CN103772644B - 改性水性聚氨酯树脂及合成方法 - Google Patents

改性水性聚氨酯树脂及合成方法 Download PDF

Info

Publication number
CN103772644B
CN103772644B CN201410027501.9A CN201410027501A CN103772644B CN 103772644 B CN103772644 B CN 103772644B CN 201410027501 A CN201410027501 A CN 201410027501A CN 103772644 B CN103772644 B CN 103772644B
Authority
CN
China
Prior art keywords
aqueous polyurethane
add
synthetic method
polyurethane resin
modified aqueous
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
CN201410027501.9A
Other languages
English (en)
Other versions
CN103772644A (zh
Inventor
王福生
张蕾
刘淑芳
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.)
Shandong Judong New Material Co ltd
Original Assignee
Following Chemical Co Ltd In Shandong
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 Following Chemical Co Ltd In Shandong filed Critical Following Chemical Co Ltd In Shandong
Priority to CN201410027501.9A priority Critical patent/CN103772644B/zh
Publication of CN103772644A publication Critical patent/CN103772644A/zh
Application granted granted Critical
Publication of CN103772644B publication Critical patent/CN103772644B/zh
Expired - Fee Related 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
    • C08G18/08—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
    • C08G18/08—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
    • C08G18/28—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
    • C08G18/65—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
    • C08G18/70—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

Abstract

本发明公开了一种改性水性聚氨酯树脂由下列重量比的原料组成：异佛尔酮二异氰酸酯10-20％，聚酯多元醇10-20％，二羟甲基丙酸5-10％，三乙胺5-10％，一缩二乙二醇5-10％，去离子水40-60％，二乙烯三胺1-3％。合成方法包括：（1）将异佛尔酮二异氰酸酯装入搅拌器中，滴加聚醚多元醇和二羟甲基丙酸，于60～80℃左右反应约3-5小时；（2）加入一缩二乙二醇扩链反应1～5小时并降温至室温；（3）加入溶有三乙胺的去离子水在高速分散机上乳化，加入二乙烯三胺进行改性得到淡黄色、半透明的水性聚氨酯分散体。本发明采用逐步聚合反应，小分子多元醇进行改性从而提高水性聚氨酯的性能应用更加广泛，另外还能降低成本。

Description

改性水性聚氨酯树脂及合成方法
技术领域：
本发明涉及高分子聚合物领域中的一种改性水性聚氨酯树脂及合成方法。
背景技术：
水性聚氨酯具有不燃、无毒、不污染环境、节能等优点，同时具有高强度、耐磨损、使用安全等优异性能，因此获得了广泛的应用，已成为国内外新材料领域的一个重要发展方向。到目前为止，我国工业化的水性聚氨酯品种少、产量小，很难满足现在的多样化需求，产品的成膜性、柔韧性、耐候性及耐水性性能较差，主要用作一般性能的皮革处理及织物处理。性能的缺陷严重限制了水性聚氨酯在涂料领域的推广和应用。
发明内容：
本发明的目的是针对现有技术存在的问题，提供一种成膜性、柔韧性、耐候性及耐水性性能更好，应用更加广泛，成本更加低廉的改性水性聚氨酯树脂及合成方法。
一种改性水性聚氨酯树脂是由下列重量比的原料组成：
异佛尔酮二异氰酸酯10-20％
聚酯多元醇10-20％
二羟甲基丙酸5-10％
三乙胺5-10％
一缩二乙二醇5-10％
去离子水40-60％
二乙烯三胺1-3％
按照前述的改性水性聚氨酯树脂的合成方法包括：
（1）将异佛尔酮二异氰酸酯装入搅拌器中，滴加聚醚多元醇和二羟甲基丙酸，于60～80℃左右反应约3-5小时；
（2）加入一缩二乙二醇扩链反应1～5小时并降温至室温；
（3）加入溶有三乙胺的去离子水在高速分散机上乳化，加入二乙烯三胺进行改性得到淡黄色、半透明的水性聚氨酯分散体。
上述改性水性聚氨酯树脂的合成方法，步骤（1）中反应过程中用丙酮调节体系的黏度，用正二丁胺法滴定异氰酸根的浓度。
本发明采用逐步聚合反应，分子链上含有多个活性基团，采用小分子多元醇进行改性从而提高水性聚氨酯的性能。采用小分子多元醇改性一方面可以提高聚氨酯膜物理性能和手感，其成膜性、柔韧性、耐候性及耐水性性能均得以提高，应用更加广泛，另外还能降低成本。本发明在改性水性聚氨酯方面日益凸显其优越性。
具体实施方式
实例1：
按照下列重量比进行备料：异佛尔酮二异氰酸酯（IPDI）15％，聚酯多元醇15％，二羟甲基丙酸10％，三乙胺7％，二乙烯三胺3％，一缩二乙二醇10％，去离子水40％。
其合成方法是将IPDI装入配有温度计、搅拌器的反应器中，向反应容器中滴加聚醚多元醇和二羟甲基丙酸，于70℃左右反应约3h，反应过程中可用丙酮溶剂调节体系的黏度，用正二丁胺法滴定异氰酸根的浓度。所得的亲水改性聚氨酯预聚体用一缩二乙二醇扩链反应约1.5h后降温至室温，用溶有三乙胺的去离子水加入二乙烯三胺进行改性，并在高速分散机上乳化，得到淡黄色、半透明的水性聚氨酯分散体。
实例2：
按照下列重量比进行备料：异佛尔酮二异氰酸酯（IPDI）18％，聚酯多元醇15％，二羟甲基丙酸10％，三乙胺10％，一缩二乙二醇5％，二乙烯三胺2％，去离子水40％。
其合成方法是将IPDI装入配有温度计、搅拌器的反应器中，向反应容器中滴加聚醚多元醇和二羟甲基丙酸，于75℃左右反应约2.5h，用丙酮溶剂调节体系的黏度，用正二丁胺法滴定异氰酸根的浓度。所得的亲水改性聚氨酯预聚体用一缩二乙二醇扩链反应约3h后降温至室温，用溶有三乙胺的去离子水加入二乙烯三胺进行改性，并在高速分散机上乳化，得到淡黄色、半透明的水性聚氨酯分散体。
实施例2中用正二丁胺法滴定异氰酸根的浓度测试方法是利用异氰酸酯基与过量的二正丁胺反应生产脲，再用盐酸滴定过量的二正丁胺来定量计算异氰酸酯基的含量
R-NCO+(C4H9)2NH→RNHCON（C4H9)2（C4H9）2NH+HCL→（C2H9）2NH·HCL
操作步骤
准确称取3克的样品于干净锥形瓶中，加入20ml无水甲苯（或1+1甲苯环已酮）,使样品溶解，用移液管加入10.0ml二正丁胺-甲苯溶液，摇匀后，室温放置20～40min，加入40～50ml异丙醇（或乙醇），以几滴溴甲酚绿为指示剂，用0.5mol/lHCL标准溶液滴定，当溶液由蓝色变黄色为终点。并做空白试验。
结果计算公式：
式中:V0——空白耗用HCL标准溶液的体积，(ml）；
V1——试样耗用HCL标准溶液的体积，(ml）；
c——HCL标准溶液的浓度，(mol/L）；
m——试样的质量，(g)。
检测时间分析
取样：5～10min；
称量样品：约1min；
加入溶剂并摇匀：约2min；
加入二正丁胺后摇匀：8～15min；
室温放置：20～40min；
加溶剂及指示剂：3～5min；
滴定：5～10min；
计算：2～5min；
合计时间：46～89min。
即当检验结果出来时，产品在反应釜中已继续反应了47～89min，一般在近反应终点时需每隔半小时或20分钟取样进行检验，以确定反应终点。
式中:V0——空白耗用HCL标准溶液的体积，(ml）；
V1——试样耗用HCL标准溶液的体积，(ml）；
c——HCL标准溶液的浓度，(mol/L）；
m——试样的质量，(g)。
1.3检测时间分析
取样：5～10min；
称量样品：约1min；
加入溶剂并摇匀：约2min；
加入二正丁胺后摇匀：8～15min；
室温放置：20～40min；
加溶剂及指示剂：3～5min；
滴定：5～10min；
计算：2～5min；
合计时间：46～89min。
即当检验结果出来时，产品在反应釜中已继续反应了47～89min，一般在近反应终点时需每隔半小时或20分钟取样进行检验，以确定反应终点。
上述实例的预聚反应是IPDI与聚醚多元醇、二羟甲基丙酸进行聚合反应，生成具有一定分子量的、以—NCO为端基的预聚体，预聚体中—NCO的含量，决定了后继反应的配方及工艺条件，并影响最终制品膜的物理化学性能，而反应时间对—NCO的残留量有至关重要的影响。实例2采用了二丁胺法跟踪了预聚反应过程中—NCO含量随反应时间的变化，在反应初期，—NCO含量随反应时间的增加急剧减少，这是由于反应初期—NCO基团和—OH基团浓度均较高，反应较为剧烈，之后—NCO含量的下降趋势相对较为平缓。当预聚反应到3h左右时，—NCO含量趋于或低于理论值。3h之后—NCO含量变化不明显，因此，确定了3h左右为适宜的预聚反应合成时间。
本发明产生的水性聚氨酯(Pu)分散体可应用于轻纺、皮革加工、涂料、木材加工、建筑、造纸、印染和胶粘剂等行业。皮革加工中用PU乳液涂饰后的皮革，具有光泽高、手感好、耐磨耗、不易断裂、弹性好、耐低温性和耐挠屈性能优良等特点，克服了丙烯酸类树脂涂饰剂“热粘冷脆”的缺陷。此外水性PU对织物的成膜性好、粘接强度高，能赋予织物柔软、丰满的手感，改善织物耐磨性、抗皱性、回弹性、通透性、耐水性和耐热性等，在织物涂层整理中有广泛的应用。

Claims (3)

1.一种改性水性聚氨酯树脂的合成方法，其特征在于，改性水性聚氨酯树脂是由下列重量比的原料组成：
异佛尔酮二异氰酸酯10-20％
聚酯多元醇10-20％
二羟甲基丙酸5-10％
三乙胺5-10％
一缩二乙二醇5-10％
二乙烯三胺1-3％
去离子水40-60％
合成方法如下：
（1）将异佛尔酮二异氰酸酯装入搅拌器中，滴加聚酯多元醇和二羟甲基丙酸，于60～80℃反应3-5小时；
（2）加入一缩二乙二醇扩链反应1～5小时并降温至室温；
（3）加入溶有三乙胺的去离子水在高速分散机上乳化，加入二乙烯三胺进行改性得到淡黄色、半透明的水性聚氨酯分散体。
2.根据权利要求1所述的改性水性聚氨酯树脂的合成方法，其特征在于：步骤（1）中用丙酮调节体系的黏度。
3.根据权利要求1或2所述的改性水性聚氨酯树脂的合成方法，其特征在于：步骤（1）中用正二丁胺法滴定异氰酸根的浓度，即利用异氰酸酯基与过量的二正丁胺反应生产脲，再用盐酸滴定过量的二正丁胺来定量计算异氰酸酯基的含量。
CN201410027501.9A 2014-01-21 2014-01-21 改性水性聚氨酯树脂及合成方法 Expired - Fee Related CN103772644B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410027501.9A CN103772644B (zh) 2014-01-21 2014-01-21 改性水性聚氨酯树脂及合成方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410027501.9A CN103772644B (zh) 2014-01-21 2014-01-21 改性水性聚氨酯树脂及合成方法

Publications (2)

Publication Number Publication Date
CN103772644A CN103772644A (zh) 2014-05-07
CN103772644B true CN103772644B (zh) 2016-02-24

Family

ID=50565449

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410027501.9A Expired - Fee Related CN103772644B (zh) 2014-01-21 2014-01-21 改性水性聚氨酯树脂及合成方法

Country Status (1)

Country Link
CN (1) CN103772644B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105838228A (zh) * 2016-04-29 2016-08-10 李强 一种稳定型水性聚氨酯涂料及其制备方法
CN112898891A (zh) * 2019-12-03 2021-06-04 常州乐丽得新材料有限公司 一种水性led光固化强耐腐蚀金属涂料及其制备方法
CN110957058B (zh) * 2019-12-25 2022-09-16 陕西科技大学 一种导电皮革及其制备方法
CN112250812A (zh) * 2020-10-23 2021-01-22 辽宁恒星精细化工有限公司 一种水性聚氨酯抗皱整理剂及其制备方法和耐久抗皱型尼龙56面料

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432797A (zh) * 2011-08-18 2012-05-02 山东圣光化工集团有限公司 端羟基醇酸树脂改性水性聚氨酯及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432797A (zh) * 2011-08-18 2012-05-02 山东圣光化工集团有限公司 端羟基醇酸树脂改性水性聚氨酯及其制备方法

Also Published As

Publication number Publication date
CN103772644A (zh) 2014-05-07

Similar Documents

Publication Publication Date Title
CN107793544B (zh) 一种环保聚氨酯固化剂及其制备方法和应用
CN103772644B (zh) 改性水性聚氨酯树脂及合成方法
CN102993404B (zh) 一种光敏氟硅嵌段聚氨酯丙烯酸酯低聚物及其制备方法
CN101443378B (zh) 水系多异氰酸酯改性体、无黄变型涂料组合物和粘合剂组合物
CN101235130B (zh) 一种阳离子水性聚氨酯乳液及其制备方法
CN104231209A (zh) 一种高硬度水性聚氨酯分散液的制备方法
CN107674173B (zh) 水性聚氨酯交联剂及其制备方法
CN105968304B (zh) 一种高性能水性聚氨酯固化剂及其制备方法与应用
CN102618204A (zh) 一种人造革粘接层用热熔粘合剂及其制备方法、应用
CN103224605A (zh) 一种低游离异氰酸酯单体的聚氨酯固化剂及其制备方法
CN105175679A (zh) 环氧树脂改性的水性聚氨酯乳液及其制备方法
CN101701059A (zh) 阳离子型萜烯基环氧树脂多元醇水分散体制备方法及用途
CN104193916A (zh) 一种耐热型水性聚氨酯及其制备方法
CN104497947B (zh) 异型材包覆用湿固化聚氨酯热熔胶的制备方法及应用
CN106750084A (zh) 高固含量二液型粘结层聚氨酯树脂及其制备方法
CN107814936A (zh) 一种poss改性的低游离单体聚氨酯固化剂
CN114230764B (zh) 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用
CN103421462B (zh) 一种高初粘性水性聚氨酯胶粘剂及其制备方法
CN106243312B (zh) 一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法
CN110835398A (zh) 一种松香基水性聚氨酯乳液的制备方法
CN104878604A (zh) 一种阳离子型水性聚氨酯羊毛防毡缩乳液制备方法
CN104211899A (zh) 聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法与在涂料中的应用
CN106010418B (zh) 环保型高强度假发帘子胶用聚氨酯胶粘剂及其制备方法
CN102504178A (zh) 新型单组分水性聚氨酯涂层剂的制备方法
CN110423323B (zh) 一种水溶性封闭型聚氨酯固化剂及其制备方法和应用

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: Quanta Road Economic Development Zone 257300 Shandong city of Dongying province Guangrao County No. 9

Applicant after: The following Chemical Co.,Ltd. in Shandong

Address before: Quanta Road Economic Development Zone 257300 Shandong city of Dongying province Guangrao County No. 9

Applicant before: SHANDONG FUTURE CHEMICAL TECHNOLOGY Co.,Ltd.

COR Change of bibliographic data
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20210323

Address after: 257300 716-009, 7th floor, Jingwei building, 790 Le'an street, Guangrao County, Dongying City, Shandong Province

Patentee after: SHANDONG JUDONG NEW MATERIAL Co.,Ltd.

Address before: 257300 No.9, Guangda Road, economic development zone, Guangrao County, Dongying City, Shandong Province

Patentee before: The following Chemical Co.,Ltd. in Shandong

TR01 Transfer of patent right
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20140507

Assignee: Qingdao Xinsheng Times Innovation Technology Co.,Ltd.

Assignor: SHANDONG JUDONG NEW MATERIAL Co.,Ltd.

Contract record no.: X2022980024681

Denomination of invention: Modified waterborne polyurethane resin and its synthesis method

Granted publication date: 20160224

License type: Common License

Record date: 20221227

EE01 Entry into force of recordation of patent licensing contract
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160224

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