CN106752851B - 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法 - Google Patents

一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法 Download PDF

Info

Publication number
CN106752851B
CN106752851B CN201710136955.3A CN201710136955A CN106752851B CN 106752851 B CN106752851 B CN 106752851B CN 201710136955 A CN201710136955 A CN 201710136955A CN 106752851 B CN106752851 B CN 106752851B
Authority
CN
China
Prior art keywords
inorganic silicon
aqueous polyurethane
chain extender
organic
added
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.)
Expired - Fee Related
Application number
CN201710136955.3A
Other languages
English (en)
Other versions
CN106752851A (zh
Inventor
罗运军
马少宇
柴春鹏
葛震
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.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
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 Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN201710136955.3A priority Critical patent/CN106752851B/zh
Publication of CN106752851A publication Critical patent/CN106752851A/zh
Application granted granted Critical
Publication of CN106752851B publication Critical patent/CN106752851B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines 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
    • C08G18/28—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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/74—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明涉及一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，属于涂料工业领域。通过有机硅替代部分聚醚二元醇与二异氰酸酯在催化剂作用下反应，并用亲水扩链剂扩链，再引入无机硅，经成盐剂中和、后扩链剂封端后得到，其中无机硅在稳定剂的作用下稳定存在于体系中。本发明利用有机硅的表面能低，与水性聚氨酯相容性差的特点，通过共聚的方式将其引入水性聚氨酯体系中，乳液在成膜过程中有机硅向表面迁移，产生微观粗糙，达到消光的效果；同时引入无机硅进一步降低光泽度，且提高树脂的热稳定性。本发明制备工艺简单，安全环保，成本较低，具有较高工业应用价值。

Description

一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法
技术领域
本发明涉及一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，属于涂料工业领域。
背景技术
水性聚氨酯是以水为分散相，聚氨酯溶解或分散于水中形成的二元胶态体系。水性聚氨酯具有无毒、不易燃、不污染、安全可靠、易操作和改性等特点，因此在涂料、胶黏剂和皮革涂饰剂等领域有广泛应用。消光的涂料有优雅、柔和、自然的外观，符合现在人们的生活需求，受到了广大消费者的青睐。合成消光树脂可避免直接添加消光粉所带来的乳液稳定性差、乳液的黏度升高、胶膜的耐刮性下降等缺陷，进而受到了广泛关注。中国专利104974324公开了一种反应型自消光水性聚氨酯消光树脂的制备方法，该专利在水性聚氨酯体系中同时引入羧酸型和磺酸型两种亲水扩链剂，羧酸型亲水扩链剂为常用的亲水扩链剂，但磺酸型亲水扩链剂的价格较为昂贵，不利于工业化生产。中国专利103113554公开了一种紫外光固化消光树脂的制备方法，首先将除水后的聚己二酸-1,4-丁二醇酯二醇和三羟甲基丙烷与二异氰酸酯反应得到第一中间体，然后将第一中间体与羟基硅油、羟基苯硫醚和端羟基丙烯酸酯在催化剂和阻聚剂的作用下反应，得到紫外光固化消光树脂，其中二异氰酸酯和端羟基丙烯酸酯均采用滴加的方式加入，制备过程比较复杂，并且紫外光源对人的眼睛和皮肤有较大伤害。
发明内容
本发明的目的是为了解决现有技术的问题和不足，提供一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，该方法利用有机硅的表面能低，与水性聚氨酯相容性差的特点，通过共聚的方式将其引入水性聚氨酯体系中，乳液在成膜过程中有机硅向表面迁移，产生微观粗糙，达到消光的效果；同时引入无机硅进一步降低光泽度，且提高树脂的热稳定性。
本发明的目的是通过下述技术方案实现的。
一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，具体步骤如下：
步骤一、将有机硅和聚醚二元醇真空除水后，在惰性气保护和机械搅拌下加入二异氰酸酯，在催化剂作用下反应至剩余异氰酸根的含量达到理论值a后得到产物A；定义R为原料中异氰酸根与所有羟基的物质的量比，则需R＞1。
步骤二、将亲水扩链剂加入到步骤一得到的产物A中，继续反应至剩余异氰酸根的含量达到理论值b后，得到产物B；亲水性扩链剂的质量占预聚体总质量的3～10％。
步骤三、将无机硅加入到步骤二所得的产物B中，混合均匀，得到产物C；无机硅的质量占预聚体总质量的1～10％。
步骤四、将产物C降至室温，然后加入成盐剂，直至成盐剂与亲水扩链剂的中和反应完全，得到预聚体；成盐剂与亲水扩链剂的物质的量比为1:1。
步骤五、将步骤四所得的预聚体在高速分散下乳化，乳化开始后立即加入后扩链剂和稳定剂，得到有机/无机硅复合改性水性聚氨酯消光树脂；后扩链剂中胺基与预聚体中剩余异氰酸根的物质的量比为1:1，稳定剂的质量为无机硅的质量的2倍。
步骤一、二所述的异氰酸根理论值的计算公式分别为：
其中n(NCO)＝二异氰酸酯中异氰酸根的物质的量(mol)；n1(OH)＝有机硅中羟基的物质的量(mol)；n2(OH)＝聚醚二元醇中羟基的物质的量(mol)；n3(OH)＝亲水扩链剂中羟基的物质的量(mol)；M(NCO)＝异氰酸根的摩尔质量，为固定值42g/mol；m＝预聚体的总质量(g)。
步骤一所述的有机硅包括端羟丙基聚二甲基硅氧烷(PDMS)、端羟基聚二甲基硅氧烷(DHPDMS)。
步骤一所述聚醚二元醇包括聚四氢呋喃醚二醇(PTMG)、聚丙二醇(PPG)或聚己内脂二醇(PCL)。
步骤一所述的二异氰酸酯包括异氟尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、1,6-己基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)或四甲基环己基二异氰酸酯(TMXDI)。
步骤一所述的催化剂包括二月桂酸二丁基锡(DBTDL)、叔丁基锡或有机铋催化剂。
步骤二所述的亲水性扩链剂包括二羟甲基丙酸(DMPA)、2,2-二羟甲基丁酸。
步骤三所述的无机硅包括二氧化硅(SiO2)、滑石粉、层状硅酸盐。
步骤四所述的成盐剂包括三乙胺(TEA)，三正丁胺。
步骤五所述的后扩链剂包括乙二胺(EDA)、水合肼。
步骤五所述的稳定剂包括聚丙烯酸钠(PAAS)、有机蒙脱土。
有益效果
1、本发明通过有机硅替代部分聚醚二元醇，以共聚的方式引入到水性聚氨酯中，达到良好的消光效果。
2、本发明在有机硅改性水性聚氨酯的基础上再引入无机硅，得到有机/无机硅复合改性水性聚氨酯消光树脂，进一步降低光泽度，同时提高了水性聚氨酯消光树脂的热稳定性，
3、本发明制备工艺简单，安全环保，成本较低，具有较高工业应用价值。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PTMG和22.0g PDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；将2.1g SiO2溶于20ml丁酮中，超声分散10min后加入到反应体系中反应30min；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全，在乳化过程中加入4.2g PAAS维持SiO2的稳定。将乳液在40℃下旋蒸除去丁酮，得到有机/无机硅复合改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机/无机硅复合改性水性聚氨酯消光树脂胶膜。
实施例2
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PTMG和22.0g PDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；将1.7g滑石粉溶于20ml丁酮中，超声分散10min后加入到反应体系中反应30min；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全，在乳化过程中加入3.4g PAAS维持SiO2的稳定。将乳液在40℃下旋蒸除去丁酮，得到有机/无机硅复合改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机/无机硅复合改性水性聚氨酯消光树脂胶膜。
实施例3
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PTMG和22.0g DHPDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；将1.3g SiO2溶于20ml丁酮中，超声分散10min后加入到反应体系中反应30min；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全，在乳化过程中加入2.6g PAAS维持SiO2的稳定。将乳液在40℃下旋蒸除去丁酮，得到有机/无机硅复合改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机/无机硅复合改性水性聚氨酯消光树脂胶膜。
实施例4
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PTMG和22.0g PDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；将0.9g SiO2溶于20ml丁酮中，超声分散10min后加入到反应体系中反应30min；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全，在乳化过程中加入1.8g有机蒙脱土维持SiO2的稳定。将乳液在40℃下旋蒸除去丁酮，得到有机/无机硅复合改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机/无机硅复合改性水性聚氨酯消光树脂胶膜。
实施例5
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PPG和22.0g PDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；将0.4g SiO2溶于20ml丁酮中，超声分散10min后加入到反应体系中反应30min；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全，在乳化过程中加入0.8g PAAS维持SiO2的稳定。将乳液在40℃下旋蒸除去丁酮，得到有机/无机硅复合改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机/无机硅复合改性水性聚氨酯消光树脂胶膜。
对比实施例1
在装有搅拌器、回流冷凝管、温度计的反应器中加入5.5g PTMG和22.0g PDMS，110℃下真空除水1h；然后降温至80℃加入11.6g IPDI和0.01g催化剂DBTDL后反应2h；再降温至60℃加入1.5g DMPA，升温至80℃反应3h；降温到室温加入1.1g TEA中和反应10min，得到水性聚氨酯预聚体；将预聚体在搅拌速率为2500r/min下乳化10min，先加入128.7g去离子水后立即加入1.5g EDA，使乳液中剩余的-NCO反应完全。将乳液在40℃下旋蒸除去丁酮，得到有机硅改性水性聚氨酯消光树脂乳液。取适量乳液在聚四氟乙烯模具板中流延成膜，室温干燥7d，70℃下干燥24h，得到有机硅改性水性聚氨酯消光树脂胶膜。
下面对上述实施例1～5和对比实施例1中得到的水性聚氨酯消光树脂进行测试，乳液粒径采用激光粒度仪测试，光泽度采用60°光度计测试，热稳定性采用热重分析仪测试，测试结果如下表所示：
由上表数据可知，与对比实施例1相比，本发明所制备的有机/无机硅改性水性聚氨酯消光树脂胶膜的60°光泽度均在30以下，最低可达2.5，具有很好的消光效果；同时，无机硅的引入显著提高了树脂的热稳定性。与现有技术相比，本发明制备工艺简单，安全环保，成本较低，具有较高工业应用价值。
上述实施例为本发明较佳的实施方式，但本发明的实施方式不受上述实施例限制。

Claims (4)

1.一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，其特征在于：具体步骤如下：
步骤一、将有机硅和聚醚二元醇真空除水后，在惰性气保护和机械搅拌下加入二异氰酸酯，在催化剂作用下反应至剩余异氰酸根的含量达到理论值a后得到产物A；定义R为原料中异氰酸根与所有羟基的物质的量比，则需R＞1；
步骤二、将亲水扩链剂加入到步骤一得到的产物A中，继续反应至剩余异氰酸根的含量达到理论值b后，得到产物B；亲水性扩链剂的质量占预聚体总质量的3～10％；
步骤三、将无机硅加入到步骤二所得的产物B中，混合均匀，得到产物C；无机硅的质量占预聚体总质量的1～10％；
步骤四、将产物C降至室温，然后加入成盐剂，直至成盐剂与亲水扩链剂的中和反应完全，得到预聚体；成盐剂与亲水扩链剂的物质的量比为1:1；
步骤五、将步骤四所得的预聚体在高速分散下乳化，乳化开始后立即加入后扩链剂和稳定剂，得到有机/无机硅复合改性水性聚氨酯消光树脂；后扩链剂中胺基与预聚体中剩余异氰酸根的物质的量比为1:1，稳定剂的质量为无机硅的质量的2倍；
步骤一、二所述的异氰酸根理论值的计算公式分别为：
其中n(NCO)＝二异氰酸酯中异氰酸根的物质的量(mol)；n1(OH)＝有机硅中羟基的物质的量(mol)；n2(OH)＝聚醚二元醇中羟基的物质的量(mol)；n3(OH)＝亲水扩链剂中羟基的物质的量(mol)；M(NCO)＝异氰酸根的摩尔质量，为固定值42g/mol；m＝预聚体的总质量(g)；
步骤一所述的有机硅包括端羟丙基聚二甲基硅氧烷、端羟基聚二甲基硅氧烷；步骤三所述的无机硅包括：二氧化硅和滑石粉。
2.如权利要求1所述的一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，其特征在于：步骤一所述聚醚二元醇包括聚四氢呋喃醚二醇、聚丙二醇或聚己内脂二醇；步骤一所述的二异氰酸酯包括异氟尔酮二异氰酸酯、甲苯二异氰酸酯、1,6-己基二异氰酸酯或二苯基甲烷二异氰酸酯。
3.如权利要求1所述的一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，其特征在于：步骤一所述的催化剂包括二月桂酸二丁基锡或有机铋催化剂；步骤二所述的亲水性扩链剂包括二羟甲基丙酸、2,2-二羟甲基丁酸。
4.如权利要求1所述的一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法，其特征在于：步骤四所述的成盐剂包括三乙胺，三正丁胺；步骤五所述的后扩链剂包括乙二胺、水合肼；步骤五所述的稳定剂包括聚丙烯酸钠、有机蒙脱土。
CN201710136955.3A 2017-03-09 2017-03-09 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法 Expired - Fee Related CN106752851B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710136955.3A CN106752851B (zh) 2017-03-09 2017-03-09 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710136955.3A CN106752851B (zh) 2017-03-09 2017-03-09 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法

Publications (2)

Publication Number Publication Date
CN106752851A CN106752851A (zh) 2017-05-31
CN106752851B true CN106752851B (zh) 2019-07-23

Family

ID=58961741

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710136955.3A Expired - Fee Related CN106752851B (zh) 2017-03-09 2017-03-09 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法

Country Status (1)

Country Link
CN (1) CN106752851B (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276554B (zh) * 2018-01-30 2019-09-03 商洛学院 一种铁尾矿改性水性聚氨酯及其制备方法
CN108330732A (zh) * 2018-01-31 2018-07-27 上海宏盾防伪材料有限公司 一种具有耐刮伤功能哑度可调的水性聚氨酯涂料
CN108864925A (zh) * 2018-07-05 2018-11-23 何治伟 一种水性消光树脂的制备方法
CN110452351A (zh) * 2019-08-22 2019-11-15 山东星宇手套有限公司 一种水性聚氨酯乳液、制备方法和浸胶手套
CN111848914A (zh) * 2020-06-10 2020-10-30 华南理工大学 一种低吸水率的自消光光固化水性聚氨酯丙烯酸酯固化膜及其制备方法与应用
CN111849337B (zh) * 2020-07-22 2021-11-23 清远市美佳乐环保新材股份有限公司 一种以油性消光树脂为核的自消光乳液制备方法
CN112280003A (zh) * 2020-11-04 2021-01-29 湖南中泰特种装备有限责任公司 一种共聚型消光水性聚氨酯乳液及其制备方法
CN115851052A (zh) * 2022-11-28 2023-03-28 广东粤港澳大湾区黄埔材料研究院 一种低污染、低表面能水性无氟涂料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542109B (zh) * 2015-12-22 2018-07-06 亚士漆(上海)有限公司 一种通透哑光水性聚氨酯乳液的制备方法及采用该方法制成的通透哑光水性聚氨酯乳液
CN105506997B (zh) * 2016-01-27 2019-05-31 优美特（北京）环境材料科技股份公司 一种消光型水性聚氨酯皮革涂饰剂及其制备方法

Also Published As

Publication number Publication date
CN106752851A (zh) 2017-05-31

Similar Documents

Publication Publication Date Title
CN106752851B (zh) 一种有机/无机硅复合改性水性聚氨酯消光树脂的制备方法
TWI293962B (en) Polyurethane-polyurea dispersions
CN105506997B (zh) 一种消光型水性聚氨酯皮革涂饰剂及其制备方法
CN101225150B (zh) 水分散有机硅-聚氨酯嵌段共聚物的合成方法及应用
CN107141434B (zh) 一种用于合成革面料的水性聚氨酯树脂及其制备方法
CN108546323B (zh) 阳离子自消光树脂及其制备方法和应用
CN106432679A (zh) 一种水性聚氨酯油墨连接料及其制备方法
CN113248755A (zh) 一种纳米二氧化硅/羟基硅烷偶联剂复合改性聚氨酯超疏水膜的制备方法
CN111909351A (zh) 一种超纤含浸用水性聚氨酯的合成方法及应用
CN109535372B (zh) 一种水性聚氨酯及其制备方法
CA2947490C (en) Radiation curable aqueous compositions with controlled polymer flow
CN104448206B (zh) 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用
CN107141442A (zh) 一种端羟基液体橡胶改性水性聚氨酯消光树脂的方法
CN110248977B (zh) 水性涂料组合物
CN109970948A (zh) 一种高含固阴离子水性聚氨酯乳液及其制备方法
KR101296172B1 (ko) 양이온성 수분산수지의 제조방법 및 상기 수지를 포함하는 수계 코팅 조성물
CN109957089A (zh) 一种高附着水性聚氨酯镜面树脂及其制备方法和应用
CN108329342B (zh) 一种有机硅偶联剂及其制备方法和应用
CN114276519B (zh) 一种自消光水性聚氨酯及其制备方法
CN110408313B (zh) 一种聚丙烯腈中空微球改性的水性聚氨酯消光树脂及制备方法
TWI400258B (zh) 含有懸垂式烷氧矽烷基團之聚胺酯／脲
CN102796447A (zh) 新型水性聚氨酯皮革涂饰剂及其制备方法
CN113861371A (zh) 一种自消光型水性聚氨酯的制备方法
CN111647306B (zh) 原位生成有机化SiO2环保增强型水性聚氨酯油墨及制备方法
CN113121773A (zh) 一种磺酸型无溶剂水性聚氨酯树脂及其制备方法

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
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190723

Termination date: 20200309