CN118272004A - Polyethylene adhesive and preparation method thereof - Google Patents
Polyethylene adhesive and preparation method thereof Download PDFInfo
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- CN118272004A CN118272004A CN202410692840.2A CN202410692840A CN118272004A CN 118272004 A CN118272004 A CN 118272004A CN 202410692840 A CN202410692840 A CN 202410692840A CN 118272004 A CN118272004 A CN 118272004A
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- polyethylene
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- -1 Polyethylene Polymers 0.000 title claims abstract description 76
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 41
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 18
- 238000010008 shearing Methods 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000013530 defoamer Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- IZDNNHOZVXRIGA-UHFFFAOYSA-N 2h-1,2-benzoxazin-3-amine Chemical compound C1=CC=C2ONC(N)=CC2=C1 IZDNNHOZVXRIGA-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- ZPKSAIWDCQVXSQ-UHFFFAOYSA-N (4-aminophenoxy)boronic acid Chemical compound NC1=CC=C(OB(O)O)C=C1 ZPKSAIWDCQVXSQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 3
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 claims description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000008064 anhydrides Chemical group 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
Abstract
The invention relates to the technical field of adhesives, and discloses a polyethylene adhesive and a preparation method thereof, wherein polyethylene, maleic anhydride grafted polyethylene, silicon-containing benzoxazine, an antioxidant 626, a polyether modified organosilicon defoamer and a polyvinyl alcohol thickener are added into a stirrer to be stirred and mixed, and then sheared by a high-speed shearing machine to obtain the polyethylene adhesive; in the high-speed shearing process, anhydride groups in the maleic anhydride grafted polyethylene react with hydroxyl groups in the silicon-containing benzoxazine, so that the interfacial compatibility with the polyethylene is increased, a cross-linked network is formed between the maleic anhydride grafted polyethylene and the polyethylene, and the maleic anhydride grafted polyethylene and the chain in the epoxy resin are entangled, so that more force can be removed when external force is applied, and the maleic anhydride grafted polyethylene has better tensile property; and the benzoxazine can form a heat-resistant phenolic resin structure at high temperature, so that the polyethylene shows higher thermal decomposition temperature and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a polyethylene adhesive and a preparation method thereof.
Background
The adhesive is used in the production process of shoes, boxes and leather bags, the adhesive also plays a certain role in the quality of products, and the adhesive falls off under the action of high temperature, so that the quality of shoes is affected, therefore, the adhesive in the process of technology needs to have better stretching capability and high temperature resistance, as reported in patent CN105925224A, and the preparation method thereof, the adhesive of the composite material prepared from carbon fibers, glass fibers and resin materials can lead the structure of the composite material to be more stable, effectively improve the mechanical strength and the safety performance, and can be widely applied to the manufacture of small airplanes, but the high temperature resistance effect of the composite material is not improved.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a polyethylene adhesive and a preparation method thereof, which have better high temperature resistance and tensile property.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a polyethylene adhesive comprising the following components by weight: 40-50 parts of polyethylene, 1-2 parts of maleic anhydride grafted polyethylene, 5-12 parts of silicon-containing benzoxazine, 0.2-0.4 part of antioxidant 626, 0.04-0.1 part of polyether modified organosilicon defoamer and 0.2-0.3 part of polyvinyl alcohol thickener.
Preferably, the preparation method of the silicon-containing benzoxazine comprises the following steps:
(1) Adding 4-aminophenylboric acid and 4, 6-diamino-2-hydroxy-1, 3, 5-triazine into a solvent in N, N-dimethylformamide, introducing nitrogen for protection, uniformly stirring, reacting for 5-7 hours at 70-90 ℃, cooling to room temperature after finishing, filtering, washing and drying to obtain triazinylboric acid;
(2) Adding triazinyl boric acid, formaldehyde water solution and p-nitrophenol into toluene solvent, fully dissolving, performing cyclization reaction, reacting for 10-15h at 60-90 ℃, performing reduced pressure distillation after the reaction is finished, washing with deionized water, and recrystallizing the crude product dichloromethane to obtain triazinyl benzoxazine;
(3) Adding triazinyl benzoxazine into ethanol solvent, then continuously adding ferric chloride and active carbon, stirring and mixing, continuously adding hydrazine hydrate solution, stirring and reacting for 15-25h at 70-85 ℃, precipitating with deionized water after the reaction, filtering and washing to obtain amino benzoxazine;
(4) Adding amino benzoxazine and hexamethylene diisocyanate into N, N-dimethylformamide solvent, stirring uniformly, then continuously adding silane modified epoxy resin into the mixture, reacting for 6-15h at 90-120 ℃, decompressing and distilling the mixture after the reaction, washing the mixture with deionized water and ethanol, and drying the mixture to obtain the silicon-containing benzoxazine.
Preferably, the mass ratio of the 4-aminophenylboronic acid to the 4, 6-diamino-2-hydroxy-1, 3, 5-triazine in the (1) is 1.2-1.5:1.
Preferably, the mass ratio of the triazinyl boric acid to the aqueous solution of formaldehyde to the p-nitrophenol in the step (2) is 1:1.3-1.6:1.2-1.4.
Preferably, the mass ratio of the triazinyl benzoxazine, the ferric chloride, the activated carbon and the hydrazine hydrate in the step (3) is 1:0.02-0.03:0.04-0.08:0.02-0.04.
Preferably, the mass ratio of the amino benzoxazine, the hexamethylene diisocyanate and the silane modified epoxy resin in the (4) is 1.1-1.3:1:1.2-1.5.
Preferably, the preparation method of the silane modified epoxy resin in the step (4) comprises the following steps:
S1, adding hydroxyl-terminated polydimethylsiloxane and epoxy resin into an N, N-dimethylformamide solvent, uniformly stirring, continuously adding a phosphoric acid catalyst into the mixture, carrying out ring-opening addition, reacting at 85-110 ℃ for 6-10h, removing the solvent by reduced pressure distillation after the reaction is finished, filtering and drying to obtain the silane modified epoxy resin.
Preferably, the mass ratio of the hydroxyl-terminated polydimethylsiloxane, the epoxy resin and the phosphoric acid catalyst in the S1 is 1:0.8-1.3:0.02-0.04.
Preferably, the preparation method of the polyethylene adhesive comprises the following steps: adding polyethylene, maleic anhydride grafted polyethylene, silicon-containing benzoxazine, an antioxidant 626, a polyether modified organosilicon defoamer and a polyvinyl alcohol thickener into a stirrer, stirring and mixing, and then shearing by a high-speed shearing machine to obtain the polyethylene adhesive.
(III) beneficial technical effects
The invention adds polyethylene, maleic anhydride grafted polyethylene, silicon-containing benzoxazine, antioxidant 626, polyether modified organosilicon defoamer and polyvinyl alcohol thickener into a stirrer to be stirred and mixed, and then the mixture is sheared by a high-speed shearing machine to obtain the polyethylene adhesive.
In the high-speed shearing process, anhydride groups in the maleic anhydride grafted polyethylene react with hydroxyl groups in the silicon-containing benzoxazine, so that the interfacial compatibility with the polyethylene is increased, a cross-linked network is formed between the maleic anhydride grafted polyethylene and the polyethylene, and the maleic anhydride grafted polyethylene and the chain in the epoxy resin are entangled, so that more force can be removed when external force is applied, and the maleic anhydride grafted polyethylene has better tensile property; and the benzoxazine can form a heat-resistant phenolic resin structure at high temperature, so that the polyethylene shows higher thermal decomposition temperature and high temperature resistance, and meanwhile, the triazinyl has better high temperature resistance, and the synergistic effect plays a role in high temperature resistance, wherein boron element, silicon element and high temperature resistant groups form a high temperature resistant system together.
Detailed Description
Defoaming agent: polyether modified organosilicon, YT-508; brand number EASYTECHDF-942.
And (3) a thickening agent: polyvinyl alcohol, trade name PVA1799.
Example 1
(1) Adding 4-aminophenylboric acid and 4, 6-diamino-2-hydroxy-1, 3, 5-triazine into a solvent in N, N-dimethylformamide, wherein the mass ratio of the 4-aminophenylboric acid to the 4, 6-diamino-2-hydroxy-1, 3, 5-triazine is 1.2:1, introducing nitrogen for protection, uniformly stirring, reacting for 5 hours at 70 ℃, cooling to room temperature after finishing, filtering, washing and drying to obtain triazinylboric acid;
(2) Adding triazinyl boric acid, formaldehyde aqueous solution and p-nitrophenol into toluene solvent, wherein the mass ratio of the triazinyl boric acid to the formaldehyde aqueous solution to the p-nitrophenol is 1:1.3:1.2, fully dissolving, performing cyclization reaction, reacting for 10 hours at 60 ℃, performing reduced pressure distillation after the reaction is finished, washing with deionized water, and recrystallizing the crude product dichloromethane to obtain triazinyl benzoxazine;
(3) Adding triazinyl benzoxazine into ethanol solvent, then continuously adding ferric chloride and active carbon, wherein the mass ratio of the triazinyl benzoxazine to the ferric chloride to the active carbon to the hydrazine hydrate is 1:0.02:0.04:0.02, stirring and mixing, continuously adding hydrazine hydrate solution, stirring and reacting for 15 hours at 70 ℃, and obtaining amino benzoxazine through deionized water precipitation, filtering and washing after the reaction;
(4) Adding hydroxyl-terminated polydimethylsiloxane and epoxy resin into an N, N-dimethylformamide solvent, uniformly stirring, continuously adding a phosphoric acid catalyst into the solvent, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the epoxy resin to the phosphoric acid catalyst is 1:0.8:0.02, carrying out ring-opening addition, reacting at 85 ℃ for 6 hours, removing the solvent by reduced pressure distillation after the reaction is finished, filtering and drying to obtain silane modified epoxy resin;
(5) Adding amino benzoxazine and hexamethylene diisocyanate into N, N-dimethylformamide solvent, stirring uniformly, then continuously adding silane modified epoxy resin into the mixture, wherein the mass ratio of the amino benzoxazine to the hexamethylene diisocyanate to the silane modified epoxy resin is 1.1:1:1.2, reacting for 6 hours at 90 ℃, distilling under reduced pressure, washing with deionized water and ethanol, and drying to obtain silicon-containing benzoxazine;
(6) 40 parts by weight of polyethylene, 1 part by weight of maleic anhydride grafted polyethylene, 5 parts by weight of silicon-containing benzoxazine, 0.2 part by weight of antioxidant 626, 0.04 part by weight of polyether modified organosilicon defoamer and 0.2 part by weight of polyvinyl alcohol thickener are added into a stirrer to be stirred and mixed, and then sheared by a high-speed shearing machine to obtain the polyethylene adhesive.
Example 2
(1) Adding 4-aminophenylboric acid and 4, 6-diamino-2-hydroxy-1, 3, 5-triazine into a solvent in N, N-dimethylformamide, wherein the mass ratio of the 4-aminophenylboric acid to the 4, 6-diamino-2-hydroxy-1, 3, 5-triazine is 1.5:1, introducing nitrogen for protection, uniformly stirring, reacting for 7 hours at 90 ℃, cooling to room temperature after finishing, filtering, washing and drying to obtain triazinylboric acid;
(2) Adding triazinyl boric acid, formaldehyde aqueous solution and p-nitrophenol into toluene solvent, wherein the mass ratio of the triazinyl boric acid to the formaldehyde aqueous solution to the p-nitrophenol is 1:1.6:1.4, fully dissolving, performing cyclization reaction, reacting for 15 hours at 90 ℃, performing reduced pressure distillation after the reaction is finished, washing with deionized water, and recrystallizing the crude product dichloromethane to obtain triazinyl benzoxazine;
(3) Adding triazinyl benzoxazine into ethanol solvent, then continuously adding ferric chloride and active carbon, wherein the mass ratio of the triazinyl benzoxazine to the ferric chloride to the active carbon to the hydrazine hydrate is 1:0.03:0.08:0.04, stirring and mixing, continuously adding hydrazine hydrate solution, stirring and reacting at 85 ℃ for 25 hours, and obtaining the amino benzoxazine through deionized water precipitation, filtration and washing after the reaction;
(4) Adding hydroxyl-terminated polydimethylsiloxane and epoxy resin into an N, N-dimethylformamide solvent, uniformly stirring, continuously adding a phosphoric acid catalyst into the solvent, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the epoxy resin to the phosphoric acid catalyst is 1:1.3:0.04, carrying out ring-opening addition, reacting at 110 ℃ for 10 hours, removing the solvent by reduced pressure distillation after the reaction is finished, filtering and drying to obtain silane modified epoxy resin;
(5) Adding amino benzoxazine and hexamethylene diisocyanate into N, N-dimethylformamide solvent, stirring uniformly, then continuously adding silane modified epoxy resin into the mixture, wherein the mass ratio of the amino benzoxazine to the hexamethylene diisocyanate to the silane modified epoxy resin is 1.3:1:1.5, reacting for 15h at 120 ℃, distilling under reduced pressure, washing with deionized water and ethanol, and drying to obtain silicon-containing benzoxazine;
(6) 50 parts by weight of polyethylene, 2 parts by weight of maleic anhydride grafted polyethylene, 12 parts by weight of silicon-containing benzoxazine, 0.4 part by weight of antioxidant 626, 0.1 part by weight of polyether modified organosilicon defoamer and 0.3 part by weight of polyvinyl alcohol thickener are added into a stirrer to be stirred and mixed, and then the mixture is sheared by a high-speed shearing machine to obtain the polyethylene adhesive.
Example 3
(1) Adding 4-aminophenylboric acid and 4, 6-diamino-2-hydroxy-1, 3, 5-triazine into a solvent in N, N-dimethylformamide, wherein the mass ratio of the 4-aminophenylboric acid to the 4, 6-diamino-2-hydroxy-1, 3, 5-triazine is 1.35:1, introducing nitrogen for protection, uniformly stirring, reacting for 6 hours at 90 ℃, cooling to room temperature after finishing, filtering, washing and drying to obtain triazinylboric acid;
(2) Adding triazinyl boric acid, formaldehyde aqueous solution and p-nitrophenol into toluene solvent, wherein the mass ratio of the triazinyl boric acid to the formaldehyde aqueous solution to the p-nitrophenol is 1:1.45:1.3, fully dissolving, performing cyclization reaction, reacting for 12.5 hours at 85 ℃, performing reduced pressure distillation after the reaction is finished, washing with deionized water, and recrystallizing the crude product dichloromethane to obtain triazinyl benzoxazine;
(3) Adding triazinyl benzoxazine into ethanol solvent, then continuously adding ferric chloride and active carbon, wherein the mass ratio of the triazinyl benzoxazine to the ferric chloride to the active carbon to the hydrazine hydrate is 1:0.025:0.06:0.03, stirring and mixing, continuously adding hydrazine hydrate solution, stirring and reacting for 20 hours at 77.5 ℃, precipitating deionized water after the reaction, filtering and washing to obtain amino benzoxazine;
(4) Adding hydroxyl-terminated polydimethylsiloxane and epoxy resin into an N, N-dimethylformamide solvent, uniformly stirring, continuously adding a phosphoric acid catalyst into the solvent, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the epoxy resin to the phosphoric acid catalyst is 1:1.05:0.03, carrying out ring-opening addition, reacting for 8 hours at 97.5 ℃, removing the solvent by reduced pressure distillation after the completion, filtering and drying to obtain silane modified epoxy resin;
(5) Adding amino benzoxazine and hexamethylene diisocyanate into N, N-dimethylformamide solvent, stirring uniformly, then continuously adding silane modified epoxy resin into the mixture, wherein the mass ratio of the amino benzoxazine to the hexamethylene diisocyanate to the silane modified epoxy resin is 1.2:1:1.35, reacting for 10.5 hours at 105 ℃, distilling under reduced pressure, washing with deionized water and ethanol, and drying to obtain silicon-containing benzoxazine;
(6) 45 parts by weight of polyethylene, 1.5 parts by weight of maleic anhydride grafted polyethylene, 8.5 parts by weight of silicon-containing benzoxazine, 0.3 part by weight of antioxidant 626, 0.07 part by weight of polyether modified silicone defoamer and 0.25 part by weight of polyvinyl alcohol thickener are added into a stirrer to be stirred and mixed, and then sheared by a high-speed shearing machine to obtain the polyethylene adhesive.
Comparative example 1
45 Parts by weight of polyethylene, 1.5 parts by weight of maleic anhydride grafted polyethylene, 0.3 part by weight of antioxidant 626, 0.07 part by weight of polyether modified silicone defoamer and 0.25 part by weight of polyvinyl alcohol thickener are added into a stirrer to be stirred and mixed, and then sheared by a high-speed shearing machine to obtain the polyethylene adhesive.
The thermal performance of the polyethylene adhesive is tested by a thermogravimetric analyzer, the temperature is increased at 25 ℃/min under nitrogen atmosphere, and the maximum temperature is 800 ℃; the tensile properties were tested by a tensile tester at a tensile rate of 10mm/min with a sample of 70mm by 6mm.
Table 1: high temperature resistance testing and tensile testing.
Project | Tensile Strength (Mpa) | Elongation at break (%) | Mass loss 20% temperature (DEG C) | Mass loss 50% temperature (. Degree.C.) |
Example 1 | 41.2 | 142.1 | 461.3 | 501.2 |
Example 2 | 45.7 | 146.3 | 468.1 | 509.1 |
Example 3 | 43.5 | 144.7 | 463.6 | 503.4 |
Comparative example 1 | 28.6 | 112.5 | 441.2 | 481.3 |
As can be seen from Table 1, examples 1 to 3 of the present invention have better tensile strength and elongation at break than comparative example 1; comparative example 1, in which no silicon-containing benzoxazine was added, showed a lower mass loss of 20% and 50% compared to examples 1-3, indicating a better high temperature resistance.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. A polyethylene adhesive, characterized by comprising the following components by weight: 40-50 parts by weight of polyethylene, 1-2 parts by weight of maleic anhydride grafted polyethylene, 5-12 parts by weight of silicon-containing benzoxazine, 0.2-0.4 part by weight of antioxidant 626, 0.04-0.1 part by weight of polyether modified organosilicon defoamer and 0.2-0.3 part by weight of polyvinyl alcohol thickener;
the preparation method of the silicon-containing benzoxazine comprises the following steps:
(1) Adding 4-aminophenylboric acid and 4, 6-diamino-2-hydroxy-1, 3, 5-triazine into a solvent in N, N-dimethylformamide, introducing nitrogen for protection, uniformly stirring, reacting for 5-7 hours at 70-90 ℃, cooling to room temperature after finishing, filtering, washing and drying to obtain triazinylboric acid;
(2) Adding triazinyl boric acid, formaldehyde water solution and p-nitrophenol into toluene solvent, fully dissolving, performing cyclization reaction, reacting for 10-15h at 60-90 ℃, performing reduced pressure distillation after the reaction is finished, washing with deionized water, and recrystallizing the crude product dichloromethane to obtain triazinyl benzoxazine;
(3) Adding triazinyl benzoxazine into ethanol solvent, then continuously adding ferric chloride and active carbon, stirring and mixing, continuously adding hydrazine hydrate solution, stirring and reacting for 15-25h at 70-85 ℃, precipitating with deionized water after the reaction, filtering and washing to obtain amino benzoxazine;
(4) Adding amino benzoxazine and hexamethylene diisocyanate into N, N-dimethylformamide solvent, stirring uniformly, then continuously adding silane modified epoxy resin into the mixture, reacting for 6-15h at 90-120 ℃, decompressing and distilling the mixture after the reaction, washing the mixture with deionized water and ethanol, and drying the mixture to obtain the silicon-containing benzoxazine.
2. The polyethylene adhesive according to claim 1, wherein the mass ratio of 4-aminophenylboronic acid, 4, 6-diamino-2-hydroxy-1, 3, 5-triazine in (1) is 1.2-1.5:1.
3. The polyethylene adhesive according to claim 1, wherein the mass ratio of triazinyl boric acid, formaldehyde in aqueous solution and p-nitrophenol in (2) is 1:1.3-1.6:1.2-1.4.
4. The polyethylene adhesive according to claim 1, wherein the mass ratio of triazinyl benzoxazine, ferric chloride, activated carbon and hydrazine hydrate in (3) is 1:0.02-0.03:0.04-0.08:0.02-0.04.
5. The polyethylene adhesive according to claim 1, wherein the mass ratio of the amino benzoxazine, the hexamethylene diisocyanate and the silane-modified epoxy resin in (4) is 1.1-1.3:1:1.2-1.5.
6. The polyethylene adhesive according to claim 1, wherein the silane-modified epoxy resin in (4) is prepared by the following method:
S1, adding hydroxyl-terminated polydimethylsiloxane and epoxy resin into an N, N-dimethylformamide solvent, uniformly stirring, continuously adding a phosphoric acid catalyst into the mixture, carrying out ring-opening addition, reacting at 85-110 ℃ for 6-10h, removing the solvent by reduced pressure distillation after the reaction is finished, filtering and drying to obtain the silane modified epoxy resin.
7. The polyethylene adhesive according to claim 6, wherein the mass ratio of the hydroxyl terminated polydimethylsiloxane, the epoxy resin, and the phosphoric acid catalyst in S1 is 1:0.8-1.3:0.02-0.04.
8. A method of preparing a polyethylene adhesive according to any one of claims 1 to 7, wherein the method of preparing a polyethylene adhesive comprises: adding polyethylene, maleic anhydride grafted polyethylene, silicon-containing benzoxazine, an antioxidant 626, a polyether modified organosilicon defoamer and a polyvinyl alcohol thickener into a stirrer, stirring and mixing, and then shearing by a high-speed shearing machine to obtain the polyethylene adhesive.
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CN111849411A (en) * | 2020-08-05 | 2020-10-30 | 安徽国成顺风风力发电有限公司 | Preparation method of corrosion-resistant structural adhesive for wind power blade |
EP3831814A1 (en) * | 2019-12-03 | 2021-06-09 | Shandong University | A benzoxazine adhesive for polyethylene and the preparation and application method thereof |
CN112940628A (en) * | 2021-04-13 | 2021-06-11 | 北京中航技气动液压设备有限责任公司 | High-temperature-resistant UV (ultraviolet) viscosity-reducing adhesive capable of improving initial viscosity |
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EP3831814A1 (en) * | 2019-12-03 | 2021-06-09 | Shandong University | A benzoxazine adhesive for polyethylene and the preparation and application method thereof |
CN111849411A (en) * | 2020-08-05 | 2020-10-30 | 安徽国成顺风风力发电有限公司 | Preparation method of corrosion-resistant structural adhesive for wind power blade |
CN112940628A (en) * | 2021-04-13 | 2021-06-11 | 北京中航技气动液压设备有限责任公司 | High-temperature-resistant UV (ultraviolet) viscosity-reducing adhesive capable of improving initial viscosity |
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