Search

CN-121518080-B - Modified castor oil-based polyurethane adhesive and preparation method and application thereof

CN121518080BCN 121518080 BCN121518080 BCN 121518080BCN-121518080-B

Abstract

The invention relates to the technical field of organic polymer adhesives, and particularly discloses a modified castor oil-based polyurethane adhesive and a preparation method and application thereof. The adhesive is composed of, by weight, 30.0-50.0 parts of modified castor oil and 0.0-30.0 parts of refined castor oil, 30.0-50.0 parts of polyisocyanate or polyisocyanate modifier and 0.00-0.05 parts of water scavenger, wherein the modified castor oil is prepared from the refined castor oil and cysteamine through a sulfhydryl-alkene addition reaction. The amino group of the modified castor oil is alkalescent, the reaction speed with isocyanate groups is high, and hydrogen bonds are easy to generate between urea bonds generated by the reaction of the amino group and the isocyanate groups, so that the adhesive is endowed with thixotropic property and high strength. The adhesive disclosed by the invention is simple in composition, high in reaction speed and good in thixotropic property and bonding strength.

Inventors

  • WU DAWEI
  • CHU XUELIANG
  • ZHENG YAOCHEN
  • WU DATAO
  • GAO ZHENGGUO
  • DOU WENGUANG
  • ZHENG YU
  • LI DUANLI

Assignees

  • 烟台瑞龙新材料有限公司

Dates

Publication Date
20260508
Application Date
20260113

Claims (8)

  1. 1. The modified castor oil-based polyurethane adhesive is characterized by comprising, by weight, A, B parts of modified castor oil 30.0-50.0 parts, refined castor oil 0.0-30.0 parts, and a component B comprising polyisocyanate or a polyisocyanate modifier 30.0-50.0 parts and a water scavenger 0.00-0.05 parts; the preparation method of the modified castor oil comprises the following steps: S1, feeding a mixture of refined castor oil and cysteamine according to a molar ratio of 1:2-3, adding an initiator and a solvent with the cysteamine mole number of 3-8%, and stirring to obtain a solution with a mass concentration of 25-50%; s2, reacting 10-24 h under the conditions of high-purity nitrogen atmosphere, stirring and 60-85 ℃ to obtain a product solution; s3, removing the solvent in the product solution, and drying to constant weight to obtain the product modified castor oil; the mass of the component A is 50-72% of the sum of the mass of the component A and the mass of the component B.
  2. 2. The modified castor oil-based polyurethane adhesive of claim 1, wherein the modified castor oil has a molecular structural formula of Wherein, if a-b is a single bond of C-C, R= If a-b is a C=C double bond, R=H, and a-b is the number of double bonds≤1.
  3. 3. The modified castor oil-based polyurethane adhesive of claim 1, wherein the polyisocyanate has the structural formula 、 、 、 、 、 、 、 、 Or (b) At least one of them.
  4. 4. The modified castor oil-based polyurethane adhesive of claim 1, wherein the polyisocyanate modifier is at least one of TDI trimer, HDI trimer, IPDI trimer, polyphenyl polymethylene polyisocyanate, PM-200, NT-8075, S-325, or S-310.
  5. 5. The modified castor oil-based polyurethane adhesive according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and azobicyclohexylcarbonitrile, and the solvent is at least one of 1, 4-dioxane, tetrahydrofuran, methyl ethyl ketone, butyl acetate, ethyl acetate, and toluene.
  6. 6. The modified castor oil-based polyurethane adhesive of claim 1, wherein the water scavenger is at least one of p-toluenesulfonyl isocyanate, 3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine, ‌ -butyl-2- (1-ethylpentyl) oxazolidine, 2-methyl-2-ethyl-3-hydroxyethyl-1, 3-oxazolidine ‌.
  7. 7. The method for preparing the modified castor oil-based polyurethane adhesive according to any one of claims 1 to 6, wherein the method comprises the following steps of: 30.0-50.0 parts of modified castor oil and 0.0-30.0 parts of refined castor oil, and 30.0-50.0 parts of polyisocyanate or polyisocyanate modifier and 0.00-0.05 parts of water scavenger; and mixing the component A, then degassing under vacuum, filling in a package, and sealing, and mixing the component B, then degassing under vacuum at room temperature, filling in the package, and sealing to obtain the polyurethane adhesive.
  8. 8. Use of a modified castor oil-based polyurethane adhesive according to any of claims 1-6 in packaging and packaging of new energy batteries.

Description

Modified castor oil-based polyurethane adhesive and preparation method and application thereof Technical Field The invention belongs to the technical field of organic polymer adhesives, and particularly relates to a modified castor oil-based polyurethane adhesive and a preparation method and application thereof. Background Castor oil is a vegetable oil expressed from castor seeds and contains both reactive hydroxyl groups and carbon-carbon double bonds in each molecular chain of its molecular structure. Compared with various vegetable oils such as tung oil, soybean oil, linseed oil and the like, castor oil has larger polarity, can be compatible with various isocyanate compounds and react to prepare polyurethane materials with various different purposes. Multiple adhesives can be used in the packaging and preparing process of the new energy battery. The polyurethane adhesive has excellent shear strength, impact resistance and high and low temperature resistance, can firmly adhere to various base materials such as metal, fabric, leather, wood, plastic and the like, and is widely applied to assembly procedures such as encapsulation, adhesion, encapsulation and the like of an automobile battery pack. The adhesive strength, thixotropic property and curing speed of the adhesive are important indexes for evaluating the application performance and the construction performance of the adhesive, and higher requirements are provided for the formulation design and the material selection of the adhesive. In particular, with the enhancement of human environmental awareness and the gradual decrease of the dependency on petrochemical resources, new challenges are presented to the preparation of high-performance adhesives by using renewable resources (renewable resources have the problems of few types, complex components, difficult modification and the like). In order to solve the problems in the prior art, it is necessary to provide a castor oil-based polyurethane adhesive which has thixotropic properties, a high reaction speed and high adhesive properties. Disclosure of Invention Aiming at the defects in the prior art, the invention provides the castor oil-based polyurethane adhesive which has thixotropic property and can react rapidly, and the preparation method and the application thereof, wherein a large number of multiple hydrogen bonds can be formed between primary amino (-NH 2) and acyl semicarbazide bond of isocyanate (-NCO) on a molecular chain of the modified castor oil, so that the adhesive has good thixotropic property and high strength, and in addition, the amino is alkalescent, can catalyze the reaction of-NH 2 and hydroxyl (-OH) with-NCO, and can finish the curing process efficiently. In order to achieve the above purpose, the present invention adopts the following technical scheme: The invention provides a thixotropic and quick-reaction castor oil-based polyurethane adhesive, which comprises, by weight, 30.0-50.0 parts of modified castor oil and 0.0-30.0 parts of refined castor oil, wherein the component B comprises 30.0-50.0 parts of polyisocyanate or a polyisocyanate modifier and 0.00-0.05 parts of a water scavenger; the preparation method of the modified castor oil comprises the following steps: S1, feeding a mixture of refined castor oil and cysteamine according to a molar ratio of 1:2-3, adding an initiator and a solvent with the cysteamine mole number of 3-8%, and stirring to obtain a solution with a mass concentration of 25-50%; s2, reacting 10-24 h under the conditions of high-purity nitrogen atmosphere, stirring and 60-85 ℃ to obtain a product solution; S3, removing the solvent in the product solution by using a rotary evaporator, and then placing the product solution in a40 ℃ vacuum drying oven to dry the product solution to constant weight to obtain the product modified castor oil. Further, the molecular structural formula of the modified castor oil isWherein, if a-b is a single bond of C-C, R=If a-b is a C=C double bond, R=H, and a-b is the number of double bonds≤1. Further, the diisocyanate has the structural formula(IPDI)、(HMDI)、(MDI)、(HDI)、(TDI) 、(TDI)、(TMXDI)、(XDI)、(TMDI) orIn (TMDI) at least one kind. Further, the polyisocyanate and the polyisocyanate modifier are at least one of TDI trimer, HDI trimer, IPDI trimer, polyphenyl polymethylene polyisocyanate (PAPI), PM-200 (Van der Waals), NT-8075 (Wuhanshiquan), S-325 (Wuhanshiquan) or S-310 (Wuhanshiquan). Further, the initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate and azodicyclohexyl carbonitrile, and the solvent is at least one of 1, 4-dioxane, tetrahydrofuran, methyl ethyl ketone, butyl acetate, ethyl acetate and toluene. Further, the water scavenger is at least one of p-toluenesulfonyl isocyanate, 3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine, ‌ -butyl-2- (1-ethylpentyl) oxazolidine and 2-methyl-2-ethyl-3-hydroxyethyl-1, 3-oxazolidine ‌. The second aspect of the invention provid