CN114478990B - 一种高生物相容性本体抗菌防霉tpu材料及其制备方法 - Google Patents
一种高生物相容性本体抗菌防霉tpu材料及其制备方法 Download PDFInfo
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- CN114478990B CN114478990B CN202210059876.8A CN202210059876A CN114478990B CN 114478990 B CN114478990 B CN 114478990B CN 202210059876 A CN202210059876 A CN 202210059876A CN 114478990 B CN114478990 B CN 114478990B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
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- 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 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
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- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 abstract 1
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- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical group O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000000944 Soxhlet extraction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
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- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 208000026935 allergic disease Diseases 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3874—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing heterocyclic rings having at least one sulfur atom in the ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种高生物相容性本体抗菌防霉TPU材料及其制备方法。以质量份数计，该TPU材料原料组成包括：催化剂0～0.01份，抗氧剂0～0.35份，二元醇50～70份，二异氰酸酯20～40份，扩链剂2～10份，氨基修饰的1,2‑苯并异噻唑啉‑3‑酮0.01～0.5份。制备方法包括：将二元醇和可选择性加入的催化剂、抗氧剂于95～105℃搅拌分散得到前驱体B；将前驱体B、二异氰酸酯、扩链剂、氨基修饰的1,2‑苯并异噻唑啉‑3‑酮加入到双螺杆挤出机中，挤出得到高生物相容性本体抗菌防霉TPU材料。
Description
技术领域
本发明涉及热塑性聚氨酯弹性体领域，具体涉及一种高生物相容性本体抗菌防霉TPU材料及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是一类加热可以塑化，化学结构上没有或很少有化学交联的聚氨酯，在宽广的硬度范围内具有高强度、高模量、较好的弹性、优良的耐磨性和良好的耐油性，因此，广泛应用于医学、工业、农业、军事等各大领域。
然而，TPU材料在适宜的温度和湿度条件下，表面极易滋生细菌，严重限制了TPU材料在智能穿戴、医疗等有较高抗菌性能要求领域的应用。
目前，对于抗菌TPU的制备，主要是通过物理共混的方式，将有机或无机抗菌剂加入到TPU中。
公开号为CN106084176A的专利说明书公开了一种环保型抗菌热塑性聚氨酯弹性体的制备方法，采用有机无机纳米复合抗菌剂，先利用机械分散法分散在多元醇中，再通过原位聚合法，实现纳米材料的均匀分散，同时采用一步本体聚合法，通过双螺杆挤出机合成环保型抗菌热塑性聚氨酯弹性体。
无机抗菌剂抗菌效果最好，持续时间长，抗菌广谱性好，是理想的抗菌剂。但是，无机抗菌剂如银、锌、铜、氧化锌等，会影响TPU的耐黄变性能，导致制品容易变色，并且会影响到产品机械性能。
有机抗菌剂大多为小分子杀菌剂，具有初始杀菌能力强、杀菌即效和抗菌谱广等优点，而且无论是粉状还是液体都比较容易分散到高分子材料中，合成技术比较成熟，价格相对便宜。
但是，由于TPU材料为强极性材料，与有机抗菌剂相容性差，抗菌剂容易在TPU材料中迁移出来，导致材料抗菌时效性短，并且有机抗菌剂迁移到制品表面，会严重影响制品的生物安全性。
公开号为CN 112961491 A的专利说明书公开了一种抗菌聚氨酯发泡材料，利用抗菌剂1,2-苯并异噻唑啉-3-酮的NH基团、2-羟甲基-1,2-苯并异噻唑啉-3-酮的OH基团与异氰酸酯的异氰酸根键合，但由于抗菌剂中的NH基团、OH基团都为单官能团，在与异氰酸酯的反应过程中会形成封端，导致分子链长度较短。此外，NH基团的键合率最高也只有78％，即剩余20％多的抗菌剂仍易析出。
发明内容
针对上述技术问题以及本领域存在的不足之处，本发明提供了一种高生物相容性本体抗菌防霉TPU材料，其侧链含有异噻唑啉酮基团，具有高键合率，且不会因提前封端而导致材料的聚合度低。该热塑性聚氨酯弹性体材料表现出优异的抗菌防霉效果和较高的生物安全性。
具体技术方案如下：
一种高生物相容性本体抗菌防霉TPU材料，以质量份数计，原料组成包括：
所述氨基修饰的1,2-苯并异噻唑啉-3-酮具有如下式(I)所示结构：
式(I)中，R为-CH2CH2N(CH2CH2NH2)2。
在上述用量范围内，通过调整二元醇、二异氰酸酯、扩链剂和氨基修饰的1,2-苯并异噻唑啉-3-酮的添加比例，可确保异氰酸根-NCO与羟基-OH和氨基-NH2恰好完全反应。
所述氨基修饰的1,2-苯并异噻唑啉-3-酮的一种优选制备方法包括：
在25～30℃范围内将2,2-二硫化二苯甲酰氯滴加到甲苯和三(2-氨基乙基)胺的混合物中，0.5～1小时滴加完毕，然后继续保温反应55～65min，再加入催化剂三乙胺、氢氧化钠水溶液，升温至54～56℃，在8小时内将双氧水溶液加入到上述反应体系中，滴加结束后将三(2-氨基乙基)胺和甲苯蒸出，剩余液体分出下层有机相，除水干燥即得浅黄色的所述氨基修饰的1,2-苯并异噻唑啉-3-酮液体。
在一优选例中，所述氨基修饰的1,2-苯并异噻唑啉-3-酮的制备方法中，相对于34.4克2,2-二硫化二苯甲酰氯，甲苯用量为200mL，三(2-氨基乙基)胺用量为200mL，催化剂三乙胺用量为20.2克，氢氧化钠水溶液用量为200mL，氢氧化钠浓度为0.08g/mL，双氧水溶液用量为40.8克，H2O2质量浓度为10％。
上述氨基修饰的1,2-苯并异噻唑啉-3-酮的制备方法的流程如下：
在上述氨基修饰的1,2-苯并异噻唑啉-3-酮的制备方法中，2,2-二硫化二苯甲酰氯的滴加速度(具体反映在滴加所用时间)和滴加量是较为关键的因素，对其严格控制可实现每个酰氯基团与一个单独的三(2-氨基乙基)胺进行反应。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，所述催化剂为有机锡、有机铋类中的至少一种。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，所述原料组成包括0.01～0.35质量份的所述抗氧剂。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，以质量份数计，所述抗氧剂包括：
主抗氧剂 0.01～0.2质量份，
辅助抗氧剂 0～0.15质量份。
进一步优选，所述主抗氧剂为抗氧剂1010、抗氧剂245、抗氧剂246中的至少一种；
所述辅助抗氧剂为抗氧剂1076、抗氧剂168、抗氧剂1310中的至少一种。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，所述二元醇为聚酯二元醇、聚醚二元醇、聚丁二烯二元醇、聚碳酸酯二元醇、聚碳酸酯-醚二元醇中的一种或两种的混合物。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，所述二异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或两种的混合物。
在一优选例中，所述的高生物相容性本体抗菌防霉TPU材料，所述扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇中的一种或两种的混合物。
本发明还提供了所述的高生物相容性本体抗菌防霉TPU材料的制备方法，包括步骤：
(1)将所述二元醇和可选择性加入的所述催化剂、所述抗氧剂于95～105℃搅拌分散得到前驱体B；
(2)将所述前驱体B、所述二异氰酸酯、所述扩链剂、所述氨基修饰的1,2-苯并异噻唑啉-3-酮加入到双螺杆挤出机中，挤出得到所述高生物相容性本体抗菌防霉TPU材料。
在一优选例中，所述双螺杆挤出机：挤出温度为160～200℃，螺杆转速为150～300rpm，螺杆长径比为60～120:1。
本发明与现有技术相比，主要优点包括：
本发明提供的一种高生物相容性本体抗菌防霉热塑性聚氨酯弹性体材料，通过特殊的分子结构设计，合成了具有两个活泼氨基的1,2-苯并异噻唑啉-3-酮衍生物；然后通过异氰酸根与氨基和羟基基团的反应，合成了侧链含有异噻唑啉酮基团的热塑性聚氨酯弹性体材料；TPU制品在使用过程中，侧链上的异噻唑啉酮基团与细菌、真菌细胞内含硫的蛋白质、酶等相互作用，使侧链中的S-N键断裂，与蛋白质或酶中的硫形成二硫S-S键，破坏细胞的正常功能。并且，由于氨基修饰的1,2-苯并异噻唑啉-3-酮单体通过异氰酸根与氨基的化学反应连接在TPU分子主链上，从根本上解决了物理共混添加方式容易产生析出的风险，避免了制品在使用过程中析出物进入人体细胞，从而引起过敏、皮肤刺激等生物相容性问题的风险。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
各实施例、对比例选用的部分试剂以及制备方法说明如下：
P1110：由己二酸和己二醇反应得到的、数均分子量为1000的聚酯二元醇，自制；
P1220：由己二酸和己二醇反应得到的、数均分子量为2000的聚酯二元醇，自制；
PM10：由四氢呋喃开环聚合得到的、数均分子量为1000的聚醚二元醇，购自basf；
BDO：1,4-丁二醇，长连化工；
MDI：二苯基甲烷二异氰酸酯，万华化学；
主抗氧剂：抗氧剂1010，科莱恩；
辅助抗氧剂：抗氧剂1076，科莱恩；
催化剂：辛酸亚锡；购自曹氏化工。
氨基修饰的1,2-苯并异噻唑啉-3-酮的制备：在25～30℃范围内，将34.4克2,2-二硫化二苯甲酰氯以1g/min的流量滴加入装有200mL甲苯和200mL三(2-氨基乙基)胺的烧瓶中，滴加完毕后继续保温反应1小时，然后加入20.2克催化剂三乙胺、200mL氢氧化钠水溶液(0.08g/mL)，升温至55℃，在8小时内将40.8克10wt％双氧水溶液加入到上述反应体系中，滴加结束后将三(2-氨基乙基)胺和甲苯蒸出，剩余液体倒入500mL烧杯中，分出下层有机相，除水干燥即得浅黄色的氨基修饰的1,2-苯并异噻唑啉-3-酮，记为抗菌剂A。
各实施例、对比例的TPU材料的原料组成、用量和性能测试结果如表1(各组分用量单位为克)所示，制备TPU材料所采用的双螺杆挤出工艺如下：将主抗氧剂、辅助抗氧剂、催化剂加入到大分子二元醇中，100℃下搅拌4h，搅拌速度为60转/分钟，使抗氧剂、催化剂在大分子二元醇中分散均匀，分别得到前驱体B；上述混合好的前驱体B、二异氰酸酯、扩链剂和上述过程制备的氨基修饰的1,2-苯并异噻唑啉-3-酮(抗菌剂A，对比例不添加氨基修饰的1,2-苯并异噻唑啉-3-酮，其它操作均相同)，通过浇注机加入到双螺杆挤出机浇注口中；挤出机浇注口采用干燥的氮气保护。浇筑口到模头的温度为200-160℃，双螺杆长径比为90:1，螺杆转速为280r/min。
本发明各实施例、对比例的TPU材料的性能测试方法如下：
抗菌率测试：在注塑温度为200℃下，注塑边长为50mm，厚度为2mm的方形试片，按照国标GB 21551.2-2010标准进行抗菌率测试。
生物相容性测试：按照ISO 10993-2010标准进行测试，测试项目包括：皮肤刺激、细胞毒性和过敏性能。
析出性能测试：在注塑温度为200℃下，注塑边长为120mm，厚度为2mm的方形试片；在温度为45℃、湿度为85％的条件下悬挂放置168小时，观察试片表面析出等级。等级划分标准为：
0级：肉眼观察不到任何析出物
1级：极轻微析出，肉眼观察似有似无
2级：轻微析出，肉眼可以观察到
3级：大量析出。
对实施例1-3和对比例1-3的TPU样品，采用甲苯做溶剂进行索氏抽提，对抽提前后的TPU样品进行质量测试，并计算抽提前后的质量差。
表1
由表1中数据可以看出，加入氨基修饰的1,2-苯并异噻唑啉-3-酮抗菌剂，可以显著改善TPU材料的抗菌性能，并且抗菌剂不会从TPU基材中析出，不会对材料的生物相容性产生影响。索氏抽提前后，TPU样品的质量没有变化，说明抗菌剂在TPU合成过程中与NCO基团完全反应，使材料的生物安全性得到保证。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (7)
1.一种高生物相容性本体抗菌防霉TPU材料，其特征在于，以质量份数计，原料组成包括：
催化剂 0~0.01份且不为0，
抗氧剂 0~0.35份且不为0，
二元醇 50~70份，
二异氰酸酯 20~40份，
扩链剂 2~10份，
氨基修饰的1,2-苯并异噻唑啉-3-酮 0.01~0.5份；
所述氨基修饰的1,2-苯并异噻唑啉-3-酮具有如下式（I）所示结构：
（I）；
式（I）中，R为-CH2CH2N(CH2CH2NH2)2；
所述氨基修饰的1,2-苯并异噻唑啉-3-酮的制备方法包括：
在25~30℃范围内将2,2-二硫化二苯甲酰氯滴加到甲苯和三(2-氨基乙基)胺的混合物中，0.5~1小时滴加完毕，然后继续保温反应55~65 min，再加入催化剂三乙胺、氢氧化钠水溶液，升温至54~56℃，在8小时内将双氧水溶液加入到上述反应体系中，滴加结束后将三(2-氨基乙基)胺和甲苯蒸出，剩余液体分出下层有机相，除水干燥即得浅黄色的所述氨基修饰的1,2-苯并异噻唑啉-3-酮液体。
2.根据权利要求1所述的高生物相容性本体抗菌防霉TPU材料，其特征在于，所述氨基修饰的1,2-苯并异噻唑啉-3-酮的制备方法中，相对于34.4克2,2-二硫化二苯甲酰氯，甲苯用量为200 mL，三(2-氨基乙基)胺用量为200 mL，催化剂三乙胺用量为20.2克，氢氧化钠水溶液用量为200 mL，氢氧化钠浓度为0.08 g/mL，双氧水溶液用量为40.8克，H2O2质量浓度为10%。
3.根据权利要求1所述的高生物相容性本体抗菌防霉TPU材料，其特征在于，所述二元醇为聚酯二元醇、聚醚二元醇、聚丁二烯二元醇、聚碳酸酯二元醇、聚碳酸酯-醚二元醇中的一种或两种的混合物。
4.根据权利要求1所述的高生物相容性本体抗菌防霉TPU材料，其特征在于，所述二异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或两种的混合物。
5.根据权利要求1所述的高生物相容性本体抗菌防霉TPU材料，其特征在于，所述扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇中的一种或两种的混合物。
6.根据权利要求1~5任一权利要求所述的高生物相容性本体抗菌防霉TPU材料的制备方法，其特征在于，包括步骤：
（1）将所述二元醇和所述催化剂、所述抗氧剂于95~105℃搅拌分散得到前驱体B；
（2）将所述前驱体B、所述二异氰酸酯、所述扩链剂、所述氨基修饰的1,2-苯并异噻唑啉-3-酮加入到双螺杆挤出机中，挤出得到所述高生物相容性本体抗菌防霉TPU材料。
7.根据权利要求6所述的制备方法，其特征在于，所述双螺杆挤出机：挤出温度为160~200℃，螺杆转速为150~300 rpm，螺杆长径比为60~120:1。
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| CN112961491A (zh) * | 2021-01-25 | 2021-06-15 | 上海大学 | 一种抗菌聚氨酯发泡材料及其制备方法 |
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