CN111004363A - 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法 - Google Patents

一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法 Download PDF

Info

Publication number
CN111004363A
CN111004363A CN201911305622.4A CN201911305622A CN111004363A CN 111004363 A CN111004363 A CN 111004363A CN 201911305622 A CN201911305622 A CN 201911305622A CN 111004363 A CN111004363 A CN 111004363A
Authority
CN
China
Prior art keywords
hexamethylene diisocyanate
curing agent
toluene diisocyanate
diisocyanate
trimer 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.)
Pending
Application number
CN201911305622.4A
Other languages
English (en)
Inventor
莫振兴
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.)
Changzhou Humon Chemical Co Ltd
Original Assignee
Changzhou Humon Chemical 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 Changzhou Humon Chemical Co Ltd filed Critical Changzhou Humon Chemical Co Ltd
Priority to CN201911305622.4A priority Critical patent/CN111004363A/zh
Publication of CN111004363A publication Critical patent/CN111004363A/zh
Pending legal-status Critical Current

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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/795—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of mixtures of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates with aromatic isocyanates or isothiocyanates

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

本发明提供了一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，在反应釜中冲入氮气；步骤二：加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和改性剂的混合物进行搅拌，然后在60‑65℃进行保温3.5小时；随后加入三聚催化剂在60‑65℃进行保温反应；检测NCO含量，当NCO小于36％时，加入抑制剂，然后升温到100摄氏度保温2‑3分钟；通过蒸馏去除甲苯二异氰酸酯单体和六亚甲基二异氰酸酯单体；冷却降温后将最后得到的甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂包装。本发明制备过程简单，将原材料进行适当过量添加，最后进行压滤和蒸馏出多余的原料，能在较低的温度下进行很好的聚合反应，适合大批量工业化生产。

Description

一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化 剂的制备方法
技术领域
本发明涉及固化剂制备技术领域，尤其涉及一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法。
背景技术
作为聚氨酯胶黏剂用固化剂，甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体具有初粘力强，最终粘结强度高的特点，而且比甲苯二异氰酸酯三聚体具有更好的耐黄变性。
例如中国专利“CN101307128B”公开了一种高相容性MDI和TDI混合三聚体固化剂的制备方法，其特征在于，包括下述步骤：一、将MDI和TDI在溶剂中与含有1～3个羟基的小分子量醇进行预聚反应，其中MDI与TDI质量比为0.5～2∶1，小分子量醇占MDI和TDI总质量的5％～12％；二、预聚反应完后，加入三聚催化剂进行三聚反应，同时加入分子量调节剂，三聚催化剂的加入量为步骤一反应后理论剩余MDI和TDI总质量的0.1～0.3％，分子量调节剂的加入量为MDI和TDI总质量的1～1.5％，反应完后加入阻聚剂终止反应制得。该技术方案不适用于工业化大规模生产，制备效率低下。
发明内容
为克服现有技术中存在的不适用于工业化大规模生产，制备效率低下的问题，本发明提供了一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法。
本发明通过以下技术方案实现上述目的：一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，包括以下步骤：
步骤一：在反应釜中冲入氮气；
步骤二：加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和改性剂的混合物进行搅拌，然后在60-65℃进行保温3.5小时；
步骤三：随后加入三聚催化剂在60-65℃进行保温反应；
步骤四：检测NCO含量，当NCO小于36％时，加入抑制剂，然后升温到100℃保温2-3分钟；
步骤五：通过蒸馏去除甲苯二异氰酸酯单体和六亚甲基二异氰酸酯单体；
步骤六：冷却降温后将最后得到的甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂包装。
在此基础上，所述改性剂为聚乙二醇，聚丙二醇，聚乙二醇单甲醚和聚乙二醇单丁醚中的一种或多种。
在此基础上，所述三聚催化剂为2,4,6-三(二甲氨基甲基)苯酚。
在此基础上，步骤三中三聚催化剂与步骤二中混合物的重量比为1:500。
在此基础上，所述抑制剂为硫酸二甲酯。
在此基础上，所述抑制剂与步骤二中混合物的重量比为1:1000。
在此基础上，甲苯二异氰酸酯和六亚甲基二异氰酸酯的配比为21:29。
与现有技术相比，本发明的有益效果是：本发明制备过程简单，将原材料进行适当过量添加，最后进行压滤和蒸馏出多余的原料，能在较低的温度下进行很好的聚合反应，适合大批量工业化生产。
具体实施方式
以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
本发明示意性的示出了一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法。
在反应釜中冲入氮气；加入甲苯二异氰酸酯21份、六亚甲基二异氰酸酯29份和聚乙二醇25份的混合物进行搅拌，然后在60-65℃进行保温3.5小时；随后加入2,4,6-三(二甲氨基甲基)苯酚0.1份在60-65℃进行保温反应；检测NCO含量，当NCO小于36％时，加入硫酸二甲酯0.05份，然后升温到100℃保温2-3分钟；通过蒸馏去除甲苯二异氰酸酯单体和六亚甲基二异氰酸酯单体；冷却降温后将最后得到的甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂包装。
本发明的有益效果是：本发明制备过程简单，将原材料进行适当过量添加，最后进行压滤和蒸馏出多余的原料，能在较低的温度下进行很好的聚合反应，适合大批量工业化生产。
上述说明示出并描述了本发明的优选实施例，如前所述，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述发明构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。

Claims (7)

1.一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于，包括以下步骤：
步骤一：在反应釜中冲入氮气；
步骤二：加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和改性剂的混合物进行搅拌，然后在60-65℃进行保温3.5小时；
步骤三：随后加入三聚催化剂在60-65℃进行保温反应；
步骤四：检测NCO含量，当NCO小于36％时，加入抑制剂，然后升温到100℃保温2-3分钟；
步骤五：通过蒸馏去除甲苯二异氰酸酯单体和六亚甲基二异氰酸酯单体；
步骤六：冷却降温后将最后得到的甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂包装。
2.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：所述改性剂为聚乙二醇，聚丙二醇，聚乙二醇单甲醚和聚乙二醇单丁醚中的一种或多种。
3.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：所述三聚催化剂为2,4,6-三(二甲氨基甲基)苯酚。
4.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：步骤三中三聚催化剂与步骤二中混合物的重量比为1:500。
5.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：所述抑制剂为硫酸二甲酯。
6.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：所述抑制剂与步骤二中混合物的重量比为1:1000。
7.根据权利要求1所述的一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法，其特征在于：甲苯二异氰酸酯和六亚甲基二异氰酸酯的配比为21:29。
CN201911305622.4A 2019-12-18 2019-12-18 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法 Pending CN111004363A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911305622.4A CN111004363A (zh) 2019-12-18 2019-12-18 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911305622.4A CN111004363A (zh) 2019-12-18 2019-12-18 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法

Publications (1)

Publication Number Publication Date
CN111004363A true CN111004363A (zh) 2020-04-14

Family

ID=70116597

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911305622.4A Pending CN111004363A (zh) 2019-12-18 2019-12-18 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法

Country Status (1)

Country Link
CN (1) CN111004363A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679698A (zh) * 2020-12-10 2021-04-20 福建奥翔体育塑胶科技股份有限公司 一种环保无溶剂三聚体固化剂
CN113667080A (zh) * 2021-07-01 2021-11-19 华南理工大学 一种hdi-tdi混合多聚体固化剂及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679698A (zh) * 2020-12-10 2021-04-20 福建奥翔体育塑胶科技股份有限公司 一种环保无溶剂三聚体固化剂
CN113667080A (zh) * 2021-07-01 2021-11-19 华南理工大学 一种hdi-tdi混合多聚体固化剂及其制备方法

Similar Documents

Publication Publication Date Title
US10781345B1 (en) Method of preparing polyurethane hot melt adhesive with high temperature resistance
US9593089B2 (en) Process for preparing TDI isocyanurate
CN111004363A (zh) 一种甲苯二异氰酸酯和六亚甲基二异氰酸酯混合三聚体固化剂的制备方法
JP2004250429A5 (zh)
EP2978789B1 (en) Process for making urethane-isocyanurates
JP2004250662A5 (zh)
CN101205290A (zh) 异氰酸酯改性的环氧丙烯酸酯及其制备方法
JP2020500232A (ja) イソシアヌレート基を有するｔｄｉ系低粘度ポリイソシアネート
CN112375535B (zh) 一种塑塑复合聚氨酯胶粘剂及其制备方法
KR20210100673A (ko) 폴리이소시아누레이트 기재 중합체 및 섬유 강화된 복합재
CN109456459A (zh) 一种提高水性聚氨酯耐水或耐溶剂性的方法
CN101407571A (zh) 一种固化剂甲苯二异氰酸酯及4,4’-二苯基甲烷二异氰酸酯混合预聚物及其制备方法
CN106674465B (zh) 聚氨酯鞋底用树脂及制备方法和应用
CN109824865B (zh) 具有储存稳定性的多异氰酸酯固化剂制备方法及固化剂
CN115286738B (zh) 一种聚丙烯酸天门冬氨酸酯树脂及其制备方法
CA1037639A (en) Copolymerization process
CN110885436B (zh) 具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法
CN113316601B (zh) 制备具有低单体异氰酸酯排放的热熔粘合剂的方法
CN104356020A (zh) 一种新的酰胺基酯及其合成方法、应用
CN103865467A (zh) 一种高性能不黄变型聚氨酸酯胶粘剂及其制备方法
CN110128692B (zh) 一种阻燃b1级聚氨酯仿木门及其制备方法
CN114163971A (zh) Pur热熔胶及其制备方法
CN114369189A (zh) 一种脱卤剂、制备甲苯二异氰酸酯和甲苯二异氰酸酯三聚体的方法
CN113088067B (zh) 一种高折射环硫改性树脂及其制备方法
CN110734731A (zh) 一种超支化聚脲无醛木材胶黏剂及制备方法和应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200414