CN105385148B - 磺酸化石墨烯改性水性聚氨酯树脂及制法 - Google Patents

磺酸化石墨烯改性水性聚氨酯树脂及制法 Download PDF

Info

Publication number
CN105385148B
CN105385148B CN201510886002.XA CN201510886002A CN105385148B CN 105385148 B CN105385148 B CN 105385148B CN 201510886002 A CN201510886002 A CN 201510886002A CN 105385148 B CN105385148 B CN 105385148B
Authority
CN
China
Prior art keywords
added
chain extender
sulfonic acid
polyurethane resin
aqueous polyurethane
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.)
Active
Application number
CN201510886002.XA
Other languages
English (en)
Other versions
CN105385148A (zh
Inventor
孙凡
郝智平
张初银
朱加秋
于吉鹏
金美金
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.)
ZHEJIANG HUAFENG SYNTHETIC RESIN CO Ltd
Original Assignee
ZHEJIANG HUAFENG SYNTHETIC RESIN 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 ZHEJIANG HUAFENG SYNTHETIC RESIN CO Ltd filed Critical ZHEJIANG HUAFENG SYNTHETIC RESIN CO Ltd
Priority to CN201510886002.XA priority Critical patent/CN105385148B/zh
Publication of CN105385148A publication Critical patent/CN105385148A/zh
Application granted granted Critical
Publication of CN105385148B publication Critical patent/CN105385148B/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—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
    • C08G18/10—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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end 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
    • C08G18/40—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
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 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
    • C08G18/6637—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
    • C08G18/6666—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明公开了一种磺酸化石墨烯改性水性聚氨酯树脂及制法，所述磺酸化石墨烯改性水性聚氨酯树脂，是采用包括如下重量份数的组分制备的：聚二元醇8％～20％，反应性硅油2.0％～4.5％，二异氰酸酯4.0％～10.0％，扩链剂.0％～3.0％，催化剂0.001％～0.003％，抗氧化剂0.4％～0.8％，去离子水60％～75％，三乙胺0.5％～1.5％，乙二胺0.4％～1.2％，磺酸化石墨烯0.02～0.10％，本发明制得的磺酸化石墨烯改性水性聚氨酯树脂，制成合成革后，具有优异机械强度、良好的耐水性、耐酸碱性和耐高温性能等特点。

Description

磺酸化石墨烯改性水性聚氨酯树脂及制法
技术领域
本发明涉及改性水性聚氨酯树脂及制法。
背景技术
聚氨酯树脂应用于合成革产业已经有五十多年的历史，涉及服装、鞋材、箱包、家居装饰及汽车等各个领域，随着人们对生活品质的更高追求，环保型合成革的需求越来越大。水性聚氨酯以水代替有机溶剂作为分散介质，其分散液中不含或含有极少量有机溶剂，涂膜具有不燃、无毒、节能和不污染环境等特点，目前水性聚氨酯产品已大量用于皮革修饰剂领域。水性聚氨酯应用最广泛的是内乳化法,即在聚氨酯分子链段中引入亲水性成分，无需乳化剂即可形成稳定乳液的方法，如常用的二羟甲基丙酸(DMPA)，其优点是分子量小，且由于位阻作用大部分羧基得以保留，因而具有较高乳化效率。离子型小分子的引入带给聚氨酯亲水性的同时，也造成水性聚氨酯相对于溶剂型聚氨酯较差的机械性能，耐热性和耐水性差。
石墨烯是一种新型二维纳米材料，基本结构单元为sp2杂化碳原子构成的六圆环，厚度仅为一个碳原子厚度，石墨烯近乎透明，具有良好的导热性能和异常高的机械强度，其独特的结构具有巨大的比表面积，与大部分材料相比具备良好的相容性，是复合材料的理想模板和载体。但石墨烯巨大的表面能使得其极易在体系中团聚，形成类石墨结构，丧失其独特性能并影响体系的相容性，大部分研究通过加入硅烷偶联剂，聚乙烯吡咯烷酮等分散剂改善石墨烯在复合材料中的分散，但团聚现象仍然存在，而且分散剂的引入会影响材料的综合性能。申请号为201510289998.6的中国专利申请中公开了一种石墨烯/水性聚氨酯复合材料的制备方法，首先采用改进的Hummers法制得氧化石墨烯水分散液；然后利用乙二胺还原改性氧化石墨烯得到改性石墨烯水溶液；再以二异氰酸酯、低聚物二元醇及扩链剂，合成线性聚氨酯预聚体；最后向线性聚氨酯预聚体中加入中和剂进行中和，将改性石墨烯水溶液与其共混，制得石墨烯/水性聚氨酯复合材料。但是该体系中还原态的石墨烯无法单层分散，将团聚在复合材料中，影响复合材料的流平性和机械性能。
发明内容
本发明的目的是磺酸化石墨烯改性水性聚氨酯树脂及制法，以克服现有技术的不足。
所述的磺酸化石墨烯改性水性聚氨酯树脂，是采用包括如下重量份数的组分制备的：
各个组分的百分比之和为100％。
所述的聚二元醇为聚酯二元醇和聚醚二元醇的混合物，重量比为：聚酯二元醇∶聚醚二元醇＝1∶1～4；
所述聚酯二元醇为数均分子量1000～2000的聚碳酸酯二元醇与数均分子量1000～3000的聚己二酸1,4-丁二醇酯二元醇的混合物，重量比为：聚碳酸酯二元醇:聚己二酸1,4-丁二醇酯二元醇＝1∶1～2；
所述聚醚二元醇为数均分子量1000～2000的聚四氢呋喃二元醇与数均分子量1000～2000的聚氧化丙烯二元醇的混合物，重量比为：聚四氢呋喃二元醇:聚氧化丙烯二元醇＝1∶0.5～1；
所述反应性硅油包括氨基硅油、羟基硅油、聚醚改性羟基硅油中的一种或多种的混合物，数均分子量为1000～3000，官能度为2；
所述的扩链剂为非离子型扩链剂和离子型扩链剂的混合物，所述非离子型扩链剂和离子型扩链剂的重量比为1:0.5～1.5，优选1:0.5～1.15；
所述的非离子型扩链剂包括乙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、一缩二乙二醇中的一种或多种；
所述的离子型扩链剂包括2,2-二羟甲基丁酸、2,2-二羟甲基丙酸中的一种或两种混合物；
所述的异氰酸酯为二苯基甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或其组合；
所述催化剂为有机铋类催化剂；
所述抗氧剂为抗氧剂1010和抗氧化168(1:1)的混合物；
所述的磺酸化石墨烯制备方法：
(1)将石墨粉加入到浓硫酸、浓硝酸和高锰酸钾的冷却混合液中,在45℃～55℃下反应1h～1.5h，滴加30wt％双氧水至混合液呈亮黄色分散液后，过滤获得氧化石墨烯GO；
浓硫酸的重量浓度为98％，浓硝酸的重量浓度为65％；
所述石墨粉与高锰酸钾的质量比为1:4～8，所述浓硫酸体积与所述石墨粉的质量的比例为20～30:1，所述浓硝酸体积与所述石墨粉的质量的比例为5～15:1；
(2)将步骤(1)中获得氧化石墨烯GO，分散于去离子水中，加入苯磺酸重氮盐，反应0.5h～1h,重氮基团与sp2杂化碳原子反应接枝得到磺酸化氧化石墨烯S-GO溶液；
所述氧化石墨烯GO、去离子水和苯磺酸重氮盐的质量比为1:400～600:0.25；
(3)加入硼氢化钠于60℃～65℃下反应0.5h～1h,过滤得到磺酸化石墨烯S-Graphene；
所述硼氢化钠与氧化石墨烯的质量比为1:0.5。
所述的磺酸化石墨烯改性水性聚氨酯树脂的制备方法，包括如下步骤：
(1)于20℃～40℃下，将聚二元醇、反应性硅油、非离子型扩链剂和抗氧剂加入二异氰酸酯，40℃～50℃真空条件下反应1.5～2.0h；
(2)缓慢加入离子型扩链剂，搅拌20～30min，加入催化剂，于70℃～80℃反应2～3h，加入丙酮，控制粘度范围在5000～10000cps/50℃；
(3)降至室温，加入三乙胺、乙二胺、磺酸修饰石墨烯和去离子水搅拌1～3小时乳化，真空脱去丙酮，即得所述的磺酸化石墨烯改性水性聚氨酯树脂。
用上述方法制得的磺酸化石墨烯改性水性聚氨酯树脂，制成合成革后，具有优异机械强度、良好的耐水性、耐酸碱性和耐高温性能等特点。
具体实施方式
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定。实施例中采用的实施条件可以根据具体厂家的条件和要求做一些非本质的改进和调整。
磺酸修饰石墨烯的制备：
实施例1
将5g石墨加入120ml重量浓度为98％的浓硫酸、50ml重量浓度为65％的浓硝酸、25g高锰酸钾混合液中45℃反应1.5h，滴加30％双氧水反应至混合液呈亮黄色分散液后，过滤获得氧化石墨烯GO；
取2g氧化石墨烯分散于1.0L去离子水中，加入0.5g苯磺酸重氮盐，反应1h，重氮基团与sp2杂化碳原子反应接枝得到磺酸化氧化石墨烯S-GO；加入1g硼氢化钠于60℃反应1h得到磺酸化石墨烯1。
实施例2
将5g石墨加入100ml重量浓度为98％的浓硫酸、25ml重量浓度为65％的浓硝酸、20g高锰酸钾混合液中55℃反应1h，滴加30％双氧水反应至混合液呈亮黄色分散液后，过滤获得氧化石墨烯GO；
取2g氧化石墨烯分散于0.8L去离子水中，加入0.5g苯磺酸重氮盐，反应1h，重氮基团与sp2杂化碳原子反应接枝得到磺酸化氧化石墨烯S-GO；加入1g硼氢化钠于60℃反应1h得到磺酸化石墨烯2。
实施例3
配方见下表
其中：
聚酯二元醇：聚醚二元醇＝3∶5＝1∶1.67，重量比；
聚酯二元醇：聚碳酸酯二元醇∶聚己二酸1,4-丁二醇酯二元醇＝1∶1；
聚醚二元醇：聚四氢呋喃二元醇∶聚氧化丙烯二元醇＝1:1，重量比；
扩链剂：非离子型扩链剂∶离子型扩链剂＝1∶0.7；
制备方法：
(1)将聚己二酸1,4-丁二醇酯二醇、聚碳酸酯二元醇、聚四氢呋喃二醇、聚氧化丙烯二元醇、羟基硅油、1,4-丁二醇、抗氧剂1010和抗氧剂168混合，搅拌，于40℃下加入甲苯二异氰酸酯，50℃真空条件下反应1.5小时；
(2)加入2，2-二羟甲基丙酸，搅拌20分钟；再加入异辛酸铋，于70℃反应3小时，再加入丙酮调节粘度；
(3)降至室温，加入三乙胺、乙二胺和磺酸修饰石墨烯，最后加入去离子水乳化，搅拌分散1小时，真空脱去丙酮，即得所述的磺酸化石墨烯改性水性聚氨酯树脂。
实施例4
配方见下表
其中：
聚酯二元醇：聚醚二元醇＝5∶15＝1∶3，重量比；
聚酯二元醇：
聚碳酸酯二元醇∶聚己二酸1,4-丁二醇酯二元醇＝1∶1.5；
聚醚二元醇：
聚四氢呋喃二元醇∶聚氧化丙烯二元醇＝1∶0.5，重量比；
扩链剂：
非离子型扩链剂∶离子型扩链剂＝1.95∶1.05＝1∶0.54；
制备方法：
(1)将聚己二酸1,4-丁二醇酯二醇、聚碳酸酯二元醇、聚四氢呋喃二醇、聚氧化丙烯二元醇、羟基硅油、1,4-丁二醇、抗氧剂1010和抗氧剂168于20℃下加入二苯基甲烷二异氰酸酯和甲苯二异氰酸酯，40℃真空条件下反应2小时；
(2)加入2，2-二羟甲基丙酸，搅拌20分钟；再加入异辛酸铋，于80℃反应2小时后，加入丙酮调节粘度；
(3)降至室温，加入三乙胺、乙二胺和磺酸修饰石墨烯2，加入去离子水乳化，搅拌分散3小时，并脱去丙酮即得所述的磺酸化石墨烯改性水性聚氨酯树脂。
对比例1
(1)先将2.0kg聚己二酸1,4-丁二醇酯二醇、1.0kg聚碳酸酯二元醇、2.5kg聚四氢呋喃二醇、2.5kg聚氧化丙烯二元醇、2.0kg羟基硅油、0.40kg 1,4-丁二醇、0.20kg抗氧剂1010和0.20kg抗氧剂168加入带搅拌器的反应器，搅拌均匀，于40℃下加入3.95kg甲苯二异氰酸酯，温控至50℃真空条件下反应1.5小时；(2)缓慢加入0.60kg 2，2-二羟甲基丙酸，搅拌20分钟；再加入0.001kg异辛酸铋，于70℃反应3小时，再加入7.66kg丙酮调节粘度；(3)降至室温，加入0.46kg三乙胺和0.37kg乙二胺，最后加入75kg冰去离子水乳化，搅拌分散1小时真空脱去丙酮，即得水性聚氨酯树脂。
对比例2
(1)3.0kg聚己二酸1,4-丁二醇酯二醇、2.0kg聚碳酸酯二元醇、10.0kg聚四氢呋喃二醇、5.0kg聚氧化丙烯二元醇、3.0kg羟基硅油、1.05kg 1,4-丁二醇、0.40kg抗氧剂1010和0.40kg抗氧剂168加入带搅拌器的反应器，搅拌均匀，于20℃下加入3.05kg二苯基甲烷二异氰酸酯和7.08kg甲苯二异氰酸酯，温控至40℃真空条件下反应2小时；(2)缓慢加入0.60kg2，2-二羟甲基丙酸，搅拌20分钟；再加入0.002kg异辛酸铋，于80℃反应2小时后，加入2.07kg丙酮调节粘度；(3)降至室温，加入1.48kg三乙胺和0.65kg乙二胺，加入60kg冰去离子水乳化，搅拌分散3小时并脱去丙酮即得水性聚氨酯树脂。
应用实施例3～4和对比例1～2所制得的水性树脂制成的革样的各项物性测试结果列于表1,耐水性以涂膜浸泡于水中无变化的时间评估，耐酸性以涂膜浸泡于1.0mol/L的硫酸溶液中无变化的时间评估，耐碱性以涂膜浸泡于1.0mol/L的NaOH溶液中无变化的时间评估，耐热性以高温软化点高低评估，机械性能以冲击强度大小来评估。
表1性能测试结果
由表1可知，应用磺酸化石墨烯改性水性聚氨酯树脂制成的革样的耐水性、耐高温性、耐酸碱性和冲击强度明显高于纯水性聚氨酯树脂制成的革样。
综上，本发明制备的一种磺酸修饰石墨烯改性耐水耐热水性聚氨酯树脂具有高机械性能，优异的耐水耐热性和耐酸碱性能，有利于水性产品的进一步发展和开拓。
尽管上述实施例已经对本发明的技术方案进行了详细地描述，但本发明的技术方案并不限于以上实施例，在不脱离本发明的思想和宗旨情况下，对本发明申请专利范围的内容所作的等效变化或修饰，都应为本发明的技术范畴。

Claims (4)

1.磺酸石墨烯改性水性聚氨酯树脂，其特征在于，是采用包括如下重量份数的组分制备的：
各个组分的百分比之和为100％；
所述的磺酸石墨烯是这样制备的：
(1)将石墨粉加入到浓硫酸、浓硝酸和高锰酸钾的混合液中反应，加入双氧水至混合液呈亮黄色分散液后，过滤，获得氧化石墨烯GO；
(2)将步骤(1)中获得氧化石墨烯GO，分散于水中，加入苯磺酸重氮盐反应，重氮基团与sp2杂化碳原子反应接枝，得到磺酸氧化石墨烯S-GO溶液；
(3)加入硼氢化钠下反应，过滤得到磺酸石墨烯；
所述的聚二元醇为聚酯二元醇和聚醚二元醇的混合物，重量比为：聚酯二元醇∶聚醚二元醇＝1∶1～4；
所述聚酯二元醇为数均分子量1000～2000的聚碳酸酯二元醇与数均分子量1000～3000的聚己二酸1,4-丁二醇酯二元醇的混合物，重量比为：聚碳酸酯二元醇:聚己二酸1,4-丁二醇酯二元醇＝1∶1～2；
所述聚醚二元醇为数均分子量1000～2000的聚四氢呋喃二元醇与数均分子量1000～2000的聚氧化丙烯二元醇的混合物，重量比为：聚四氢呋喃二元醇:聚氧化丙烯二元醇＝1∶0.5～1。
2.根据权利要求1所述的磺酸石墨烯改性水性聚氨酯树脂，其特征在于，所述反应性硅油包括氨基硅油、羟基硅油、聚醚改性羟基硅油中的一种或多种的混合物，数均分子量为1000～3000，官能度为2；
所述的扩链剂为非离子型扩链剂和离子型扩链剂的混合物，所述非离子型扩链剂和离子型扩链剂的重量比为1:0.5～1.5；
所述的二异氰酸酯为二苯基甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或其组合；
所述催化剂为有机铋类催化剂；
所述抗氧化剂为抗氧剂1010和抗氧化剂168的重量比为1:1的混合物。
3.根据权利要求2所述的磺酸石墨烯改性水性聚氨酯树脂，其特征在于，所述的非离子型扩链剂包括乙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、一缩二乙二醇中的一种或多种；所述的离子型扩链剂包括2,2-二羟甲基丁酸、2,2-二羟甲基丙酸中的一种或两种混合物。
4.制备权利要求1～3任一项所述的磺酸石墨烯改性水性聚氨酯树脂的方法，其特征在于，包括如下步骤：
(1)于20℃～40℃下，将聚二元醇、反应性硅油、非离子型扩链剂和抗氧化剂加入二异氰酸酯，40℃～50℃真空条件下反应1.5～2.0h；
(2)加入离子型扩链剂，搅拌20～30min，加入催化剂，于70℃～80℃反应2～3h，加入丙酮，控制粘度范围在5000～10000cps/50℃；
(3)降至室温，加入三乙胺、乙二胺、磺酸石墨烯和去离子水搅拌1～3小时乳化，真空脱去丙酮，即得所述的磺酸石墨烯改性水性聚氨酯树脂。
CN201510886002.XA 2015-12-04 2015-12-04 磺酸化石墨烯改性水性聚氨酯树脂及制法 Active CN105385148B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510886002.XA CN105385148B (zh) 2015-12-04 2015-12-04 磺酸化石墨烯改性水性聚氨酯树脂及制法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510886002.XA CN105385148B (zh) 2015-12-04 2015-12-04 磺酸化石墨烯改性水性聚氨酯树脂及制法

Publications (2)

Publication Number Publication Date
CN105385148A CN105385148A (zh) 2016-03-09
CN105385148B true CN105385148B (zh) 2018-08-28

Family

ID=55417949

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510886002.XA Active CN105385148B (zh) 2015-12-04 2015-12-04 磺酸化石墨烯改性水性聚氨酯树脂及制法

Country Status (1)

Country Link
CN (1) CN105385148B (zh)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590399A (zh) * 2016-12-30 2017-04-26 康伦国 一种石墨烯‑有机硅改性聚氨酯水性涂料
CN106632965A (zh) * 2016-12-30 2017-05-10 康伦国 一种石墨烯‑有机硅改性水性聚氨酯树脂
CN106702750A (zh) * 2016-12-30 2017-05-24 康伦国 一种石墨烯‑有机硅改性聚氨酯树脂合成革
CN107383302B (zh) * 2017-07-13 2020-05-05 陕西科技大学 磺化改性氧化石墨烯/高固含量水性聚氨酯的制备方法
CN111171276B (zh) * 2020-01-09 2022-03-25 上海工程技术大学 一种改性石墨烯水性聚脲树脂及其制备方法和应用
CN111718611A (zh) * 2020-07-04 2020-09-29 上海灿达建材科技有限公司 一种抗病毒的保护膜及其制备方法
CN112280520A (zh) * 2020-10-10 2021-01-29 永一胶粘(中山)有限公司 一种高导热水性聚氨酯/聚硅氧烷压敏胶及其制备方法和应用
CN112322171B (zh) * 2020-11-23 2022-11-15 陕西煤业化工技术研究院有限责任公司 一种石墨烯基阻燃抗静电聚脲喷涂剂及其使用方法
CN113174087B (zh) * 2021-05-06 2022-04-01 福建师范大学泉港石化研究院 一种含阻燃元素与双键的改性石墨烯阻燃剂及其制备方法
CN114133785B (zh) * 2021-12-18 2023-08-22 江苏云合新材料科技有限公司 一种环保型水性油墨及其制作方法
CN116120510A (zh) * 2022-11-23 2023-05-16 三晃树脂（佛山）有限公司 一种包装印刷用水性聚氨酯及其制备方法
CN117263174B (zh) * 2023-11-21 2024-02-02 新乡学院 一种磺酸石墨烯电极材料及其合成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580577A (zh) * 2009-06-18 2009-11-18 建德市顺发化工助剂有限公司 用于人造革的改性水性聚氨酯树脂及其制备方法
WO2012116293A2 (en) * 2011-02-25 2012-08-30 Henkel Corporation Self-aligned graphene polymer nanocomposites
CN104004341A (zh) * 2014-05-23 2014-08-27 华南理工大学 一种氧化石墨烯磺酸盐型水性聚氨酯复合材料及制备方法
CN104861643A (zh) * 2015-05-29 2015-08-26 安徽大学 一种石墨烯/水性聚氨酯复合材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580577A (zh) * 2009-06-18 2009-11-18 建德市顺发化工助剂有限公司 用于人造革的改性水性聚氨酯树脂及其制备方法
WO2012116293A2 (en) * 2011-02-25 2012-08-30 Henkel Corporation Self-aligned graphene polymer nanocomposites
CN104004341A (zh) * 2014-05-23 2014-08-27 华南理工大学 一种氧化石墨烯磺酸盐型水性聚氨酯复合材料及制备方法
CN104861643A (zh) * 2015-05-29 2015-08-26 安徽大学 一种石墨烯/水性聚氨酯复合材料的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Preparation of Graphitic Oxide";Hummer,W.et al.;《Am. Chem. Soc.》;19580320;第80卷;第1339页 *
"Synthesis of Water Soluble Graphene";Yongchao Si et al.;《Nano Letters》;20080523;第8卷(第6期);第1679-1682页 *
"纳米材料改性水性聚氨酯研究进展";王寅等;《化工进展》;20150228;第34卷(第2期);第463-469页 *

Also Published As

Publication number Publication date
CN105385148A (zh) 2016-03-09

Similar Documents

Publication Publication Date Title
CN105385148B (zh) 磺酸化石墨烯改性水性聚氨酯树脂及制法
CN104628982B (zh) 一种碱木质素基水性聚氨酯的制备方法
CN102618204B (zh) 一种人造革粘接层用热熔粘合剂及其制备方法、应用
CN102093517B (zh) 用于合成革面料的水性聚氨酯-丙烯酸酯树脂及其制备方法
CN104861643A (zh) 一种石墨烯/水性聚氨酯复合材料的制备方法
CN112457462B (zh) 一种非离子型水性聚氨酯及其制备方法和应用
CN107759764B (zh) 二氧化硅负载的高强度水性聚氨酯乳液的生产工艺
CN107163217B (zh) 一种纳米金刚石改性水性聚氨酯的制备方法
CN105111412B (zh) 一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法
CN102993402B (zh) 一种环氧聚氨酯乳液的制备方法
CN107903358A (zh) 用于纺织品印花的无溶剂自交联改性水性聚氨酯树脂
CN108330712A (zh) 印花胶浆用聚（碳酸酯-醚）型聚氨酯乳液及制备方法
CN115354505B (zh) 一种合成革用生物基无溶剂聚氨酯面层树脂及其制备方法
CN103805122A (zh) 一种水性聚氨酯贴布胶及其制备方法
CN110714338A (zh) 一种抗老化pu面料的制备方法
CN114381191A (zh) 具有高拉伸强度、高耐水性涂层薄膜的羟基硅油改性水性聚氨酯涂料
CN114085349A (zh) 有机硅改性的聚氨酯树脂及其制造方法
CN108977157A (zh) 一种水性聚氨酯胶黏剂及其制备方法
CN113549187B (zh) 一种超纤革用水性聚氨酯及其制备方法
CN112280459B (zh) 一种阻燃型植物油基水性聚氨酯涂料及其制备方法
CN102251401A (zh) 一种高光亮镜面合成革处理剂及制备方法
CN110845954A (zh) 一种具有阻燃效果的合成革用水性表处剂及其制备方法
CN111393596A (zh) 一种蓖麻油改性水性聚氨酯纳米乳液及其制备方法
KR102365989B1 (ko) 장갑의 제조 방법
CN107236511B (zh) 一种鞋用聚氨酯胶粘剂组合物及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant