CN114149735A - Adhesive primer composition and preparation method thereof - Google Patents
Adhesive primer composition and preparation method thereof Download PDFInfo
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- CN114149735A CN114149735A CN202210116985.9A CN202210116985A CN114149735A CN 114149735 A CN114149735 A CN 114149735A CN 202210116985 A CN202210116985 A CN 202210116985A CN 114149735 A CN114149735 A CN 114149735A
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- component
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- soybean oil
- polyhydroxy compound
- oil polyol
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- 239000000853 adhesive Substances 0.000 title claims abstract description 29
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 65
- 150000003077 polyols Chemical class 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 44
- 239000003549 soybean oil Substances 0.000 claims abstract description 44
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 238000010931 ester hydrolysis Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- 239000000047 product Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 41
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 37
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 30
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004743 Polypropylene Substances 0.000 claims description 20
- -1 polypropylene Polymers 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 18
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
- 239000002987 primer (paints) Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 16
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 14
- 238000001746 injection moulding Methods 0.000 description 12
- 239000012778 molding material Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000002860 competitive effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an adhesive primer composition and a preparation method thereof, belonging to the field of adhesives, wherein the adhesive primer composition comprises a component A and a component B, wherein the component A comprises a polyhydroxy compound containing a polyolefin structure and modified graphite oxide, the hydroxyl content in the polyhydroxy compound is more than 3%, and the hydroxyl in the polyhydroxy compound is obtained by ester hydrolysis; the component B is a soybean oil polyol modified product, and the soybean oil polyol modified product is obtained by reacting soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, and then continuously reacting the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A. Through the processing scheme of this application, improved the adhesion between TPE and the glass and had the shading effect.
Description
Technical Field
The invention relates to the field of adhesives, and particularly relates to an adhesive primer composition and a preparation method thereof.
Background
To improve adhesion on synthetic rubbers, in particular thermoplastic elastomers, and also on low-surface-energy substrates, a large number of adhesive primer compositions have been developed. Where low surface energy is defined as the difference between the surface energies of two bonded surfaces, such as TPE (thermoplastic elastomer) and glass, being greater than 20. These substrates are particularly important because they are present in window panel bonding in vehicles, such as automobiles, and such bonding is a very important bonding application.
At present, three components (a curing agent, a main body resin, a catalyst and a filler) are adopted for common primer coating, but the primer coating has poor adhesion, is easy to generate phenomena such as degumming and the like, has only transparent or white color, and cannot realize the light blocking effect on glass.
Disclosure of Invention
Accordingly, in order to overcome the above-mentioned disadvantages of the prior art, the present invention provides an adhesive primer composition having good adhesion and a light-shielding effect, and a method for preparing the same.
In order to achieve the above object, the present invention provides an adhesive primer composition for bonding a thermoplastic elastomer and a low surface energy substrate, comprising a component a and a component B, wherein the component a comprises a polyol having a polyolefin structure and a modified graphite oxide, the polyol has a hydroxyl group content of more than 3%, and the polyol has a hydroxyl group obtained by ester hydrolysis; the component B is a soybean oil polyol modified product, and the soybean oil polyol modified product is obtained by reacting soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, and then continuously reacting the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A.
In one embodiment, the modified graphite oxide is obtained by modifying graphene oxide with a modifying group.
In one embodiment, the polyhydroxy compound is a low-polarity polymer containing hydroxyl groups, which is obtained by performing a grafting reaction on chlorinated polypropylene with a chlorine content ranging from 20% to 35% and vinyl acetate, and hydrolyzing the grafted product in an alkaline environment.
In one embodiment, the polyol is a low polarity polymer containing hydroxyl groups obtained by hydrolyzing an ethylene-vinyl acetate copolymer having a vinyl acetate content of 1% to 50% in an alkaline environment.
The invention also provides a preparation method of the adhesive primer, which comprises the following steps: step one, preparing a component A, mixing a polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion, wherein the hydroxyl content in the polyhydroxy compound is more than 3%, the hydroxyl in the polyhydroxy compound is obtained by ester hydrolysis, and the weight of the modified graphite oxide is 0.5-5% of that of the polyhydroxy compound; step two, preparing a component B, namely reacting the soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, continuing to react the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A, monitoring the viscosity of reactants, and obtaining a soybean oil polyol modified product when the viscosity is not continuously increased; preparing a primer, respectively preparing a component A solution and a component B solution with preset solid contents, and mixing the component A and the component B according to a preset mixing ratio, wherein the preset solid content range is 5% -30%, and the preset mixing ratio range is 10-1: 1.
In one embodiment, the preparation of the polyol comprises the steps of: carrying out grafting reaction on chlorinated polypropylene with chlorine content ranging from 20% to 35% and vinyl acetate for 4-6 hours under the catalysis of an initiator, wherein the reaction temperature ranges from 60 ℃ to 80 ℃, and the chlorinated polypropylene: vinyl acetate: the weight ratio of the initiator is 100: 1-20: 0.5; precipitating the product in ethanol, and drying the precipitate; preparing a toluene solution in which the precipitate is dissolved into an alkaline solution system, and hydrolyzing the precipitate for 12-24 hours at 60-80 ℃ in an alkaline environment; and standing and separating the hydrolysate, and performing rotary evaporation and rotary drying on an upper organic phase to obtain the polyhydroxy compound.
In one embodiment, the initiator is azobisisobutyronitrile or benzoyl peroxide.
In one embodiment, the preparation of the polyol comprises the steps of: stirring an ethylene-vinyl acetate copolymer with 1-50% of vinyl acetate content for 5-7 h for hydrolysis in an alkaline environment at the temperature of 20-80 ℃; adjusting the alkaline pH value to be neutral, and standing for liquid separation; and placing the organic layer in an alcohol environment for precipitation to obtain the precipitate of the polyhydroxy compound.
In one embodiment, the basic pH is adjusted to neutral using HCl solution.
In one embodiment, the alcohol environment is a methanol environment or an ethanol environment.
Compared with the prior art, the invention has the advantages that: the two components which are difficult to bond can be bonded together with the help of a base coat, for example, TPE and glass are firmly bonded, the interface bonding force is larger than the body strength of the injection molding material, the bonding part is not easy to separate, and the bonding part is ensured to have a good light-blocking effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a reaction scheme of chain radical initiated vinyl acetate polymerization to obtain reaction primary products containing different graft products in an example of the present invention;
FIG. 2 is a reaction scheme of chain radical initiated vinyl acetate polymerization to obtain reaction initial products containing different graft products in an example of the present invention;
FIG. 3 shows the results of peel force tests for examples one-five of the present invention and comparative examples one-five;
FIG. 4 shows the results of peel force test data for examples six to ten of the present invention and comparative examples six to ten;
FIG. 5 shows the comparison of the performance of the products of the first and sixth examples of the present invention with that of a conventional product, Tokuba 1660 available from Tokuba rubber Co.
Detailed Description
The following describes embodiments of the present application in detail.
The following description of the embodiments of the present application is provided by way of specific examples, and other advantages and effects of the present application will be readily apparent to those skilled in the art from the disclosure herein. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. The present application is capable of other and different embodiments and its several details are capable of modifications and/or changes in various respects, all without departing from the spirit of the present application. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present application, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number and aspects set forth herein. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects may be practiced without these specific details.
The embodiment of the application provides an adhesive primer composition for bonding a thermoplastic elastomer and a low-surface-energy substrate, which is characterized by comprising an A component and a B component.
The component A comprises polyhydroxy compound containing polyolefin structure and modified graphite oxide, wherein the hydroxyl content in the polyhydroxy compound is more than 3%, and the hydroxyl in the polyhydroxy compound is obtained by ester hydrolysis. The polyhydroxy compound can be chlorinated polyolefin which is grafted by vinyl acetate and obtained by graft modification of chlorinated polyolefin, and then chlorinated polyolefin of hydroxyl addition is obtained by alkaline hydrolysis of vinyl acetate in the chlorinated polyolefin; the polyhydroxy compound can also be olefin-vinyl alcohol copolymer with hydroxyl added by directly alkaline hydrolyzing vinyl acetate in the olefin-vinyl acetate copolymer.
The component B is a soybean oil polyol modified product, the soybean oil polyol modified product is obtained by reacting soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, and then continuously reacting the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A. The component B can be soybean oil polyol added with hydrogenated bisphenol A, which is obtained by fully reacting soybean oil polyol with isocyanate, such as HMDI (hexamethylene diisocyanate), after vacuum dehydration of the soybean oil polyol, blocking the soybean oil polyol by the HMDI, adding dried hydrogenated bisphenol A, and modifying the blocked soybean oil polyol by the oxidized bisphenol A; and (3) reacting the soybean oil polyalcohol added by the hydrogenated bisphenol A with HMDI again, monitoring the viscosity of the reaction system, filtering the product in a hot oven after the viscosity is not increased continuously, and encapsulating the product in an aluminum tube to obtain the reaction product, namely the component B finally obtained.
The modified graphite oxide acts as a filler. In one embodiment, the modified graphite oxide is obtained by modifying graphene oxide with a modifying group. The modifying group may be an oxygen-containing functional group such as a hydroxyl group, a carboxyl group, and an epoxy group. The modified graphite oxide can be purchased directly or prepared. In one embodiment, the modified graphite oxide is modified graphene oxide of model number SE2430W-N of Hexagon materials science and technology, Inc.
In one embodiment, the polyhydroxy compound is a low-polarity polymer containing hydroxyl groups, which is obtained by performing a grafting reaction on chlorinated polypropylene with a chlorine content ranging from 20% to 35% and vinyl acetate, and hydrolyzing the grafted product in an alkaline environment.
In one embodiment, the polyol is a low polarity polymer containing hydroxyl groups obtained by hydrolyzing an ethylene-vinyl acetate copolymer having a vinyl acetate content of 1% to 50% in an alkaline environment.
The embodiment of the application also provides a preparation method of the adhesive primer, all reagents adopted in the method are industrial grade reagents, and the method comprises the following steps:
step one, preparing a component A, mixing a polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion, wherein the weight of the modified graphite oxide is 0.5-5% of that of the polyhydroxy compound.
And step two, preparing a component B, namely reacting the soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, continuing to react the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A, monitoring the viscosity of reactants, and obtaining a soybean oil polyol modified product when the viscosity is not continuously increased.
When the component B is soybean oil triol, the chemical reaction formula for preparing the soybean oil polyol modified product is shown in figure 1.
The chemical formula of the component B is as follows:
Preparing a primer, respectively preparing a component A solution and a component B solution with preset solid contents, and mixing the component A and the component B according to a preset mixing ratio, wherein the preset solid content range is 5% -30%, and the preset mixing ratio range is 10-1: 1. Preferably, when the weight part of the component A and the component B is 10:1, the obtained adhesive primer has the best effect.
In one embodiment, the preparation of the polyol comprises the steps of:
carrying out grafting reaction on chlorinated polypropylene with chlorine content ranging from 20% to 35% and vinyl acetate for 4-6 hours under the catalysis of an initiator, wherein the reaction temperature ranges from 60 ℃ to 80 ℃, and the chlorinated polypropylene: vinyl acetate: the weight ratio of the initiator is 100: 1-20: 0.5; precipitating the product in ethanol, and drying the precipitate; preparing a toluene solution dissolving the precipitate into an alkaline solution system, and hydrolyzing the precipitate for 12-24 hours at 60-80 ℃ in an alkaline environment; and standing the hydrolysate for liquid separation, and performing rotary evaporation and spin drying on an upper organic phase to obtain the polyhydroxy compound. In one embodiment, the initiator is Azobisisobutyronitrile (AIBN) or Benzoyl Peroxide (BPO).
When the initiator is BPO, the chlorinated polypropylene grafting principle is as follows:
step 1, an initiator BPO is firstly heated and decomposed to generate free radicals
，
Step 2, as shown in figure 2, the free radicals attack C-H bonds or C-Cl bonds of chlorinated polypropylene respectively, and react with Chloropropene (CPP) to generate chain free radicals; the chain radicals initiate the polymerization of vinyl acetate (VAc) and give reaction starting products containing different graft products.
In the above mechanism, the initiator BPO is heated firstDecompose to produce free radicals
Then, the free radicals attack C-H bonds and C-Cl bonds of chlorinated polypropylene respectively, and react with Chloropropene (CPP) to generate chain free radicals; the chain radicals initiate the polymerization of vinyl acetate (VAc) and give reaction starting products containing different graft products. The second reaction formula and the third reaction formula are mechanisms for generating different grafting products in the same time period. The separation of the different grafting products is not required in the reaction of this example. Precipitating the initial reaction product in ethanol, and drying the precipitate to obtain the grafted product. Preparing a toluene solution for dissolving the grafting product into an alkaline solution system, and hydrolyzing the precipitate for 12-24 h at 60-80 ℃ in an alkaline environment. The toluene solution can be adjusted to an alkaline solution system by adding a mixed solution of a KOH aqueous solution and an organic solvent to the toluene solution. The mixed solution of the KOH aqueous solution and the organic solvent can be a mixed solution of toluene/DMF/KOH, and the ratio of the substances can be 1: 1: 1-100: 50: 50. the KOH solution may be a 25 ℃ saturated solution of KOH. The vinyl acetate is subjected to alkaline hydrolysis to generate hydroxyl, and finally the chlorinated polypropylene with hydroxyl added can be obtained, and the structure formula can be as follows
Or
. The AIBN and BPO reaction mechanisms are similar, only the free radicals generated are different.
The chlorinated polypropylene (CPP) raw material may be any of various commercially available materials as long as the chlorine content is in the range of 20% to 35%, and examples thereof include 360T (chlorine content 30%), M430P (chlorine content 20%), 500M (chlorine content 25%), DX-526P (chlorine content 26%), HM-21P (chlorine content 21%) manufactured by Toyo Boseki Kabushiki Kaisha, and the like.
In one embodiment, the preparation of the polyol comprises the steps of:
stirring an ethylene-vinyl acetate copolymer with 1-50% of vinyl acetate content for 5-7 h for hydrolysis in an alkaline environment at the temperature of 20-80 ℃;
adjusting the alkaline pH value to be neutral, and standing for liquid separation;
and (3) putting the organic layer in an alcohol environment for precipitation to obtain a precipitate of the polyhydroxy compound.
The ethylene-vinyl acetate copolymer (EVA) raw material may be various materials commercially available as long as the vinyl acetate content ranges from 1% to 50%, and may be, for example, dupont EVA 40w (VAc content 40%), EVA 210w (VAc content 28%), EVA 3135 (VAc content 12%), exxonmobil Ultra UL 7510 (VAc content 18.70%), mitsui EVA 550 (VAc content 14%), or the like. In this example, the chemical formula of the polyhydroxy compound obtained by hydrolysis of EVA may be
。
In one embodiment, the basic pH is adjusted to neutral using HCl solution.
In one embodiment, the alcohol environment is a methanol environment or an ethanol environment. The alcohol environment may be methanol, ethanol, or other alcohols that can provide hydroxyl groups.
According to the adhesive primer composition and the preparation method thereof, two components which are difficult to bond can be bonded together with the help of one primer, for example, TPE and glass are firmly bonded, the interface bonding force is larger than the bulk strength of an injection molding material, the bonding part is difficult to separate, and the bonding part is ensured to have a good light-blocking effect.
Examples one to five
Step one, preparation of component a, chlorinated polypropylene (example one 822s, example two 360T, example three 500M, example four DX526P, example five HM-21P), VAc and BPO in a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely, carrying out vacuum dehydration on the soybean oil triol, and then reacting the soybean oil triol with HMDI for 6 hours at 70 ℃, wherein the molar ratio is 1: 3.05, then putting the dried hydrogenated bisphenol A, and reacting at 70 ℃ overnight, wherein the molar ratio of the hydrogenated bisphenol A to the HMDI is 1: 1; and then adding HMDI into the reaction kettle, wherein the ratio of the HMDI to the hydrogenated bisphenol A is 1: monitoring the viscosity of the system, filtering the product in a hot oven after the viscosity does not increase continuously, and encapsulating the product in an aluminum tube to obtain a component B.
Step three, preparing the primer, wherein the weight ratio of the effective components of the component A and the component B is 10:1, and in the embodiment, the component A solution and the component B solution are 15% toluene solutions, so that the preset mixing ratio is 10: 1.
In the first to fifth embodiments, the CPPs are the same except for the CPP used.
Comparison example 1
Step one, preparing a component A, namely mixing chlorinated polypropylene (822 s), VAc and BPO according to a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 0.5% of the weight of the polyol.
Step two, preparing a component B, wherein MDI (diphenylmethane diisocyanate) molecules are directly dispersed in MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example two
Step one, preparing a component A, namely mixing chlorinated polypropylene (822 s), VAc and BPO according to a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 0.5% of the weight of the polyol.
Step two, preparing a component B, wherein HMDI (dicyclohexyl methane diisocyanate) molecules are directly dispersed in MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example three
Step one, preparing a component A, namely mixing chlorinated polypropylene (822 s), VAc and BPO according to a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
And step two, preparing the component B, wherein the silicon-oxygen coupling agent molecules are directly dispersed in the MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example four
Step one, preparing a component A, namely mixing chlorinated polypropylene (822 s), VAc and BPO according to a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely, dispersing TSE-100 (the Asahi-3 functional HDI prepolymer) in MIBK (methyl isobutyl ketone) with the solid content of 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example five
Step one, preparing a component A, namely mixing chlorinated polypropylene (822 s), VAc and BPO according to a weight ratio of 20: 1:0.5, dissolving in toluene, filling nitrogen to remove oxygen, reacting for 6 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, adding a potassium hydroxide solution of DMF/water into the system, reacting overnight at 60 ℃, adding HCl to adjust the pH to be neutral, precipitating the product with methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely reacting CP450 (Dow 3-functional polyol PPG type) with MDI (diphenyl-methane-diisocyanate) at the temperature of 120 ℃ under the vacuum condition after vacuum dehydration, wherein the molar ratio is 1: 3.1, after 45 minutes of reaction, the product was sealed inside an aluminum tube to exclude moisture and taken out at the time of formulation.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
The primers of the first to fifth examples and the first to fifth comparative examples were used to bond glass and different thermoplastic elastomers, and the peel force test was performed according to the national standard GB 2792-1998, and FIG. 3 shows the peel force test results of the first to fifth examples and the first to fifth comparative examples.
In the table of fig. 3, TPS and TPV are different types of thermoplastic articles, and comparative examples one to five show that the TPV and the glass cannot be stably bonded by the glue of any example, and although TPS and glass can be bonded by comparative examples one to five, a degumming phenomenon occurs at the bonding position of TPS and glass in a peeling test, and residues are left on the glass. In addition, the adhesive force at the time of fracture is weaker than the bulk strength of the injection molding materials (TPS, TPV).
In the first to fifth embodiments, the adhesive primer can stably bond any injection molding material (TPS, TPV) and glass, and in a peel test, a degumming phenomenon does not occur at a bonding position of the TPS and the glass at all, and only a fracture occurs. And the cohesive force at the time of fracture is stronger than the body strength of the injection molding materials (TPS, TPV).
Examples six to ten
Step one, preparing a component A, namely reacting an ethylene-vinyl acetate copolymer (six EVA 40W in example, seven EVA 7510 in example, eight EVA 210W in example, nine EVA 3135 in example, and ten EVA 550 in example) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain the component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely, carrying out vacuum dehydration on the soybean oil triol, and then reacting the soybean oil triol with HMDI for 6 hours at 70 ℃, wherein the molar ratio is 1: 3.05, then putting the dried hydrogenated bisphenol A, and reacting at 70 ℃ overnight, wherein the molar ratio of the hydrogenated bisphenol A to the HMDI is 1: 1; and then adding HMDI into the reaction kettle, wherein the ratio of the HMDI to the hydrogenated bisphenol A is 1: monitoring the viscosity of the system, filtering the product in a hot oven after the viscosity does not increase continuously, and encapsulating the product in an aluminum tube to obtain a component B.
Step three, preparing the primer, wherein the weight ratio of the effective components of the component A and the component B is 10:1, and in the embodiment, the component A solution and the component B solution are 15% toluene solutions, so that the preset mixing ratio is 10: 1.
In the sixth to tenth embodiments, the materials are the same except for different EVA.
Comparative example six
Step one, reacting ethylene-vinyl acetate copolymer (EVA 40W) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, wherein MDI (diphenylmethane diisocyanate) molecules are directly dispersed in MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example seven
Step one, reacting ethylene-vinyl acetate copolymer (EVA 40W) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, wherein HMDI (dicyclohexyl methane diisocyanate) molecules are directly dispersed in MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Eight comparative examples
Step one, reacting ethylene-vinyl acetate copolymer (EVA 40W) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
And step two, preparing the component B, wherein the silicon-oxygen coupling agent molecules are directly dispersed in the MIBK (methyl isobutyl ketone), and the solid content is 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Nine comparative examples
Step one, reacting ethylene-vinyl acetate copolymer (EVA 40W) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely, dispersing TSE-100 (the Asahi-3 functional HDI prepolymer) in MIBK (methyl isobutyl ketone) with the solid content of 15%.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
Comparative example ten
Step one, reacting ethylene-vinyl acetate copolymer (EVA 40W) in a KOH solution of DMF/water at 75 ℃ overnight, adjusting the pH value to be neutral by using HCl, then precipitating in methanol, drying to obtain a polyhydroxy compound, and mixing the polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset ratio to obtain a component A. The weight of the modified graphite oxide was 5% of the weight of the polyol.
Step two, preparing a component B, namely reacting CP450 (3-functional polyol, Dow PPG) with MDI (diphenylmethane diisocyanate) at the temperature of 120 ℃ under the vacuum condition after vacuum dehydration, wherein the molar ratio is 1: 3.1, after 45 minutes of reaction, the product was sealed inside an aluminum tube to exclude moisture and taken out at the time of formulation.
And step three, preparing a primer, mixing a toluene solution with 15% of the component A and a component B solution, wherein the weight ratio of the effective components of the component A to the effective components of the component B is 10: 1.
The primer of the six to ten embodiments and the six to ten comparative examples is used for bonding glass and different thermoplastic elastomers, and the peel force test is carried out according to the national standard GB 2792-1998, and FIG. 4 shows the peel force test results of the six to ten embodiments and the six to ten comparative examples.
In the table of fig. 4, TPS, TPV are different types of thermoplastics, and the percentage is the probability of glue remaining on the substrate. The six to ten comparative examples show that the TPV and the glass cannot be stably bonded by the glue of any example, and although the TPS and the glass can be bonded by the six to ten comparative examples, the bonding part of the TPS and the glass is degummed and remains on the glass in the peeling test. In addition, the adhesive force at the time of fracture is weaker than the bulk strength of the injection molding materials (TPS, TPV).
In the sixth to tenth embodiments, the adhesion primer can stably bond any injection molding material (TPS, TPV) and glass, and in a peel test, a degumming phenomenon does not occur at a bonding position of the TPS and the glass at all, and only a fracture occurs. And the cohesive force at the time of fracture is stronger than the body strength of the injection molding materials (TPS, TPV).
For better comparison and analysis of the product performance of the present application, fig. 5 shows the comparison results of the product of example one and example six with the product of the prior art, shozuabin 1660, shozuabin rubber corporation.
In the table of fig. 5, TPS, TPV are different types of thermoplastics, and the percentage is the probability of glue remaining on the substrate. The glass and the ink are bonded for 24 hours in the final strength test, in the peeling test, any injection molding material (TPS, TPV) and the glass are stably bonded in the first embodiment, the sixth embodiment and the competitive products, and in the peeling test, the bonding part of the TPS and the glass is not degummed at all and only is broken; and the cohesive force at the time of fracture is stronger than the body strength of the injection molding materials (TPS, TPV). However, in the aging test of 10 days at 90 ℃, the first and sixth examples still stably bond any injection molding material (TPS, TPV) and glass, and in the peeling test, the bonding part of TPS and glass is not degummed at all, and only fracture occurs; however, although the competitive product is broken, the residual rate of the base material is reduced to 80-95%, and the bonding force during the breaking is weaker than that in the final strength test, so that the subsequent treatment is not facilitated. In the test of aging for 10 days at 85 ℃ and 85% humidity, the first embodiment and the sixth embodiment stably bond any injection molding material (TPS, TPV) and glass, and in a peeling test, the bonding part of the TPS and the glass is not degummed at all and only breaks; however, although the competitive product is broken, the residual rate of the base material is reduced to 65-70%, and the bonding force during the breaking is weaker than that in the final strength test, so that the subsequent treatment is not facilitated. It is particularly emphasized that the adhesive primer compositions of the present application have consistently stable performance in all types of tests, whether substrate residue or adhesion. The performance of the competitive products is gradually reduced along with the severe change of the environment, the application range is narrow, and the promotion is not facilitated.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. An adhesive primer composition for bonding a thermoplastic elastomer and a low surface energy substrate, comprising an A-component and a B-component, wherein,
the component A comprises a polyhydroxy compound containing a polyolefin structure and modified graphite oxide, wherein the content of hydroxyl in the polyhydroxy compound is more than 3 percent, and the hydroxyl in the polyhydroxy compound is obtained by ester hydrolysis;
the component B is a soybean oil polyol modified product, and the soybean oil polyol modified product is obtained by reacting soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, and then continuously reacting the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A.
2. The adhesive primer composition according to claim 1, wherein the modified graphite oxide is obtained by modifying graphene oxide with a modifying group.
3. The adhesive primer composition according to claim 1, wherein the polyol is a low-polarity polymer containing hydroxyl groups obtained by graft reaction of chlorinated polypropylene having a chlorine content ranging from 20% to 35% with vinyl acetate, and hydrolysis of the grafted product in an alkaline environment.
4. The adhesive primer composition according to claim 1, wherein the polyol is a low-polarity polymer containing a hydroxyl group obtained by hydrolyzing an ethylene-vinyl acetate copolymer having a vinyl acetate content of 1% to 50% in an alkaline environment.
5. A process for preparing an adhesive primer, comprising the steps of:
step one, preparing a component A, mixing a polyhydroxy compound containing a polyolefin structure and modified graphite oxide according to a preset proportion, wherein the hydroxyl content in the polyhydroxy compound is more than 3%, the hydroxyl in the polyhydroxy compound is obtained by ester hydrolysis, and the weight of the modified graphite oxide is 0.5-5% of that of the polyhydroxy compound;
step two, preparing a component B, namely reacting the soybean oil polyol with isocyanate, then reacting with hydrogenated bisphenol A in a preset weight ratio to obtain soybean oil polyol added with hydrogenated bisphenol A, continuing to react the isocyanate with the soybean oil polyol added with the hydrogenated bisphenol A, monitoring the viscosity of reactants, and obtaining a soybean oil polyol modified product terminated by the isocyanate when the viscosity is not continuously increased;
preparing a primer, respectively preparing a component A solution and a component B solution with preset solid contents, and mixing the component A and the component B according to a preset mixing ratio, wherein the preset solid content range is 5% -30%, and the preset mixing ratio range is 10-1: 1.
6. The method of preparing an adhesive primer according to claim 5, wherein preparing the polyol comprises the steps of:
carrying out grafting reaction on chlorinated polypropylene with chlorine content ranging from 20% to 35% and vinyl acetate for 4-6 hours under the catalysis of an initiator, wherein the reaction temperature ranges from 60 ℃ to 80 ℃, and the chlorinated polypropylene: vinyl acetate: the weight ratio of the initiator is 100: 1-20: 0.5;
precipitating the product in ethanol, and drying the precipitate;
preparing a toluene solution in which the precipitate is dissolved into an alkaline solution system, and hydrolyzing the precipitate for 12-24 hours at 60-80 ℃ in an alkaline environment;
and standing and separating the hydrolysate, and performing rotary evaporation and rotary drying on an upper organic phase to obtain the polyhydroxy compound.
7. The method of preparing an adhesive primer according to claim 6, wherein the initiator is azobisisobutyronitrile or benzoyl peroxide.
8. The method of preparing an adhesive primer according to claim 5, wherein preparing the polyol comprises the steps of:
stirring an ethylene-vinyl acetate copolymer with 1-50% of vinyl acetate content for 5-7 h for hydrolysis in an alkaline environment at the temperature of 20-80 ℃;
adjusting the alkaline pH value to be neutral, and standing for liquid separation;
and placing the organic layer in an alcohol environment for precipitation to obtain the precipitate of the polyhydroxy compound.
9. The process for preparing an adhesive primer according to claim 8, wherein the alkaline pH is adjusted to neutral using HCl solution.
10. The method of making an adhesive primer according to claim 8, wherein the alcoholic environment is a methanol environment or an ethanol environment.
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| US20170204310A1 (en) * | 2016-01-19 | 2017-07-20 | H.B. Fuller Company | One-part polyurethane adhesive composition, method of making a laminate, and laminate |
| CN109439233A (en) * | 2018-11-06 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of environmentally-friendly acrylic ester structure glue and preparation method thereof |
| CN110591521A (en) * | 2019-09-04 | 2019-12-20 | 湖北回天新材料股份有限公司 | Primer for bonding automobile composite material and preparation method thereof |
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| US6087444A (en) * | 1996-09-20 | 2000-07-11 | Ppg Industries Ohio, Inc. | Humidity resistant aqueous urethane resins based on hydrophobic polyhydroxy compounds and coatings |
| CN1735672A (en) * | 2002-11-06 | 2006-02-15 | 东亚合成株式会社 | Adhesive composition and method of bonding |
| JP2006137793A (en) * | 2004-11-10 | 2006-06-01 | Toyobo Co Ltd | Adhesive and circuit board using it |
| JP2006335989A (en) * | 2005-06-06 | 2006-12-14 | Sekisui Chem Co Ltd | Surface protective film |
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