备有机硅改性TPU医用导管:
(1)聚己二酸丁二醇酯合成过程中加入占原料总质量20%的3-氨丙基三乙氧基硅烷,氮气保护下搅拌升温,得到有机硅改性聚己二酸丁二醇酯。
(2)以质量份数计,将69.90份有机硅改性聚己二酸丁二醇酯(PBA,M=3000),0.1份偶联剂KH-550,加入反应釜A中,保持温度为100℃;将23.60份MDI-100加入反应釜B中,保持温度为70℃;将6.36份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.04份异辛酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液(0.2wt%)中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
实施例2
按照以下方法制备有机硅改性TPU医用导管:
(1)聚己内酯多元醇合成过程中加入占原料总质量15%的七甲基三硅氧烷,氮气保护下搅拌升温,得到有机硅改性聚己内酯多元醇。
(2)以质量份数计,将49.74份有机硅改性聚己内酯(PCL,M=2000),0.5份偶联剂KH-560,加入反应釜A中,保持温度为100℃;将38.27份MDI-100加入反应釜B中,保持温度为70℃;将11.47份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.02份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液(0.5wt%)中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
实施例3
按照以下方法制备有机硅改性TPU医用导管:
(1)聚四亚甲基醚二醇合成过程中加入占原料总质量25%的六甲基环三硅氧烷,氮气保护下搅拌升温,得到有机硅改性聚四亚甲基醚二醇。
(2)以质量份数计,将64.72份有机硅改性聚四亚甲基醚二醇(PTMG,M=1000),0.4份偶联剂KH-550,加入反应釜A中,保持温度为100℃;将28.91份MDI-100加入反应釜B中,保持温度为70℃;将5.94份1,6-己二醇加入反应釜C中,保持温度为60℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液(0.3wt%)中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
对比例1
本对比例与实施例3相比,不同点仅在于所用聚四亚甲基醚二醇未经过有机硅改性,具体制备方法如下:
以质量份数计,将64.72份聚四亚甲基醚二醇(PTMG,M=1000),0.4份偶联剂KH-550,加入反应釜A中,保持温度为100℃;将28.91份MDI-100加入反应釜B中,保持温度为70℃;将5.94份1,6-己二醇加入反应釜C中,保持温度为60℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液(0.3wt%)中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
对比例2
本对比例与实施例3相比,不同点仅在于未添加硅烷偶联剂及聚乙烯吡咯烷酮(PVP)亲水涂层,具体制备方法如下:
(1)聚四亚甲基醚二醇合成过程中加入占原料总质量25%的六甲基环三硅氧烷,氮气保护下搅拌升温,得到有机硅改性聚四亚甲基醚二醇。
(2)以质量份数计,将64.98份有机硅改性聚四亚甲基醚二醇(PTMG,M=1000),加入反应釜A中,保持温度为100℃;将29.03份MDI-100加入反应釜B中,保持温度为70℃;将5.96份1,6-己二醇加入反应釜C中,保持温度为60℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒,干燥、熟化得到TPU颗粒;再经过双螺杆挤出机加工得到有机硅改性TPU管。
将实施例1-3和对比例1-2的有机硅改性TPU医用导管进行性能测试,测试方法如下:邵氏硬度测试执行GB/T531.2-2009标准;回弹测试执行GB/T1681-2009标准;拉伸强度测试执行GB/T528-2009标准;撕裂强度测试执行GB/T529-2008标准;磨耗测试执行GB/T9867-2008标准;玻璃化转变温度测试执行GB/T19466.2-2004标准。
测试结果如表1所示。
表1实施例1-3和对比例1-2的产品性能测试结果
从表1可以看出,与对比例1-2相比,本发明采用有机硅改性多元醇为原料与二异氰酸酯、扩链剂反应,原位合成引入有机硅组分,制备的材料手感弹性好,提高了制品力学性能、磨耗性能以及耐低温性能;同时,借助硅烷偶联剂进行表面处理,TPU水下切粒过程中在材料表面制备一层聚乙烯吡咯烷酮(PVP)亲水涂层,提高了材料的亲水润湿性能。
Claims (10)
2.根据权利要求1所述的有机硅改性TPU医用导管,其特征在于:有机硅改性多元醇为有机硅改性聚酯多元醇、有机硅改性聚己内酯多元醇、有机硅改性聚碳酸酯多元醇、有机硅改性聚丁二烯多元醇、有机硅改性聚四亚甲基醚二醇中的一种或多种;聚合物多元醇的数均分子量为1000-3000。
3.根据权利要求2所述的有机硅改性多元醇,其特征在于:有机硅改性多元醇所用的有机硅改性剂为小分子羟基硅烷、氨基硅烷、环氧基硅烷、羧基硅烷、丙烯酰氧基硅烷中的一种或多种,其数均分子量为100-800。
4.根据权利要求1所述的有机硅改性TPU医用导管,其特征在于:二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种。
5.根据权利要求1所述的有机硅改性TPU医用导管,其特征在于:扩链剂为含有2-10个碳原子的小分子二醇。
6.根据权利要求1所述的有机硅改性TPU医用导管,其特征在于:催化剂为有机铋催化剂。
7.根据权利要求1所述的有机硅改性TPU医用导管,其特征在于:偶联剂为有机硅偶联剂。
8.一种权利要求1-7任一项所述的有机硅改性TPU医用导管的制备方法,其特征在于:包括以下步骤:
(1)在多元醇聚合物合成过程中加入有机硅改性剂,氮气保护下搅拌升温,得到有机硅改性多元醇;
(2)将有机硅改性聚酯多元醇、偶联剂加入反应釜A中,在95-105℃温度下搅拌;将二异氰酸酯加入反应釜B中,在60-75℃温度下搅拌;将扩链剂加入反应釜中C,保持温度为40-60℃;通过灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后在聚乙烯吡咯烷酮水溶液中切粒,干燥、熟化得到含有聚乙烯吡咯烷酮涂层的TPU颗粒,再经过双螺杆挤出机加工得到有机硅改性TPU医用导管。
9.根据权利要求8所述的有机硅改性TPU医用导管的制备方法,其特征在于:步骤(2)中聚乙烯吡咯烷酮水溶液的浓度为0.1-0.5wt%。
10.根据权利要求8所述的有机硅改性TPU医用导管的制备方法,其特征在于:步骤(2)中TPU原料组分体系的异氰酸酯指数为0.99-1.03。
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