CN110317316B - 一种合成皮革用抗菌耐污聚氨酯的制备方法 - Google Patents
一种合成皮革用抗菌耐污聚氨酯的制备方法 Download PDFInfo
- Publication number
- CN110317316B CN110317316B CN201910591449.2A CN201910591449A CN110317316B CN 110317316 B CN110317316 B CN 110317316B CN 201910591449 A CN201910591449 A CN 201910591449A CN 110317316 B CN110317316 B CN 110317316B
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- stain
- reaction
- synthetic leather
- resistant polyurethane
- 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
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 239000002649 leather substitute Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000003607 modifier Substances 0.000 claims abstract description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- -1 2-substituted benzothiazole Chemical class 0.000 claims abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 5
- TYRZAGMAVZESQX-UHFFFAOYSA-N 2-amino-5-chlorobenzenethiol Chemical compound NC1=CC=C(Cl)C=C1S TYRZAGMAVZESQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002009 diols Chemical class 0.000 claims abstract description 5
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 5
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 26
- 238000012360 testing method Methods 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 5
- 241000894006 Bacteria Species 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 241000233866 Fungi Species 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 230000000172 allergic effect Effects 0.000 abstract description 2
- 208000010668 atopic eczema Diseases 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000037307 sensitive skin Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 206010015150 Erythema Diseases 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 231100000321 erythema Toxicity 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 206010040914 Skin reaction Diseases 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035483 skin reaction Effects 0.000 description 2
- 231100000430 skin reaction Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CTMWGJPCHIIGBY-UHFFFAOYSA-N 1-(2-chlorophenyl)-n-(1,1-dioxothiolan-3-yl)methanimine Chemical compound ClC1=CC=CC=C1C=NC1CS(=O)(=O)CC1 CTMWGJPCHIIGBY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
-
- 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
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
-
- 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
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种合成皮革用抗菌耐污聚氨酯的制备方法,以2‑氨基‑5氯硫酚和2,2‑二羟甲基丙酸为起始物料,在催化剂氯化锌和无水硫酸铜的作用下,成环为2‑取代苯并噻唑衍生物A,接着2‑取代苯并噻唑衍生物A与N,N‑二甲基十二烷基胺在微波加热下发生取代反应,得到了改性剂B,最后,甲苯‑2,6二异氰酸酯与聚四氢呋喃二醇和改性剂B发生缩聚反应得到了改性的聚氨酯,该聚氨酯嵌段引入了双抗菌活性基团噻唑基团和季铵盐,可抑制和杀死多种细菌和霉菌,另经抗敏性测试,皮革中引入的活性基团对身体无过敏性伤害,由于双抗菌活性基团均是以化学键的方式嵌入到聚氨酯中,具有良好的耐洗性,不易脱落,可长久的维持革制品的抗菌性能。
Description
技术领域
本发明属于革制品技术领域,具体涉及一种合成皮革用抗菌耐污聚氨酯的制备方法。
背景技术
聚氨酯合成革属于聚氨酯弹性体的一类,具有光泽柔和、自然,手感柔软,真皮感强的外观,具有与基材粘接性能优异、抗磨损、耐挠曲、抗老化等优异的机械性能,同时还具备耐寒性好、透气、可洗涤、加工方便、价格优廉等优点,是天然皮革最为理想的替代品。
据皮革原材料的质地和加工目的,加工出来的皮革成品可用于制造男女服装、箱包和鞋帽等日常用品,用途广泛,由于会接触到人体皮肤,所以由人体皮肤毛孔分泌出来汗渍和湿气会附着在皮质上,时间一长,皮质容易滋生霉菌、细菌、真菌等微生物,其分泌物引起高聚物的生物降解,使得皮革面出现裂纹,这样就会影响皮革制品的使用寿命和使用效果,并与肌肤接触,加剧了各类疾病的扩散和传播,对人体健康造成了巨大的威胁,另外,现有的革制品防水性能不够,在潮湿雨天环境,放置的革制品更易滋生细菌,产生大量的菌斑霉斑等污迹,随着经济技术的发展,人们对健康越来越重视,因此,开发出多功能性的合成革为行业发展所需。
发明内容
本发明的目的在于提供一种合成皮革用抗菌耐污聚氨酯的制备方法,现有的合成革中,一般采用额外添加抗菌剂用以维持皮革的抗菌防霉性能,但是耐洗性较差,难以长久的维持合成革的抗菌性能。
本发明需要解决的技术问题为:
1、如何提供一种同时具有抗菌和耐污性能的改性剂;
2、现有的革制品清洗后抑菌效果差;
3、如何提高革制品的耐污性,使其具有自洁性能;
本发明的目的可以通过以下技术方案实现:
一种合成皮革用抗菌耐污聚氨酯的制备方法,具体包括以下步骤:
第一步、0.1mol 2-氨基-5氯硫酚、0.11-0.12mol 2,2-二羟甲基丙酸和5mmol催化剂加入到反应瓶中,通入氮气保护,在无溶剂条件下,升温至100-110℃反应4-5h,反应结束后,冷却到室温,即得到式A结构的2-取代苯并噻唑衍生物,反应式如下:
第二步、向第一步制备的2-取代苯并噻唑衍生物中加入150ml二氧六环,接着加入0.11-0.12mol N,N-二甲基十二烷基胺,搅拌溶解后,放入到微波反应器中,回流反应3h,反应结束后,取出,经纯化,即得到式B结构的改性剂,反应式如下:
第三步、将100g甲苯-2,6二异氰酸酯、60-80g聚四氢呋喃二醇、10-15g改性剂和0.5g催化剂,升温至80℃进行缩聚2h,即得到式C结构的抗菌耐污聚氨酯,反应式如下:
进一步,第一步中,所述的催化剂为氯化锌和无水硫酸铜,氯化锌和无水硫酸铜的质量比为1:1。
进一步,第二步中,微波反应器的功率为600W,回流反应的温度为100-110℃。
进一步,第二步中,所述的纯化具体为:取出后自然冷却至室温,接着放入到0-5℃的环境中静置4-5h,析出结晶,过滤,采用丙酮重结晶,即得到式B结构的改性剂。
进一步,第三步中,所述的催化剂为辛酸亚锡。
本发明的有益效果:
本发明提供的一种合成皮革用抗菌耐污聚氨酯的制备方法,以2-氨基-5氯硫酚和2,2-二羟甲基丙酸为起始物料,在催化剂氯化锌和无水硫酸铜的作用下,成环为2-取代苯并噻唑衍生物A,接着2-取代苯并噻唑衍生物A与N,N-二甲基十二烷基胺在微波加热下发生取代反应,得到了改性剂B,改性剂B中的噻唑基团和季铵盐具有良好的抑菌性,其中十二烷基为疏水基团,因此制备的改性剂B同时具有抗菌和耐污性能;
最后,甲苯-2,6二异氰酸酯与聚四氢呋喃二醇和改性剂B发生缩聚反应得到了改性的聚氨酯,该聚氨酯嵌段引入了双抗菌活性基团噻唑基团和季铵盐,可抑制和杀死多种细菌和霉菌,另经抗敏性测试,皮革中引入的活性基团对身体无过敏性伤害,由于双抗菌活性基团均是以化学键的方式嵌入到聚氨酯中,具有良好的耐洗性,不易脱落,可长久的维持革制品的抗菌性能;
另外,聚氨酯中还嵌段引入了长链疏水基团十二烷基基团,使得聚氨酯本身既具有良好的疏水性能,可防止水和水溶性等液体、灰尘等固体的粘附,具有良好的自洁性能,同时,该疏水性的聚氨酯制成的革制品,缺乏细菌霉菌繁殖的潮湿环境,继而进一步的防止革制品的霉变,延长了革制品的使用寿命,长久的维持革制品的干净整洁。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅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它实施例,都属于本发明保护的范围。
实施例1
一种合成皮革用抗菌耐污聚氨酯的制备方法,具体包括以下步骤:
第一步、0.1mol 2-氨基-5氯硫酚、0.11mol 2,2-二羟甲基丙酸和5mmol催化剂加入到反应瓶中,通入氮气保护,在无溶剂条件下,升温至100℃反应5h,反应结束后,冷却到室温,即得到式A结构的2-取代苯并噻唑衍生物,收率为97.4%,HRMS m/z(ESI+)calcd forC11H12ClNO2S([M+H]+),258.0374;
反应式如下:
所述的催化剂为氯化锌和无水硫酸铜,氯化锌和无水硫酸铜的质量比为1∶1;
第二步、向第一步制备的2-取代苯并噻唑衍生物中加入150ml二氧六环,接着加入0.11mol N,N-二甲基十二烷基胺,搅拌溶解后,放入到微波反应器中,在功率为600W,温度为105℃下回流反应3h,反应结束后,取出,自然冷却至室温,接着放入到0-5℃的环境中静置4h,析出结晶,过滤,采用丙酮重结晶即得到式B结构的改性剂,收率为96.2%;反应式如下:
第三步、将100g甲苯-2,6二异氰酸酯、68g聚四氢呋喃二醇、12g改性剂和0.5g催化剂辛酸亚锡,升温至80℃进行缩聚2h,即得到式C结构的抗菌耐污聚氨酯;
反应式如下:
抗菌耐污聚氨酯C的红外表征如下所示:IR(KBr):(苯环)、2988/2864(-CH2-、-CH3),2271(-NCO),1752(-COO-)、1680(-CONH-)、1667-1425(噻唑环),1004、897(季铵盐)cm-1。
实施例2
采用湿法制造工艺将抗菌耐污聚氨酯渗透到非织造布间得到抗菌耐污合成皮革,接触角为122°。
对比例1
无添加的聚氨酯合成革。
对比例2
聚氨酯乳液由100g聚氨酯和10份皮革防霉抗菌剂混合得到,采用湿法制造工艺将聚氨酯乳液渗透到非织造布间得到合成皮革;该皮革防霉抗菌剂有机硅季铵盐防霉抗菌剂。
合成皮革的性能测试
(1)抗菌性测试
分别对新制合成革和洗涤50次的合成革进行测试,洗涤方法按照在耐洗牢度试验机上进行,洗涤方法为:洗衣粉4g/L,浴比(合成革和洗涤液的质量比为1:25),温度25℃,时间10min为一次洗涤;
表一、新制合成革的抑菌率
表二、洗涤50次的合成革的抑菌率
(2)抗敏性测试
选取45名年龄在18-40岁皮肤无异常的健康男女志愿者和45名敏感肌肤年龄在18-40岁的健康男女志愿者作为受试对象,受试部位为上臂内侧,分为3组,每组30人,每组分别有15名皮肤无异常的志愿者和15名敏感肌肤的志愿者,每组对应测试同一个实施例的合成皮革;
取10cm2实施例2以及对比实施例1和2制得的合成皮革,将皮革用无刺激胶带贴敷于受试者前臂曲侧,胶带粘在皮革边角四周,用手掌轻压使之均匀地贴敷于皮肤上,持续24h,去除皮革30min后,待粘接痕消失后观察皮肤反应。实验结果显示,90名志愿者,其中45名皮肤无异常的志愿者皮肤无反应;45名敏感肌肤志愿者中,有1名对于对比例1的皮革有微弱红斑,待2h后微弱红斑彻底消失,有2名对对比例2中的皮革有红斑且有瘙痒症状,用冷水冰敷后,3h后完全消失,其余27名敏感肌肤志愿者皮肤均无反应。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (5)
1.一种合成皮革用抗菌耐污聚氨酯的制备方法,其特征在于:具体包括以下步骤:
第一步、0.1mol 2-氨基-5氯硫酚、0.11-0.12mol 2,2-二羟甲基丙酸和5mmol催化剂加入到反应瓶中,通入氮气保护,在无溶剂条件下,升温至100-110℃反应4-5h,反应结束后,冷却到室温,即得到式A结构的2-取代苯并噻唑衍生物,反应式如下:
第二步、向第一步制备的2-取代苯并噻唑衍生物中加入150ml二氧六环,接着加入0.11-0.12mol N,N-二甲基十二烷基胺,搅拌溶解后,放入到微波反应器中,回流反应3h,反应结束后,取出,经纯化,即得到式B结构的改性剂,反应式如下:
第三步、将100g甲苯-2,6二异氰酸酯、60-80g聚四氢呋喃二醇、10-15g改性剂和0.5g催化剂,升温至80℃进行缩聚2h,即得到式C结构的抗菌耐污聚氨酯,反应式如下:
2.根据权利要求1所述的一种合成皮革用抗菌耐污聚氨酯的制备方法,其特征在于:第一步中,所述的催化剂为氯化锌和无水硫酸铜,氯化锌和无水硫酸铜的质量比为1:1。
3.根据权利要求1所述的一种合成皮革用抗菌耐污聚氨酯的制备方法,其特征在于:第二步中,微波反应器的功率为600W,回流反应的温度为100-110℃。
4.根据权利要求1所述的一种合成皮革用抗菌耐污聚氨酯的制备方法,其特征在于:第二步中,所述的纯化具体为:取出后自然冷却至室温,接着放入到0-5℃的环境中静置4-5h,析出结晶,过滤,采用丙酮重结晶,即得到式B结构的改性剂。
5.根据权利要求1所述的一种合成皮革用抗菌耐污聚氨酯的制备方法,其特征在于:第三步中,所述的催化剂为辛酸亚锡。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910591449.2A CN110317316B (zh) | 2019-07-02 | 2019-07-02 | 一种合成皮革用抗菌耐污聚氨酯的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910591449.2A CN110317316B (zh) | 2019-07-02 | 2019-07-02 | 一种合成皮革用抗菌耐污聚氨酯的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110317316A CN110317316A (zh) | 2019-10-11 |
CN110317316B true CN110317316B (zh) | 2021-11-30 |
Family
ID=68122352
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910591449.2A Active CN110317316B (zh) | 2019-07-02 | 2019-07-02 | 一种合成皮革用抗菌耐污聚氨酯的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110317316B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110923946B (zh) * | 2019-11-20 | 2022-08-23 | 苏州市雄林新材料科技有限公司 | 一种纳米抗菌透气tpu薄膜及其制备方法 |
CN111206434A (zh) * | 2020-02-19 | 2020-05-29 | 扬州市德运塑业科技股份有限公司 | 一种抗菌耐磨合成革及制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0749556B2 (ja) * | 1988-03-19 | 1995-05-31 | 神東塗料株式会社 | 防振ゴム用塗料、及びそれを用いた防振ゴムの塗装法、並びにそれによって得られた塗装防振ゴム |
EP0520160A1 (en) * | 1991-06-28 | 1992-12-30 | BOC HEALTH CARE, Inc. | Process for antimicrobial treatment of polyurethane |
KR20110090967A (ko) * | 2008-10-28 | 2011-08-10 | 바스프 에스이 | 하이브리드 네트워크 중 항균제를 함유하는 조성물 |
JP6240399B2 (ja) * | 2012-05-29 | 2017-11-29 | 太陽インキ製造株式会社 | 感光性組成物及びその硬化層を有するプリント配線板 |
CN106192370B (zh) * | 2016-06-30 | 2018-06-19 | 杭州湘隽阻燃科技有限公司 | 一种耐久阻燃抗菌防霉织物及其制备方法与应用 |
-
2019
- 2019-07-02 CN CN201910591449.2A patent/CN110317316B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN110317316A (zh) | 2019-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110317316B (zh) | 一种合成皮革用抗菌耐污聚氨酯的制备方法 | |
KR101753506B1 (ko) | 변경된 응력 프로파일을 갖는 의복 | |
CN106565546A (zh) | 一种月桂酰精氨酸乙酯甘醇酸盐及其制备方法和用途 | |
CN102604032B (zh) | 一种温敏扩链剂及温度、pH双敏感的聚氨酯水凝胶 | |
TW200909539A (en) | Aqueous polyurethaneurea compositions including dispersions and films | |
JPS61146802A (ja) | 透湿性且つ耐油性作業用手袋およびその製造方法 | |
JP6508519B2 (ja) | ウレタン樹脂組成物、及び、皮革様シート | |
CN106726636A (zh) | 一种物理抗菌湿巾 | |
CN106222328B (zh) | 一种持久抗菌抑菌型皮革的制造方法 | |
JP2022166147A (ja) | 水性ポリウレタン分散体、プレポリマー、およびそれから作製された造形物品 | |
CN104726001A (zh) | 一种皮革表面处理剂 | |
CN112878054B (zh) | 一种耐洗性涤纶亲水整理剂及其制备方法 | |
KR20160148614A (ko) | 통기가능하고 가교가능한 열가소성 폴리우레탄 | |
CN108486875B (zh) | 一种医疗卫生用抗菌无纺布及其制备方法和应用 | |
CN104151522B (zh) | 一种软质湿法防水透气透湿聚氨酯树脂及其制备方法 | |
CN108774789B (zh) | 一种抗菌防敏功能性面料 | |
CN106723390A (zh) | 一种多功效保暖内衣及其制备方法 | |
CN110604502B (zh) | 一种具有高耐洗性的防霉毛巾及其制备方法 | |
ES2701263T3 (es) | Guante antitranspirante | |
CN109757788B (zh) | 一种无毒海绵文胸 | |
CN116769441B (zh) | 一种内衣背扣的制备方法及产品 | |
CN214271460U (zh) | 一种厚型免复合拖鞋用聚氨酯合成革结构 | |
CN110105765A (zh) | 一种耳机的耳塞耳挂抗菌配方 | |
CN215873498U (zh) | 一种凉感文胸模杯及其纹胸 | |
CN110183602A (zh) | 一种卤素氨基噻吩类抗菌扩链剂及其制备方法与应用 |
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: 20211208 Address after: 511500 plot B10, Xiongxing industrial city, high tech Industrial Development Zone, Qingyuan City, Guangdong Province (workshop 1) Patentee after: Guangdong Casio New Material Co.,Ltd. Address before: 721000 Fufeng science and Technology Industrial Park, jiangzhang Town, Fufeng County, Baoji City, Shaanxi Province Patentee before: Qi Yuxia |