CN112341803B - 一种超支化tpu亲水薄膜及其制备方法 - Google Patents
一种超支化tpu亲水薄膜及其制备方法 Download PDFInfo
- Publication number
- CN112341803B CN112341803B CN202011349428.9A CN202011349428A CN112341803B CN 112341803 B CN112341803 B CN 112341803B CN 202011349428 A CN202011349428 A CN 202011349428A CN 112341803 B CN112341803 B CN 112341803B
- Authority
- CN
- China
- Prior art keywords
- tpu
- hyperbranched
- film
- seed oil
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 241000208688 Eucommia Species 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 150000003384 small molecules Chemical group 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 8
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 241000208689 Eucommia ulmoides Species 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims 1
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 38
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 32
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 32
- 230000035699 permeability Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种超支化TPU亲水薄膜及其制备方法。其原料包括二异氰酸酯，杜仲籽油，甲酸，过氧化氢，丙酮，羟基化合物等。制备方法为：将杜仲籽油和甲酸混合搅拌，加入过氧化氢、羟基化合物、光引发剂混合均匀，于UV光下照射反应，得到杜仲籽油基多元醇；将杜仲籽油基多元醇脱水，加入二异氰酸酯、小分子扩链剂，保温反应，得到TPU；将TPU溶解，制得铸膜液，将其制成膜。本发明通过紫外光催化的方法制备超支化生物油基多元醇，再用湿法成膜的方法制备了亲水透气的TPU薄膜。本发明不仅成膜工艺简单可控，利于规模生产，还充分利用了生物资源，实现了原料可再生，提高了TPU薄膜的亲水透气性能。
Description
技术领域
本发明涉及一种超支化热塑性聚氨酯弹性体(简称TPU)亲水薄膜及制备方法，属于功能型高分子材料技术领域。
背景技术
TPU薄膜是一种以TPU粒子为主要原材料的新型、高性能、环保型薄膜材料，从化学构成上可以分为聚酯薄膜和聚醚薄膜两种；从制备方法可以分为熔体加工和溶液加工。TPU薄膜具有强度高、韧性好、耐磨、耐寒、耐油、可降解等优良特性，既可以单独使用，也可以与其他材料复合后使用。近年来，TPU薄膜制品被广泛用在鞋类、防水透湿织物、高档手袋及皮具、充气囊体等领域，但是普通TPU薄膜仍然存在亲水效果差、耐久性差、使用率低等问题，因此通过改进TPU的结构，使其具备更多的亲水基团，从而提高TPU的亲水性能便成为了关键。
通过紫外催化的方法获得超支化杜仲籽油多元醇，再通过湿法成膜的方法制备超支化的亲水薄膜。湿法成膜是高聚物溶液在凝固浴中发生的相分离过程，利用溶剂和凝固剂在体系中浓度的差异，发生的双向扩散的方法。通过紫外催化以及湿法成膜不仅可以从原料上引入亲水基团，赋予薄膜优良的亲水性能，还能充分利用生物资源，减轻对石油资源的依赖。因此发明一种具有大量亲水基团的超支化亲水薄膜，不仅具有极好的亲水透气性，还具有良好的机械强度、耐腐蚀性、耐摩擦性、耐老化性、耐寒性等优异性能
发明内容
本发明所要解决的技术问题是：现有TPU薄膜亲水效果差、耐久性差、使用率低、资源匮乏等问题。
为了解决上述技术问题，本发明提供了一种超支化TPU亲水薄膜，其特征在于，原料包括按重量份数计的以下组分：
优选地，所述的二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、4,4′-二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)和1,5-萘二异氰酸酯(NDI)中的至少一种。
优选地，所述的羟基化合物为二乙醇胺和异丙醇中的至少一种。
优选地，所述的小分子扩链剂为1,4-丁二醇(BDO)和1,6-己二醇(HDO)中的一种或两种。
优选地，所述的光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)和三芳基硫鎓盐(4-(苯硫基)苯基二苯基硫鎓六氟磷酸)(TAS)中的一种或两种。
优选地，所述的催化剂1为氢氧化钠(NaOH)和碳酸钠(Na2CO3)中的至少一种；所述的催化剂2为二月桂酸二丁基锡和辛酸亚锡中的至少一种。
优选地，所述的溶剂为N,N'-二甲基甲酰胺(DMF)；所述的非溶剂为水、甲醇、乙醇和异丙醇中的一种或几种。
本发明还提供了上述杜仲籽油改性亲水性热塑性聚氨酯的制备方法，其特征在于，包括如下步骤：
步骤1)：在催化剂1作用下，将杜仲籽油和甲酸混合搅拌，再缓慢加入过氧化氢，连续搅拌，然后加入羟基化合物，搅拌静置，与溶解于丙酮的光引发剂混合均匀，于UV光下照射反应，得到杜仲籽油基多元醇；
步骤2)：将杜仲籽油基多元醇脱水，在氮气保护的条件下加入二异氰酸酯和催化剂2保温反应，向体系中加入小分子扩链剂，保温反应，得到TPU；
步骤3)：将TPU和溶剂在60～85℃下持续搅拌至完全溶解，制得铸膜液，将其静置，密封除泡，再在干净的玻璃板上制成液膜，然后立即将玻璃板浸入非溶剂中浸泡24～48h；待铸膜液分相成膜后，将制得的薄膜从玻璃板上转移至蒸馏水中浸泡萃取出过量的溶剂和非溶剂。
优选地，所述步骤1)具体为：在催化剂1作用下，将杜仲籽油和甲酸在30～50℃的条件下搅拌1～2h，再缓慢加入过氧化氢，在50～70℃条件下连续搅拌6～8h，然后加入羟基化合物，搅拌静置，与溶解于丙酮的光引发剂混合均匀，放在400～475W的UV光下照射反应3～8min，得到羟值在240～320mgKOH/g的杜仲籽油基多元醇。
优选地，所述步骤2)具体为：将杜仲籽油基多元醇在90～110℃温度下脱水90～120min，降温至65～85℃，在氮气保护的条件下加入二异氰酸酯和催化剂2保温反应60～90min，将体系温度降至40～60℃，向体系中加入小分子扩链剂，保温反应20～70min。
本发明采用湿法成膜的工艺制备亲水透气的TPU薄膜，采用生物基多元醇作为原料制备亲水TPU，不仅解决了能源问题，还赋予产品优异的亲水性能。该工艺制备的TPU薄膜不仅具备优异的亲水透气性，而且简单可控，利于大规模生产。
与现有技术相比，本技术的有益效果是：
本发明通过湿法成膜的工艺制备了超支化TPU亲水薄膜。利用分子设计的原理制备了超支化杜仲籽油基多元醇，作为原料合成了亲水性聚酯。可再生材料作为基础原料，使制备的TPU薄膜不仅具有优异的亲水透气性能，还使材料具有一定的生物降解性，减轻对石油资源的依赖以及对环境的污染。另外，通过湿法成膜的技术制备的TPU薄膜具备较好的亲水透气性能，且该工艺简单可控，利于大规模生产。本发明提供的一种超支化TPU亲水薄膜的制备方法，工艺简单，成本低，适合工艺生产开发。
进一步，用羟值滴定分析法，测的超支化杜仲籽油基多元醇的羟值为240～320mgKOH/g。根据接触角测试仪上实施的滴定技术，测得接触角为20.3～43.5°。在万能材料试验机上测得拉伸强度为28～45Mpa，断裂伸长率400～600％。H2渗透率为3×10-8～5×10- 8mol·(m-2·s-1·Pa-1)；气体渗透量为0.409～0.689mm/s；透湿率为6000～10000g/(m2·24h)。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，作详细说明如下。
本发明的各实施例中所用的原料除下述特殊说明外，其他均购探索平台。杜仲籽油为自提取药品，二月桂酸二丁基锡购自上海国药集团化学试剂有限公司。
用羟值滴定分析法，测试超支化杜仲籽油基多元醇的羟值；采用接触角测量仪(A801S，美国KINO Industry公司)测其水接触角；采用万能材料试验机(SUN500，意大利Cardano ALCamp公司)参照GB/T 1040-2006进行力学性能测试，拉伸速率为30mm/min；采用透气量测试仪(YG46E-I型，温州百恩仪器有限公司)，按GB/T5453-1997对膜进行透气测试；使用压差法气体渗透仪(GBT-301型，中国济南赛成电子科技有限公司)，按GB/T1038-2000对样品进行气体渗透测试；根据美国标准(ASTME96BW-2000)，用YG601H型电脑式透湿测试仪进行透湿性能测试。
实施例1
一种超支化TPU亲水薄膜及其制备方法：
其所用的原料，按重量份数计算，其组成及含量如下：
(1)、用氢氧化钠作催化剂，使杜仲籽油和甲酸在40℃的条件下搅拌1h，再缓慢加入过氧化氢，在60℃条件下连续搅拌6h。然后再加入二乙醇胺，搅拌静置，用丙酮溶解TPO静置。将二者混合均匀，放在435W的UV光下照射反应6min。反应得到羟值在252mg KOH/g的杜仲籽油基多元醇。
(2)、杜仲籽油基多元醇在95℃温度下脱水90min。降温至75℃，在氮气保护的条件下加入二异氰酸酯和二月桂酸二丁基锡保温反应80min。将体系温度降至50℃，向体系中加入小分子扩链剂，保温反应30min。
(3)、将上述制备的TPU和DMF加入三口瓶中，在70℃下持续搅拌至完全溶解，制得铸膜液。将其静置，密封除泡，再在干净的玻璃板上制成厚度为0.3mm的均匀液膜，然后立即将玻璃板浸入非溶剂中浸泡24h；等到铸膜液分相成膜后，将制得的薄膜从玻璃板上转移至蒸馏水中浸泡萃取出过量的溶剂和非溶剂。
所得杜仲籽油基热塑性聚氨酯弹性体，测得的超支化杜仲籽油基多元醇的羟值为243mg KOH/g；经检测本发明接触角为30.5°；拉伸强度为35Mpa，断裂伸长率为480％；所得TPU薄膜，经检测薄膜厚度为0.35mm，H2渗透率分别为3.2×10-8mol·(m-2·s-1·Pa-1)；气体渗透量为0.483mm/s；在温度为37℃，相对湿度为50％条件下，透湿量为7800g/(m2·24h)。
实施例2
一种超支化TPU亲水薄膜及其制备方法：
其所用的原料，按重量份数计算，其组成及含量如下：
(1)、用氢氧化钠作催化剂，使杜仲籽油和甲酸在40℃的条件下搅拌1h，再缓慢加入过氧化氢，在60℃条件下连续搅拌6h。然后再加入二乙醇胺，搅拌静置,用丙酮溶解TPO静置。将二者混合均匀，放在435W的UV光下照射反应6min。反应得到羟值在293mg KOH/g的杜仲籽油基多元醇。
(2)、杜仲籽油基多元醇在95℃温度下脱水90min。降温至75℃，在氮气保护的条件下加入二异氰酸酯和二月桂酸二丁基锡保温反应80min。将体系温度降至50℃，向体系中加入小分子扩链剂，保温反应30min。
(3)、将上述制备的TPU和DMF加入三口瓶中，在70℃下持续搅拌至完全溶解，制得铸膜液。将其静置，密封除泡，再在干净的玻璃板上制成厚度为0.3mm的均匀液膜，然后立即将玻璃板浸入非溶剂中浸泡24h；等到铸膜液分相成膜后，将制得的薄膜从玻璃板上转移至蒸馏水中浸泡萃取出过量的溶剂和非溶剂。
所得杜仲籽油基热塑性聚氨酯弹性体，测得的超支化杜仲籽油基多元醇的羟值为260mg KOH/g；经检测本发明接触角为27.2°；拉伸强度为39.1Mpa，断裂伸长率为593％；所得TPU薄膜，经检测薄膜厚度为0.3mm，H2渗透率分别为3.5×10-8mol·(m-2·s-1·Pa-1)；气体渗透量为0.598mm/s；在温度为37℃，相对湿度为50％条件下，透湿量为9500g/(m2·24h)。
实施例3
一种超支化TPU亲水薄膜及其制备方法：
其所用的原料，按重量份数计算，其组成及含量如下：
(1)、用氢氧化钠作催化剂，使杜仲籽油和甲酸在40℃的条件下搅拌1h，再缓慢加入过氧化氢，在60℃条件下连续搅拌6h。然后再加入二乙醇胺，搅拌静置，用丙酮溶解TPO静置。将二者混合均匀，放在435W的UV光下照射反应6min。反应得到羟值在298mg KOH/g的杜仲籽油基多元醇。
(2)、杜仲籽油基多元醇在95℃温度下脱水90min。降温至75℃，在氮气保护的条件下加入二异氰酸酯和二月桂酸二丁基锡保温反应80min。将体系温度降至50℃，向体系中加入小分子扩链剂，保温反应30min。
(3)、将上述制备的TPU和DMF加入三口瓶中，在70℃下持续搅拌至完全溶解，制得铸膜液。将其静置，密封除泡，再在干净的玻璃板上制成厚度为0.3mm的均匀液膜，然后立即将玻璃板浸入非溶剂中浸泡24h；等到铸膜液分相成膜后，将制得的薄膜从玻璃板上转移至蒸馏水中浸泡萃取出过量的溶剂和非溶剂。
所得杜仲籽油基热塑性聚氨酯弹性体，测得的超支化杜仲籽油基多元醇的羟值为272mg KOH/g；经检测本发明接触角为29.1°；拉伸强度为36Mpa，断裂伸长率为520％；所得TPU薄膜，经检测薄膜厚度为0.38mm，H2渗透率分别为3.1×10-8mol·(m-2·s-1·Pa-1)；气体渗透量为0.478mm/s；在温度为37℃，相对湿度为50％条件下，透湿量为7500g/(m2·24h)。
Claims (9)
1.一种超支化TPU亲水薄膜，其特征在于，原料包括按重量份数计的以下组分：
所述的超支化 TPU 亲水薄膜 的制备方法，包括如下步骤：
步骤1)：在催化剂1作用下，将杜仲籽油和甲酸混合搅拌，再缓慢加入过氧化氢，连续搅拌，然后加入羟基化合物，搅拌静置，与溶解于丙酮的光引发剂混合均匀，于UV光下照射反应，得到杜仲籽油基多元醇；
步骤2)：将杜仲籽油基多元醇脱水，在氮气保护的条件下加入二异氰酸酯和催化剂2保温反应，向体系中加入小分子扩链剂，保温反应，得到TPU；
步骤3)：将TPU和溶剂在60～85℃下持续搅拌至完全溶解，制得铸膜液，将其静置，密封除泡，再在干净的玻璃板上制成液膜，然后立即将玻璃板浸入非溶剂中浸泡24～48h；待铸膜液分相成膜后，将制得的薄膜从玻璃板上转移至蒸馏水中浸泡萃取出过量的溶剂和非溶剂。
2.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、4,4′-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和1,5-萘二异氰酸酯中的至少一种。
3.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的羟基化合物为二乙醇胺和异丙醇中的至少一种。
4.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的小分子扩链剂为1,4-丁二醇和1,6-己二醇中的一种或两种。
5.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦和三芳基硫鎓盐中的一种或两种。
6.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的催化剂1为氢氧化钠和碳酸钠中的至少一种；所述的催化剂2为二月桂酸二丁基锡和辛酸亚锡中的至少一种。
7.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述的溶剂为N,N- 二甲基甲酰胺 ；所述的非溶剂为水、甲醇、乙醇和异丙醇中的一种或几种。
8.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述步骤1)具体为：在催化剂1作用下，将杜仲籽油和甲酸在30～50℃的条件下搅拌1～2h，再缓慢加入过氧化氢，在50～70℃条件下连续搅拌6～8h，然后加入羟基化合物，搅拌静置，与溶解于丙酮的光引发剂混合均匀，放在400～475W的UV光下照射反应3～8min，得到羟值在240～320mgKOH/g的杜仲籽油基多元醇。
9.如权利要求1所述的超支化TPU亲水薄膜，其特征在于，所述步骤2)具体为：将杜仲籽油基多元醇在90～110℃温度下脱水90～120min，降温至65～85℃，在氮气保护的条件下加入二异氰酸酯和催化剂2保温反应60～90min，将体系温度降至40～60℃，向体系中加入小分子扩链剂，保温反应20～70min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011349428.9A CN112341803B (zh) | 2020-11-26 | 2020-11-26 | 一种超支化tpu亲水薄膜及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011349428.9A CN112341803B (zh) | 2020-11-26 | 2020-11-26 | 一种超支化tpu亲水薄膜及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112341803A CN112341803A (zh) | 2021-02-09 |
| CN112341803B true CN112341803B (zh) | 2022-06-10 |
Family
ID=74366035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011349428.9A Active CN112341803B (zh) | 2020-11-26 | 2020-11-26 | 一种超支化tpu亲水薄膜及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112341803B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024862A (zh) * | 2021-04-06 | 2021-06-25 | 上海应用技术大学 | 一种超支化tpu亲水薄膜及其制备方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8507701B2 (en) * | 2004-08-23 | 2013-08-13 | Biobased Technologies Llc | Methods of preparing hydroxy functional vegetable oils |
| WO2009020774A1 (en) * | 2007-08-06 | 2009-02-12 | Dow Global Technologies Inc. | Polyol blends and their use in making polymers |
| US20100104872A1 (en) * | 2008-09-17 | 2010-04-29 | Archer-Daniels-Midland Company | Biobased waterborne synthetic polyurethane hybrid latexes and films |
| CN103360565B (zh) * | 2013-07-22 | 2016-01-06 | 中国林业科学研究院林产化学工业研究所 | 蓖麻油基阻燃多元醇聚氨酯薄膜的制备方法 |
| CN107012692B (zh) * | 2017-05-19 | 2019-02-12 | 陕西科技大学 | 一种生物基无溶剂聚氨酯合成革的生产方法 |
| CN110724239A (zh) * | 2019-11-27 | 2020-01-24 | 昆山嘉力普制版胶粘剂油墨有限公司 | 一种水性聚氨酯乳液及其制备方法和应用 |
| CN111040419B (zh) * | 2019-12-24 | 2021-11-02 | 齐鲁工业大学 | 一种生物基聚酯型聚氨酯薄膜及其制备方法 |
-
2020
- 2020-11-26 CN CN202011349428.9A patent/CN112341803B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112341803A (zh) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Synthesis and properties of castor oil-based waterborne polyurethane/sodium alginate composites with tunable properties | |
| Liang et al. | Castor oil-based cationic waterborne polyurethane dispersions: Storage stability, thermo-physical properties and antibacterial properties | |
| Xiao et al. | Self-healing supramolecular waterborne polyurethane based on host–guest interactions and multiple hydrogen bonds | |
| Jiang et al. | Effect of bio-based polyols and chain extender on the microphase separation structure, mechanical properties and morphology of rigid polyurethane foams | |
| Li et al. | Effect of polyether/polyester polyol ratio on properties of waterborne two-component polyurethane coatings | |
| CN104327238B (zh) | 一种有机硅阳离子水性聚氨酯的制备方法 | |
| CN102851987B (zh) | 一种超支化水性聚氨酯涂层剂 | |
| Huang et al. | Blending polar rubber with polyurethane to construct self-healing rubber with multiple hydrogen bond networks | |
| CN112430308B (zh) | 一种生物基高性能水性聚氨酯树脂的制备方法及其产品 | |
| CN103739826A (zh) | 一种聚氨酯型两性表面活性剂的制备方法 | |
| CN111187428B (zh) | 木质素基多元醇、改性木质素基聚氨酯材料、改性木质素基聚氨酯薄膜及制备方法和应用 | |
| CN111138631A (zh) | 一种高强度高阻隔tpu复合材料的制备方法 | |
| Li et al. | Fluorinated polyurethane based on liquid fluorine elastomer (LFH) synthesis via two-step method: the critical value of thermal resistance and mechanical properties | |
| WO2020042523A1 (zh) | 高耐候性红色水性聚氨酯乳液的合成方法 | |
| CN105801799B (zh) | 一种功能多元醇在制备多功能聚氨酯中的应用 | |
| CN108559046A (zh) | 一种臭氧化改性木质素聚氨酯及其制备方法 | |
| CN103183801B (zh) | Cimv小麦秸秆木质素聚氨酯薄膜的制备方法 | |
| CN112341803B (zh) | 一种超支化tpu亲水薄膜及其制备方法 | |
| CN111253549A (zh) | 一种含磷棕榈油基纯水性聚氨酯纳米乳液及制备方法 | |
| CN102604036B (zh) | 一种葡萄糖改性水性聚氨酯乳液的制备方法 | |
| CN107099131A (zh) | 一种超支化共混软硬段共改性后扩链阻燃水性聚氨酯 | |
| CN105542115B (zh) | 一种煤基腐殖酸改性水性聚氨酯复合材料的制备方法 | |
| Xia et al. | Design strategy for waterborne polyurethane with sodium sulfonate groups on the soft segments | |
| CN105419612A (zh) | 一种自闭型聚氨酯防水涂料及其生产工艺 | |
| CN112480649A (zh) | 一种二氧化钛/tpu复合型亲水薄膜及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240122 Address after: 509 Kangrui Times Square, Keyuan Business Building, 39 Huarong Road, Gaofeng Community, Dalang Street, Longhua District, Shenzhen City, Guangdong Province, 518110 Patentee after: Shenzhen Litong Information Technology Co.,Ltd. Country or region after: China Address before: 200235 No. 120, Xuhui District, Shanghai, Caobao Road Patentee before: SHANGHAI INSTITUTE OF TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240207 Address after: 528251 Factory Building E, No. 2 Nansha Road, Nansha Community, Danzao Town, Nanhai District, Foshan City, Guangdong Province (Residence Declaration) Patentee after: Foshan Yiou New Material Co.,Ltd. Country or region after: China Address before: 509 Kangrui Times Square, Keyuan Business Building, 39 Huarong Road, Gaofeng Community, Dalang Street, Longhua District, Shenzhen City, Guangdong Province, 518110 Patentee before: Shenzhen Litong Information Technology Co.,Ltd. Country or region before: China |