CN111057487A - Low-temperature-resistant flame-retardant hot melt adhesive and preparation method thereof - Google Patents
Low-temperature-resistant flame-retardant hot melt adhesive and preparation method thereof Download PDFInfo
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- 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
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
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- 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
- C09J11/04—Non-macromolecular additives inorganic
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- 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
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- 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
- C09J11/08—Macromolecular additives
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- 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
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The low-temperature-resistant flame-retardant hot melt adhesive consists of the following components in parts by weight: 40-60 parts of ethylene polymer; 5-10 parts of maleic anhydride grafted high-density polyethylene and 5-15 parts of maleic anhydride grafted ethylene-octylene copolymer; 0.5-2 parts of maleic anhydride grafted polyethylene wax; 0.5-2 parts of antioxidant; 15-38 parts of antimony bromide synergistic flame retardant; the ethylene polymer comprises a mixture of one or more of the following: EVA with 5-28% of vinyl acetate vinegar, EBA with 5-30% of butyl acrylate vinegar, EMA with 8-40% of methyl acrylate and EEA with 15-30% of ethyl acrylate; the bromine-antimony synergistic flame retardant is a compound of decabromodiphenylethane and antimony trioxide or a compound of decabromodiphenylethane and silane grafted surface modified antimony trioxide. The low-temperature resistant cold bending of the invention meets the requirements of 40 ℃ below zero/4 h, no crack and no brittle fracture.
Description
Technical Field
The invention relates to a low-temperature-resistant flame-retardant hot melt adhesive and a preparation method thereof, in particular to a co-extrusion type heat-shrinkable double-wall pipe flame-retardant hot melt adhesive and a preparation method thereof.
Background
Hot melt adhesives, reaction and radiation curing hot melt adhesives, acrylate adhesives and the like have appeared in the 60 s, and in the hot melt adhesives taking EVA resin as a base material, ethylene-ethyl acrylate copolymer resin is doped to improve the adhesiveness to non-adhesive materials, and isocyanate prepolymer is added to prepare a crosslinking hot melt adhesive, so that the initial adhesive force can be improved, and the crosslinking hot melt adhesive has good stability.
Some co-extrusion hot melt adhesives on the market are flammable and toxic, and most hot melt adhesives are added with auxiliary agents such as rosin, terpene resin, tackifier and the like, so that the hot melt adhesives are easy to brittle under low temperature conditions, and flow under high temperature conditions to cause the sealing effect to be deteriorated or lost.
The new energy automobile industry in China begins at the beginning of the 21 st century, and in recent years, new energy automobiles in China have been put into the industrialization stage under the background of intensive support policies. The flame retardance of the B-class voltage insulation protection heat-shrinkable sleeve related to the flame retardance of the B-class voltage insulation protection heat-shrinkable sleeve is compulsorily regulated to meet the GB/T2408-2008 level and vertical method for measuring the combustion performance of plastics, namely, the HB level of horizontal combustion and the V0 level of vertical combustion. In the existing automobile wire harness recommendation standard QC/T29106-2016, a clear specification is made on the temperature resistance grade of an automobile wire harness double-wall pipe, and the double-wall pipe needs to meet flame retardance, and has the characteristic of low temperature resistance, compared with the existing international universal reference standard UL224, the specification is that the double-wall pipe meets the requirements of no crack and no brittle fracture in a-30 ℃ cold bending test, and the double-wall pipe meets the requirements of no crack and no brittle fracture in a-40 ℃ cold bending test. The low temperature resistance of the existing polyolefin hot melt adhesive can not meet the requirement under the condition that the low temperature resistance is reduced by 10 ℃. And the flame-retardant rubber-containing layer of the double-wall pipe is required to meet V0 grade and HB grade for the first time. Therefore, the development of the low-temperature-resistant flame-retardant hot melt adhesive meets the requirements of GB/T2408 + 2008 plastic combustion performance determination horizontal method and vertical method for HB level horizontal combustion and V0 level vertical combustion, and the low-temperature-resistant high-temperature-resistant 125 ℃ hot melt adhesive has important significance for the development of the new energy automobile industry in China.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the flame-retardant hot melt adhesive for the automobile wire harness overcomes the problems that the conventional double-wall pipe for the automobile wire harness cannot meet the flame-retardant grade requirements of a B-grade voltage part of a new energy automobile (the whole heat-shrinkable double-wall pipe (an outer skin and a hot melt adhesive layer) meets the requirements of a GB/T2408 + 2008 plastic combustion performance level method and a vertical method level combustion HB level and a vertical combustion V0 level), the conventional double-wall pipe for the automobile wire harness meets the requirements of-30 ℃ cold bending, crack free and brittle failure, the automobile wire harness recommended standard QC/T29106-2016 and the temperature-resistant grade A low temperature resistance of the double-wall pipe for the automobile wire harness meets the requirements of-40 ℃, so that the flame-retardant hot melt adhesive for the automobile wire harness can resist the temperature and meet the requirements of-40 ℃ to 125 ℃ and the preparation.
In order to solve the technical problem, the invention provides the following scheme: a low-temperature-resistant flame-retardant hot melt adhesive comprises the following components in parts by weight:
40-60 parts of ethylene polymer;
5-10 parts of maleic anhydride grafted high-density polyethylene;
5-15 parts of maleic anhydride grafted ethylene-octylene copolymer;
0.5-2 parts of maleic anhydride grafted polyethylene wax;
0.5-2 parts of antioxidant pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine;
15-38 parts of antimony bromide synergistic flame retardant;
the ethylene polymer comprises a mixture of one or more of the following: EVA with 5-28% of vinyl acetate vinegar, EBA with 5-30% of butyl acrylate vinegar, EMA with 8-40% of methyl acrylate and EEA with 15-30% of ethyl acrylate;
the bromine-antimony synergistic flame retardant is a compound of decabromodiphenylethane and antimony trioxide or a compound of decabromodiphenylethane and silane grafted surface modified antimony trioxide.
The technical proposal is further limited in that the compounding ratio of the decabromodiphenylethane to the antimony trioxide is 3: 1.
The technical scheme is further limited in that the compounding ratio of the decabromodiphenylethane to the silane grafted surface modified antimony trioxide is 3: 2.
In order to solve the technical problem, the invention provides the following scheme: a preparation method of a low-temperature-resistant flame-retardant hot melt adhesive comprises the following steps:
step 1, weighing 40-60 parts of ethylene polymer, 5-10 parts of maleic anhydride grafted high-density polyethylene, 5-15 parts of maleic anhydride grafted ethylene-octylene copolymer, 0.5-2 parts of maleic anhydride grafted polyethylene wax, 0.5-2 parts of antioxidant pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine and 15-38 parts of antimony bromide synergistic flame retardant;
step 2: the materials except the bromine and antimony synergistic flame retardant are firstly subjected to reaction treatment for 1 hour in a reaction kettle at the temperature of 120-plus 150 ℃, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by using an internal mixer, then the bromine and antimony synergistic flame retardant is added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed.
The technical proposal is further limited in that the compounding ratio of the decabromodiphenylethane to the antimony trioxide is 3: 1.
The technical scheme is further limited in that the compounding ratio of the decabromodiphenylethane to the silane grafted surface modified antimony trioxide is 3: 2.
Compared with the prior art, the invention has the following beneficial effects:
1. the low temperature resistant polyolefin polymer is added to improve the low temperature resistant characteristic of the hot melt adhesive so that the hot melt adhesive can meet the conditions of-40 ℃/4h and then is free from cracks and brittle fracture in a cold bending test, and a small amount of bromine and antimony synergistic flame retardant is added so that the hot melt adhesive has good flame retardance, and compared with the traditional heat-shrinkable double-wall pipe hot melt adhesive for automobile wire harnesses, the flame retardance of the hot melt adhesive meets the requirements of GB/T2408 + 2008 plastic combustion performance determination horizontal method and vertical method for HB level of horizontal combustion and V0 level of vertical combustion, meanwhile, the low temperature resistance characteristic meets the technical conditions of the automobile wire harness of QCT 29106 along 2014 in appendix B, the heat-shrinkable double-wall tube for the automobile wire harness has no crack and no brittle fracture requirement in a low temperature resistance-40 ℃/4h cold bending test, and has higher low temperature resistance characteristic compared with the existing automobile wire harness double-wall tube with reference UL224 standard at the low temperature of-30 ℃. The double-wall heat-shrinkable sleeve is particularly suitable for new energy automobiles and traditional automobile wire harnesses. Bromide in the bromine and antimony synergistic flame retardant is non-ether bromide, so that the RoHS environmental protection requirement and the management requirement on hazardous substances and recoverable utilization rate of automobiles are met.
2. The low-temperature-resistant flame-retardant hot melt adhesive and the preparation method thereof have the flame retardant property meeting the HB level of horizontal combustion and V0 level of vertical combustion in GB/T2408-2008 determination of plastic combustion performance. The product can resist high and low temperatures and can meet the requirements of cold bending at 40 ℃ below zero/4 h without fracture and crack. The long-term use temperature range is-40 to 125 ℃ grade requirement. The low-temperature-resistant flame-retardant hot melt adhesive has the advantages of low cost, easiness in preparation, few formula components and application temperature range, and can replace the conventional similar hot melt adhesive only meeting the temperature of-30-125 ℃.
3. The components of the hot melt adhesive disclosed by the invention are prepared by adopting maleic anhydride grafted modified polyolefin as a main base material, and the main hot melt adhesive auxiliary materials which are commonly used in the existing hot melt adhesive and cannot resist low-temperature cold bending, such as rosin, terpene resin, tackifying resin and the like, are replaced, so that the characteristics of no brittle fracture and no crack under the low-temperature cold bending of-40 ℃ are realized.
Detailed Description
A low-temperature-resistant flame-retardant hot melt adhesive comprises the following components in parts by weight:
40-60 parts of ethylene polymer;
5-10 parts of HPDE-g-MAH (maleic anhydride grafted high-density polyethylene);
5-15 parts of P0E-g-MAH (maleic anhydride grafted ethylene-octylene copolymer);
0.5-2 parts of maleic anhydride grafted polyethylene wax;
antioxidant 1010, namely pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or antioxidant 1098, namely 0.5-2 parts of N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine;
15-38 parts of antimony bromide synergistic flame retardant.
The ethylene polymer comprises a mixture of one or more of the following: EVA (ethylene-vinyl acetate copolymer) with the content of vinyl acetate of 5-28%, EBA (ethylene-butyl acrylate copolymer) with the content of butyl acrylate of 5-30%, EMA (ethylene-methyl acrylate copolymer) with the content of methyl acrylate of 8-40%, and EEA (ethylene-ethyl acrylate) with the content of ethyl acrylate of 15-30%.
The bromine-antimony synergistic flame retardant is a compound of decabromodiphenylethane and antimony trioxide (the compounding ratio is 3: 1) or a compound of decabromodiphenylethane and silane grafted surface modified antimony trioxide (the compounding ratio is 3: 2).
The low-temperature-resistant flame-retardant hot melt adhesive is a polyolefin flame-retardant hot melt adhesive, and the flame-retardant grade of the low-temperature-resistant flame-retardant hot melt adhesive meets the requirements of V0 level of vertical combustion and HB level of horizontal combustion in the standards of GBT 2408-2008 plastic combustion performance determination by a horizontal method and a vertical method.
The applicable temperature range of the low-temperature resistant flame-retardant hot melt adhesive meets the requirements of-40 ℃ to 125 ℃.
The maleic anhydride grafted ethylene-octylene copolymer (P0E-g-MAH) introduces strong polar side groups on the POE nonpolar molecular main chain, and the maleic anhydride grafted POE can be a bridge for improving the adhesion and compatibility of polar materials and nonpolar materials, so that the maleic anhydride grafted POE can be used as a good toughening agent and a compatilizer, has a better toughening effect than that of pure POE without grafting, and is suitable for the compatilizers and the tougheners of various plastic alloy materials.
The maleic anhydride grafted high-density polyethylene (HPDE-g-MAH) and the addition of maleic anhydride grafted polyethylene wax can improve and improve the compatibility and the adhesion of the PE matrix and the filler interface. The high-density polyethylene grafted and modified by maleic anhydride has the effect that the softening point temperature of the high-density polyethylene is higher, so that the softening point temperature of the hot melt adhesive is increased. Greatly improves the mechanical property and the heat resistance of the composite material.
The preparation method of the low-temperature-resistant flame-retardant hot melt adhesive comprises the following steps:
step 1: weighing 40-60 parts of ethylene polymer, 5-10 parts of HPDE-g-MAH (maleic anhydride grafted high-density polyethylene), 5-15 parts of P0E-g-MAH (maleic anhydride grafted ethylene-octylene copolymer), 0.5-2 parts of maleic anhydride grafted polyethylene wax, 1010 or 10980.5-2 parts of antioxidant and 15-38 parts of antimony bromide synergistic flame retardant;
step 2: the materials except the bromine and antimony synergistic flame retardant are firstly subjected to reaction treatment for 1 hour in a reaction kettle at the temperature of 120-plus 150 ℃, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by using an internal mixer, then the bromine and antimony synergistic flame retardant is added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed. Preparation of example 1
Weighing 40 parts of ethylene polymer according to parts by weight, wherein the ethylene polymer comprises 12 parts of EVA (particularly Taiwan Fupu EVA UE 508), 15 parts of EBA (particularly repsol EBA PA-20020) and 13 parts of EEA (particularly DuPont Dow EEA 2715 AC), 1 part of HPDE-g-MAH 5 (particularly maleic anhydride grafted modified Taiwan plastic HDPE 8010), 0E-g-MAH 5 part (particularly maleic anhydride grafted modified Dow DuPont POE 8100), 1 part of maleic anhydride grafted polyethylene wax (particularly Saunor chemical engineering, MPE type), 0.5 part of antioxidant 1010, namely tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 15 parts of bromine antimony synergistic flame retardant (decabromodiphenylethane: antimony trioxide 3: 1);
the materials except 15 parts of the antimony bromide synergistic flame retardant are firstly subjected to reaction treatment for 1 hour at the temperature of 120-150 ℃ by a reaction kettle, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by an internal mixer, then 15 parts of the antimony bromide synergistic flame retardant are added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed.
The performance test was as follows:
the low temperature is resistant to 40 ℃ below zero/4 h, and the outer skin and the adhesive layer of the double-wall heat-shrinkable sleeve after low-temperature cold bending are not cracked or brittle.
After the high temperature resistance is 125 ℃/168h, the glue layer does not flow, and the outer skin does not slip.
The flame retardance test is carried out according to the GB/T2408 standard, and the requirements of horizontal burning HB level and vertical burning V0 level are met
Peel strength: 6.5N/mm.
Preparation of example 2
Weighing 50 parts of ethylene polymer by weight, wherein the ethylene polymer comprises 10 parts of EBA (specifically, Acoma EBA 18MA 02), 15 parts of EMA (specifically, Acoma EMA24MA 005) and 25 parts of EEA (specifically, NUC-6510/Japan Eucalyptus card); weighing 8 parts of HPDE-g-MAH (specifically maleic anhydride grafted modified Taiwan plastic HDPE 8010), 15 parts of P0E-g-MAH, 0.5 part of maleic anhydride grafted polyethylene wax (specifically Xeno chemical industry, model MPE), and 25 parts of antioxidant 1098, namely N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine, 1 part of bromine-antimony synergistic flame retardant (decabromodiphenylethane: silane surface modified antimony trioxide is 3: 2);
the materials except 25 parts of the antimony bromide synergistic flame retardant are firstly subjected to reaction treatment for 1 hour at the temperature of 120-150 ℃ by a reaction kettle, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by an internal mixer, then 25 parts of the antimony bromide synergistic flame retardant are added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed.
The performance test was as follows:
the low temperature resistance is-40 ℃/4h, and the outer skin and the adhesive layer of the double-wall heat-shrinkable sleeve for the new energy automobile have no cracks or brittle fracture after low-temperature cold bending.
After the high temperature resistance is 125 ℃/168h, the glue layer does not flow, and the outer skin does not slip.
The flame retardance test is carried out according to the GB/T2408 standard, and the requirements of horizontal burning HB level and vertical burning V0 level are met
Peel strength: 5.5N/mm. (requirement ≥ 3.2N/mm)
Preparation of example 3
Weighing 60 parts of ethylene polymer according to parts by weight, wherein the ethylene polymer comprises 30 parts of EMA (specifically, Acoma EMA24MA 005) and 30 parts of EVA (specifically, Beijing organic EVA 14-2); weighing 10 parts of HPDE-g-MAH (specifically maleic anhydride grafted Taiwan plastic HDPE 8010), 10 parts of P0E-g-MAH (specifically maleic anhydride grafted Dow Dupont POE 8150), 2 parts of maleic anhydride grafted polyethylene wax (specifically Sainuo chemical industry, model MPE), 2 parts of antioxidant 1098, namely N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine and 38 parts of bromine-antimony synergistic flame retardant (3: 1 parts of decabromodiphenylethane: antimony trioxide);
the materials except 38 parts of the antimony bromide synergistic flame retardant are firstly subjected to reaction treatment for 1 hour at the temperature of 120-150 ℃ by a reaction kettle, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by an internal mixer, then 38 parts of the antimony bromide synergistic flame retardant are added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed.
The double-wall heat-shrinkable sleeve for the new energy automobile is used for extrusion production, and the performance test is as follows:
the low temperature resistance is-40 ℃/4h, and the outer skin and the adhesive layer of the double-wall heat-shrinkable sleeve for the new energy automobile have no cracks or brittle fracture after low-temperature cold bending.
After the high temperature resistance is 125 ℃/168h, the glue layer does not flow, and the outer skin does not slip.
The flame retardance test is carried out according to the GB/T2408 standard, and the requirements of horizontal burning HB level and vertical burning V0 level are met
Peel strength: 4.4N/mm. (requirement ≥ 3.2N/mm)
Claims (6)
1. A low-temperature-resistant flame-retardant hot melt adhesive comprises the following components in parts by weight:
40-60 parts of ethylene polymer;
5-10 parts of maleic anhydride grafted high-density polyethylene;
5-15 parts of maleic anhydride grafted ethylene-octylene copolymer;
0.5-2 parts of maleic anhydride grafted polyethylene wax;
0.5-2 parts of antioxidant pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine;
15-38 parts of antimony bromide synergistic flame retardant;
the ethylene polymer comprises a mixture of one or more of the following: EVA with 5-28% of vinyl acetate vinegar, EBA with 5-30% of butyl acrylate vinegar, EMA with 8-40% of methyl acrylate and EEA with 15-30% of ethyl acrylate;
the bromine-antimony synergistic flame retardant is a compound of decabromodiphenylethane and antimony trioxide or a compound of decabromodiphenylethane and silane grafted surface modified antimony trioxide.
2. The low-temperature-resistant flame-retardant hot melt adhesive according to claim 1, wherein the compounding ratio of decabromodiphenylethane to antimony trioxide is 3: 1.
3. The low-temperature-resistant flame-retardant hot melt adhesive according to claim 1, wherein the compounding ratio of decabromodiphenylethane to silane-grafted surface-modified antimony trioxide is 3: 2.
4. The preparation method of the low-temperature-resistant flame-retardant hot melt adhesive as claimed in claim 1, characterized by comprising the following steps:
step 1, weighing 40-60 parts of ethylene polymer, 5-10 parts of maleic anhydride grafted high-density polyethylene, 5-15 parts of maleic anhydride grafted ethylene-octylene copolymer, 0.5-2 parts of maleic anhydride grafted polyethylene wax, 0.5-2 parts of antioxidant pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine and 15-38 parts of antimony bromide synergistic flame retardant;
step 2: the materials except the bromine and antimony synergistic flame retardant are firstly subjected to reaction treatment for 1 hour in a reaction kettle at the temperature of 120-plus 150 ℃, then the molten rubber material is subjected to banburying and forced feeding single-screw granulation by using an internal mixer, then the bromine and antimony synergistic flame retardant is added according to the weight proportion, and after the materials are uniformly stirred and dispersed by a stirrer, the double-screw granulation is completed.
5. The preparation method of the low-temperature-resistant flame-retardant hot melt adhesive according to claim 4, wherein the compounding ratio of decabromodiphenylethane to antimony trioxide is 3: 1.
6. The preparation method of the low-temperature-resistant flame-retardant hot melt adhesive according to claim 4, wherein the compounding ratio of decabromodiphenylethane to silane-grafted surface-modified antimony trioxide is 3: 2.
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Citations (7)
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