CN114891181A - 一种聚氨酯树脂及其镜面合成革 - Google Patents
一种聚氨酯树脂及其镜面合成革 Download PDFInfo
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- CN114891181A CN114891181A CN202210585285.4A CN202210585285A CN114891181A CN 114891181 A CN114891181 A CN 114891181A CN 202210585285 A CN202210585285 A CN 202210585285A CN 114891181 A CN114891181 A CN 114891181A
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- polyurethane resin
- polyurethane
- polyol
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- synthetic leather
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- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 35
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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 21
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 235000011037 adipic acid Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
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- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 3
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- KYRZZPALUVQDRB-UHFFFAOYSA-N 2-methyl-1,4-dioxocane-5,8-dione Chemical compound CC1COC(=O)CCC(=O)O1 KYRZZPALUVQDRB-UHFFFAOYSA-N 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
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- 239000003963 antioxidant agent Substances 0.000 description 3
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 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
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000654 additive Substances 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- 239000000376 reactant Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C08G18/65—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
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- 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
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
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- C08G18/54—Polycondensates of aldehydes
- C08G18/546—Oxyalkylated polycondensates of aldehydes
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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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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-
- 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
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- 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
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/108—Slipping, anti-blocking, low friction
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明是一种聚氨酯树脂以及由该聚氨酯树脂作为面层材料制备得到的镜面合成革。聚氨酯树脂包括如下重量份的组分原料:聚氨酯预聚体14~46份;多异氰酸酯5~26份;聚合物多元醇20~56份;本发明的聚氨酯树脂作为合成革面层材料,通过离型纸转移工艺涂覆于贝斯表面得到镜面合成革,应用于鞋材、服饰以及箱包等领域;合成革在保证了较好的低温耐折性的前提下,仍具备优良的爽滑度和防粘性;此外,长时间的高温高湿环境下,合成革也不会出现析出现象。
Description
技术领域
本发明涉及一种聚氨酯树脂,并涉及由该聚氨酯树脂制备得到的镜面合成革。
背景技术
聚氨酯在微观形态上,可以看作是由软段结构与硬段结构交替组成的嵌段共聚物,其软段和硬段均容易出现结晶,而且结晶共聚物内部存在折射率不同的晶区和非晶区,通常是半透明或不透明的,由此制备的聚氨酯合成革大多也是呈不透明状。不过,对于一些特殊外观的聚氨酯合成革,例如镜面革,对于聚氨酯的透明性要求较高,但目前主流的镜面革,其透亮度一般,手痕严重,并且存在低温耐曲挠性差等问题,已经很难满足如今客户的需求;而具备耐低温的镜面革又存在滑爽度不佳,表面容易发粘、粘灰,且易发雾等问题。
如何在保证聚氨酯透明性的前提下,提升镜面聚氨酯合成革的表面滑爽度、抗手痕性能及低温耐曲挠性能是开发的重点和难点。
发明内容
技术问题:本发明的目的在于克服以上缺陷,提供一种聚氨酯树脂,以及由该聚氨酯树脂作为面层材料制备得到的镜面合成革。本发明的聚氨酯树脂作为合成革面层材料,通过离型纸转移工艺涂覆于贝斯表面得到镜面合成革,应用于鞋材、服饰以及箱包等领域。
技术方案:本发明的一种聚氨酯树脂,包括如下重量份的组分原料:
聚氨酯预聚体 14~46份;
多异氰酸酯 5~26份;
聚合物多元醇 20~56份。
所述的聚氨酯预聚体包括多异氰酸酯与扩链剂反应得到的聚氨酯预聚体;所述的聚氨酯预聚体的异氰酸酯指数为0.3~0.7。
所述的多异氰酸酯包括二苯基甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、萘二异氰酸酯NDI、异佛尔酮异氰酸酯IPDI以及其异构体和/或衍生物和/或改性聚合物中的一种以上。
所述的聚合物多元醇为聚醚多元醇和聚酯多元醇的混合物。
所述的扩链剂为乙二醇、丙二醇、丁二醇、新戊二醇中的一种及以上。
所述的聚醚多元醇为聚四氢呋喃醚多元醇,数均分子量1500~3000。
所述的聚酯多元醇包括至少一种C4以上C10以下的二元酸与至少一种C3以上C10以下的二元醇反应得到的聚酯多元醇,数均分子量1000~3000;
所述的C4以上C10以下的二元酸为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、葵二酸中的一种及以上;
所述的C3以上C10以下的二元醇为丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、葵二醇中的一种及以上。
所述的聚醚多元醇与聚酯多元醇的质量比为2:3~4:1。
所述的聚氨酯树脂还包括2~8重量份的交联剂和0.2-1.0重量份的终止剂。
所述的交联剂为甲醚化氨基树脂,终止剂为乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇。
本发明的聚氨酯树脂作为合成革面层材料,通过离型纸转移工艺涂覆于贝斯表面得到镜面合成革,应用于鞋材、服饰以及箱包等领域。
有益效果:本发明具有以下优点:采用特定聚氨酯预聚体和聚合物多元醇,有效避免了聚氨酯树脂聚氨酯硬段过于集中,从而有效降低聚氨酯硬段的结晶性,提升其透明度;采用聚氨酯树脂作为面层材料制备的镜面合成革透亮度好且耐手痕和耐低温性能也十分优异,更重要的是,合成革在保证了较好的低温耐折性的前提下,仍具备优良的爽滑度和防粘性;此外,长时间的高温高湿环境下,合成革也不会出现析出现象。
具体实施方式
所述的一种聚氨酯树脂,包括如下重量分的组份原料:
聚氨酯预聚体 14~46份;
多异氰酸酯 8~26份;
聚合物多元醇 20~56份;
所述的聚氨酯预聚体包括多异氰酸酯与扩链剂反应得到的聚氨酯预聚体;
所述的聚氨酯预聚体的异氰酸酯指数为0.3~0.7;
所述的多异氰酸酯包括二苯基甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、萘二异氰酸酯NDI、异佛尔酮异氰酸酯IPDI以及其异构体和/或衍生物和/或改性聚合物中的一种以上;
所述的扩链剂为乙二醇、丙二醇、丁二醇、新戊二醇中的一种及以上;
所述的聚合物多元醇为聚醚多元醇和聚酯多元醇的混合物;
所述的聚醚多元醇为聚四氢呋喃醚多元醇,数均分子量1500~3000;
所述的聚酯多元醇包括至少一种C4以上C10以下的二元酸与至少一种C3以上C10以下的二元醇反应得到的聚酯多元醇,数均分子量1000~3000;
所述的C4以上C10以下的二元酸为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、葵二酸中的一种及以上;
所述的C3以上C10以下的二元醇为丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、葵二醇中的一种及以上;
作为示例的,所述的聚酯多元醇包括聚己二酸丙二醇酯多元醇、聚丁二酸丙二醇酯多元醇、聚己二酸丁二醇酯多元醇、聚丁二酸丁二醇酯多元醇中的一种及以上;
所述的聚醚多元醇与聚酯多元醇的质量比为2:3~4:1。
进一步的,所述的聚氨酯树脂,还包括2~8重量份的交联剂和0.2-1.0重量份的终止剂;
所述的交联剂为甲醚化氨基树脂,终止剂为乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇;
作为示例的,所述的交联剂为湛新公司的CYMEL 303LF、CYMEL 308的甲醚化氨基树脂;
所述的交联剂和终止剂在聚氨酯预聚体、多异氰酸酯、聚合物多元醇反应后加入;
作为示例的,所述的终止剂在聚氨酯预聚体、多异氰酸酯、聚合物多元醇反应后加入,交联剂在终止剂加入之后再加入;
所述的聚醚型聚氨酯树脂的制备方法,包括以下步骤:
将聚氨酯预聚体、聚合物多元醇、多异氰酸酯在熔融温度以上充分反应后,加入终止剂和交联剂得到。
优选的,上述制备过程可在溶剂的存在下进行;
优选的,上述制备过程可在本领域公知的催化剂存在下进行,以加快反应速率。
优选的,可在聚醚型聚氨酯树脂加入任选的抗氧化剂、流平剂等助剂;
进一步的,所述的催化剂包括环保金属类催化剂和/或胺类催化剂,金属类催化剂包括金属有机铋、有机锌、氧化银、特殊有机锡中的一种及以上,胺类催化剂包括热敏延迟DBU盐胺类、凝胶胺类催化剂中的一种及以上;
进一步的,抗氧剂为抗氧剂245、抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂1098中的一种及以上;
流平剂为羟基有机硅;
在本发明实例中,所述的聚氨酯树脂的制备方法,具体包括以下步骤:
将扩链剂、多异氰酸酯在适量的溶剂,70~80℃充分反应后,得到聚氨酯预聚体;
将聚氨酯预聚体、聚合物多元醇加入反应釜中,添加适量的溶剂在40~60℃搅拌均匀后,加入多异氰酸酯并升温至70~80℃充分反应后,粘度达到10-16万cps后,加入终止剂封端后,最后加入交联剂、流平剂、任选的助剂搅拌均匀后得到聚氨酯树脂;
其中,溶剂的添加量没有特别的限定,保证反应物可充分接触反应即可,若反应后期粘度过高可补加溶剂;
在本发明的一些示例中,总溶剂的添加量为60~75%,基于聚氨酯树脂的总质量来计算,溶剂可采用N,N-二甲基甲酰胺、甲苯、丁酮等。
若添加助剂,助剂可在反应前期或者后期加入,其中,流平剂优选的在反应后期加入;
作为示例的,所述的羟基聚醚或聚酯改性羟基有机硅流平剂,例如毕克化学BYK-3700、道康宁DC-1248、天泰化工TD-5088;
本发明的聚氨酯树脂作为合成革面层材料,通过离型纸转移工艺涂覆于贝斯表面得到合成革,鞋材、服饰以及箱包等领域。
在本发明实例中,聚氨酯合成革的具体制备方法如下:
将聚氨酯树脂和溶剂按照质量比100:80~100混合均匀,按照0.15mm的涂布厚度涂覆于镜面离型纸上,在120-140℃条件下烘烤3-5min得到镜面膜,在镜面膜上涂覆粘结层树脂后贴上贝斯层,继续在120-140℃条件下烘烤5-8min,除去离型纸得镜面聚氨酯合成革。
进一步的,在聚氨酯树脂涂覆于贝斯表面前,在树脂中加入促进剂进一步增加面层材料性能,所述的促进剂为磺酸催化剂,例如CYCAT 4040、CYCAT 600等,促进剂的添加量0.5~4%。基于聚氨酯树脂总质量来计算。
下面通过实施例对本发明作进一步的说明,实施例中所描述的具体的物料配比、制备工艺及结果等仅用于说明本发明,并不能以此限制本发明的保护范围。
实施例1
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为0.62;聚合物多元醇为质量比为33:20的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量1000);终止剂为新戊二醇;交联剂为CYMEL 303LF。
实施例2
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与乙二醇反应得到,异氰酸酯指数为0.33;聚合物多元醇为质量比为18:12的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量1000);终止剂为己二醇;交联剂为CYMEL 308。
实施例3
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丙二醇反应得到,异氰酸酯指数为0.55;聚合物多元醇为质量比为40:10的聚四氢呋喃醚多元醇(分子量2000)和聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例4
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为0.43;聚合物多元醇为质量比为14:7的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量3000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例5
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与乙二醇反应得到,异氰酸酯指数为0.7;聚合物多元醇为质量比为18:8的聚四氢呋喃醚多元醇(分子量2000)和聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为乙二醇;交联剂为CYMEL 303LF;流平剂为BYK-3700。
实施例6
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为1.2;聚合物多元醇为质量比为33:20的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量1000);终止剂为新戊二醇;交联剂为CYMEL 303LF。
实施例7
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丙二醇反应得到,异氰酸酯指数为0.55;聚合物多元醇为聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为丁二醇;交联剂为CYMEL308。
实施例8
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丙二醇反应得到,异氰酸酯指数为0.55;聚合物多元醇为质量比为25:25的聚四氢呋喃醚多元醇(分子量2000)和聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例9
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丙二醇反应得到,异氰酸酯指数为0.55;聚合物多元醇为质量比为42:8的聚四氢呋喃醚多元醇(分子量2000)和聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例10
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丙二醇反应得到,异氰酸酯指数为0.55;聚合物多元醇为质量比为40:10的聚氧化乙烯多元醇(分子量2000)和聚丁二酸丙二醇酯多元醇(分子量2000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例11
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为0.43;聚合物多元醇为质量比为14:7的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸乙二醇酯多元醇(分子量3000);终止剂为丁二醇;交联剂为CYMEL 308。
实施例12
聚氨酯树脂包括如下重量分的组份原料:
聚氨酯预聚体 33份;
MDI 26份;
聚合物多元醇 21份;
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为0.43;聚合物多元醇为质量比为14:7的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量3000)。
实施例13
聚氨酯树脂包括如下重量分的组份原料:
其中,聚氨酯预聚体为MDI与丁二醇反应得到,异氰酸酯指数为0.43;聚合物多元醇为质量比为14:7的聚四氢呋喃醚多元醇(分子量1500)和聚己二酸己二醇酯多元醇(分子量3000);终止剂为丁醇;交联剂为CYMEL 308。
对比例1
与实施例1的不同在于,聚氨酯预聚体为MDI与聚合物多元醇反应得到,其他原料种类和配比与实施例1相同。
实施例和对比例的聚氨酯树脂的制备方法:
分别将上述的聚氨酯预聚体、聚合物多元醇加入反应釜中,添加适量的溶剂在45℃搅拌均匀后,加入多异氰酸酯并升温至80℃充分反应后,加入任选的终止剂继续反应,最后加入任选的交联剂得到聚氨酯树脂;
其中,总溶剂的添加量为70%,基于聚氨酯树脂的总质量来计算。
含有实施例和对比例的合成革面层材料制备方法:
将上述实施例和对比例的聚氨酯树脂和溶剂按照质量比100:80混合均匀,按照0.15mm的涂布厚度涂覆于镜面离型纸上,在120-140℃条件下烘烤3-5min得到镜面膜,在镜面膜上涂覆粘结层树脂后贴上贝斯层,继续在120-140℃条件下烘烤5-8min,除去离型纸得镜面聚氨酯合成革。
在聚氨酯树脂涂覆于贝斯表面前,在树脂中加入促进剂进一步增加面层材料性能,所述的促进剂为磺酸催化剂,例如CYCAT 4040、CYCAT 600等,促进剂的添加量0.5~4%,基于聚氨酯树脂总质量来计算。
性能测试:
透光率:将镜面膜上的离型纸去除后,采用透光率测试其透光率;
摩擦系数:裁剪两块相同的聚氨酯合成革,其中一块固定,另外一块固定在滑块上,滑块按照标准GB/T 10006规定的试验速度在固定试样滑过,通过读取摩擦系数仪读取其摩擦系数,摩擦系数越大,爽滑性越差;
低温耐折:将聚氨酯合成革裁剪成45*70mm样片,在-15℃温度下,在低温耐折试验机上进行测试,每弯折5000次确认一次样片情况,若样片断裂则记录为其耐折次数;
防粘性:将相同的两块聚氨酯合成革对贴,至于120℃烘箱中,20KG压力条件下,热压30分钟,观察革样防粘性能,采取打分模式,分数越高(1~10分),防粘效果越好;
抗手痕:在聚氨酯合成革镜面革样均匀涂抹油渍,用白色无纺布轻轻擦拭5-10次,观察革样表面油渍残留情况,残留油渍越少,抗手痕效果越好,采取打分模式,分数越高(1~10分),抗手痕效果越好;
析出性:聚氨酯合成革镜悬挂在恒温恒湿箱中,一周后观察革样表面析出情况,恒温恒湿箱设定的条件为温度70℃,湿度95%。
实施例和对比例的聚氨酯合成革性能测试结果如下表1:
表1:
Claims (10)
1.一种聚氨酯树脂,其特征在于包括如下重量份的组分原料:
聚氨酯预聚体14~46份;
多异氰酸酯5~26份;
聚合物多元醇20~56份;
所述的聚氨酯预聚体包括多异氰酸酯与扩链剂反应得到的聚氨酯预聚体。
2.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的聚氨酯预聚体的异氰酸酯指数为0.3~0.7。
3.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的多异氰酸酯包括二苯基甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、萘二异氰酸酯NDI、异佛尔酮异氰酸酯IPDI以及其异构体和/或衍生物和/或改性聚合物中的一种以上。
4.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的聚合物多元醇为聚醚多元醇和聚酯多元醇的混合物;所述的聚醚多元醇为聚四氢呋喃醚多元醇,数均分子量1500~3000。
5.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的扩链剂为乙二醇、丙二醇、丁二醇、新戊二醇中的一种及以上。
6.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的聚酯多元醇包括至少一种C4以上C10以下的二元酸与至少一种C3以上C10以下的二元醇反应得到的聚酯多元醇,数均分子量1000~3000;
所述的C4以上C10以下的二元酸为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、葵二酸中的一种及以上;
所述的C3以上C10以下的二元醇为丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、葵二醇中的一种及以上。
7.根据权利要求4所述的一种聚氨酯树脂,其特征在于,所述的聚醚多元醇与聚酯多元醇的质量比为2:3~4:1。
8.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的聚氨酯树脂还包括2~8重量份的交联剂和0.2-1.0重量份的终止剂。
9.根据权利要求8所述的一种聚氨酯树脂,其特征在于,所述的交联剂为甲醚化氨基树脂,终止剂为乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇。
10.根据权利要求1所述的一种聚氨酯树脂,其特征在于,所述的聚氨酯树脂作为合成革面层材料,通过离型纸转移工艺涂覆于贝斯表面得到镜面合成革,应用于鞋材、服饰以及箱包领域。
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