CN116445111B - Hot melt adhesive and preparation method thereof - Google Patents
Hot melt adhesive and preparation method thereof Download PDFInfo
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- CN116445111B CN116445111B CN202310282764.3A CN202310282764A CN116445111B CN 116445111 B CN116445111 B CN 116445111B CN 202310282764 A CN202310282764 A CN 202310282764A CN 116445111 B CN116445111 B CN 116445111B
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- ethylene
- vinyl acetate
- acetate resin
- resin
- melt adhesive
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 131
- 239000011347 resin Substances 0.000 claims abstract description 131
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 86
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 86
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 43
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 31
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 31
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 8
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000004822 Hot adhesive Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention belongs to the technical field of organic polymer adhesives, and particularly relates to a hot melt adhesive and a preparation method thereof. The products developed by the invention comprise ethylene-vinyl acetate resin and low-density polyethylene resin; wherein the mass ratio of the ethylene-vinyl acetate resin to the low-density polyethylene resin is 10:1-10:3, a step of; and, the ethylene-vinyl acetate resin is grafted with maleic anhydride and organosilane; the low-density polyethylene resin is grafted with maleic anhydride; at least a portion of the ethylene vinyl acetate resin and the low density polyethylene resin are co-grafted with the same maleic anhydride molecule. In addition, the preparation method also comprises spherical nano silicon dioxide with the mass of organosilane being 10-12%; the sphericity of the spherical nano silicon dioxide is 0.75-0.85; and polytetrafluoroethylene resin with mass of 3-6% of ethylene-vinyl acetate resin. The product developed by the invention has good stability and can effectively prolong the service life of the product.
Description
Technical Field
The invention belongs to the technical field of organic polymer adhesives. More particularly, to a hot melt adhesive and a preparation method thereof.
Background
Ethylene-vinyl acetate is used as a hot melt adhesive product, is the most widely used product at present and has the largest dosage, and is widely used for wireless binding of books, manufacturing of wood laminate, edge sealing of plate furniture, manufacturing of non-woven fabrics and the like. Compared with other hot melt adhesive series products, the adhesive has excellent adhesive property and has hot adhesive force on almost all materials; in addition, the viscosity of the adhesive is low after melting, and the adhesive is easy to spread in the sizing process; in addition, the composite material has excellent electrical performance, good compatibility with other compounding agents, wide range of compounding agent selection and reasonable selection according to specific use requirements.
However, existing ethylene-vinyl acetate hot melt adhesive products also have a number of significant disadvantages: mainly, the adhesive strength is low, and the hot melt adhesive is not resistant to high and low temperatures, fat oil and the like due to the natural property of the hot melt adhesive. The main body of the ethylene-vinyl acetate hot melt adhesive is formed by blending polymer materials with different properties, the colloid has limited heat resistance and low thermal stability in the preparation and use processes, the application range of the colloid is limited, and the added auxiliary material tackifier reduces the melt viscosity to improve the wettability and the initial adhesion performance of the adhered object, and most of the materials are substances with smaller molecular weight, and the substances are also not resistant to high temperature.
Based on the analysis, the ethylene-vinyl acetate is independently adopted as a base polymer, the complex technical requirements of industrial development cannot be met by carrying out certain-range proportioning adjustment, and the ethylene-vinyl acetate can be applied to a wider application field only by carrying out more complex modification.
Disclosure of Invention
The invention aims to overcome the defects and defects that the adhesive property of the existing EVA hot melt adhesive product is obviously reduced along with the extension of the service life due to the fact that the stability of the property of the existing EVA hot melt adhesive product is common and the added various components are easy to phase separate in the actual use process of the product.
The invention aims to provide a hot melt adhesive.
The invention also aims to provide a preparation method of the hot melt adhesive.
The above object of the present invention is achieved by the following technical scheme:
a hot melt adhesive comprising an ethylene-vinyl acetate resin and a low density polyethylene resin;
wherein the mass ratio of the ethylene-vinyl acetate resin to the low-density polyethylene resin is 10:1-10:3, a step of;
and, the ethylene-vinyl acetate resin is grafted with maleic anhydride and organosilane;
the low-density polyethylene resin is grafted with maleic anhydride;
at least a portion of the ethylene vinyl acetate resin and the low density polyethylene resin are co-grafted with the same maleic anhydride molecule.
According to the technical scheme, the ethylene-vinyl acetate resin is used as matrix resin and is assisted with low-density polyethylene resin with specific content, then at least part of molecular chains of the ethylene-vinyl acetate resin and the low-density polyethylene resin can be grafted with the same maleic anhydride molecule together, and the inventor finds that the two molecules are grafted with the same maleic anhydride molecule together in the practical research process, on one hand, chemical bond acting force can be formed between macromolecular chains of the two resins, so that a certain-strength mutual traction effect occurs between two different molecular chains after heating and hot melting or use, and a certain space still exists between the molecular weight of the maleic anhydride molecule and the molecular chain of the low-density polyethylene resin, so that the two molecules can be prevented from forming a strong acting force, and the spreading of a product on the surface of a substrate in the use process is influenced;
in addition, the inventor finds that, on the basis of the mutual restraint of the ethylene-vinyl acetate resin and the low-density polyethylene resin by singly relying on maleic anhydride molecules, organosilane is introduced, specifically, the organosilane is grafted on the molecular chain of the ethylene-vinyl acetate resin, the extension direction of the long chain of the molecular chain of the ethylene-vinyl acetate resin can be effectively regulated, and the stress is different from that of the site grafted with maleic anhydride, so that in the mixing process, curling and winding can be formed between the molecular chain of the ethylene-vinyl acetate resin and the molecular chain of the low-density polyethylene resin, thereby forming mutual entanglement in a three-dimensional space, improving the cohesive force of a product, and the entanglement force depends on the combined action of chemical bonds and physical entanglement, so that depolymerization is not easy to occur in the use process, and the adhesive property of the product is improved, and the adhesive property of the product is stable and reliable for a long term.
Further, the preparation method also comprises spherical nano silicon dioxide with the mass of organosilane being 10-12%; the sphericity of the spherical nano silicon dioxide is 0.75-0.85.
According to the technical scheme, a certain amount of spherical nano silicon dioxide is further introduced into the adhesive system as an inorganic filler, on the one hand, silicon hydroxyl groups on the surface of the nano silicon dioxide can be well compatible between the resin system and organosilane, on the other hand, the polarity of the nano silicon dioxide can be compatible with that of the surface of a substrate, the wetting spreading capacity of the hot melt adhesive on the surface of the substrate is improved, and particularly, when the sphericity of the spherical nano silicon dioxide is in the range of 0.75-0.85, when different particles are randomly arranged and oriented in the hot melt adhesive, a relatively uniform interface can be obtained, so that the situation that after the hot melt adhesive is used, the adhesion performance difference of different parts on the surface of the substrate is overlarge is avoided to a certain extent, the whole failure is gradually caused due to local adhesion failure, and the service life of a product is effectively prolonged.
Further, the organosilane is selected from any one of 3, 3-trifluoro propyl methyl dimethoxy silane, hexadecyl trimethoxy silane or heptadecafluoro decyl trimethoxy silane.
Further, the adhesive also comprises polytetrafluoroethylene resin with the mass of 3-6% of the mass of the ethylene-vinyl acetate resin.
According to the technical scheme, polytetrafluoroethylene resin is further introduced, and the polytetrafluoroethylene resin tends to be stably dispersed in a fibrous state with relatively higher strength in a mixed resin system, so that the polytetrafluoroethylene resin can cooperate with matrix resin to form a mixed resin system with a more complex physical-chemical entanglement structure, after the product is used, after the product is cured, even if the product is subjected to environmental heat impact and pressure impact subsequently, the product can trigger the molecular chain of the product to relax or slide at a higher temperature or pressure, and therefore the heat resistance of the product is enhanced.
The preparation method of the hot melt adhesive comprises the following specific preparation steps:
raw material preparation:
the mass ratio is 10:1-10:3 weighing ethylene-vinyl acetate resin and low-density polyethylene resin;
ethylene-vinyl acetate resin grafted organosilane:
the dibutyl tin dilaurate is used as a catalyst, the mixture is mixed with ethylene-vinyl acetate resin and is led into a reactor, the reaction is catalyzed for 6 to 8 hours at the temperature of more than 90 ℃ under the anhydrous condition, and the material is discharged, so that the pretreated ethylene-vinyl acetate resin is obtained;
grafting of maleic anhydride:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 10-15% of maleic anhydride of the ethylene-vinyl acetate resin and 3-5% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction, cooling the mixture, and discharging the mixture to obtain the hot melt adhesive product.
Further, the specific preparation steps further comprise:
in the process of grafting organosilane on the ethylene-vinyl acetate resin, spherical nano silicon dioxide with the mass of 10-12% of that of the organosilane is added.
Further, the specific preparation steps comprise:
ethylene-vinyl acetate resin grafted organosilane:
the preparation method comprises the steps of taking dibutyltin dilaurate as a catalyst, mixing the dibutyltin dilaurate with ethylene-vinyl acetate resin, introducing the mixture into a reactor, adding organosilane, carrying out catalytic reaction for 6-8h at the temperature of above 90 ℃ under anhydrous condition, adding spherical nano silicon dioxide with the mass of 10-12% of organosilane, continuously stirring and reacting for 40-60min while the mixture is hot, cooling, and discharging to obtain the pretreated ethylene-vinyl acetate resin.
Further, the specific preparation steps further comprise:
during the grafting process of the maleic anhydride, polytetrafluoroethylene resin with the mass of 3-6% of that of the ethylene-vinyl acetate resin is added.
Further, the specific preparation steps further comprise:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 10-15% of maleic anhydride of the ethylene-vinyl acetate resin and 3-5% of initiator of the ethylene-vinyl acetate resin, heating for reaction, adding polytetrafluoroethylene resin after the grafting reaction is finished, continuously stirring for 30-45min while the mixture is hot, cooling, and discharging to obtain the hot melt adhesive product.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
Raw material preparation:
the mass ratio is 10:1 weighing ethylene-vinyl acetate resin and low-density polyethylene resin; and 10% of maleic anhydride, 3% of initiator and 10% of organosilane;
ethylene-vinyl acetate resin grafted organosilane:
dibutyl tin dilaurate is used as a catalyst, and the dibutyl tin dilaurate and ethylene-vinyl acetate resin are mixed according to the mass ratio of 1:20, mixing and introducing the mixture into a reactor, adding organosilane, stirring and catalyzing the mixture at a constant temperature of 90 ℃ and a stirring speed of 300r/min for 6 hours under anhydrous conditions, adding spherical nano silicon dioxide with the mass of 10% of the organosilane after the reaction is finished, cooling and discharging the mixture to obtain pretreated ethylene-vinyl acetate resin; the organosilane is selected from 3, 3-trifluoro propyl methyl dimethoxy silane;
grafting of maleic anhydride:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 10% of maleic anhydride of the ethylene-vinyl acetate resin and 3% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction for 3 hours under the condition that the temperature is 120 ℃ and the stirring speed is 300r/min, adding 3% of polytetrafluoroethylene resin of the mass of the ethylene-vinyl acetate resin after the grafting reaction is finished, continuously stirring the mixture for 30 minutes while the mixture is still hot, cooling the mixture, and discharging the mixture to obtain a hot melt adhesive product; the initiator is prepared from benzoyl peroxide and cumene peroxide according to a mass ratio of 2:1 are compounded.
Example 2
Raw material preparation:
the mass ratio is 10:2 weighing ethylene-vinyl acetate resin and low-density polyethylene resin; and 12% of maleic anhydride, 4% of initiator and 12% of organosilane;
ethylene-vinyl acetate resin grafted organosilane:
dibutyl tin dilaurate is used as a catalyst, and the dibutyl tin dilaurate and ethylene-vinyl acetate resin are mixed according to the mass ratio of 1:25, mixing and introducing the mixture into a reactor, adding organosilane, stirring at a constant temperature of 95 ℃ and a stirring speed of 400r/min under anhydrous conditions for catalytic reaction for 7 hours, adding spherical nano silicon dioxide with 11% of the mass of the organosilane after the reaction is finished, wherein the sphericity of the spherical nano silicon dioxide is 0.8, cooling, and discharging to obtain pretreated ethylene-vinyl acetate resin; the organosilane is selected from 3, 3-trifluoro propyl methyl dimethoxy silane;
grafting of maleic anhydride:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 12% of maleic anhydride of the ethylene-vinyl acetate resin and 4% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction for 4 hours under the condition that the temperature is 125 ℃ and the stirring speed is 400r/min, adding 5% of polytetrafluoroethylene resin of the mass of the ethylene-vinyl acetate resin after the grafting reaction is finished, continuously stirring the mixture for 35min while the mixture is still hot, cooling the mixture, and discharging the mixture to obtain a hot melt adhesive product; the initiator is prepared from benzoyl peroxide and cumene peroxide according to a mass ratio of 3:1 are compounded.
Example 3
Raw material preparation:
the mass ratio is 10:3 weighing ethylene-vinyl acetate resin and low-density polyethylene resin; and 15% of maleic anhydride, 5% of initiator and 15% of organosilane;
ethylene-vinyl acetate resin grafted organosilane:
dibutyl tin dilaurate is used as a catalyst, and the dibutyl tin dilaurate and ethylene-vinyl acetate resin are mixed according to the mass ratio of 1:30, mixing and introducing the mixture into a reactor, adding organosilane, stirring at a constant temperature of 100 ℃ and a stirring speed of 500r/min under anhydrous conditions for catalytic reaction for 8 hours, adding spherical nano silicon dioxide with the mass of 12% of the organosilane after the reaction is finished, wherein the sphericity of the spherical nano silicon dioxide is 0.85, cooling, and discharging to obtain pretreated ethylene-vinyl acetate resin; the organosilane is selected from 3, 3-trifluoro propyl methyl dimethoxy silane;
grafting of maleic anhydride:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 15% of maleic anhydride of the ethylene-vinyl acetate resin and 5% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction for 5 hours under the condition that the temperature is 130 ℃ and the stirring speed is 500r/min, adding 6% of polytetrafluoroethylene resin of the mass of the ethylene-vinyl acetate resin after the grafting reaction is finished, continuously stirring the mixture for 45 minutes while the mixture is still hot, cooling the mixture, and discharging the mixture to obtain a hot melt adhesive product; the initiator is prepared from benzoyl peroxide and cumene peroxide according to a mass ratio of 4:1 are compounded.
Example 4
The difference between this embodiment and embodiment 1 is that: no nano silica was added and the rest of the conditions remained unchanged.
Example 5
The difference between this embodiment and embodiment 1 is that: the sphericity of the nano silicon dioxide is 0.65, and the rest conditions are kept unchanged.
Example 6
The difference between this embodiment and embodiment 1 is that: no polytetrafluoroethylene resin was added and the rest of the conditions remained unchanged.
Comparative example 1
Raw material preparation:
the mass ratio is 10:1 weighing ethylene-vinyl acetate resin and low-density polyethylene resin; and 10% of maleic anhydride, 3% of initiator and 10% of organosilane;
ethylene-vinyl acetate resin grafted organosilane:
adding spherical nano silicon dioxide with the mass of 10% of organosilane, wherein the sphericity of the spherical nano silicon dioxide is 0.75, cooling, discharging to obtain pretreated ethylene-vinyl acetate resin; the organosilane is selected from 3, 3-trifluoro propyl methyl dimethoxy silane;
grafting of maleic anhydride:
mixing ethylene-vinyl acetate resin and low-density polyethylene resin, pouring the mixture into a reactor, adding 10% of maleic anhydride of the ethylene-vinyl acetate resin, 10% of organosilane of the ethylene-vinyl acetate resin and 3% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction for 3 hours under the conditions of the temperature of 120 ℃ and the stirring rotation speed of 300r/min, and adding 3% of polytetrafluoroethylene resin of the mass of the ethylene-vinyl acetate resin and 10% of spherical nano silicon dioxide of the mass of the organosilane after the grafting reaction is finished, wherein the sphericity of the spherical nano silicon dioxide is 0.75, and the organosilane is selected from 3, 3-trifluoropropyl methyl dimethoxy silane; continuously stirring for 30min while the mixture is hot, cooling, and discharging to obtain a hot melt adhesive product; the initiator is prepared from benzoyl peroxide and cumene peroxide according to a mass ratio of 2:1 are compounded.
Comparative example 2
The difference between this comparative example and example 1 is that: no organosilane was added and the remaining conditions remained unchanged.
The products obtained in examples 1-6 and comparative examples 1-2 were subjected to performance tests, and specific test methods and test results are as follows:
shear strength test: an electronic tension meter is adopted, and the stretching rate is not 10mm/min according to GB/T7124-2008;
tensile strength test: testing the product by adopting a universal tensile testing machine according to GB/T528-2009;
specifically, according to the above standard, before the aging test, the corresponding shear strength and tensile strength of each example or comparative example product are tested to obtain a shear strength 1 and a tensile strength 1 respectively; then placing the products of each example or comparative example into an aging test box, continuously and rapidly aging for 28 days under the conditions of 68% relative humidity, 35% oxygen concentration and 55 ℃ temperature, taking out the sample in the test box, cooling to room temperature, and testing the shear strength and the tensile strength of the products again by adopting the standard to obtain the shear strength 2 and the tensile strength 2 respectively; the specific test results are shown in Table 1;
table 1: product performance test results
As shown by the test results in Table 1, the product obtained by the invention has excellent ageing resistance and can effectively resist ageing conditions of temperature, oxygen and high humidity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A hot melt adhesive comprising an ethylene-vinyl acetate resin and a low density polyethylene resin;
wherein the mass ratio of the ethylene-vinyl acetate resin to the low-density polyethylene resin is 10:1-10:3, a step of;
and, the ethylene-vinyl acetate resin is grafted with maleic anhydride and organosilane;
the low-density polyethylene resin is grafted with maleic anhydride;
at least a portion of the ethylene-vinyl acetate resin and the low density polyethylene resin are co-grafted with the same maleic anhydride molecule;
the hot melt adhesive also comprises spherical nano silicon dioxide with the mass of organosilane accounting for 10-12 percent; the sphericity of the spherical nano silicon dioxide is 0.75-0.85.
2. A hot melt adhesive according to claim 1, wherein said organosilane is selected from any one of 3, 3-trifluoropropyl methyl dimethoxy silane, cetyl trimethoxy silane or heptadecafluoro decyl trimethoxy silane.
3. The hot melt adhesive according to claim 1, further comprising a polytetrafluoroethylene resin having a mass of ethylene-vinyl acetate resin of 3 to 6%.
4. A process for preparing a hot melt adhesive according to any one of claims 1 to 3, characterized in that the specific preparation steps comprise:
raw material preparation:
the mass ratio is 10:1-10:3 weighing ethylene-vinyl acetate resin and low-density polyethylene resin;
ethylene-vinyl acetate resin grafted organosilane:
mixing dibutyl tin dilaurate serving as a catalyst with ethylene-vinyl acetate resin, introducing the mixture into a reactor, adding organosilane, carrying out catalytic reaction for 6-8 hours at the temperature of more than 90 ℃ under anhydrous condition, adding spherical nano silicon dioxide with the mass of 10-12% of that of the organosilane, continuously stirring and reacting for 40-60 minutes while the mixture is hot, cooling, and discharging to obtain pretreated ethylene-vinyl acetate resin;
grafting of maleic anhydride:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 10-15% of maleic anhydride of the ethylene-vinyl acetate resin and 3-5% of initiator of the ethylene-vinyl acetate resin, heating the mixture for reaction, cooling the mixture, and discharging the mixture to obtain the hot melt adhesive product.
5. The method for preparing a hot melt adhesive according to claim 4, wherein the specific preparation steps further comprise:
during the grafting process of the maleic anhydride, polytetrafluoroethylene resin with the mass of 3-6% of that of the ethylene-vinyl acetate resin is added.
6. The method for preparing a hot melt adhesive according to claim 5, wherein the specific preparation steps further comprise:
mixing the pretreated ethylene-vinyl acetate resin and the low-density polyethylene resin, pouring the mixture into a reactor, adding 10-15% of maleic anhydride of the ethylene-vinyl acetate resin and 3-5% of initiator of the ethylene-vinyl acetate resin, heating for reaction, adding polytetrafluoroethylene resin after the grafting reaction is finished, continuously stirring for 30-45min while the mixture is hot, cooling, and discharging to obtain the hot melt adhesive product.
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