CN107828038A - 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法 - Google Patents

一种封闭性湿法合成革用聚氨酯固化剂及其制备方法 Download PDF

Info

Publication number
CN107828038A
CN107828038A CN201711058662.4A CN201711058662A CN107828038A CN 107828038 A CN107828038 A CN 107828038A CN 201711058662 A CN201711058662 A CN 201711058662A CN 107828038 A CN107828038 A CN 107828038A
Authority
CN
China
Prior art keywords
wet
curing agent
synthetic leather
closure
polyurethane curing
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.)
Granted
Application number
CN201711058662.4A
Other languages
English (en)
Other versions
CN107828038B (zh
Inventor
张彪
季明洋
李晓飞
姚克俭
戴永祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
Original Assignee
HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd filed Critical HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
Priority to CN201711058662.4A priority Critical patent/CN107828038B/zh
Publication of CN107828038A publication Critical patent/CN107828038A/zh
Application granted granted Critical
Publication of CN107828038B publication Critical patent/CN107828038B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
    • C08G18/30—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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明公开了一种封闭性湿法合成革用聚氨酯固化剂及其制备方法，将二苯基甲烷二异氰酸酯在溶剂DMF中与聚醚二元醇、聚酯二元醇、多官能度的小分子扩链剂按一定工艺和步骤进行加成反应得到异氰酸酯预聚物，再与异氰酸酯封闭剂反应即得。本发明制得的产品应用于湿法聚氨酯合成革的生产，可明显提高革的剥离强度。

Description

一种封闭性湿法合成革用聚氨酯固化剂及其制备方法
技术领域
本发明涉及聚氨酯固化剂领域，具体是一种封闭性湿法合成革用聚氨酯固化剂及其制备方法。
背景技术
聚氨酯固化剂和其他高分子材料固化剂一样，应用很广泛，均是使热固型材料发生不可逆的化学反应来完成的，能明显提高材料的机械性能、耐热性能、耐水解性能和耐腐蚀性能等。最常用的聚氨酯固化剂是甲苯二异氰酸酯(TDI)和三羟甲基丙烷TMP的加成物，但该产品有大量游离的异氰酸酯，挥发性强，毒性较大，而且TDI型产品的耐黄变性能较差。同样是芳香族异氰酸酯，二苯基甲烷二异氰酸酯的毒性小，耐黄变性能较为优越。
二苯基甲烷二异氰酸酯(MDI)广泛应用于湿法聚氨酯合成革树脂的生产，用MDI合成的聚氨酯树脂，成革强度高，弹性好手感佳，可广泛应用于沙发革、鞋革、服装革、电子包装革等的加工制作。常用异氰酸酯固化剂价格高，一般适用于干法合成革的生产，在湿法加工过程中能使用的异氰酸酯固化剂很少。市售异氰酸酯固化剂在湿法配料过程中会与填料、颜料和树脂发生反应，导致粘度快速增长，使物料存放期太短，不能满足工业化大生产的需要。如果能将裸露的异氰酸酯暂时封闭起来，在常温下不反应，在高温下快速反应，肯定能满足湿法聚氨酯合成革对固化剂的长期需求。针对合成革湿法行业的聚氨酯固化剂研究很少，鲜见工业化产品。
专利CN200910082371.8一种部分封闭型聚氨酯固化剂及其制备方法介绍了一种半封闭型异氰酸酯固化剂，该专利大量使用低分子量的多元醇与MDI反应，固化剂脆性太强不能满足湿法合成革对手感的要求；因为部分封闭仍有裸露的异氰酸酯，存放稳定性不超过20天；使用溶剂为酯类，相对于湿法聚氨酯合成革原料，价格较贵，难以回收。部分封闭的聚氨酯固化剂可以适应聚氨酯胶膜的生产，但应用于聚氨酯合成革湿法生产存在很多问题：一、部分封闭的异氰酸酯存放稳定性差；二、湿法聚氨酯合成革生产配料时有众多挑战，要即配即用，生产节奏难以把握；三、湿法聚氨酯合成革生产过程中用到大量的水，会消耗固化剂，使固化剂失效。
专利CN200810033516.0一种封闭型自交联单组分聚氨酯粘合剂及其制备方法，采用较少量的封闭剂对多官能度异氰酯进行预先部分封闭，减少封闭剂的使用，有利于胶膜的性能和强度，但预先封闭可能导致最终成品不均一，如有的TDI两端都被封闭了，有的TDI一端被封闭了，且封闭剂解封后会产生大量TDI单体，毒性较大。该专利产品与一般聚氨酯固化剂一样，都是由小分子多元醇与异氰酸酯反应，残留异氰酸酯单体或封闭的异氰酸酯单体，此类固化剂平均分子量较小，使用后会明显提高聚氨酯胶膜的强度，造成硬度上升，伸长率下降的现象，对聚氨酯胶膜的软硬度和手感影响较大。湿法聚氨酯合成革生产所需固化剂要求对手感影响较小。另湿法聚氨酯合成革生产时将配好的浆料涂覆到布基上，布料结合的牢度因工艺条件变化时有波动，如果加入固化剂能明显改善，将极大得提高生产效率和产品质量。
发明内容
本发明的目的是提供一种封闭性湿法合成革用聚氨酯固化剂及其制备方法，以解决现有技术聚氨酯固化存在的问题。
为了达到上述目的，本发明所采用的技术方案为：
一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：由4,4′-二苯基甲烷二异氰酸酯MDI在溶剂DMF中与助剂、聚醚二元醇、聚酯二元醇、多官能度的小分子扩链剂进行加成反应生成异氰酸酯预聚物，再由异氰酸酯预聚物与异氰酸酯类封闭剂反应获得，其中：
4,4′-二苯基甲烷二异氰酸酯MDI占体系总重量的20～25％；
溶剂DMF占体系总重量的40～60％；
助剂占体系总重量的0.004％；
聚醚二元醇及聚酯二元醇与小分子扩链剂的摩尔比为1:0.8～1.2。
异氰酸酯类封闭剂用量由残留的异氰酸酯基团计算确定。.
所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：固含量为50±5％，封闭-NCO含量为1.0～6.0wt％，25℃粘度为100～500mPa.s。
所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：多官能度的小分子扩链剂为三羟甲基丙烷、丙三醇和蓖麻油中的一种或多种的任意重量比的混合物。
所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：助剂为延缓反应的磷酸或苯甲酰氯。
所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：异氰酸酯封闭剂为甲乙酮肟和丙酮肟中的一种或两种任意重量比的混合物。
一种封闭性湿法合成革用聚氨酯固化剂的方法，其特征在于，依次包括以下步骤：
(1)、在反应釜中投入部分溶剂DMF、以及按配比投入助剂和4,4’-二苯基甲烷二异氰酸MDI，充分搅匀后再按配比加入聚醚多元醇和聚酯多元醇，固含量控制在60％～80％，并在反应釜中60-70℃温度下反应2-3小时；
(2)、NCO含量达到理论值后，按配比投入多官能度的小分子扩链剂，控制反应釜在60-70℃温度条件下反应1小时；
(3)、NCO含量达到理论值后，按配比投入异氰酸酯类封闭剂，控制反应釜在60-70℃温度条件下反应1小时；
(4)、反应结束后加入剩余的溶剂DMF，搅拌均匀；
(5)、取样检测，若25℃下粘度为100～500mPa.s，则冷却出料。
所述的一种封闭性湿法合成革用聚氨酯固化剂的方法，其特征在于：步骤(2)、(3)判断NCO含量是否达到理论值是用二正丁胺法测定的。
本发明加工方法中，每个步骤溶剂DMF的用量根据固含量控制，即加入的溶剂确保固含量控制在60％～80％。
本发明填补了湿法用聚氨酯固化剂的空白，该固化剂对手感和硬度影响较小，可明显提高布料结合的强度。通过在合成初期加入聚醚二元醇和聚酯二元醇，软段的引入可明显提高固化剂的平均分子量；布料结合的强度，是通过异氰酸酯类封闭剂解封后发生化学反应，提高树脂强度以及布料间的作用力来实现。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施方式，进一步阐述本发明。
实施例1：
注：实施例中的原料均为聚氨酯行业常规品种，厂家很多，如聚四氢呋喃醚二醇PTMG为河南能源化工集团精细化工有限公司生产，聚氧化丙烯二醇PPG为淄博德信联邦化工有限公司生产，聚己二酸丁二醇酯二醇为青岛新宇田化工有限公司，三羟甲基丙烷TMP为佛山今佳新材料科技有限公司提供，4,4’-二苯基甲烷二异氰酸酯MDI为烟台万华聚氨酯股份有限公司生产，甲乙酮肟MEKO为浙江圣安化工股份有限公司生产，N,N-二甲基甲酰胺DMF为安阳九天精细化学有限公司生产。
本发明按以下步骤进行制备：
1、在反应釜中投入部分溶剂150份DMF、20份磷酸和220份MDI充分搅匀后，加入全部聚醚多元醇和聚酯多元醇，固含量控制在73％，60-70℃反应2.5小时；
2、NCO含量降到10.5％以下，投入三羟甲基丙烷，控制60-70℃反应约1小时；
3、NCO含量降到6.0％以下，投入封闭剂，控制60-70℃反应约1小时；
4、反应结束后加入剩余的溶剂DMF，搅拌均匀；
5、取样检测25℃粘度100～500mPa.s，冷却出料。
实施方案2：
本发明按以下步骤进行制备：
1、在反应釜中投入部分溶剂200份DMF、0.02份磷酸和230份MDI充分搅匀后，加入全部聚醚多元醇和聚酯多元醇，固含量控制在67％，60-70℃反应2.5小时；
2、NCO含量降到10.4％以下，投入三羟甲基丙烷，控制60-70℃反应约1小时；
3、NCO含量降到5.9％以下，投入封闭剂，控制60-70℃反应约1小时；
4、反应结束后加入剩余的溶剂DMF，搅拌均匀；
5、取样检测25℃粘度100～500mPa.s，冷却出料。
分别将实施例树脂与市售树脂按相同的沙发革湿法配方和工艺制样，物性对比如表1所示：
表1物性对比表
由表1可见，本发明提供的树脂可明显提高剥离强度和布料结合效果。原空白样，树脂浆料的成革泡孔层的强度很高(强度过剩)，但是布料结合不牢，测试剥离容易剥到布面，导致强度不高。后加入实施例调整后，剥离强度和布料结合明显好转，其中实施例2更优，这是因为硬段含量更高。实施例1产品的手感比实施例2产品的好。

Claims (7)

1.一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：由4,4′-二苯基甲烷二异氰酸酯 MDI在溶剂DMF中与助剂、聚醚二元醇、聚酯二元醇、多官能度的小分子扩链剂进行加成反应生成异氰酸酯预聚物，再由异氰酸酯预聚物与异氰酸酯类封闭剂反应获得，其中：
4,4′-二苯基甲烷二异氰酸酯 MDI占体系总重量的20~25%；
溶剂DMF占体系总重量的40~60%；
助剂占体系总重量的0.004%；
聚醚二元醇及聚酯二元醇与小分子扩链剂的摩尔比为1:0.8 ~1.2；
异氰酸酯类封闭剂用量由残留的异氰酸酯基团计算确定。
2.根据权利要求1所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：固含量为50±5%，封闭-NCO含量为1.0～6.0wt％，25℃粘度为100～500mPa.s。
3.根据权利要求1所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：多官能度的小分子扩链剂为三羟甲基丙烷、丙三醇和蓖麻油中的一种或多种的任意重量比的混合物。
4.根据权利要求1所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：助剂为延缓反应的磷酸或苯甲酰氯。
5.根据权利要求1所述的一种封闭性湿法合成革用聚氨酯固化剂，其特征在于：异氰酸酯封闭剂为甲乙酮肟和丙酮肟中的一种或两种任意重量比的混合物。
6.一种封闭性湿法合成革用聚氨酯固化剂的方法，其特征在于，依次包括以下步骤：
（1）、在反应釜中投入部分溶剂DMF、以及按配比投入助剂和4,4’-二苯基甲烷二异氰酸MDI，充分搅匀后再按配比加入聚醚多元醇和聚酯多元醇，固含量控制在60%~80%，并在反应釜中60-70℃温度下反应2-3小时；
（2）、NCO含量达到理论值后，按配比投入多官能度的小分子扩链剂，控制反应釜在60-70℃温度条件下反应1小时；
（3）、NCO含量达到理论值后，按配比投入异氰酸酯类封闭剂，控制反应釜在60-70℃温度条件下反应1小时；
（4）、反应结束后加入剩余的溶剂DMF，搅拌均匀；
（5）、取样检测，若25℃下粘度为100～500mPa.s，则冷却出料。
7.根据权利要求6所述的一种封闭性湿法合成革用聚氨酯固化剂的方法，其特征在于：步骤（2）、（3）判断NCO含量是否达到理论值是用二正丁胺法测定的。
CN201711058662.4A 2017-11-01 2017-11-01 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法 Active CN107828038B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711058662.4A CN107828038B (zh) 2017-11-01 2017-11-01 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711058662.4A CN107828038B (zh) 2017-11-01 2017-11-01 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法

Publications (2)

Publication Number Publication Date
CN107828038A true CN107828038A (zh) 2018-03-23
CN107828038B CN107828038B (zh) 2020-07-17

Family

ID=61651482

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711058662.4A Active CN107828038B (zh) 2017-11-01 2017-11-01 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法

Country Status (1)

Country Link
CN (1) CN107828038B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880048A (zh) * 2019-01-24 2019-06-14 扬州工业职业技术学院 一种耐溶剂型聚氨酯底料及其制备方法
CN114920903A (zh) * 2022-06-30 2022-08-19 浙江华峰合成树脂有限公司 一种封闭型异氰酸酯固化剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101230124A (zh) * 2007-01-27 2008-07-30 周建明 一种固化剂4,4’-二苯基甲烷二异氰酸酯预聚物及其制备方法
CN101544742A (zh) * 2009-04-15 2009-09-30 北京科聚化工新材料有限公司 一种部分封闭型聚氨酯固化剂及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101230124A (zh) * 2007-01-27 2008-07-30 周建明 一种固化剂4,4’-二苯基甲烷二异氰酸酯预聚物及其制备方法
CN101544742A (zh) * 2009-04-15 2009-09-30 北京科聚化工新材料有限公司 一种部分封闭型聚氨酯固化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
俞佳等，: ""封端型水性聚氨酯交联剂的合成及应用"", 《印染》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880048A (zh) * 2019-01-24 2019-06-14 扬州工业职业技术学院 一种耐溶剂型聚氨酯底料及其制备方法
CN114920903A (zh) * 2022-06-30 2022-08-19 浙江华峰合成树脂有限公司 一种封闭型异氰酸酯固化剂及其制备方法和应用
CN114920903B (zh) * 2022-06-30 2024-02-02 浙江华峰合成树脂有限公司 一种封闭型异氰酸酯固化剂及其制备方法和应用

Also Published As

Publication number Publication date
CN107828038B (zh) 2020-07-17

Similar Documents

Publication Publication Date Title
JP2018172690A (ja) ポリウレタン、その製造方法及び用途
CN104263310B (zh) 一种单组份湿固化聚氨酯胶粘剂及其制备方法
CN1322085C (zh) 一种低温涂布的单组分无溶剂聚氨酯粘合剂及其制备方法
CN107163895A (zh) 纸塑复合用单组份聚氨酯热熔胶黏剂及其制备方法
CN103059261B (zh) 改性二苯基甲烷二异氰酸酯缩二脲固化剂及其制备方法
CN107987779A (zh) 一种反应型聚氨酯热熔胶及其制备方法和应用
CN110229645B (zh) 高初粘单组份湿气固化反应型聚氨酯热熔胶及其制备方法
EP1873177A1 (en) Isocyanate-terminated urethane prepolymer, process for producing the same, and adhesive comprising the urethane prepolymer
CN107459959B (zh) 一种软包装用耐蒸煮无溶剂粘合剂及其制备方法
CN106750084A (zh) 高固含量二液型粘结层聚氨酯树脂及其制备方法
CN105308087A (zh) 1液湿气固化型聚氨酯组合物
CN107417874B (zh) 一种封端型双组份无溶剂防水透湿聚氨酯树脂及其制备方法
CN106978126A (zh) 一种常温快速固化的单组份聚氨酯胶黏剂及其制备方法
CN114450323A (zh) 低游离聚氨酯预聚物组合物
CN107286312A (zh) 一种阴离子-非离子水性聚氨酯分散体及其制备方法与应用
CN107828038A (zh) 一种封闭性湿法合成革用聚氨酯固化剂及其制备方法
KR20160118976A (ko) 고강도 폴리우레탄 및 그 제조방법
CN112625213A (zh) 一种无溶剂封闭型聚氨酯树脂组合物、聚氨酯材料和皮革产品
CN114262597A (zh) 一种单组分热固型聚氨酯改性环氧结构胶及其制备方法
KR101871139B1 (ko) 폴리우레탄 접착제 조성물, 그리고 이의 제조 방법
CN105315949B (zh) 一种具有很短开放时间和高弹性的聚氨酯胶黏剂及其应用
WO2021262845A1 (en) Polyol compositions and methods
CN103305177A (zh) 一种单组份聚氨酯胶粘剂的制备方法
TWI696679B (zh) 濕氣硬化型胺基甲酸酯熱熔樹脂組成物、積層體及鞋
CN101775120A (zh) 一种固化剂二异氰酸酯预聚物及其制备方法

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