CN112375206A - 一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法 - Google Patents

一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法 Download PDF

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CN112375206A
CN112375206A CN202011523641.7A CN202011523641A CN112375206A CN 112375206 A CN112375206 A CN 112375206A CN 202011523641 A CN202011523641 A CN 202011523641A CN 112375206 A CN112375206 A CN 112375206A
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leather
component
physical
antioxidant
resin
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CN112375206B (zh
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施静
息锁柱
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Zhejiang Zhaoze Industrial Co ltd
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Zhejiang Zhaoze Industrial Co ltd
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Abstract

本发明涉及皮革技术领域，尤其是一种皮革用高物性无溶剂聚氨酯面料树脂，包括A组分和B组分，所述A组分包括以下原料组分：聚己内酯聚碳酸酯共聚物多元醇、多官能度聚己内酯多元醇、异氰酸酯、小分子醇、环氧树脂、消泡剂、流平剂、催化剂、抗氧剂，所述B组分包括以下原料组分：异氰酸酯、植物油、多官能度聚己内酯多元醇、抗氧剂。还公开了上述聚氨酯面料树脂的制备方法。本发明所得到的一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法，可以代替溶剂型面层树脂生产聚氨酯皮革，能够帮助无溶剂PU皮革行业实现完全环保作业。其生产出的无溶剂面料具有非常高的物性。

Description

一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法
技术领域
本发明涉及皮革技术领域，尤其是一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法。
背景技术
无溶剂聚氨酯树脂，其主体原料为多元醇，目前普遍选用低结晶性的聚醚多元醇或者中小分子量的聚酯多元醇，其生产出来的树脂膜，物性偏低，达不到目前油性面料树脂的物性。目前，无溶剂PU皮革通常采用的工艺是先用溶剂型PU刮涂面层，然后再刮涂无溶剂PU发泡料，再与皮胚贴合。现有工艺仍然采用溶剂型的PU面层树脂，达不到完全环保，成为无溶剂PU皮革行业的一大诟病。
发明内容
本发明的目的是为了解决上述技术的不足而提供一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法，采用无溶剂，更加环保。
为了达到上述目的，本发明所设计的一种皮革用高物性无溶剂聚氨酯面料树脂，包括A组分和B组分，所述A组分按照质量百分数计算，包括以下原料组分：70-90%聚己内酯聚碳酸酯共聚物多元醇、2-15%多官能度聚己内酯多元醇、1-5%异氰酸酯、2-10%小分子醇、3-10%环氧树脂、0.1-1%消泡剂、0.1-1%流平剂、0.1-1%催化剂、0.2-2%抗氧剂，所述B组分按照质量百分数计算，包括以下原料组分：50-70%异氰酸酯、5-20%植物油、10-30%多官能度聚己内酯多元醇、0.2-2%抗氧剂。
作为优化，所述聚己内酯聚碳酸酯共聚物多元醇为聚己内酯多元醇与碳酸二甲酯、碳酸二乙酯中的一种，以及与1,4-丁二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,4-二羟甲基环己烷中的一种或者多种的组合聚合反应的产物，数均分子量为500-2000 g/mol，粘度＜5000cps/25℃。
进一步优化，所述聚己内酯多元醇为ε-己内酯与乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、一缩二乙二醇、3-甲基-1,5-戊二醇中的一种或者多种组合聚合反应的产物，数均分子量为240-750 g/mol，粘度＜2000cps/25℃。
作为优化，所述多官能度聚己内酯多元醇为ε-己内酯与TMP、甘油、季戊四醇、三羟甲基乙烷、1,2,6-己三醇中的一种或者多种聚合的产物，数均分子量为430-1000 g/mol，官能度为3-4，粘度＜8000cps/25℃。
作为优化，所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯、MDI-50（50%4,4-二苯基甲烷二异氰酸酯，50%2,4-二苯基甲烷二异氰酸酯的混合物）、甲苯二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、1,6己二异氰酸酯中的一种或者多种组合。
作为优化，所述小分子醇为乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、一缩二乙二醇、一缩二丙二醇、3-甲基-1,5-戊二醇、甘油、三羟甲基丙烷中的一种或者多种组合。
作为优化，所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂中的一种或者多种组合，所述双酚A型环氧树脂，环氧当量为175-195 g/eq，粘度为5000-15000 cps/25℃；所述双酚F型环氧树脂，环氧当量为160-205 g/eq，粘度为400-15000 cps/25℃。
作为优化，所述消泡剂为聚硅氧烷消泡剂。
作为优化，所述流平剂为聚硅氧烷流平剂。
作为优化，所述催化剂为有机铋催化剂。
作为优化，所述抗氧剂为受阻酚抗氧剂、亚磷酸酯抗氧剂中的一种或两种，其中所述受阻酚抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1135、抗氧剂1035、抗氧剂1098中的一种或多种组合；所述亚磷酸酯抗氧剂为抗氧剂168、抗氧剂TPP、抗氧剂TNPP中的一种或多种组合。
作为优化，所述植物油为蓖麻油。
作为优化，使用时，所述A组分、B组分的混合按质量比为1:0.2～1:10。
一种上述皮革用高物性无溶剂聚氨酯面料树脂的制备方法，包括以下步骤：
（1）A组分的制备：将聚己内酯聚碳酸酯共聚物多元醇投入反应釜中，搅拌升温至120±10℃，于真空度-0.09MPa～-0.01MPa条件下抽真空脱水2～3小时，后降温至80±10℃，加入异氰酸酯，反应3～5小时，至NCO含量＜0.2%，降温至50±10℃，加入多官能度聚己内酯多元醇、小分子醇、环氧树脂、消泡剂、流平剂、催化剂、抗氧剂，搅拌3～5小时，至预定羟值60～150mgKOH/g，即制得A组分；
（2）B组分的制备：将异氰酸酯、植物油、多官能度聚己内酯多元醇、抗氧剂投入反应釜中，升温至80±10℃，反应5～8小时，至NCO含量达到预定值10～26%，即制得B组分。
具体使用过程中，所述A组分、B组分的混合按质量比为1:0.2～1:10为优。
本发明所得到的一种皮革用高物性无溶剂聚氨酯面料树脂及其制备方法，具有如下的优点和有益效果：
（1）、本技术方案提出的一种皮革用高物性无溶剂聚氨酯面料树脂，用以代替无溶剂PU皮革现有工艺中的溶剂型的PU面层树脂，使无溶剂PU皮革生产实现完全环保作业，完全清洁化。
（2）、无溶剂PU皮革生产工艺为浇注型工艺，即将储罐中的A组分、B组分按特定的比例输入到浇注机头高速混合，然后注射、刮涂于基材上，进入烘道，反应成型。因此，这就要求A组分、B组分都要具有非常低的粘度。多元醇中，聚碳酸酯二元醇结晶性最高，物性最好，但，聚碳酸酯二元醇多为固体，而液体聚碳酸酯二元醇，中分子量以上产品在低温下粘度都较高，不宜作为无溶剂大剂量主体原料使用。本发明选用的聚己内酯聚碳酸酯共聚物多元醇，即具有聚碳酸酯二元醇的高结晶性、高物性，又拥有低粘度的特征。其生产出的无溶剂面料具有非常高的物性。
（3）、本发明树脂A组分、B组分分别引入适量多官能度聚己内酯多元醇，提供树脂的交联度，有效提升树脂物性，同时又具有足够的柔软度。
（4）、本发明树脂A组分引入适量环氧树脂，有效增强树脂物性，调节树脂粘度。
（5）、本发明树脂B组分引入适量植物油，有效调整树脂的交联度，及树脂粘度，保证树脂在低粘条件下，具有高物性。
具体实施方式
下面通过实施例对本发明作进一步的描述。
实施例1：
本实施例描述的一种皮革用高物性无溶剂聚氨酯面料树脂的制备方法，包括如下步骤：
（1）A组分的制备：将300份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为1800 g/mol，粘度2700cps/25℃）投入反应釜中，搅拌升温至110℃，于真空度-0.09MPa条件下抽真空脱水2小时，后降温至70℃，加入10份4,4-二苯基甲烷二异氰酸酯、2.5份MDI-50（50%4,4-二苯基甲烷二异氰酸酯，50%2,4-二苯基甲烷二异氰酸酯的混合物），反应3小时，至NCO含量<0.2%，降温至40℃，加入9.4份多官能度聚己内酯多元醇（数均分子量为1000 g/mol，官能度3）、3.1份乙二醇、9.4份二丙二醇、15.6份双酚F型环氧树脂（环氧当量170 g/eq，粘度3500 cps/25℃）、0.6份聚硅氧烷消泡剂、0.8份聚硅氧烷流平剂、1.1份有机铋催化剂、1.5份抗氧剂1010，搅拌3小时，至羟值达到80.08mgKOH/g，即制得A组分。
（2）B组分的制备：将110.6份甲苯二异氰酸酯、28份4,4-二苯基甲烷二异氰酸酯、53.3份蓖麻油、76.7份多官能度聚己内酯多元醇（数均分子量为2600 g/mol，官能度3.2）、0.8份抗氧剂168投入反应釜中，升温至70℃，反应5小时，至NCO含量达到19.43%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.31。
实施例2：
本实施例描述的一种皮革用高物性无溶剂聚氨酯面料树脂的制备方法，包括如下步骤：
（1）A组分的制备：将200份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为2000 g/mol，粘度4600cps/25℃）投入反应釜中，搅拌升温至130℃，于真空度-0.01MPa条件下抽真空脱水3小时，后降温至90℃，加入5.2份甲苯二异氰酸酯，反应5小时，至NCO含量<0.2%，降温至60℃，加入6.2份多官能度聚己内酯多元醇（数均分子量为1200 g/mol，官能度3.5）、4.1份2-甲基-1,3-丙二醇、8.2份一缩二乙二醇、12.3份双酚A型环氧树脂（环氧当量178 g/eq，粘度6000cps/25℃）、0.4份聚硅氧烷消泡剂、0.5份聚硅氧烷流平剂、0.7份有机铋催化剂、1份抗氧剂1076，搅拌5小时，至羟值达到95.56mgKOH/g，即制得A组分。
（2）B组分的制备：将63.9份异佛尔酮二异氰酸酯、45份碳化二亚胺改性二苯基甲烷二异氰酸酯、36份蓖麻油、44份多官能度聚己内酯多元醇（数均分子量为1800 g/mol，官能度3.6）、0.6份抗氧剂TPP投入反应釜中，升温至90℃，反应8小时，至NCO含量达到15.37%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.47 。
实施例3：
本实施例描述的一种皮革用高物性无溶剂聚氨酯面料树脂的制备方法，包括如下步骤：
（1）A组分的制备：将160份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为1500 g/mol，粘度2100cps/25℃）投入反应釜中，搅拌升温至120℃，于真空度-0.095MPa条件下抽真空脱水3小时，后降温至80℃，加入5.6份二环己基甲烷二异氰酸酯、3.6份1,6己二异氰酸酯，反应4小时，至NCO含量<0.2%，降温至50℃，加入8.5份多官能度聚己内酯多元醇（数均分子量为1600 g/mol，官能度3.2）、1.7份1,3-丙二醇、3.4份3-甲基-1.5戊二醇、11.8份双酚F型环氧树脂（环氧当量183g/eq，粘度12000cps/25℃）、0.3份聚硅氧烷消泡剂、0.4份聚硅氧烷流平剂、0.6份有机铋催化剂、0.8份抗氧剂1135，搅拌4小时，至羟值达到71.06mgKOH/g，即制得A组分。
（2）B组分的制备：将77.9份异佛尔酮二异氰酸酯、37.6份4,4-二苯基甲烷二异氰酸酯、17.5份蓖麻油、32.5份多官能度聚己内酯多元醇（数均分子量为800 g/mol，官能度3）、0.5份抗氧剂168投入反应釜中，升温至80℃，反应6小时，至NCO含量达到20.99%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.25 。
对比例1（常规液体聚碳酸酯二元醇）
（1）将200份液体聚碳酸酯二元醇（数均分子量为1500g/mol，粘度2.7万cps/25℃）投入反应釜中，搅拌升温至110℃，于真空度-0.09MPa～-0.01MPa条件下抽真空脱水2小时，后降温至70℃，加入3.7份甲苯二异氰酸酯、1.3份MDI-50（50%4,4-二苯基甲烷二异氰酸酯，50%2,4-二苯基甲烷二异氰酸酯的混合物），反应3小时，至NCO含量<0.2%，降温至40℃，加入10.2份多官能度聚己内酯多元醇（数均分子量为800 g/mol，官能度3）、2份2-甲基-1,3-丙二醇、6.1份二丙二醇、10.2份双酚F型环氧树脂（环氧当量195g/eq，粘度900cps/25℃）、0.4份聚硅氧烷消泡剂、0.5份聚硅氧烷流平剂、0.7份有机铋催化剂、1份抗氧剂1035，搅拌3小时，至羟值达到92.84mgKOH/g，即制得A组分。
（2）将93.1份MDI-50（50%4,4-二苯基甲烷二异氰酸酯，50%2,4-二苯基甲烷二异氰酸酯的混合物）、64.8份甲苯二异氰酸酯、52份蓖麻油、78份多官能度聚己内酯多元醇（数均分子量为1300 g/mol，官能度3）、0.8份抗氧剂TNPP投入反应釜中，升温至90℃，反应8小时，至NCO含量达到16.85%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.41。
对比例2（聚醚二元醇）
（1）将63份PPG2000、147份PPG1000投入反应釜中，搅拌升温至130℃，于真空度-0.09MPa条件下抽真空脱水3小时，后降温至70℃，加入2.7份4,4-二苯基甲烷二异氰酸酯，反应5小时，至NCO含量<0.2%，降温至60℃，加入8.5份多官能度聚己内酯多元醇（数均分子量为1100 g/mol，官能度3.4）、4.3份乙二醇、2.1份2-甲基-1,3-丙二醇、12.8份双酚A型环氧树脂（环氧当量182g/eq，粘度1.1万cps/25℃）、0.6份聚硅氧烷消泡剂、0.7份聚硅氧烷流平剂、1份有机铋催化剂、1.5份抗氧剂1098，搅拌5小时，至羟值达到125.9mgKOH/g，即制得A组分。
（2）将219.3份甲苯二异氰酸酯、64.5份碳化二亚胺改性二苯基甲烷二异氰酸酯、74份蓖麻油、126份多官能度聚己内酯多元醇（数均分子量为1100 g/mol，官能度3.3）、1.4份抗氧剂168投入反应釜中，升温至70℃，反应8小时，至NCO含量达到20.53%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.46。
对比例3（聚酯二元醇）
（1）将230份聚己二酸一缩二乙二醇酯（数均分子量1700g/mol，粘度7500cps/25℃）投入反应釜中，搅拌升温至130℃，于真空度-0.01MPa条件下抽真空脱水3小时，后降温至70℃，加入3.4份4,4-二苯基甲烷二异氰酸酯，反应3小时，至NCO含量<0.2%，降温至60℃，加入16.3份多官能度聚己内酯多元醇（数均分子量为700 g/mol，官能度3.7）、7份乙二醇、2.3份一缩二乙二醇酯、9.3份双酚F型环氧树脂（环氧当量170g/eq，粘度3500cps/25℃）、0.7份聚硅氧烷消泡剂、0.8份聚硅氧烷流平剂、1.2份有机铋催化剂、1.6份抗氧剂1010，搅拌5小时，至羟值达到121.88mgKOH/g，即制得A组分。
（2）将216.7份甲苯二异氰酸酯、90.3份碳化二亚胺改性二苯基甲烷二异氰酸酯、96.6份蓖麻油、133.4份多官能度聚己内酯多元醇（数均分子量为1300 g/mol，官能度3.1）、2.7份抗氧剂168投入反应釜中，升温至70℃，反应5小时，至NCO含量达到19.57%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.47。
对比例4（无环氧树脂）
（1）将225份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为1800 g/mol，粘度2700cps/25℃）投入反应釜中，搅拌升温至130℃，于真空度-0.09MPa条件下抽真空脱水2小时，后降温至90℃，加入3.1份4,4-二苯基甲烷二异氰酸酯、2.1份甲苯二异氰酸酯，反应5小时，至NCO含量<0.2%，降温至40℃，加入6.9份多官能度聚己内酯多元醇（数均分子量为1000g/mol，官能度3.5）、2.3份乙二醇、6.9份二丙二醇、0.5份聚硅氧烷消泡剂、0.6份聚硅氧烷流平剂、0.8份有机铋催化剂、1.2份抗氧剂1010，搅拌3小时，至羟值达到90.34mgKOH/g，即制得A组分。
（2）将236.5份甲苯二异氰酸酯、60份4,4-二苯基甲烷二异氰酸酯、110.7份蓖麻油、159.3份多官能度聚己内酯多元醇（数均分子量为1000 g/mol，官能度3）、1.7份抗氧剂168投入反应釜中，升温至90℃，反应5小时，至NCO含量达到17.73%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.38。
对比例5（无多官能度聚己内酯多元醇）
（1）将176份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为1800 g/mol，粘度2700cps/25℃）投入反应釜中，搅拌升温至110℃，于真空度-0.09MPa条件下抽真空脱水2小时，后降温至70℃，加入2.4份4,4-二苯基甲烷二异氰酸酯、1.7份甲苯二异氰酸酯，反应3小时，至NCO含量<0.2%，降温至50℃，加入1.8份乙二醇、5.4份二丙二醇、10.8份双酚F型环氧树脂（环氧当量183g/eq，粘度12000cps/25℃）、0.36份聚硅氧烷消泡剂、0.45份聚硅氧烷流平剂、0.63份有机铋催化剂、0.88份抗氧剂1010，搅拌3小时，至羟值达到83.21mgKOH/g，即制得A组分。
（2）将151份甲苯二异氰酸酯、38.3份4,4-二苯基甲烷二异氰酸酯、45.5份蓖麻油、24.5份三羟甲基丙烷、0.78份抗氧剂168投入反应釜中，升温至70℃，反应5小时，至NCO含量达到21.99%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.28。
对比例6（无植物油）
（1）将143份聚己内酯聚碳酸酯共聚物多元醇（数均分子量为1800 g/mol，粘度2700cps/25℃）投入反应釜中，搅拌升温至120℃，于真空度-0.09MPa条件下抽真空脱水2小时，后降温至80℃，加入2份4,4-二苯基甲烷二异氰酸酯、1.4份甲苯二异氰酸酯，反应3～5小时，至NCO含量<0.2%，降温至50℃，加入4.4份多官能度聚己内酯多元醇（数均分子量为1000 g/mol，官能度3.5）、1.5份乙二醇、4.4份二丙二醇、8.8份双酚F型环氧树脂（环氧当量183g/eq，粘度12000cps/25℃）、0.3份聚硅氧烷消泡剂、0.37份聚硅氧烷流平剂、0.5份有机铋催化剂、0.72份抗氧剂1010，搅拌3小时，至羟值达到86.18mgKOH/g，即制得A组分。
（2）将194份MDI-50（50%4,4-二苯基甲烷二异氰酸酯，50%2,4-二苯基甲烷二异氰酸酯的混合物）、135份甲苯二异氰酸酯、42份多官能度聚己内酯多元醇（数均分子量为2000g/mol，官能度3）、28份三羟甲基丙烷、1.2份抗氧剂168投入反应釜中，升温至80℃，反应8小时，至NCO含量达到25.34%，即制得B组分。
使用时，A组分与B组分的混合质量比为1:0.25 。
按照设定比例，在无溶剂复合机上，将A组分、B组分混合后涂于离型纸上，进烘箱，120℃经3分钟烘干，再刮涂一层无溶剂底层树脂，最后贴合皮胚，制得无溶剂聚氨酯皮革。
对比例7（溶剂型面层树脂）
将125份聚己二酸乙二醇1.4-丁二醇酯（数均分子量为2000 g/mol）投入反应釜中，搅拌升温至120℃，于真空度-0.09MPa条件下抽真空脱水2小时，后降温至50℃，加入204份二甲基甲酰胺、0.2份抗氧剂1010、4.8份乙二醇、7份1.4-丁二醇搅拌均匀，加入55份4,4-二苯基甲烷二异氰酸酯、0.1份有机铋催化剂，升温至80℃，反应完全，补加4,4-二苯基甲烷二异氰酸酯起粘，待粘度升至预定值20万cps/75℃，加入87份二甲基甲酰胺、157份乙酸乙酯，粘度达到10万cps/25℃，即制得溶剂型面层树脂。
将溶剂型面层树脂稀释后，涂于离型纸上，进烘箱烘干，再涂一层无溶剂底层树脂，然后贴合皮胚，制得聚氨酯皮革。
将实施例1～3和对比例1～6的A组分、B组分，以及对比例7的测试粘度，结果列于表1。
表1：
Figure DEST_PATH_IMAGE001
由表1可知，由于常规液体聚碳酸酯二元醇粘度过大，由其作为主体原料制备的A组分相应的粘度也过高，导致无法输入到无溶剂复合机上，只能通过手工搅拌，再刮涂到离型纸上，进烘箱烘干后，再涂一层无溶剂底层树脂，最后贴合皮胚，制得无溶剂聚氨酯皮革。
应用实施例1～3和对比例1～7所制得的聚氨酯皮革的各项物性测试结果列于表2。其中，断裂强度、断裂伸长率、100%模量测试方法按GB/T 8949-2008的规定。
表2：
Figure RE-GDA0002898003600000101
综上，本发明产品皮革用高物性无溶剂聚氨酯面料树脂，可以代替溶剂型面层树脂 生产聚氨酯皮革，能够帮助无溶剂PU皮革行业实现完全环保作业。从表2中可以看出， 本发明选用的聚己内酯聚碳酸酯共聚物多元醇在低粘度的条件下，能够拥有聚碳酸酯二 元醇的高物性。在耐磨、耐热方面，明显好于常规溶剂型面层树脂。
以上结合具体实施例描述了本发明的技术原理。这些描述只是为了解释本发明的原理，而不能以任何方式解释为对本发明保护范围的限制。基于此处的解释，本领域的技术人员不需要付出创造性的劳动即可联想到本发明的其它具体实施方式，这些方式都将落入本发明的保护范围之内。

Claims (14)

1.一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于：包括A组分和B组分，所述A组分按照质量百分数计算，包括以下原料组分：70-90%聚己内酯聚碳酸酯共聚物多元醇、2-15%多官能度聚己内酯多元醇、1-5%异氰酸酯、2-10%小分子醇、3-10%环氧树脂、0.1-1%消泡剂、0.1-1%流平剂、0.1-1%催化剂、0.2-2%抗氧剂，所述B组分按照质量百分数计算，包括以下原料组分：50-70%异氰酸酯、5-20%植物油、10-30%多官能度聚己内酯多元醇、0.2-2%抗氧剂。
2.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于：所述聚己内酯聚碳酸酯共聚物多元醇为聚己内酯多元醇与碳酸二甲酯、碳酸二乙酯中的一种，以及与1,4-丁二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,4-二羟甲基环己烷中的一种或者多种的组合聚合反应的产物，数均分子量为500-2000 g/mol，粘度＜5000cps/25℃。
3.根据权利要求2所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于：所述聚己内酯多元醇为ε-己内酯与乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、一缩二乙二醇、3-甲基-1,5-戊二醇中的一种或者多种组合聚合反应的产物，数均分子量为240-750 g/mol，粘度＜2000cps/25℃。
4.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述多官能度聚己内酯多元醇为ε-己内酯与TMP、甘油、季戊四醇、三羟甲基乙烷、1,2,6-己三醇中的一种或者多种聚合的产物，数均分子量为430-1000 g/mol，官能度为3-4，粘度＜8000cps/25℃。
5.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯、MDI-50、甲苯二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、1,6己二异氰酸酯中的一种或者多种组合。
6.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述小分子醇为乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、一缩二乙二醇、一缩二丙二醇、3-甲基-1,5-戊二醇、甘油、三羟甲基丙烷中的一种或者多种组合。
7.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂中的一种或者多种组合，所述双酚A型环氧树脂，环氧当量为175-195 g/eq，粘度为5000-15000 cps/25℃；所述双酚F型环氧树脂，环氧当量为160-205 g/eq，粘度为400-15000 cps/25℃。
8.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述消泡剂为聚硅氧烷消泡剂。
9.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述流平剂为聚硅氧烷流平剂。
10.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述催化剂为有机铋催化剂。
11.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述抗氧剂为受阻酚抗氧剂、亚磷酸酯抗氧剂中的一种或两种，其中所述受阻酚抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1135、抗氧剂1035、抗氧剂1098中的一种或多种组合；所述亚磷酸酯抗氧剂为抗氧剂168、抗氧剂TPP、抗氧剂TNPP中的一种或多种组合。
12.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:所述植物油为蓖麻油。
13.根据权利要求1所述的一种皮革用高物性无溶剂聚氨酯面料树脂，其特征在于:使用时，所述A组分、B组分的混合按质量比为1:0.2～1:10。
14.一种如权利要求1-13任意一项所述皮革用高物性无溶剂聚氨酯面料树脂的制备方法，其特征在于，包括以下步骤：
（1）A组分的制备：将聚己内酯聚碳酸酯共聚物多元醇投入反应釜中，搅拌升温至120±10℃，于真空度-0.09MPa～-0.01MPa条件下抽真空脱水2～3小时，后降温至80±10℃，加入异氰酸酯，反应3～5小时，至NCO含量＜0.2%，降温至50±10℃，加入多官能度聚己内酯多元醇、小分子醇、环氧树脂、消泡剂、流平剂、催化剂、抗氧剂，搅拌3～5小时，至预定羟值60～150mgKOH/g，即制得A组分；
（2）B组分的制备：将异氰酸酯、植物油、多官能度聚己内酯多元醇、抗氧剂投入反应釜中，升温至80±10℃，反应5～8小时，至NCO含量达到预定值10～26%，即制得B组分。
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