CN106750149A - 一种发泡型水性聚氨酯的制备方法及应用方法 - Google Patents

一种发泡型水性聚氨酯的制备方法及应用方法 Download PDF

Info

Publication number
CN106750149A
CN106750149A CN201611065570.4A CN201611065570A CN106750149A CN 106750149 A CN106750149 A CN 106750149A CN 201611065570 A CN201611065570 A CN 201611065570A CN 106750149 A CN106750149 A CN 106750149A
Authority
CN
China
Prior art keywords
aqueous polyurethane
expansion type
type aqueous
added
preparation
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
CN201611065570.4A
Other languages
English (en)
Other versions
CN106750149B (zh
Inventor
马兴元
赵昭
张铭芮
丁博
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.)
Liaocheng xinrunda plastic products Co.,Ltd.
Original Assignee
Shaanxi University of Science and Technology
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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201611065570.4A priority Critical patent/CN106750149B/zh
Publication of CN106750149A publication Critical patent/CN106750149A/zh
Application granted granted Critical
Publication of CN106750149B publication Critical patent/CN106750149B/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
    • C08G18/75—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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/4825—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • C08G18/65—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/65—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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • C08J2375/08—Polyurethanes from polyethers

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)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

一种发泡型水性聚氨酯的制备方法及应用方法，将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在80～95℃下反应30～35min，然后脱水后加入二异氰酸酯，再于80～85℃下反应2～2.5h，再加入DMPA和1,4‑丁二醇，在80～85℃反应1.5～2h，降温到40～45℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在40～45℃反应1～1.5h，得到发泡型水性聚氨酯。本发明所得发泡型水性聚氨酯，具有良好的发泡作用，合成过程没有使用任何溶剂，可用于水性聚氨酯合成革发泡贝斯、水性聚氨酯涂层布和水性聚氨酯发泡薄膜等产品的生产，解决了生产中因为使用溶剂型聚氨酯而产生的溶剂污染和溶剂残留问题。

Description

一种发泡型水性聚氨酯的制备方法及应用方法
技术领域
本发明涉及水性聚氨酯技术领域，特别涉及一种发泡型水性聚氨酯的制备及应用方法。
背景技术
随着国家和人民对环境保护的高度重视及要求的不断提高，溶剂型聚氨酯由于其严重的溶剂污染而逐渐被无污染型的聚氨酯代替，其中水性聚氨酯(WPU)由于环保性和良好的综合性能在聚氨酯领域具有十分广阔的前景。其中，一些具有特殊性能的水性聚氨酯的开发逐步成为该领域研究的热点。
目前，水性聚氨酯可采用外乳化法和内乳化法制备。外乳化法即在外加乳化剂的条件下依靠高剪切力将聚氨酯强制乳化于水中，该方法制备的WPU粒子粒径粗大，稳定性较差，国内外目前已很少采用这种制备方法。内乳化法是指，在预聚体合成的这个过程中，将具有亲水作用的基团引入到PU的主链上，利用亲水基团使PU链段本身具有亲水性。然后在剪切外力作用下，分散到水中形成WPU乳液。这种生产WPU乳液的方法，可以得到稳定性好和机械性能优异的PU，是目前生产WPU的普遍方法。
根据水性聚氨酯合成方法的特点，主要包括以下几种合成工艺。
(1)预聚体分散法
预聚体分散法指先在合成聚氨酯预聚体时引入亲水基团，在不加溶剂或者加入很少溶剂的条件下进行中和乳化，乳化的同时再加入扩链剂进行后扩链，最后得到WPU树脂。这种合成工艺具有使用的溶剂少的优点，能够生成支化的大分子。
(2)丙酮法
丙酮法指在合成预聚体的过程中，使用较多的有机溶剂来稀释聚氨酯，防止粘度太大导致乳化困难，然后加水进行乳化，形成WPU，最后再将WPU乳液中的溶剂蒸离。而丙酮作为最常用的有机溶剂，所以也称丙酮法。该法合成的水性聚氨酯性能稳定，重复性好，但是使用了大量的溶剂，会对环境造成污染。
(3)熔融分散法
熔融分散法指合成含有亲水基的缩二脲基或端脲基聚氨酯低聚物，然后将其熔融，在机械搅拌下直接乳化于水中，乳化的同时再与甲醛进行扩链反应。整个反应无需溶剂，但是维持合成反应过程的温度较高，而且得到的PU分子量较低。
(4)酮亚胺/酮连氮法
酮亚胺/酮连氮法是指在预聚体分散法中用酮亚胺或酮连氮来代替二元伯胺进行后扩链。酮亚胺/酮连氮是一种封端的二胺类扩链剂，二胺在反应过程中能够稳定的解封出来，可以使扩链反应平稳的进行。所以用该法制备的水性聚氨酯具有性能良好、粒径比较均匀和乳液稳定性高的特点。
(5)保护端基乳化法
保护端基乳化法指在预聚体乳化之前用封闭剂将异氰酸酯基团封闭起来，然后进行乳化制备得到水性聚氨酯。这种水性聚氨酯在使用过程中，通过加热可以使封闭的异氰酸酯基团解封出来，这些异氰酸酯基团可以和水或其他交联剂发生反应，形成性能优异的聚氨酯材料。这种制备方法的关键是选择封闭效果好且解封温度合适的封闭剂。
依据上述传统的水性聚氨酯生产工艺，基本上都是采用间歇式的生产方式，导致生产效率低，产品质量不稳定，批差较大。而且多数的生产过程有溶剂的参与，会有溶剂的污染和残留。
发明内容
为克服现有技术中的问题，本发明目的是提供一种发泡型水性聚氨酯的制备及应用方法，该制备方法综合了外乳化和内乳化法的优点，所得发泡型水性聚氨酯，具有良好的发泡作用，合成过程没有使用任何溶剂，可用于水性聚氨酯发泡贝斯、水性聚氨酯涂层布和水性聚氨酯发泡薄膜等产品的生产，克服了现有技术中因为使用溶剂型聚氨酯而产生的溶剂污染和溶剂残留问题。
为达到上述目的，本发明采用的技术方案是：
一种发泡型水性聚氨酯的制备方法，将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在80～95℃下反应30～35min，然后脱水后加入二异氰酸酯，再于80～85℃下反应2～2.5h，再加入DMPA和1,4-丁二醇，在80～85℃反应1.5～2h，降温到40～45℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在40～45℃反应1～1.5h，得到发泡型水性聚氨酯；其中，脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：(10～15)：(8～12)：(35～45)：(4～6)：(5～8)：(9～11)：(0.1～0.3)：(2500～3500)。
本发明进一步的改进在于，脱水是在真空下进行的，并且脱水时间为15～20min。
本发明进一步的改进在于，脂肪酸为硬脂酸、月硅酸或棕榈酸。
本发明进一步的改进在于，聚合物二元醇为聚酯二元醇、聚醚二元醇或聚丁烯二醇。
本发明进一步的改进在于，聚酯二元醇为聚己二酸-1，4-丁二醇酯二醇；聚醚二元醇为聚四氢呋喃醚二醇；聚丁烯二醇为PPG。
本发明进一步的改进在于，二异氰酸酯为带有两个异氰酸酯基的化合物。
本发明进一步的改进在于，二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或4,4′-二环己基甲烷二异氰酸酯。
本发明进一步的改进在于，所述的扩链剂为乙二胺、水合肼中的一种或两种；所述的乳化剂为顺丁烯二酸二仲辛酯磺酸钠、烷基苯磺酸钠、脂肪醇聚氧乙烯醚硫酸钠、月桂醇硫酸钠中的一种或几种。
一种发泡型水性聚氨酯的应用方法，使用时，将发泡型水性聚氨酯加入泡沫发生器，通过控制空气的进入量和空气发泡机的物理机械的搅拌作用，得到水性聚氨酯发泡浆料。
与现有技术相比，本发明具有的有益效果：
其一，本发明采用了双乳化的技术，首先在预聚体合成阶段加入亲水性扩链剂DMPA将亲水基团引入，然后在二次扩链时再加入乳化剂，综合了外乳化和内乳化法的优点，能够合成革高固含量的发泡型水性聚氨酯。和现有的合成方法比较而言，本发明中采用的合成方法，在预聚体合成阶段加入的亲水性扩链剂DMPA的量比较少，因此，合成预聚体时粘度较小，预聚体乳化时就可以获得较高的固含量。在二次扩链时再加入乳化剂，不仅能够起到很好的外乳化作用，有效的提高乳液的稳定性，而且这种外加的乳化剂在水性聚氨酯物理机械发泡时起到很好的发泡和稳泡作用，采用本发明中的合成方法，就能够合成具有良好发泡作用的水性聚氨酯；其二，本发明中的合成方法，在整个过程中反应体系的粘度较小，整个合成过程中不需要外加任何的溶剂来降低反应体系的粘度，因此，最终的产品没有溶剂污染和溶剂残留的问题，克服了现有技术为了降低体系粘度加入溶剂，而产生的溶剂污染和溶剂残留问题；其三，发泡型水性聚氨酯可用于水性聚氨酯合成革发泡贝斯、水性聚氨酯涂层布和水性聚氨酯发泡薄膜等产品的生产。
具体实施方式
下面通过具体实施方式对本发明作进一步的详细说明，但本发明并不只限于这些例子。
本发明中含有扩链剂和乳化剂的去离子水溶液是通过将扩链剂和乳化剂加入到去离子水中制得；本发明中的聚合物二元醇还可以为聚碳酸酯二元醇。
实施例1
将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在80℃下反应35min，然后真空脱水15min后加入二异氰酸酯，再于80℃下反应2.5h，再加入DMPA(二羟甲基丙酸)和1,4-丁二醇，在80℃反应1.5h，降温到40℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在40℃反应1.5h，得到合成革用发泡型水性聚氨酯。其中，含有扩链剂和乳化剂的去离子水溶液是通过将扩链剂和乳化剂加入到去离子水中制得；脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：10：8：40：6：7：9：0.1：2500。
所述的脂肪酸是硬脂酸。
所述的聚合物二元醇聚己二酸-1，4-丁二醇酯二醇(PBA)。
所述的二异氰酸酯异佛尔酮二异氰酸酯(IPDI)。
所述的扩链剂为乙二胺。
所述的乳化剂为顺丁烯二酸二仲辛酯磺酸钠。
实施例2
将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在95℃下反应30min，然后真空脱水20min后加入二异氰酸酯，再于85℃下反应2h，再加入DMPA(二羟甲基丙酸)和1,4-丁二醇，在85℃反应1h，降温到45℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在45℃反应1h，得到合成革用发泡型水性聚氨酯。其中，含有扩链剂和乳化剂的去离子水溶液是通过将扩链剂和乳化剂加入到去离子水中制得；脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：15：10：35：4：8：11：0.1：3500。
所述的脂肪酸是月硅酸。
所述的聚合物二元醇聚四氢呋喃醚二醇(PTMEG)。
所述的二异氰酸酯六亚甲基二异氰酸酯(HDI)。
所述的扩链剂为水合肼。
所述的乳化剂为烷基苯磺酸钠。
实施例3
将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在85℃下反应30min，然后真空脱水17min后加入二异氰酸酯，再于82℃下反应2h，再加入DMPA(二羟甲基丙酸)和1,4-丁二醇，在83℃反应1.3h，降温到42℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在42℃反应1.2h，得到合成革用发泡型水性聚氨酯。其中，含有扩链剂和乳化剂的去离子水溶液是通过将扩链剂和乳化剂加入到去离子水中制得；脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：12：9：45：5：4：10：0.2：3000。
所述的脂肪酸是棕榈酸。
所述的聚合物二元醇PPG(聚氧化丙烯二醇)。
所述的4,4′-二环己基甲烷二异氰酸酯(H12MDI)。
所述的扩链剂为乙二胺与水合肼任意比例的混合物。
所述的乳化剂为顺丁烯二酸二仲辛酯磺酸钠、烷基苯磺酸钠与脂肪醇聚氧乙烯醚硫酸钠(AES)的任意比例的混合物。
实施例4
将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在90℃下反应35min，然后真空脱水18min后加入二异氰酸酯，再于83℃下反应2.5h，再加入DMPA(二羟甲基丙酸)和1,4-丁二醇，在84℃反应1.2h，降温到43℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在43℃反应1.1h，得到合成革用发泡型水性聚氨酯。其中，含有扩链剂和乳化剂的去离子水溶液是通过将扩链剂和乳化剂加入到去离子水中制得；脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：13：12：38：4：6：9：0.3：2800。
所述的脂肪酸是硬脂酸。
所述的聚合物二元醇聚己二酸-1，4-丁二醇酯二醇(PBA)。
所述的二异氰酸酯是4,4′-二环己基甲烷二异氰酸酯(H12MDI)。
所述的扩链剂为乙二胺。
所述的乳化剂为脂肪醇聚氧乙烯醚硫酸钠(AES)与月桂醇硫酸钠任意比例的混合物。
本发明的发泡型水性聚氨酯的应用方法：使用时将发泡型水性聚氨酯加入到空气发泡机(也叫泡沫发生器)中，通过控制空气的进入量和空气发泡机的物理机械的搅拌作用，得到一定发泡倍率的水性聚氨酯发泡浆料。
本发明所得发泡型水性聚氨酯，具有良好的发泡作用，合成过程没有使用任何溶剂，可用于水性聚氨酯合成革发泡贝斯、水性聚氨酯涂层布和水性聚氨酯发泡薄膜等产品的生产，解决上述产品生产中因为使用溶剂型聚氨酯而产生的溶剂污染和溶剂残留问题。

Claims (9)

1.一种发泡型水性聚氨酯的制备方法，其特征在于，将脂肪酸、三乙胺和聚合物二元醇加入到反应釜中，在80～95℃下反应30～35min，然后脱水后加入二异氰酸酯，再于80～85℃下反应2～2.5h，再加入DMPA和1,4-丁二醇，在80～85℃反应1.5～2h，降温到40～45℃；最后，加入含有扩链剂和乳化剂的去离子水溶液，在40～45℃反应1～1.5h，得到发泡型水性聚氨酯；其中，脂肪酸、三乙胺、聚合物二元醇、二异氰酸酯、DMPA、1,4-丁二醇、扩链剂、乳化剂、去离子水的摩尔比为10：(10～15)：(8～12)：(35～45)：(4～6)：(5～8)：(9～11)：(0.1～0.3)：(2500～3500)。
2.根据权利要求1所述的一种发泡型水性聚氨酯的制备方法，其特征在于，脱水是在真空下进行的，并且脱水时间为15～20min。
3.根据权利要求1所述的一种发泡型水性聚氨酯的制备方法，其特征在于，脂肪酸为硬脂酸、月硅酸或棕榈酸。
4.根据权利要求1所述的一种发泡型水性聚氨酯的制备方法，其特征在于，聚合物二元醇为聚酯二元醇、聚醚二元醇或聚丁烯二醇。
5.根据权利要求4所述的一种发泡型水性聚氨酯的制备方法，其特征在于，聚酯二元醇为聚己二酸-1，4-丁二醇酯二醇；聚醚二元醇为聚四氢呋喃醚二醇；聚丁烯二醇为PPG。
6.根据权利要求1所述的一种发泡型水性聚氨酯的制备方法，其特征在于，二异氰酸酯为带有两个异氰酸酯基的化合物。
7.根据权利要求1或6所述的一种发泡型水性聚氨酯的制备方法，其特征在于，二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或4,4′-二环己基甲烷二异氰酸酯。
8.根据权利要求1所述的一种发泡型水性聚氨酯的制备方法，其特征在于，所述的扩链剂为乙二胺、水合肼中的一种或两种；所述的乳化剂为顺丁烯二酸二仲辛酯磺酸钠、烷基苯磺酸钠、脂肪醇聚氧乙烯醚硫酸钠、月桂醇硫酸钠中的一种或几种。
9.一种如权利要求1所述的方法制备的发泡型水性聚氨酯的应用方法，其特征在于，使用时，将发泡型水性聚氨酯加入泡沫发生器，通过控制空气的进入量和空气发泡机的物理机械的搅拌作用，得到水性聚氨酯发泡浆料。
CN201611065570.4A 2016-11-28 2016-11-28 一种发泡型水性聚氨酯的制备方法及应用方法 Active CN106750149B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611065570.4A CN106750149B (zh) 2016-11-28 2016-11-28 一种发泡型水性聚氨酯的制备方法及应用方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611065570.4A CN106750149B (zh) 2016-11-28 2016-11-28 一种发泡型水性聚氨酯的制备方法及应用方法

Publications (2)

Publication Number Publication Date
CN106750149A true CN106750149A (zh) 2017-05-31
CN106750149B CN106750149B (zh) 2019-10-25

Family

ID=58904580

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611065570.4A Active CN106750149B (zh) 2016-11-28 2016-11-28 一种发泡型水性聚氨酯的制备方法及应用方法

Country Status (1)

Country Link
CN (1) CN106750149B (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535373A (zh) * 2018-11-19 2019-03-29 山东天庆科技发展有限公司 一种高耐曲折水性机械发泡聚氨酯树脂的制备方法
CN111019079A (zh) * 2019-12-20 2020-04-17 万华化学集团股份有限公司 一种聚氨酯或聚氨酯脲的水分散体及其制备方法和应用
CN111188205A (zh) * 2020-01-14 2020-05-22 浙江联侨新材料科技发展有限公司 水性环保箱包合成革的制备工艺
WO2022097331A1 (ja) * 2020-11-05 2022-05-12 Dic株式会社 ウレタン樹脂組成物、皮膜、積層体、及び、合成皮革

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206410A (zh) * 2011-04-21 2011-10-05 常州大学 革用高固含水性聚氨酯的制备方法
CN103694442A (zh) * 2013-12-06 2014-04-02 四川达威科技股份有限公司 皮革填充用支化结构聚氨酯-聚丙烯酸酯复合树脂的制备方法
CN105131239A (zh) * 2015-09-30 2015-12-09 北京德成嘉化工科技有限责任公司 耐水性无溶剂聚氨酯乳液及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206410A (zh) * 2011-04-21 2011-10-05 常州大学 革用高固含水性聚氨酯的制备方法
CN103694442A (zh) * 2013-12-06 2014-04-02 四川达威科技股份有限公司 皮革填充用支化结构聚氨酯-聚丙烯酸酯复合树脂的制备方法
CN105131239A (zh) * 2015-09-30 2015-12-09 北京德成嘉化工科技有限责任公司 耐水性无溶剂聚氨酯乳液及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
代少俊等: "《涂料与黏合剂》", 31 August 2014, 江苏大学出版社 *
刘益军: "《聚氨酯树脂及其应用》", 31 January 2012, 化学工业出版社 *
邓舜扬等: "《精细化工配方集锦》", 30 September 1998, 化学工业出版社 *
马兴元等: "《合成革化学与工艺学》", 30 November 2015, 中国轻工业出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535373A (zh) * 2018-11-19 2019-03-29 山东天庆科技发展有限公司 一种高耐曲折水性机械发泡聚氨酯树脂的制备方法
CN111019079A (zh) * 2019-12-20 2020-04-17 万华化学集团股份有限公司 一种聚氨酯或聚氨酯脲的水分散体及其制备方法和应用
CN111019079B (zh) * 2019-12-20 2022-02-18 万华化学集团股份有限公司 一种聚氨酯或聚氨酯脲的水分散体及其制备方法和应用
CN111188205A (zh) * 2020-01-14 2020-05-22 浙江联侨新材料科技发展有限公司 水性环保箱包合成革的制备工艺
WO2022097331A1 (ja) * 2020-11-05 2022-05-12 Dic株式会社 ウレタン樹脂組成物、皮膜、積層体、及び、合成皮革

Also Published As

Publication number Publication date
CN106750149B (zh) 2019-10-25

Similar Documents

Publication Publication Date Title
CN106750149A (zh) 一种发泡型水性聚氨酯的制备方法及应用方法
CN105131237B (zh) 全水发泡植物油基硬质聚氨酯泡沫塑料的制备方法
CN104530370A (zh) 一种无溶剂制备非离子型水性聚氨酯的方法
CN103408715A (zh) 内交联型聚碳酸亚丙酯水性聚氨酯乳液及制备方法与应用
CN103087291A (zh) 高固含量水性聚氨酯的制备方法
CN106432684A (zh) 一种自催化型腰果酚/木质素基聚氨酯泡沫及其制备方法
CN101585903A (zh) 一种水性聚氨酯及其制备方法
CN105801793A (zh) 环状二醇改性水性多异氰酸酯固化剂及其制备方法与应用
CN101328248A (zh) 一种皮革用聚氨酯-丙烯酸酯乳液的无溶剂制备方法
CN107903377A (zh) 连续式无溶剂磺酸盐水性聚氨酯分散体及其制备方法
CN109679059A (zh) 一种聚氨酯-聚脲水分散体及其制备方法与应用
CN104371085B (zh) 一种两性离子水性聚氨酯的制备方法
CN108299613A (zh) 一种抗菌型阴离子水性聚氨酯树脂及其制备方法
CN108264621A (zh) 一种水性聚氨酯非均相扩链合成方法
CN102166839A (zh) 干式转离型法聚氨酯微多孔防水透湿薄膜及其制备方法
CN107903376A (zh) 连续式无溶剂水性聚氨酯分散体及其制备方法和应用
CN106750117B (zh) 一种基于冲击混合和连续乳化的水性聚氨酯连续式合成方法
CN107828049A (zh) 一种氮丙啶型水性封闭多异氰酸酯固化剂及其制备方法
CN107964104B (zh) 无溶剂水性聚氨酯分散体及其制备方法和应用
CN105037686B (zh) 一种环氧阴极电泳涂料防缩孔树脂的制备
CN107353393A (zh) 一种蓖麻油改性聚氨酯树脂及其制备方法
CN110358046A (zh) 一种成膜性好的耐温转移涂料用水性聚氨酯乳液及其制备方法
CN105797643B (zh) 一种非离子型聚氨酯Gemini表面活性剂的制备方法
KR100314399B1 (ko) 수분산폴리우레탄을이용한인조피혁의제조방법
CN109265648A (zh) 一种零voc水性聚氨酯分散体及制备方法

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: 20200909

Address after: 252000 south of Xishou Road, Jiaming Road, Jiaming Economic Development Zone, Liaocheng City, Shandong Province

Patentee after: Liaocheng xinrunda plastic products Co.,Ltd.

Address before: 710021 Shaanxi province Xi'an Weiyang University Park No. 1

Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY