CN118027813B - Environment-friendly water-based treating agent for EVA (ethylene-vinyl acetate copolymer) surface and preparation method thereof - Google Patents
Environment-friendly water-based treating agent for EVA (ethylene-vinyl acetate copolymer) surface and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims description 58
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims description 58
- 239000000839 emulsion Substances 0.000 claims description 99
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000001556 precipitation Methods 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 33
- 229920000058 polyacrylate Polymers 0.000 claims description 32
- 239000004698 Polyethylene Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- 229920002635 polyurethane Polymers 0.000 claims description 30
- 239000004814 polyurethane Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000004321 preservation Methods 0.000 claims description 25
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 24
- 239000013067 intermediate product Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 150000001718 carbodiimides Chemical class 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 4
- 230000000655 anti-hydrolysis Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses an environment-friendly water-based EVA treating agent and a preparation method thereof, and belongs to the technical field of high polymer materials.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an environment-friendly water-based EVA treating agent and a preparation method thereof.
Background
Ethylene-vinyl acetate copolymer (EVA) foaming material has the advantages of higher rebound resilience, light weight, good toughness, low price and the like, is widely used as sole material, however, the EVA material has low surface polarity, is difficult to directly bond with other materials, and generally needs to be coated with EVA treating agent to improve the polarity of the EVA surface, so that EVA is bonded with the materials through adhesive.
The traditional treating agent is an organic solvent type, usually contains a large amount of volatile organic solvents such as acetone, toluene and the like, and the volatile organic solvents can be released into the environment, so that the environment is polluted, resources are wasted, and the health of operators using the traditional organic solvent type treating agent is endangered. The development of aqueous EVA treatment agents is a new direction, however, the aqueous EVA treatment agents are still in a development stage, the solvent water is used for simply replacing an organic solvent to prepare the EVA treatment agents, the polarity of the treatment agents is reduced, the applicability of the treatment agents to EVA substrates is reduced, the treatment agents are not matched with adhesives, the bonding strength and the peeling strength of the treatment agents are reduced, and the like.
Disclosure of Invention
Aiming at least one of the problems, the invention provides an environment-friendly water-based EVA treating agent and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
The preparation method of the environment-friendly water-based EVA treating agent comprises the following steps:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1-2 hours, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reacting for 1-2 hours, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitate in a hot toluene solvent, adding an alkaline aqueous solution to adjust the pH value to be alkaline, continuously stirring for 1-10 minutes, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, carrying out heat preservation and stirring reaction for 1-3h, and after the temperature is reduced to 40-50 ℃, adding polyacrylate emulsion, carrying out heat preservation and stirring reaction for 1-2h to obtain the modified emulsion;
(2) Preparation of the treatment agent
And adding polyurethane emulsion into the modified emulsion, adding an organosilicon cross-linking agent and an auxiliary agent, fully stirring and mixing, and then adding deionized water to adjust the solid content to prepare the treating agent.
In some preferred embodiments, the polyethylene powder has a molecular weight of 7-8kg/mol and a polymer dispersibility index of 1.83.
In some preferred embodiments, the mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate, the N-hydroxyphthalimide is 1: (6.5-7): (0.2-0.3).
In some preferred embodiments, the mass ratio of the precursor product to the trifluoroacetic acid is 1: (12-14).
In some preferred embodiments, the mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer, the polyacrylate emulsion is 10: (4-5): (12-18).
In some preferred embodiments, the volume ratio of the polyurethane emulsion to the modified emulsion is (0.4-1): 1.
In some preferred embodiments, the preparation method of the polyacrylate emulsion comprises the steps of uniformly mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and an emulsifier, heating to 50-70 ℃ in a water bath, preserving heat, slowly dropwise adding persulfate initiator solution under stirring, continuing to preserving heat and stirring for 1-30min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion.
In some preferred embodiments, the polyurethane emulsion is an aliphatic aqueous polyurethane emulsion having a solids content of 50%, a viscosity of 30s±5S, and a ph of 8±1.
In some preferred embodiments, the auxiliary agent is an anti-hydrolysis agent and an adhesion promoter in equal mass ratios; the anti-hydrolysis agent is monomer carbodiimide or polycarbodiimide; the adhesion promoter is a silane coupling agent.
The invention also provides an environment-friendly water-based EVA treating agent, which is prepared by the preparation method.
The beneficial effects of the invention are as follows:
Aiming at the problem that the adhesive strength and the peeling strength of the aqueous EVA treating agent in the prior art are not high, the aqueous EVA treating agent with high adhesive strength and peeling strength for EVA is prepared by modifying the emulsion and then mixing the polyacrylate emulsion and the polyurethane emulsion on the basis of polyethylene.
Detailed Description
The invention will be further described with reference to the following examples.
Example 1
An environment-friendly water-based EVA treating agent, the preparation method comprises the following steps:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1h, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in the hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reaction for 1h, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, adding a sodium hydroxide solution for regulating the pH value to be alkaline, continuously stirring for 5min, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, carrying out heat preservation and stirring reaction for 2 hours, adding polyacrylate emulsion after the temperature is reduced to 40-50 ℃, and carrying out heat preservation and stirring reaction for 1 hour to obtain the modified emulsion;
(2) Preparation of the treatment agent
Adding polyurethane emulsion into the modified emulsion, adding an organosilicon crosslinking agent Silicone-9301 and an auxiliary agent, fully stirring and mixing, and adding deionized water to adjust the solid content to 32% to prepare the treating agent;
Wherein the molecular weight of the polyethylene powder is 7.8kg/mol, and the polymer dispersibility index is 1.83;
The mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate to the N-hydroxyphthalimide is 1:6.7:0.24;
The mass ratio of the precursor product to the trifluoroacetic acid is 1:12.8;
The mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 10:4.6:16;
the volume ratio of the polyurethane emulsion to the modified emulsion is 0.7:1, a step of;
The preparation method of the polyacrylate emulsion comprises the following steps of firstly, mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and sodium dodecyl benzene sulfonate according to a weight ratio of 10:6:5:0.3, uniformly mixing, heating to 60 ℃ in a water bath, preserving heat, slowly dropwise adding a persulfate initiator (0.1%) solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 10min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion with the solid content of 37%;
The polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30s, and the pH is 8.2;
The addition amount of the organosilicon cross-linking agent Silicone-9301 in the treating agent is 1%, and the addition amounts of the auxiliary agents are monomer type carbodiimide and an aminosilane coupling agent respectively are 0.8% and 0.1%.
Comparative example 1
An environment-friendly water-based EVA treating agent, the preparation method comprises the following steps:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1h, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in the hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reaction for 1h, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, adding a sodium hydroxide solution for regulating the pH value to be alkaline, continuously stirring for 5min, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, carrying out heat preservation and stirring reaction for 2 hours, adding polyacrylate emulsion after the temperature is reduced to 40-50 ℃, and carrying out heat preservation and stirring reaction for 1 hour to obtain the modified emulsion;
(2) Preparation of the treatment agent
Adding polyurethane emulsion into the modified emulsion, adding an auxiliary agent, fully stirring and mixing, and adding deionized water to adjust the solid content to 32% to prepare the treating agent;
Wherein the molecular weight of the polyethylene powder is 7.8kg/mol, and the polymer dispersibility index is 1.83;
The mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate to the N-hydroxyphthalimide is 1:6.7:0.24;
The mass ratio of the precursor product to the trifluoroacetic acid is 1:12.8;
The mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 10:4.6:16;
the volume ratio of the polyurethane emulsion to the modified emulsion is 0.7:1, a step of;
The preparation method of the polyacrylate emulsion comprises the following steps of firstly, mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and sodium dodecyl benzene sulfonate according to a weight ratio of 10:6:5:0.3, uniformly mixing, heating to 60 ℃ in a water bath, preserving heat, slowly dropwise adding a persulfate initiator (0.1%) solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 10min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion with the solid content of 37%;
The polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30s, and the pH is 8.2;
the auxiliary agent is monomer carbodiimide and amino silane coupling agent, and the addition amounts of the auxiliary agent and the amino silane coupling agent are respectively 0.8% and 0.1%.
Comparative example 2
An environment-friendly water-based EVA treating agent, the preparation method comprises the following steps:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1h, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in the hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reaction for 1h, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, adding a sodium hydroxide solution for regulating the pH value to be alkaline, continuously stirring for 5min, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, carrying out heat preservation and stirring reaction for 2 hours, adding polyacrylate emulsion after the temperature is reduced to 40-50 ℃, and carrying out heat preservation and stirring reaction for 1 hour to obtain the modified emulsion;
(2) Preparation of the treatment agent
Adding an organosilicon cross-linking agent Silicone-9301 and an auxiliary agent into the modified emulsion, fully stirring and mixing, and then adding deionized water to adjust the solid content to 32% to prepare the treating agent;
Wherein the molecular weight of the polyethylene powder is 7.8kg/mol, and the polymer dispersibility index is 1.83;
The mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate to the N-hydroxyphthalimide is 1:6.7:0.24;
The mass ratio of the precursor product to the trifluoroacetic acid is 1:12.8;
The mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 10:4.6:16;
The preparation method of the polyacrylate emulsion comprises the following steps of firstly, mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and sodium dodecyl benzene sulfonate according to a weight ratio of 10:6:5:0.3, uniformly mixing, heating to 60 ℃ in a water bath, preserving heat, slowly dropwise adding a persulfate initiator (0.1%) solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 10min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion with the solid content of 37%;
The addition amount of the organosilicon cross-linking agent Silicone-9301 in the treating agent is 1%, and the addition amounts of the auxiliary agents are monomer type carbodiimide and an aminosilane coupling agent respectively are 0.8% and 0.1%.
Comparative example 3
An environment-friendly water-based EVA treating agent, the preparation method comprises the following steps:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1h, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in the hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reaction for 1h, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, adding a sodium hydroxide solution for regulating the pH value to be alkaline, continuously stirring for 5min, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, and carrying out heat preservation and stirring reaction for 2 hours to obtain the modified emulsion;
(2) Preparation of the treatment agent
Adding polyurethane emulsion into the modified emulsion, adding an organosilicon crosslinking agent Silicone-9301 and an auxiliary agent, fully stirring and mixing, and adding deionized water to adjust the solid content to 32% to prepare the treating agent;
Wherein the molecular weight of the polyethylene powder is 7.8kg/mol, and the polymer dispersibility index is 1.83;
The mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate to the N-hydroxyphthalimide is 1:6.7:0.24;
The mass ratio of the precursor product to the trifluoroacetic acid is 1:12.8;
The mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer is 10:4.6;
the volume ratio of the polyurethane emulsion to the modified emulsion is 0.7:1, a step of;
The polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30s, and the pH is 8.2;
The addition amount of the organosilicon cross-linking agent Silicone-9301 in the treating agent is 1%, and the addition amounts of the auxiliary agents are monomer type carbodiimide and an aminosilane coupling agent respectively are 0.8% and 0.1%.
Comparative example 4
An aqueous EVA treating agent, the preparation method comprises the following steps:
adding ethylene-vinyl acetate copolymer into the mixed solution of polyethylene emulsion and polyacrylate emulsion, and carrying out heat preservation and stirring reaction for 1h to obtain mixed emulsion;
Adding polyurethane emulsion into the mixed emulsion, adding an organosilicon crosslinking agent Silicone-9301 and an auxiliary agent, fully stirring and mixing, and adding deionized water to adjust the solid content to 32% to prepare the treating agent;
wherein the mass ratio of the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 4.6:16;
the solid content of the polyethylene emulsion is 34%, and the mass ratio of the polyethylene emulsion to the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 29:4.6:16;
the volume ratio of the polyurethane emulsion to the mixed emulsion is 0.7:1, a step of;
The preparation method of the polyacrylate emulsion comprises the following steps of firstly, mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and sodium dodecyl benzene sulfonate according to a weight ratio of 10:6:5:0.3, uniformly mixing, heating to 60 ℃ in a water bath, preserving heat, slowly dropwise adding a persulfate initiator (0.1%) solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 10min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion with the solid content of 37%;
The polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30s, and the pH is 8.2;
The addition amount of the organosilicon cross-linking agent Silicone-9301 in the treating agent is 1%, and the addition amounts of the auxiliary agents are monomer type carbodiimide and an aminosilane coupling agent respectively are 0.8% and 0.1%.
Comparative example 5
An aqueous EVA treating agent, the preparation method comprises the following steps:
Adding ethylene-vinyl acetate copolymer into polyacrylate emulsion, and reacting for 1h under heat preservation and stirring to obtain mixed emulsion;
Adding polyurethane emulsion into the mixed emulsion, adding an organosilicon crosslinking agent Silicone-9301 and an auxiliary agent, fully stirring and mixing, and adding deionized water to adjust the solid content to 32% to prepare the treating agent;
wherein the mass ratio of the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 4.6:16;
the volume ratio of the polyurethane emulsion to the mixed emulsion is 0.7:1, a step of;
The preparation method of the polyacrylate emulsion comprises the following steps of firstly, mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and sodium dodecyl benzene sulfonate according to a weight ratio of 10:6:5:0.3, uniformly mixing, heating to 60 ℃ in a water bath, preserving heat, slowly dropwise adding a persulfate initiator (0.1%) solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 10min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion with the solid content of 37%;
The polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30s, and the pH is 8.2;
The addition amount of the organosilicon cross-linking agent Silicone-9301 in the treating agent is 1%, and the addition amounts of the auxiliary agents are monomer type carbodiimide and an aminosilane coupling agent respectively are 0.8% and 0.1%.
Experimental example
The use properties of the aqueous EVA treatments prepared in example 1 and comparative examples 1 to 5 were measured, and the initial adhesion strength and the final adhesion strength were measured according to the rules of GB/T19340-2014 adhesive for shoes and bags, and the measurement results are shown in Table 1.
Table 1 use properties of the aqueous EVA treatments described in example 1 and comparative examples 1-5
From the comparative test results of example 1 and comparative example 1, it is understood that the addition of the silicone crosslinking agent can effectively crosslink each polymer to obtain excellent adhesive strength; from the comparison of the example 1, the comparative example 2 and the comparative example 3, the polyurethane emulsion and the polyacrylate emulsion have key effects on the adhesive performance of the treating agent, wherein the polyacrylate emulsion also has a certain stabilizing effect on the treating agent; as is clear from the comparison of example 1, comparative example 4 and comparative example 5, the adhesive property and peel strength of the treating agent which is not modified or added with the modified polyethylene emulsion are inferior as compared with the modified polyethylene emulsion, and it is also demonstrated that the modified emulsion of the invention can be well blended with EVA, and can realize good transition with EVA and adhesive resin, thereby improving the affinity of the modified emulsion as EVA treating agent with EVA.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the environment-friendly water-based treating agent for the EVA surface is characterized by comprising the following steps of:
(1) Modified emulsion preparation
S1, weighing polyethylene powder, dispersing and dissolving the polyethylene powder in a1, 2-tetrachloroethane solvent, adding di-tert-butyl azodicarbonate and N-hydroxyphthalimide, fully stirring and mixing, heating to 100-110 ℃ and carrying out heat preservation and stirring reaction for 1-2 hours, adding a reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitation in a hot toluene solvent, carrying out secondary precipitation in the methanol solvent, separating the precipitation, and drying to obtain a precursor product;
S2, weighing the precursor product, dissolving the precursor product in a1, 2-tetrachloroethane solvent, adding trifluoroacetic acid, fully stirring and mixing, heating to 100-110 ℃, keeping the temperature and stirring for reacting for 1-2 hours, adding the reaction system into a methanol solvent for precipitation after the reaction is finished, separating the precipitation, dissolving the precipitate in a hot toluene solvent, adding an alkaline aqueous solution to adjust the pH value to be alkaline, continuously stirring for 1-10 minutes, precipitating in the methanol solvent again, separating the precipitation, and drying to obtain an intermediate product;
S3, dispersing and dissolving the intermediate product in an ethyl acetate solvent, stirring and heating until the intermediate product is completely dissolved, adding an ethylene-vinyl acetate copolymer and an initiator, carrying out heat preservation and stirring reaction for 1-3h, and after the temperature is reduced to 40-50 ℃, adding polyacrylate emulsion, carrying out heat preservation and stirring reaction for 1-2h to obtain the modified emulsion;
The mass ratio of the intermediate product to the ethylene-vinyl acetate copolymer to the polyacrylate emulsion is 10: (4-5): (12-18);
The preparation method of the polyacrylate emulsion comprises the steps of uniformly mixing methyl methacrylate, phenyl methacrylate, lauryl methacrylate and an emulsifier, heating to 50-70 ℃ in a water bath, preserving heat, slowly dropwise adding persulfate initiator solution under the stirring condition, continuing to carry out heat preservation and stirring reaction for 1-30min after the dropwise adding is completed, and homogenizing to obtain the polyacrylate emulsion;
(2) Preparation of the treatment agent
And adding polyurethane emulsion into the modified emulsion, adding an organosilicon cross-linking agent and an auxiliary agent, fully stirring and mixing, and then adding deionized water to adjust the solid content to prepare the environment-friendly water-based treating agent.
2. The method for preparing an environmentally friendly aqueous treating agent for EVA surface according to claim 1, wherein the molecular weight of the polyethylene powder is 7-8kg/mol, and the polymer dispersibility index is 1.83.
3. The preparation method of the environment-friendly water-based treating agent for EVA surfaces, which is characterized in that the mass ratio of the polyethylene powder to the di-tert-butyl azodicarbonate to the N-hydroxyphthalimide is 1: (6.5-7): (0.2-0.3).
4. The method for preparing the environment-friendly water-based treating agent for EVA surfaces according to claim 1, wherein the mass ratio of the precursor product to the trifluoroacetic acid is 1: (12-14).
5. The method for preparing the environment-friendly water-based treating agent for EVA surfaces according to claim 1, wherein the volume ratio of the polyurethane emulsion to the modified emulsion is (0.4-1): 1.
6. The method for preparing the environment-friendly water-based treating agent for EVA surfaces, which is characterized in that the polyurethane emulsion is aliphatic water-based polyurethane emulsion, the solid content is 50%, the viscosity is 30 S+/-5S, and the pH is 8+/-1.
7. The method for preparing the environment-friendly water-based treating agent for EVA surfaces according to claim 1, wherein the auxiliary agent is an anti-hydrolysis agent and an adhesion promoter in equal mass ratio; the anti-hydrolysis agent is monomer carbodiimide or polycarbodiimide; the adhesion promoter is a silane coupling agent.
8. An environmentally friendly aqueous treating agent for EVA surfaces, which is characterized by being prepared by the preparation method according to any one of claims 1 to 7.
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| CN103756233A (en) * | 2014-01-09 | 2014-04-30 | 杭州电子科技大学 | Method for preparing water-based EVA (ethylene vinyl-acetate copolymer) surface treating agent |
| CN106995508A (en) * | 2016-11-25 | 2017-08-01 | 中山大学 | A kind of preparation method of hydrazides graft-modified polyolefin |
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| CN103756233A (en) * | 2014-01-09 | 2014-04-30 | 杭州电子科技大学 | Method for preparing water-based EVA (ethylene vinyl-acetate copolymer) surface treating agent |
| CN106995508A (en) * | 2016-11-25 | 2017-08-01 | 中山大学 | A kind of preparation method of hydrazides graft-modified polyolefin |
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