WO2016061753A1 - Adhesive and preparation method therefor - Google Patents

Adhesive and preparation method therefor Download PDF

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Publication number
WO2016061753A1
WO2016061753A1 PCT/CN2014/089149 CN2014089149W WO2016061753A1 WO 2016061753 A1 WO2016061753 A1 WO 2016061753A1 CN 2014089149 W CN2014089149 W CN 2014089149W WO 2016061753 A1 WO2016061753 A1 WO 2016061753A1
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Prior art keywords
parts
adhesive
ethylene
sulfur
containing antioxidant
Prior art date
Application number
PCT/CN2014/089149
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French (fr)
Chinese (zh)
Inventor
徐睿
Original Assignee
徐睿
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.)
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Publication date
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Priority to PCT/CN2014/089149 priority Critical patent/WO2016061753A1/en
Publication of WO2016061753A1 publication Critical patent/WO2016061753A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the invention relates to an adhesive and a preparation method thereof, and the adhesive can be applied in the field of high performance requirements of an adhesive for aviation, a ship, a nuclear submarine and the like.
  • Adhesives need to withstand high temperature heat aging and high dose irradiation. After high temperature heat aging and high dose irradiation treatment, they also need to withstand high temperature and high pressure water vapor. And the destruction of the material by the alkaline solution. Polyamides and polyester adhesives with good heat resistance cannot withstand high-dose irradiation, high-temperature and high-pressure steam, and alkaline solution damage to materials. Therefore, it is technically necessary to modify existing adhesives.
  • the technical problem to be solved by the present invention is to provide an adhesive which can withstand the destruction of materials by an alkaline solution after high temperature heat aging and high dose irradiation treatment.
  • an adhesive which measures the following components by weight:
  • EMA ethylene-methyl acrylate copolymer
  • the sulfur-containing antioxidant is composed of one or more of the following materials: dilauryl thiodipropionate (antioxidant DLTDP); thiodipropionate ditetradecyl ester (antioxidant DMTDP) .
  • the present invention also proposes the following technical solution: a method for preparing an adhesive, comprising the following steps:
  • Step 1 100 parts of ethylene-methyl acrylate copolymer (EMA); 30-100 parts of ethylene-octene copolymer; 5-10 parts of sulfur-containing antioxidant, according to a certain ratio, use dense at 160 ° C
  • the mixer is kneaded for 30 minutes, and the kneaded adhesive is tableted;
  • Step 2 The tableting adhesive is irradiated with an electron beam or a cobalt source, and the irradiation dose is 80-130 kGy. After the irradiation, the adhesive partially cross-links, the ring softening point is increased, and the fluidity is lowered.
  • the invention has the following beneficial effects: the adhesive of the invention can withstand the destruction of the material by the alkaline solution after high temperature heat aging and high dose irradiation treatment.
  • the present invention provides an adhesive that is weighted by the following components:
  • EMA ethylene-methyl acrylate copolymer
  • the sulfur-containing antioxidant is composed of one or more of the following materials: dilauryl thiodipropionate (antioxidant DLTDP); thiodipropionate ditetradecyl ester (antioxidant DMTDP) .
  • the preparation method of the adhesive of the invention comprises the following steps:
  • Step 1 100 parts of ethylene-methyl acrylate copolymer (EMA); 30-100 parts of ethylene-octene copolymer; 5-10 parts of sulfur-containing antioxidant, according to a certain ratio, use dense at 160 ° C
  • the mixer is kneaded for 30 minutes, and the kneaded adhesive is tableted;
  • Step 2 The tableting adhesive is irradiated with an electron beam or a cobalt source, and the irradiation dose is 80-130 kGy. After the irradiation, the adhesive partially cross-links, the ring softening point is increased, and the fluidity is lowered.
  • EMA ethylene-methyl acrylate copolymer
  • DLTDP dilauryl thiodipropionate
  • EMA ethylene-methyl acrylate copolymer
  • DLTDP dilauryl thiodipropionate
  • EMA ethylene-methyl acrylate copolymer
  • DLTDP dilauryl thiodipropionate
  • EMA ethylene-methyl acrylate copolymer
  • DLTDP dilauryl thiodipropionate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

An adhesive consists of the following components measured by weight: 100 parts of ethylene-methyl acrylate copolymer, 30 to 100 parts of ethylene-octene copolymer, and 5 to 10 parts of sulfur-containing antioxidant. The sulfur-containing antioxidant consists of one or more of the following materials: dilauryl thiodipropionate and ditetradecyl thiodipropionate. The adhesive can still bear the damage of an alkaline solution to a material after the adhesive is subjected to treatment of high-temperature thermal aging and high-dose irradiation.

Description

一种胶黏剂及其制备方法Adhesive and preparation method thereof 技术领域Technical field
本发明涉及一种胶黏剂及其制备方法，该种胶黏剂可以应用在航空、船舶、核潜艇等对胶黏剂性能要求比较高的领域中。The invention relates to an adhesive and a preparation method thereof, and the adhesive can be applied in the field of high performance requirements of an adhesive for aviation, a ship, a nuclear submarine and the like.
背景技术Background technique
在一些特殊使用场合，对于胶黏剂有较高要求，胶黏剂需要耐受高温热老化和高剂量辐照，在经过高温热老化和高剂量辐照处理以后还需要能承受高温高压水蒸汽以及碱性溶液对材料的破坏。耐热性好的聚酰胺和聚酯类胶黏剂不能耐受高剂量辐照、高温高压水蒸汽以及碱性溶液对材料的破坏。因此，在技术上迫切需要对现有的胶黏剂进行改性。In some special applications, there is a high requirement for adhesives. Adhesives need to withstand high temperature heat aging and high dose irradiation. After high temperature heat aging and high dose irradiation treatment, they also need to withstand high temperature and high pressure water vapor. And the destruction of the material by the alkaline solution. Polyamides and polyester adhesives with good heat resistance cannot withstand high-dose irradiation, high-temperature and high-pressure steam, and alkaline solution damage to materials. Therefore, it is technically necessary to modify existing adhesives.
发明内容Summary of the invention
本发明要解决的技术问题在于：提供一种在经过高温热老化和高剂量辐照处理以后还能承受碱性溶液对材料的破坏的胶黏剂。The technical problem to be solved by the present invention is to provide an adhesive which can withstand the destruction of materials by an alkaline solution after high temperature heat aging and high dose irradiation treatment.
为了解决上述技术问题，本发明提出以下技术方案：一种胶黏剂，其由重量计量的以下组分：In order to solve the above technical problems, the present invention proposes the following technical solution: an adhesive which measures the following components by weight:
乙烯-丙烯酸甲酯共聚物(EMA)       100份；100 parts of ethylene-methyl acrylate copolymer (EMA);
乙烯-辛烯共聚物                  30～100份；Ethylene-octene copolymer 30 to 100 parts;
含硫抗氧剂                       5～10份；Sulfur-containing antioxidant 5 to 10 parts;
所述含硫抗氧剂由以下物质中的一种或者多种组成：硫代二丙酸二月桂酯(抗氧剂DLTDP)；硫代二丙酸双十四醇酯(抗氧剂DMTDP)。The sulfur-containing antioxidant is composed of one or more of the following materials: dilauryl thiodipropionate (antioxidant DLTDP); thiodipropionate ditetradecyl ester (antioxidant DMTDP) .
为了解决上述技术问题，本发明还提出以下技术方案：一种胶黏剂的制备方法，包括以下步骤：In order to solve the above technical problems, the present invention also proposes the following technical solution: a method for preparing an adhesive, comprising the following steps:
步骤1：将乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物30～100份；含硫抗氧剂5～10份，按照一定比例配比，在160℃下使用密炼机混炼30分钟，把混炼好的胶黏剂压片； Step 1: 100 parts of ethylene-methyl acrylate copolymer (EMA); 30-100 parts of ethylene-octene copolymer; 5-10 parts of sulfur-containing antioxidant, according to a certain ratio, use dense at 160 ° C The mixer is kneaded for 30 minutes, and the kneaded adhesive is tableted;
步骤2：把压片好的胶黏剂使用电子束或者钴源进行辐照，辐照剂量为80～130kGy，辐照后胶黏剂发生部分交联，环球软化点提高，流动性降低。Step 2: The tableting adhesive is irradiated with an electron beam or a cobalt source, and the irradiation dose is 80-130 kGy. After the irradiation, the adhesive partially cross-links, the ring softening point is increased, and the fluidity is lowered.
本发明具有以下有益效果：本发明胶黏剂经过高温热老化和高剂量辐照处理以后还能承受碱性溶液对材料的破坏的胶黏剂。The invention has the following beneficial effects: the adhesive of the invention can withstand the destruction of the material by the alkaline solution after high temperature heat aging and high dose irradiation treatment.
具体实施方式detailed description
本发明提出一种胶黏剂，其由重量计量的以下组分：The present invention provides an adhesive that is weighted by the following components:
乙烯-丙烯酸甲酯共聚物(EMA)      100份；100 parts of ethylene-methyl acrylate copolymer (EMA);
乙烯-辛烯共聚物                 30～100份；Ethylene-octene copolymer 30 to 100 parts;
含硫抗氧剂                      5～10份。Sulfur-containing antioxidants 5 to 10 parts.
所述含硫抗氧剂由以下物质中的一种或者多种组成：硫代二丙酸二月桂酯(抗氧剂DLTDP)；硫代二丙酸双十四醇酯(抗氧剂DMTDP)。The sulfur-containing antioxidant is composed of one or more of the following materials: dilauryl thiodipropionate (antioxidant DLTDP); thiodipropionate ditetradecyl ester (antioxidant DMTDP) .
本发明胶黏剂的制备方法，包括以下步骤：The preparation method of the adhesive of the invention comprises the following steps:
步骤1：将乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物30～100份；含硫抗氧剂5～10份，按照一定比例配比，在160℃下使用密炼机混炼30分钟，把混炼好的胶黏剂压片；Step 1: 100 parts of ethylene-methyl acrylate copolymer (EMA); 30-100 parts of ethylene-octene copolymer; 5-10 parts of sulfur-containing antioxidant, according to a certain ratio, use dense at 160 ° C The mixer is kneaded for 30 minutes, and the kneaded adhesive is tableted;
步骤2：把压片好的胶黏剂使用电子束或者钴源进行辐照，辐照剂量为80～130kGy，辐照后胶黏剂发生部分交联，环球软化点提高，流动性降低。Step 2: The tableting adhesive is irradiated with an electron beam or a cobalt source, and the irradiation dose is 80-130 kGy. After the irradiation, the adhesive partially cross-links, the ring softening point is increased, and the fluidity is lowered.
通过下述实施例将有助于理解本发明，但并不能限制本发明的内容。The invention will be understood by the following examples, but does not limit the scope of the invention.
实施例1Example 1
取乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物70份；硫代二丙酸二月桂酯(抗氧剂DLTDP)5份，将上述材料在160℃下使用密炼机反复混炼30分钟，将材料压成薄片后在辐照剂量100kGy的电子束辐照下交联。 Take 100 parts of ethylene-methyl acrylate copolymer (EMA); 70 parts of ethylene-octene copolymer; 5 parts of dilauryl thiodipropionate (antioxidant DLTDP), use the above materials at 160 ° C for use The machine was repeatedly kneaded for 30 minutes, and the material was pressed into a sheet and crosslinked under electron beam irradiation with an irradiation dose of 100 kGy.
实施例2Example 2
取乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物90份；硫代二丙酸二月桂酯(抗氧剂DLTDP)12份，将上述材料在160℃下使用密炼机反复混炼30分钟，将材料压成薄片后在辐照剂量130kGy的电子束辐照下交联。Take 100 parts of ethylene-methyl acrylate copolymer (EMA); 90 parts of ethylene-octene copolymer; 12 parts of dilauryl thiodipropionate (antioxidant DLTDP), use the above materials at 160 ° C for use The machine was repeatedly kneaded for 30 minutes, and the material was pressed into a sheet and crosslinked under electron beam irradiation with an irradiation dose of 130 kGy.
实施例3Example 3
取乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物40份；硫代二丙酸二月桂酯(抗氧剂DLTDP)6份，将上述材料在160℃下使用密炼机反复混炼30分钟，将材料压成薄片后在辐照剂量90kGy的电子束辐照下交联。Take 100 parts of ethylene-methyl acrylate copolymer (EMA); 40 parts of ethylene-octene copolymer; 6 parts of dilauryl thiodipropionate (antioxidant DLTDP), use the above materials at 160 ° C for use The machine was repeatedly kneaded for 30 minutes, and the material was pressed into a sheet and crosslinked under electron beam irradiation with an irradiation dose of 90 kGy.
实施例4Example 4
取乙烯-丙烯酸甲酯共聚物(EMA)100份；乙烯-辛烯共聚物30份；硫代二丙酸二月桂酯(抗氧剂DLTDP)5份，将上述材料在160℃下使用密炼机反复混炼30分钟，将材料压成薄片后在辐照剂量100kGy的电子束辐照下交联。 Take 100 parts of ethylene-methyl acrylate copolymer (EMA); 30 parts of ethylene-octene copolymer; 5 parts of dilauryl thiodipropionate (antioxidant DLTDP), use the above materials at 160 ° C for use The machine was repeatedly kneaded for 30 minutes, and the material was pressed into a sheet and crosslinked under electron beam irradiation with an irradiation dose of 100 kGy.

Claims (2)

  1. 一种胶黏剂，其由重量计量的以下组分：An adhesive that measures the following components by weight:
    乙烯-丙烯酸甲酯共聚物                  100份；Ethylene-methyl acrylate copolymer 100 parts;
    乙烯-辛烯共聚物                        30～100份；Ethylene-octene copolymer 30 to 100 parts;
    含硫抗氧剂                             5～10份；Sulfur-containing antioxidant 5 to 10 parts;
    所述含硫抗氧剂由以下物质中的一种或者多种组成：硫代二丙酸二月桂酯；硫代二丙酸双十四醇酯。The sulfur-containing antioxidant is composed of one or more of the following: dilauryl thiodipropionate; ditetradecyl thiodipropionate.
  2. 一种如权利要求1所述的胶黏剂的制备方法，其特征在于，其包括以下步骤：A method of preparing an adhesive according to claim 1, comprising the steps of:
    步骤1：将乙烯-丙烯酸甲酯共聚物100份；乙烯-辛烯共聚物30～100份；含硫抗氧剂5～10份，按照一定比例配比，在160℃下使用密炼机混炼30分钟，把混炼好的胶黏剂压片；Step 1: 100 parts of ethylene-methyl acrylate copolymer; 30-100 parts of ethylene-octene copolymer; 5-10 parts of sulfur-containing antioxidant, according to a certain proportion, mixed at 160 ° C using an internal mixer After 30 minutes of smelting, the mixed adhesive is compressed;
    步骤2：把压片好的胶黏剂使用电子束或者钴源进行辐照，辐照剂量为80～130kGy，辐照后胶黏剂发生部分交联，环球软化点提高，流动性降低。 Step 2: The tableting adhesive is irradiated with an electron beam or a cobalt source, and the irradiation dose is 80-130 kGy. After the irradiation, the adhesive partially cross-links, the ring softening point is increased, and the fluidity is lowered.
PCT/CN2014/089149 2014-10-22 2014-10-22 Adhesive and preparation method therefor WO2016061753A1 (en)

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Application Number Priority Date Filing Date Title
PCT/CN2014/089149 WO2016061753A1 (en) 2014-10-22 2014-10-22 Adhesive and preparation method therefor

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069083A (en) * 1975-12-22 1978-01-17 Combustion Engineering, Inc. Bonding material and method
CN102250563A (en) * 2011-02-21 2011-11-23 长园集团股份有限公司 Hot melt adhesive for cable accessories in nuclear island of nuclear power plant and preparation method thereof
CN102250405A (en) * 2011-02-21 2011-11-23 长园集团股份有限公司 1E-grade K1-class halogen-free flame-retardant thermal shrinkage material for nuclear power plant and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069083A (en) * 1975-12-22 1978-01-17 Combustion Engineering, Inc. Bonding material and method
CN102250563A (en) * 2011-02-21 2011-11-23 长园集团股份有限公司 Hot melt adhesive for cable accessories in nuclear island of nuclear power plant and preparation method thereof
CN102250405A (en) * 2011-02-21 2011-11-23 长园集团股份有限公司 1E-grade K1-class halogen-free flame-retardant thermal shrinkage material for nuclear power plant and preparation method thereof

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