CN115820172B - PP film EVA hot melt adhesive capable of being peeled naturally and preparation method thereof - Google Patents
PP film EVA hot melt adhesive capable of being peeled naturally and preparation method thereof Download PDFInfo
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000155 melt Substances 0.000 claims abstract description 22
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 17
- 239000001993 wax Substances 0.000 claims abstract description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 9
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 63
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
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- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 50
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012945 sealing adhesive Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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Classifications
-
- 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
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally, which comprises the following steps: uniformly mixing EVA, maleic anhydride and activated carbon nanotubes, adding an initiator into the mixture, stirring, adding EVA, linear low-density polyethylene, waxes and an antioxidant, stirring, and heating to melt to obtain a melt; adding the pretreated nano particles and the aqueous polyurethane resin into the melting material, stirring, adjusting the temperature of the system to 120-140 ℃, adding the tackifier, stirring, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped. The invention has larger difference with the PP film structure, good natural stripping effect, and can ensure the connection and mechanical hooking of the base layer molecules of the bonded material, thereby ensuring good bonding effect and expanding the application range of the hot melt adhesive.
Description
Technical Field
The invention relates to the technical field of EVA hot melt adhesives, in particular to a PP film EVA hot melt adhesive capable of being peeled naturally and a preparation method thereof.
Background
The hot melt adhesive is a solvent-free solid plastic adhesive which is prepared by taking thermoplastic resin or thermoplastic elastomer as main components, adding tackifying resin, waxes, plasticizers, fillers and the like, and carrying out melt mixing, wherein the physical state of the adhesive is changed along with the change of temperature within a certain temperature range, and the chemical characteristics of the adhesive are unchanged.
In the adhesive market in recent years, annual output of the world hot melt adhesive is always in an increasing trend, the increasing speed of the world hot melt adhesive is highest in various adhesives, the varieties are more and more diversified, and the application is more and more extensive. Among the most important and representative types of hot melt adhesives are those based on ethylene-vinyl acetate random copolymers (EVA), abbreviated as EVA hot melt adhesives. The EVA hot melt adhesive has the advantages of quick solidification, no public hazard, strong adhesive force, certain flexibility and hardness of the adhesive layer, certain toughness, simple preparation method and maximum application and dosage in the hot melt adhesive.
The PP film is a widely applied material, has the advantages of high strength, good toughness, good heat resistance, good wear resistance, good texture and the like, and is coated with EVA hot melt adhesive to obtain the heat sealing adhesive tape. When the EVA hot melt adhesive is adopted to bond the PP film, residual adhesive is easily left on the surface of the PP film when the PP film is separated, and the heat sealing adhesive tape is applied to the metal substrate.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a PP film EVA hot melt adhesive capable of being peeled naturally and a preparation method thereof.
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 30-60 parts of EVA with 20-24% of vinyl acetate content, 1-5 parts of maleic anhydride and 1-3 parts of activated carbon nanotubes according to parts by weight, adding 0.1-1 part of initiator into the mixture, continuously stirring the mixture for 1-2 hours at the stirring temperature of 80-120 ℃, continuously adding 5-15 parts of EVA with 26-28% of vinyl acetate content, 1-10 parts of linear low-density polyethylene, 1-3 parts of waxes and 1-3 parts of antioxidant into the mixture, stirring the mixture and heating the mixture to melt to obtain a melt;
s2, adding 2-6 parts of ferric chloride and 1-3 parts of ferrous sulfate into 30-60 parts of polyvinyl alcohol solution with the concentration of 1-1.5wt% and uniformly stirring, dropwise adding into 100-200 parts of sodium hydroxide solution with the concentration of 0.1-0.5mol/L in a stirring state, stirring at the stirring speed of 500-1000r/min, continuously stirring at the temperature of 70-80 ℃ for 1-2h after the dropwise adding, dropwise adding 1-2 parts of ethyl orthosilicate, stirring at the speed of 400-600r/min under the protection of nitrogen for 1-2h, heating to 100-120 ℃, adding 1-5 parts of stearic acid, continuously stirring for 10-20min, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nano particles;
s3, adding the pretreated nano particles and 1-2 parts of the aqueous polyurethane resin into the melting material, stirring at the speed of 1000-2000r/min for 10-20min, adjusting the temperature of the system to 120-140 ℃, adding 1-5 parts of the tackifier, stirring for 5-15min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Preferably, in S1, EVA having a vinyl acetate content of 20-24% and a melt index of 220-260g/10min; EVA with 26-28% vinyl acetate content and 110-130g/10min melt index;
preferably, in S1, the initiator is dicumyl peroxide.
Preferably, in S1, the antioxidant is at least one of antioxidant 1010 and antioxidant 1098.
Preferably, in S1, the wax is at least one of paraffin wax, microcrystalline wax, PE wax, PP wax, and synthetic wax.
Preferably, the activated carbon nanotubes are prepared by the steps of: adding 1-5 parts by weight of carbon nano tube into 30-50 parts by weight of concentrated sulfuric acid with the concentration of 90-95wt%, refluxing and heating for 1-3 hours at the temperature of 160-180 ℃, filtering, washing, and vacuum drying at the temperature of 80-100 ℃ to obtain the activated carbon nano tube.
Preferably, in S3, the tackifier is at least one of rosin resin, petroleum resin, terpene resin, phenolic resin, and epoxy resin.
Preferably, in S3, the aqueous polyurethane resin has a viscosity (25 ℃ C.) of 300 mPa.S or less, an emulsion particle diameter of 200nm or less, and a solid content of 31.+ -. 0.5%.
The PP film EVA hot melt adhesive for the natural peeling is prepared according to the preparation method of the PP film EVA hot melt adhesive for the natural peeling.
The technical effects of the invention are as follows:
under the action of an initiator, the invention firstly grafts maleic anhydride and activated carbon nano-tubes on EVA molecular chains with 20-24% of vinyl acetate content, and simultaneously cooperates with pretreatment nano-particles, thereby effectively reducing the fluidity of the hot melt adhesive colloid, leading to the increase of melting temperature, further leading to the increase of softening point, improving the thermal stability of the hot melt adhesive, leading to the large difference between the hot melt adhesive and the PP film structure and good natural stripping effect.
In the invention, in S2, inorganic hydrophobic ferroferric oxide nano particles are synthesized by a coprecipitation method by utilizing an alkaline environment, and then hydrophilic silicon dioxide particles are deposited on the surfaces of the inorganic hydrophobic ferroferric oxide nano particles. According to the invention, through the hydrophilic silicon dioxide particles crosslinked in a stable network on the surface of the nano ferroferric oxide particles, the problem that the nano particles are easy to agglomerate can be solved, meanwhile, the nano particles have hydrophilic and hydrophobic characteristics, and the surface polarity is high, so that the nano particles can be better dispersed in EVA resin, and used between a PP film and a metal material, the adhesive layer is taken as a whole, the natural stripping effect on the PP film is good, the surface of the metal material is provided with polarity, the bonding strength between the surfaces is high, the stripping strength of the hot melt adhesive is greatly improved, meanwhile, the stearic acid long chain in the pretreated nano particles is matched to penetrate through the EVA structure, the stress dispersing effect can be effectively achieved, and the nano particles matched with the surface polarity is taken as flexible chain connecting points, so that the stress is rapidly dispersed, the bearing capacity is further improved, and on the other hand, the pretreated nano particles move towards the metal substrate in the bonding process due to the effect of the polarity similarity principle, along with the extension of the bonding time, the mutual permeability is good, and the falling phenomenon is not easy to occur.
The invention not only greatly improves the adhesive property of the hot melt adhesive, but also can improve the mechanical strength and dimensional stability of the colloid by preprocessing the nano particles, promote the permeation and diffusion of the colloid, and ensure the connection and mechanical hooking of the base layer molecules of the adhered material, thereby ensuring good adhesive effect and expanding the application range of the hot melt adhesive.
Drawings
FIG. 1 is a graph showing the particle size distribution of nanoparticles prepared in example 5 and comparative example 1, in which stearic acid is not grafted.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 30kg of EVA with 20% of vinyl acetate content, 1kg of maleic anhydride and 1kg of activated carbon nano tube, adding 0.1kg of dicumyl peroxide into the mixture, continuously stirring for 1h at the stirring temperature of 80 ℃, continuously adding 5kg of EVA with 26% of vinyl acetate content, 1kg of linear low-density polyethylene, 1kg of PE wax and 1kg of antioxidant 1010 into the mixture, stirring and heating to melt to obtain a melt;
the activated carbon nanotubes are prepared by the following steps: adding 1kg of carbon nano tube into 30kg of concentrated sulfuric acid with the concentration of 90wt%, refluxing and heating for 1h at 160 ℃, filtering, washing, and vacuum drying at 80 ℃ to obtain the activated carbon nano tube.
S2, adding 2kg of ferric chloride and 1kg of ferrous sulfate into 30kg of polyvinyl alcohol solution with the concentration of 1wt% and uniformly stirring, dropwise adding 100kg of sodium hydroxide solution with the concentration of 0.1mol/L in a stirring state, stirring at the speed of 500r/min, continuously stirring at the temperature of 70 ℃ for 1h after the dropwise adding is finished, dropwise adding 1kg of ethyl orthosilicate, stirring at the speed of 400r/min under the protection of nitrogen for 1h, heating to 100 ℃, adding 1kg of stearic acid, continuously stirring for 10min, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nanoparticles;
s3, adding pretreated nano particles and 1.5kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is less than or equal to 300 mPa.S, the particle size of the emulsion is less than or equal to 200nm, the solid content is 31+/-0.5%, then stirring at the speed of 1000r/min for 10min, regulating the temperature of the system to 120 ℃, adding 1kg of rosin resin, stirring for 5min, and cooling to obtain the PP film EVA hot melt adhesive capable of being stripped naturally.
Example 2
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 60kg of EVA with the vinyl acetate content of 24%, 5kg of maleic anhydride and 3kg of activated carbon nanotubes, adding 1kg of dicumyl peroxide into the mixture, continuously stirring for h at the stirring temperature of 120 ℃, continuously adding 15kg of EVA with the vinyl acetate content of 28%, 10kg of linear low-density polyethylene, 3kg of paraffin and 3kg of antioxidant 1010 into the mixture, stirring and heating to melt to obtain a melt;
the activated carbon nanotubes are prepared by the following steps: adding 5kg of carbon nano tube into 50kg of concentrated sulfuric acid with the concentration of 95wt%, refluxing and heating for 3 hours at the temperature of 180 ℃, filtering, washing, and vacuum drying at the temperature of 100 ℃ to obtain the activated carbon nano tube.
S2, adding 6kg of ferric chloride and 3kg of ferrous sulfate into 60kg of polyvinyl alcohol solution with the concentration of 1.5wt% and uniformly stirring, dropwise adding into 200kg of sodium hydroxide solution with the concentration of 0.5mol/L in a stirring state, stirring at the stirring speed of 1000r/min, continuously stirring at the temperature of 80 ℃ for 2 hours after the dropwise adding, dropwise adding 2kg of ethyl orthosilicate, stirring at the speed of 600r/min under the protection of nitrogen for 2 hours, heating to 120 ℃, adding 5kg of stearic acid, continuously stirring for 20 minutes, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nano particles;
s3, adding pretreated nano particles and 2kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is less than or equal to 300 mPa.S, the particle size of the emulsion is less than or equal to 200nm, the solid content is 31+/-0.5%, stirring for 20min at a speed of 2000r/min, adjusting the temperature of the system to 140 ℃, adding 5kg of rosin resin, stirring for 15min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Example 3
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 40kg of EVA with the vinyl acetate content of 21.5%, 1.5kg of maleic anhydride and 2kg of activated carbon nanotubes, adding 0.5kg of dicumyl peroxide into the mixture, continuously stirring the mixture for 1.5 hours at 92 ℃, continuously adding 8kg of EVA with the vinyl acetate content of 26.5%, 4kg of linear low-density polyethylene, 1kg of paraffin and 1.5kg of antioxidant 1010 into the mixture, stirring the mixture, and heating the mixture to melt to obtain a melt;
the activated carbon nanotubes are prepared by the following steps: adding 2kg of carbon nano-tubes into 35kg of concentrated sulfuric acid with 92wt% concentration, heating at 135 ℃ under reflux for 1.5h, filtering, washing, and drying at 82 ℃ under vacuum to obtain activated carbon nano-tubes.
S2, adding 3kg of ferric chloride and 1.5kg of ferrous sulfate into 35kg of polyvinyl alcohol solution with the concentration of 1.2wt% and uniformly stirring, dropwise adding 120kg of sodium hydroxide solution with the concentration of 0.15mol/L in a stirring state, continuously stirring at the temperature of 71 ℃ for 1.2 hours after the dropwise adding is finished, dropwise adding 1.5kg of ethyl orthosilicate, stirring at the speed of 450r/min for 1.2 hours under the protection of nitrogen, heating to 105 ℃, adding 2kg of stearic acid, continuously stirring for 12 minutes, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nanoparticles;
s3, adding pretreated nano particles and 1.2kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is less than or equal to 300 mPa.S, the particle size of the emulsion is less than or equal to 200nm, the solid content is 31+/-0.5%, stirring at the speed of 1200r/min for 12min, adjusting the temperature of the system to 125 ℃, adding 2kg of rosin resin, stirring for 7min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Example 4
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 55kg of EVA with the vinyl acetate content of 23.6%, 4kg of maleic anhydride and 2.4kg of activated carbon nanotubes, adding 0.9kg of dicumyl peroxide into the mixture, continuously stirring for 1.5 hours at the stirring temperature of 118 ℃, continuously adding 12kg of EVA with the vinyl acetate content of 27%, 5kg of linear low-density polyethylene, 2.8kg of PP wax and 2.5kg of antioxidant 1010 into the mixture, stirring and heating the mixture to melt to obtain a melt;
the activated carbon nanotubes are prepared by the following steps: adding 4kg of carbon nano-tubes into 42kg of concentrated sulfuric acid with the concentration of 94.5wt%, refluxing and heating for 2 hours at the temperature of 172 ℃, filtering, washing, and vacuum drying at the temperature of 92 ℃ to obtain activated carbon nano-tubes.
S2, adding 5kg of ferric chloride and 2.6kg of ferrous sulfate into 55kg of polyvinyl alcohol solution with the concentration of 1.4wt% and uniformly stirring, dripping into 180kg of sodium hydroxide solution with the concentration of 0.42mol/L in a stirring state, stirring at the stirring speed of 900r/min, continuously stirring at the temperature of 77 ℃ for 1.8 hours after dripping, dripping 1.56kg of ethyl orthosilicate into the mixture, stirring at the speed of 520r/min for 1.8 hours under the protection of nitrogen, heating to 112 ℃, adding 4kg of stearic acid, continuously stirring for 15 minutes, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nano particles;
s3, adding pretreated nano particles and 1.5kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is less than or equal to 300 mPa.S, the particle size of the emulsion is less than or equal to 200nm, the solid content is 31+/-0.5%, stirring for 18min at a speed of 1000-2000r/min, adjusting the temperature of the system to 135 ℃, adding 4kg of rosin resin, stirring for 12min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Example 5
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 50kg of EVA with 23% of vinyl acetate content, 3kg of maleic anhydride and 2kg of activated carbon nanotubes, adding 0.5kg of dicumyl peroxide into the mixture, continuously stirring for 1.5 hours at the stirring temperature of 105 ℃, continuously adding 12kg of EVA with 27% of vinyl acetate content, 5kg of linear low-density polyethylene, 2kg of PP wax and 2kg of antioxidant 1010 into the mixture, stirring and heating to melt to obtain a melt;
wherein, EVA with 23 percent of vinyl acetate content has a melt index of 240g/10min; EVA with 27% vinyl acetate content and a melt index of 120g/10min;
the activated carbon nanotubes are prepared by the following steps: adding 3kg of carbon nano-tubes into 40kg of concentrated sulfuric acid with 92wt% concentration, refluxing and heating for 2 hours at 170 ℃, filtering, washing, and vacuum drying at 90 ℃ to obtain activated carbon nano-tubes.
S2, adding 4kg of ferric chloride and 2kg of ferrous sulfate into 50kg of 1.2wt% polyvinyl alcohol solution, uniformly stirring, dropwise adding 150kg of 0.2mol/L sodium hydroxide solution in a stirring state, stirring at 800r/min, continuously stirring at 75 ℃ for 1.5h after the dropwise adding is finished, dropwise adding 1.5kg of ethyl orthosilicate, stirring at 500r/min for 1.5h under the protection of nitrogen, heating to 115 ℃, adding 2kg of stearic acid, continuously stirring for 15min, performing magnetic separation, washing with ethanol, and vacuum drying to obtain pretreated nanoparticles;
s3, adding pretreated nano particles and 1.5kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is 270 mPa.S, the particle size of emulsion is 165nm, the solid content is 31.2%, stirring at the speed of 1500r/min for 15min, regulating the temperature of the system to 132 ℃, adding 2kg of rosin resin, stirring for 10min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Comparative example 1
A preparation method of a PP film EVA hot melt adhesive capable of being peeled naturally comprises the following steps:
s1, uniformly mixing 50kg of EVA with 23% of vinyl acetate content, 3kg of maleic anhydride and 2kg of activated carbon nanotubes, adding 0.5kg of dicumyl peroxide into the mixture, continuously stirring for 1.5 hours at the stirring temperature of 105 ℃, continuously adding 12kg of EVA with 27% of vinyl acetate content, 5kg of linear low-density polyethylene, 2kg of PP wax and 2kg of antioxidant 1010 into the mixture, stirring and heating to melt to obtain a melt;
wherein, EVA with 23 percent of vinyl acetate content has a melt index of 240g/10min; EVA with 27% vinyl acetate content and a melt index of 120g/10min;
the activated carbon nanotubes are prepared by the following steps: adding 3kg of carbon nano-tubes into 40kg of concentrated sulfuric acid with 92wt% concentration, refluxing and heating for 2 hours at 170 ℃, filtering, washing, and vacuum drying at 90 ℃ to obtain activated carbon nano-tubes.
S2, adding 4kg of ferric chloride and 2kg of ferrous sulfate into 50kg of polyvinyl alcohol solution with the concentration of 1.2wt% and uniformly stirring, dropwise adding the mixture into 150kg of sodium hydroxide solution with the concentration of 0.2mol/L in a stirring state, stirring at the speed of 800r/min, continuously stirring at the temperature of 75 ℃ for 1.5 hours after the dropwise adding is finished, magnetically separating, washing with ethanol, and vacuum drying to obtain pretreated nano particles;
s3, adding pretreated nano particles and 1.5kg of aqueous polyurethane resin into the melt, wherein the viscosity (25 ℃) of the aqueous polyurethane resin is 270 mPa.S, the particle size of emulsion is 165nm, the solid content is 31.2%, stirring at the speed of 1500r/min for 15min, regulating the temperature of the system to 132 ℃, adding 2kg of rosin resin, stirring for 10min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally stripped.
Comparative example 2
A commercial Korean 28-150 hot melt adhesive was purchased from Dongguan, hongyu plastics Co., ltd.
1. Nanoparticle size distribution
The nanoparticles obtained in example 5 and comparative example 1, to which stearic acid was not grafted, were ground with an agate mortar, then placed in a beaker and subjected to ultrasonic dispersion with absolute ethanol, and tested with a laser particle sizer, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the obtained nanoparticle has a particle size distribution of about 0.8 μm before depositing silica, and a particle size distribution of about 1.2 μm after modifying the silica due to an increase in the surface area of the particles after the deposition treatment.
2. Mechanical properties
The hot melt adhesives obtained in example 5 and comparative examples 1 to 2 were subjected to mechanical properties wherein 180℃peel strength was measured according to GB/T2792-2014 test method for adhesive tape peel strength, and the test results are shown in the following table:
| test item | Example 5 | Comparative example 1 | Comparative example 2 |
| 180 ℃ peel strength, mpa | 4.8 | 2.1 | 2.8 |
| Elongation at break% | 479 | 421 | 415 |
| Melt viscosity, pa.S | 5500 | 4100 | 4500 |
| Tensile strength, MPa | 14.3 | 13.2 | 8 |
3. Residual condition of adhesive film
The hot melt adhesives obtained in examples 1-5 and comparative examples 1-2 were respectively melted and coated on a PP film in the same amount of sizing to obtain a heat-seal adhesive tape, the heat-seal adhesive tape was then stuck on a metal substrate, the heat-seal adhesive tape was left at room temperature for 30 days, the adhesive tape was torn off, the residual condition of the adhesive film was observed, and the test results were shown in the following table:
| test item | PP film | Wood material | ABS rubber |
| Example 1 | No residue | No residue | No residue |
| Example 2 | No residue | No residue | No residue |
| Example 3 | No residue | No residue | No residue |
| Example 4 | No residue | No residue | No residue |
| Example 5 | No residue | No residue | No residue |
| Comparative example 1 | A great deal of residue | A small amount of residue | A small amount of residue |
| Comparative example 2 | A small amount of residue | A small amount of residue | A small amount of residue |
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the PP film EVA hot melt adhesive capable of being peeled naturally is characterized by comprising the following steps of:
s1, uniformly mixing 30-60 parts of EVA with 20-24% of vinyl acetate content, 1-5 parts of maleic anhydride and 1-3 parts of activated carbon nanotubes according to parts by weight, adding 0.1-1 part of initiator into the mixture, continuously stirring the mixture for 1-2 hours at the stirring temperature of 80-120 ℃, continuously adding 5-15 parts of EVA with 26-28% of vinyl acetate content, 1-10 parts of linear low-density polyethylene, 1-3 parts of waxes and 1-3 parts of antioxidant into the mixture, stirring the mixture and heating the mixture to melt to obtain a melt;
s2, adding 2-6 parts of ferric chloride and 1-3 parts of ferrous sulfate into 30-60 parts of polyvinyl alcohol solution with the mass fraction of 1-1.5%, uniformly stirring, dripping into 100-200 parts of sodium hydroxide solution with the concentration of 0.1-0.5mol/L in a stirring state, continuously stirring for 1-2 hours at 70-80 ℃ after dripping, dripping 1-2 parts of ethyl orthosilicate into the solution, stirring for 1-2 hours under the protection of nitrogen, heating to 100-120 ℃, adding 1-5 parts of stearic acid, continuously stirring for 10-20 minutes, performing magnetic separation, washing with ethanol, and vacuum drying to obtain pretreated nanoparticles;
s3, adding the pretreated nano particles and 1-2 parts of aqueous polyurethane resin into the melting material, stirring for 10-20min, adjusting the temperature of the system to 120-140 ℃, adding 1-5 parts of tackifier, stirring for 5-15min, and cooling to obtain the PP film EVA hot melt adhesive capable of being naturally peeled.
2. The method for preparing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S1, the melt index of EVA having 20-24% of vinyl acetate is 220-260g/10min; EVA with 26-28% vinyl acetate content has a melt index of 110-130g/10min.
3. The method for preparing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S1, the initiator is dicumyl peroxide.
4. The method for preparing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S1, the antioxidant is at least one of antioxidant 1010 and antioxidant 1098.
5. The method for producing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S1, the wax is at least one of paraffin wax, microcrystalline wax, PE wax, PP wax, and synthetic wax.
6. The method for preparing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S3, the tackifier is at least one of rosin resin, petroleum resin, terpene resin, phenolic resin, epoxy resin.
7. The method for preparing a naturally peelable PP film EVA hot melt adhesive according to claim 1, wherein in S3, the viscosity of the aqueous polyurethane resin is less than or equal to 300 mPa.S at 25 ℃, the particle size of the emulsion is less than or equal to 200nm, and the solid content is 31+ -0.5%.
8. A PP film EVA hot melt adhesive for natural peeling, characterized in that it is produced by the method for producing PP film EVA hot melt adhesive for natural peeling according to any one of claims 1 to 7.
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| JP2007119769A (en) * | 2005-09-30 | 2007-05-17 | Du Pont Mitsui Fluorochem Co Ltd | Resin composite composition and method for production of the same |
| CN101538450A (en) * | 2009-04-29 | 2009-09-23 | 同济大学 | High speed cigarette mouth building hot melt adhesive and preparation method thereof |
| CN110713731A (en) * | 2019-10-30 | 2020-01-21 | 刘丹丹 | Method for preparing oil-absorbing and wave-absorbing composite material by using wood fiber powder |
| CN115058207A (en) * | 2022-07-01 | 2022-09-16 | 杭州志和新材料有限公司 | Wide adhesive film for thermally laminating seamless wall cloth and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119769A (en) * | 2005-09-30 | 2007-05-17 | Du Pont Mitsui Fluorochem Co Ltd | Resin composite composition and method for production of the same |
| CN101538450A (en) * | 2009-04-29 | 2009-09-23 | 同济大学 | High speed cigarette mouth building hot melt adhesive and preparation method thereof |
| CN110713731A (en) * | 2019-10-30 | 2020-01-21 | 刘丹丹 | Method for preparing oil-absorbing and wave-absorbing composite material by using wood fiber powder |
| CN115058207A (en) * | 2022-07-01 | 2022-09-16 | 杭州志和新材料有限公司 | Wide adhesive film for thermally laminating seamless wall cloth and preparation method thereof |
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