CN113801613B - Super-strong-viscosity nano-adhesive for automobile and preparation method thereof - Google Patents

Super-strong-viscosity nano-adhesive for automobile and preparation method thereof Download PDF

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CN113801613B
CN113801613B CN202111196214.7A CN202111196214A CN113801613B CN 113801613 B CN113801613 B CN 113801613B CN 202111196214 A CN202111196214 A CN 202111196214A CN 113801613 B CN113801613 B CN 113801613B
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nano
parts
super
adhesive
photoinitiator
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CN113801613A (en
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郭凯
曹磊
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Jiangsu Liancarbon Technology Co.,Ltd.
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Changzhou Bangrui New Material Technology Co ltd
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides the super-strong-viscosity nano adhesive for the automobile and the preparation method thereof, wherein the nano adhesive film has excellent adhesive property, environment-friendly raw materials, simple preparation method and larger application prospect.

Description

Super-strong-viscosity nano-adhesive for automobile and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to super-strong-viscosity nano-gel for automobiles and a preparation method thereof.
Background
The use of comprehensive adhesive and sealant is the largest in the fields of wood processing, building and light industry. Although the amount of the automobile glue is greatly increased along with the improvement of the manufacturing process level, even in foreign countries with developed automobile manufacturing industry, the amount of the automobile production glue only accounts for 3% -5% of the total production of the adhesive and the sealant. The mounting of the vehicle to the body structure, the bonding of interior trim, the bonding of seats, etc., may all be by adhesive technology. The adhesive can effectively avoid waste caused by technical materials, and reduce economic loss. The application of the adhesive technology in automobile assembly reduces the waste materials of automobile materials due to riveting, spot welding, punching and the like, and the economic effect is very considerable. In order to adapt to the development trend of energy conservation, environmental protection, low cost and long service life in modern society, higher and higher requirements on the service performance and process performance of the adhesive are provided, and the development and application of the adhesive are certainly adapted to the development requirements of automobiles.
With the importance of people on the quality of air in the automobile, the society attaches more and more importance to the source and detection of volatile organic compounds in the automobile. Low volatile organic compound (low VOC) limits legislation set by the national government. The traditional adhesive is mostly solvent type, volatilization of solvent and other small molecular substances is easy to generate, VOC volatilization of the adhesive applied in the middle of the bonding surface is slow, and further air pollution in a vehicle for a long time is caused. At present, the traditional solvent-based adhesive is gradually replaced by environment-friendly materials such as hot melt adhesive, water-based adhesive and the like, and the influence of the adhesive on the VOC emission in the vehicle is greatly reduced.
The carbon nano tube belongs to a fullerene system, has a larger length-diameter ratio, is a material with excellent optical, electric, thermal, magnetic and mechanical properties, and has wide application in the aspect of reinforcing structures. Zirconia is a nano-powder having excellent characteristics such as high melting point, high hardness, low thermal conductivity, good chemical stability and toughness. Although zirconia and carbon nanotubes can be used as fillers of adhesives, the problems of easy agglomeration, uneven dispersion and poor compatibility with matrix resin need to be overcome.
Therefore, it is an urgent problem to develop a nano adhesive for automobiles, which has strong adhesion and is environmentally friendly, for a device having a high requirement for the adhesion of the adhesive in automobiles.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the super-strong-viscosity nano-adhesive for the automobile and the preparation method thereof.
In the present invention, the content percentages are all weight percentages unless otherwise specified.
In order to achieve the above object, the present invention is achieved by the following aspects:
in a first aspect, the invention provides super-strong-viscosity nano-adhesive for automobiles, which is prepared from the following raw materials in parts by weight: 30-60 parts of polybutadiene acrylate; 1-15 parts of tackifying resin; 30-60 parts of a reactive diluent; 0.5-5 parts of carbon nano tube-loaded zirconia; 1-20 parts of a photoinitiator.
Preferably, the raw materials for preparing the nano-gel comprise, by weight: 50-60 parts of polybutadiene acrylate; 5-8 parts of tackifying resin; 50-60 parts of reactive diluent; 1-1.5 parts of carbon nanotube-loaded zirconia; 3-5 parts of a photoinitiator.
In some embodiments, the polybutadiene acrylate is prepared by anionic reaction of hydroxyl-terminated polybutadiene and an acryloyl chloride compound.
In some specific embodiments, the hydroxyl-terminated polybutadiene is selected from one or a mixture of Krasol TM LBH-2000, krasol TM LBH-3000, krasol TM LBH-P-2000, krasol TM LBH-P-3000, poly R20LM, poly R45HTLO, poly R45V series of the Clark Lei Weili;
preferably one or more of Krasol TM LBH-2000, krasol TM LBH-P-2000 and Krasol TM LBH-P-2000.
In some specific embodiments, the acryloyl chloride compound is one or more of acryloyl chloride, methacryloyl chloride, 2-ethylacryloyl chloride, or 2-propylacryloyl chloride.
In some specific embodiments, the method for preparing the polybutadiene acrylate comprises: adding potassium and naphthalene which is sublimated to remove impurities into tetrahydrofuran according to the mass ratio of 1:3-4, reacting for 24-48h under the protection of inert gas at room temperature, and filtering to obtain potassium naphthalene for later use; reacting hydroxyl-terminated polybutadiene and the potassium naphthalene under the protection of inert gas at room temperature for 1-5h, adding an acryloyl chloride compound, continuing to react for 0.5-1.5h, filtering, washing and drying to obtain polybutadiene acrylate, wherein the molar ratio of the hydroxyl-terminated polybutadiene to the potassium naphthalene to the acryloyl chloride compound is 1:2.1-2.3:2.1-2.3.
As a preferable embodiment, the hydroxyl-terminated polybutadiene reacts with potassium naphthalene to generate potassium alkoxide with high reactivity, and the potassium alkoxide can directly perform esterification reaction with an acryloyl chloride compound to generate polybutadiene acrylate without using an organic amine catalyst. The traditional organic amine catalyst is avoided, amine impurities possibly caused by the polybutadiene acrylate serving as a main monomer raw material of the nano-adhesive are greatly reduced, and the overall stability and peel strength of the system can be effectively improved.
In some specific embodiments, the tackifying resin is selected from at least one of rosin resins, petroleum resins, coumarone resins, terpene resins, oil-soluble phenolics.
In some preferred specific embodiments, the tackifying resin is a carbon five resin, specifically selected from one or more of hydrogenated carbon five resin, carbon five aliphatic petroleum resin, carbon five alicyclic petroleum resin, and carbon five modified resin.
In some preferred specific embodiments, the reactive diluent is one or a mixture of hydroxypropyl methacrylate (HPMA), 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), isobornyl methacrylate (IBOA), tetrahydrofuran acrylate (THFA), methyl laurate acrylate (LMA), ethoxyethoxyethyl acrylate (eoea).
In some preferred specific embodiments, the reactive diluent is a mixture of 1:0.5-0.8:1-1.2 of isobornyl methacrylate (IBOA), trimethylolpropane triacrylate (TMPTA) and ethoxyethoxyethyl acrylate (EOEOEA). As a preferred embodiment, the reactive diluents with different functional groups in the system of the present invention cooperate with each other to provide a large number of crosslinking sites for the photo-curing system, and the photo-initiated polymerization reaction increases the crosslinking degree of the nano-gel, thereby enhancing the mechanical properties and peel strength of the nano-gel.
In some preferred specific embodiments, the carbon nanotube-supported zirconia is prepared by: adding 1-5mg of multi-walled carbon nanotubes (MWNTs, the particle size is 20-40nm) into 100-200mL of 5-10mmol/L zirconium oxychloride solution, ultrasonically mixing for 30-60min, carrying out hydrothermal reaction in a hydrothermal kettle at 150-180 ℃ for 12-16h, cooling, filtering, washing to neutrality with water, and drying to obtain the carbon nanotube-loaded zirconium oxide. In order to avoid the zirconium oxide nano particles from agglomerating or randomly aggregating at the local part of the carbon nano tube and influencing the system performance, the concentration of the zirconium oxychloride solution is preferably 6-8 mmol/L.
In some preferred specific embodiments, the surface of the carbon nanotube-supported zirconia is modified with a silane coupling agent.
Preferably, the silane coupling agent is any one or a mixture of more than two of a coupling agent KH550, a coupling agent KH560 and a coupling agent KH 570.
In some preferred specific embodiments, the surface modification of the carbon nanotube-supported zirconia comprises the steps of: ultrasonically mixing 5-10mg of the carbon nanotube-loaded zirconia with 100-200mL of 95% concentrated sulfuric acid for 30-50min, heating to 80-90 ℃, refluxing for 4-6h, washing the product until the pH value is neutral, drying, adding 2-10mg of the product into 100-200mL of ethanol water solution (the volume ratio of ethanol to water is 3:1), ultrasonically mixing for 30-40min, adding a silane coupling agent (the volume fraction is 1-2%), continuously ultrasonically mixing for 10-30min, adding glacial acetic acid to adjust the pH value to 3-4, stirring for 5-6h at 65-75 ℃, cooling, centrifuging, washing to be neutral, and drying to obtain the silane coupling agent-modified carbon nanotube-loaded zirconia.
The inventor finds that the bonding performance is improved due to the fact that the addition amount of the carbon nano tube loaded zirconia is small, probably because the carbon nano tube loaded zirconia is used as a rigid particle to play a role in crosslinking, the crosslinking density and the cohesive force of the nano adhesive are improved, the surface modification of the silane coupling agent can improve the compatibility of the carbon nano tube and resin matrixes such as acrylic ester and the like, the surface tension and the polarity of the acrylic ester matrixes are further improved, and hydrogen bonds at the interface of the nano adhesive and the substrate are further increased. And the carbon nano tube and the zirconia are firstly synthesized into the load type nano filler, and then a certain amount of the load type nano filler is added into an acrylate system, so that the advantages of two types of nano powder can be simultaneously and efficiently exerted.
The photoinitiator is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers. In some embodiments, the photoinitiator is one or more selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, and methyl benzoylformate. Preferably 2-hydroxy-2-methyl-1-phenylpropanone (otherwise known as photoinitiator 1173).
In some specific embodiments, the raw materials for preparing the nano-gel of the present invention further include one or more of a stabilizer, a plasticizer, a coupling agent, an antioxidant, a light transmittance modifier, a compatibilizer, or an antifogging agent.
As examples of stabilizers, including, but not limited to, zinc stearate, calcium glycerophosphate, zinc carbonate; in one embodiment, the weight of the stabilizer of the present invention is 0 to 1wt% of the total weight of the raw materials for preparing the nano-gel.
Examples of plasticizers include, but are not limited to, hydrogenated terpene resins, polybutadiene oligomers, ether alcohol dibasic acid diesters, ether glycol monobasic acid diesters, dioctyl sebacate; in one embodiment, the weight of the plasticizer of the present invention is 0 to 1wt% of the total weight of the raw materials for preparing the nano-gel.
Examples of the antioxidant include, but are not limited to, one or more of hindered phenol-based antioxidants and phosphite-based antioxidants, and specifically, may be selected from compounds such as Irganox 1141, 1010, 1076, 168, BNX1000, diphenylamine, p-phenylenediamine and dihydroquinoline, and derivatives or polymers thereof, 2,6-tertiary butyl-4-methylphenol, bis (3,5-tertiary butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ β - (3,5-tertiary butyl-4-hydroxyphenyl) propionate ], bisdodecanol esters, bistetradecanol esters and bisoctadecanol esters, trioctyl, tridecyl ester, tridodecanol esters and trishexadecanol esters; in one embodiment, the weight of the antioxidant is 0-3% of the total weight of the raw materials for preparing the nano-gel.
Examples of light transmission modifiers include, but are not limited to, 1,3,5-tri-tert-butylaminobenzene, dibenzylidene sorbitol (DBS), 1,3; in one embodiment, the weight of the light transmittance modifier is 0 to 1wt% of the total weight of the raw materials for preparing the nano-gel.
Examples of the anti-fogging agent include, but are not limited to, a polyamide methanol solution, an ionic surfactant methanol solution, a polyethylene glycol perfluoroalkyl ether isopropyl alcohol solution; in one embodiment, the weight of the antifogging agent of the present invention is 0 to 1wt% of the total weight of the raw materials for preparing the nano-gel.
In a second aspect, the invention provides a preparation method of super-strong adhesive nano-gel for automobiles, which comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1-2h, controlling the temperature to be 40-60 ℃, wherein the addition amount of the first initiator is 0.5-1wt% of the total amount of the polybutadiene acrylate and the reactive diluent; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s-600mPa.s to obtain a prepolymer for later use;
(2) And (2) mixing the prepolymer obtained in the step (1) with tackifying resin, carbon nano tube loaded zirconia and a second photoinitiator for 0.5-2h, controlling the temperature to be 45-70 ℃, wherein the addition amount of the second photoinitiator is 3-4wt% of the mass of the prepolymer, and obtaining the super-strong viscous nano-gel.
As a preferred embodiment, the first and second photoinitiators are of the same type, for example photoinitiator 1173.
As a preferred embodiment, the step (2) is also added with a coupling agent KH550, a coupling agent KH560 and/or a coupling agent KH570; and/or, an antioxidant 168 and/or an antioxidant 1010 are/is also added in the step (2).
In some specific embodiments, the preparation method of the super-strong adhesive nano-gel for the automobile comprises the following steps:
(1) Mixing 50-60 parts of polybutadiene acrylate, 50-60 parts of reactive diluent and 0.8-1 part of first photoinitiator for 1-2 hours, and controlling the temperature to be 40-60 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s-600mPa.s to obtain a prepolymer for later use;
(2) Mixing the prepolymer obtained in the step (1) with 5-8 parts of tackifying resin, 1-1.5 parts of carbon nano tube loaded zirconia, 3-4 parts of second photoinitiator, 0.5-1.5 parts of silane coupling agent and 0.5-0.7 part of antioxidant for 0.5-2h, controlling the temperature to be 50-65 ℃ and obtaining the super-strong viscous nano-adhesive;
wherein the first and second photoinitiators are of the same type. The preparation method adopts the two-step method of the invention to be more beneficial to the mixing of raw materials and the stability of a system.
The inventor finds that the super-strong viscous nano-adhesive for the automobile is obtained by adopting specific types of acrylate, tackifying resin and reactive diluent and adding carbon nano-tube loaded zirconia through the interaction of raw materials, so that the super-strong viscous nano-adhesive has excellent adhesive property.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention. The reagents and starting materials used in the present invention are not specifically described and are commercially available.
The positive progress effects of the invention are as follows: the super-strong viscous nano-adhesive for the automobile with excellent performance is obtained by controlling the selection and the proportion of each raw material component, and the preparation process of the nano-adhesive is simple and the cost is low.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. It should be understood that although a few embodiments of practicing the present invention have been illustrated herein, those skilled in the art will appreciate, in light of the present disclosure, that numerous modifications may be made without departing from the spirit and intended scope of the invention. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, since the scope of the present invention will be defined only by the appended claims and equivalents thereof.
The starting materials in the following examples and comparative examples are commercially available unless otherwise specified.
Wherein the content of the first and second substances,
the carbon nano tube loaded zirconia (self-made A) is prepared by the following steps: adding 2mg of multi-walled carbon nanotubes (MWNTs, the particle size is 20-40nm) into 100mL of 6mmol/L zirconium oxychloride solution, ultrasonically mixing for 45min, carrying out hydrothermal reaction in a hydrothermal kettle at 160 ℃ for 12h, cooling, filtering, washing to be neutral, and drying to obtain the carbon nanotube-loaded zirconium oxide.
The carbon nano tube loaded zirconia (self-made B) is prepared by the following steps:
(1) Adding 2mg of multi-walled carbon nanotubes (MWNTs, the particle size is 20-40nm) into 100mL of 6mmol/L zirconium oxychloride solution, ultrasonically mixing for 45min, carrying out hydrothermal reaction in a hydrothermal kettle at 160 ℃ for 12h, cooling, filtering, washing with water to be neutral, and drying to obtain carbon nanotube-loaded zirconium oxide;
(2) Ultrasonically mixing 6mg of the carbon nano tube loaded zirconia obtained in the step (1) with 200mL of 95% concentrated sulfuric acid for 30min, heating to 80 ℃, refluxing for 6h, washing the product until the pH value is neutral, drying, adding 4mg of the product into 200mL of ethanol aqueous solution (the volume ratio of ethanol to water is 3:1), ultrasonically mixing for 40min, adding a silane coupling agent KH560 (the volume fraction is 1.5%), continuously ultrasonically mixing for 20min, adding glacial acetic acid to adjust the pH value to 3, stirring for 6h at 65 ℃, cooling, centrifuging, washing to be neutral, and drying to obtain the silane coupling agent modified carbon nano tube loaded zirconia.
The preparation method of the carbon nanotube-loaded zirconia (self-made C) is the same as that of the carbon nanotube-loaded zirconia (self-made B), and the difference is that: and (2) in the step (1), the concentration of the zirconium oxychloride solution is 10mmol/L, and finally the carbon nano tube loaded zirconium oxide modified by the silane coupling agent is obtained.
Example 1
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: polybutadiene acrylate (NISSO-PB TE-2000 from Nippon Caoda) 50 parts; tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of HDDA, IBOA and EOEOEA in a mass ratio of 1; 1.5 parts of carbon nano tube loaded zirconia (self-made A); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173) and 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173).
The preparation method of the nano-adhesive comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1h, and controlling the temperature to be 40 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s to obtain a prepolymer for later use;
(2) And (2) mixing the prepolymer obtained in the step (1) with tackifying resin, carbon nano tube loaded zirconia and a second photoinitiator for 2 hours, and controlling the temperature to be 55 ℃ to obtain the super-strong viscous nano-adhesive.
Example 2
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of HDDA, IBOA and EOEOEA in a mass ratio of 1; 1.5 parts of carbon nano tube loaded zirconia (self-made A); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
The preparation method of the polybutadiene acrylate (self-made) comprises the following steps: adding potassium and naphthalene which is sublimated to remove impurities into tetrahydrofuran according to the mass ratio of 1:3, reacting for 24 hours under the protection of inert gas at room temperature, and filtering to obtain potassium naphthalene for later use; and (2) reacting hydroxyl-terminated polybutadiene (Krasol TM LBH-2000) and the potassium naphthalene for 1h under the protection of inert gas at room temperature, adding acryloyl chloride, continuously reacting for 1.5h, filtering, washing and drying to obtain polybutadiene acrylate, wherein the molar ratio of the hydroxyl-terminated polybutadiene to the potassium naphthalene to the acryloyl chloride is 1:2.2:2.2.
the preparation method of the nano-adhesive comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1h, and controlling the temperature to be 45 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s to obtain a prepolymer for later use;
(2) And (2) mixing the prepolymer obtained in the step (1) with tackifying resin, carbon nano tube loaded zirconia, a second photoinitiator, a silane coupling agent and an antioxidant for 2 hours, and controlling the temperature to be 55 ℃ to obtain the super-strong viscous nano-adhesive.
Example 3
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of a reactive diluent (a mixture of IBOA, TMPTA and EOEOEA in a mass ratio of 1; 1.5 parts of carbon nano tube loaded zirconia (self-made A); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein, the preparation method of the polybutadiene acrylate (self-made) is the same as that of the embodiment 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Example 4
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1.5; 1.5 parts of carbon nano tube loaded zirconia (self-made A); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein the preparation method of polybutadiene acrylate (homemade) is the same as that of example 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Example 5
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1; 1.5 parts of carbon nanotube-loaded zirconia (self-made B); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein, the preparation method of the polybutadiene acrylate (self-made) is the same as that of the embodiment 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Example 6
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1; 1.5 parts of carbon nanotube-loaded zirconia (self-made C); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein the preparation method of polybutadiene acrylate (homemade) is the same as that of example 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Example 7
The super-strong-viscosity nano-adhesive for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1; 3 parts of carbon nano tube-loaded zirconia (self-made B); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein, the preparation method of the polybutadiene acrylate (self-made) is the same as that of the embodiment 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Example 8
The super-strong-viscosity nano-gel for the automobile comprises the following raw materials in parts by weight: 50 parts of polybutadiene acrylate (self-made); 6 parts of tackifying resin hydrogenated carbon five resin (the softening point of a ring and ball method is 100 ℃); 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1; 0.5 part of carbon nano tube loaded zirconium oxide (self-made B); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1.5 parts of silane coupling agent KH560 and 0.6 part of antioxidant 1010.
Wherein, the preparation method of the polybutadiene acrylate (self-made) is the same as that of the embodiment 2; the preparation method of the nano-gel is the same as that of the embodiment 2.
Comparative example 1
A nanometer glue is prepared from raw materials (without tackifying resin) in parts by weight: polybutadiene acrylate (NISSO-PB TE-2000 from Nippon Caoda) 50 parts; 55 parts of an active diluent (a mixture of IBOA, TMPTA and EOEOEA according to the mass ratio of 1; 1.5 parts of carbon nano tube loaded zirconia (self-made A); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173) and 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173).
The preparation method of the nano-gel comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1h, and controlling the temperature to be 40 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s to obtain a prepolymer for later use;
(2) And (2) mixing the prepolymer obtained in the step (1) with the carbon nano tube loaded zirconia and a second photoinitiator for 2 hours, and controlling the temperature to be 55 ℃ to obtain the nano adhesive.
Comparative example 2
The nanometer glue comprises the following raw materials in parts by weight: polybutadiene acrylate (NISSO-PB TE-2000 from Nippon Caoda) 50 parts; tackifying resin hydrogenated carbon five resin (softening point of 100 ℃ by a ring and ball method) 6 parts; 55 parts of a reactive diluent (a mixture of IBOA, TMPTA and EOEOEA in a mass ratio of 1; 1.5 parts of multi-walled carbon nanotubes (MWNTs, the particle size is 20 to 40nm); 1 part of first photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173) and 4 parts of second photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173).
The preparation method of the nano-adhesive comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1h, and controlling the temperature to be 40 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s to obtain a prepolymer for later use;
(2) And (2) mixing the prepolymer obtained in the step (1) with tackifying resin, multi-walled carbon nanotubes and a second photoinitiator for 2 hours, and controlling the temperature to be 55 ℃ to obtain the super-strong viscous nano-adhesive.
Comparative example 3
A nano-gel is prepared from the same raw materials as in example 3, except that the preparation method of the nano-gel is different: all the raw materials are directly mixed for 3 hours, and the temperature is controlled to be 50 ℃ to obtain the laminating adhesive.
And (3) performance testing:
the samples obtained in the above examples and comparative examples were subjected to the following performance tests, the test standards and methods, and the test results are shown in table 1:
(1) Initial viscosity: according to GB4852-84 test, a nano adhesive sample is tested by using an inclined plane rolling ball method, the nano adhesive is coated on a PET film with the length of 100mm and the width of 50mm and is subjected to ultraviolet light curing, the sample is placed on an inclined plane table with the inclination of 30 degrees in the test process, the initial adhesion is represented by testing the maximum ball which can be stuck by the nano adhesive, and the error is eliminated by testing each sample for three times.
(2) Permanent adhesion: with reference to the test of GB4851-2014, the time (hours) for the tape to detach from the test plate was determined by the hanging method, and the test was repeated three times and the average value was taken.
(3) 180 ° peel strength: referring to GB/T2792-81 test, 180-degree peeling force test is carried out on the nano-adhesive by an intelligent electronic tensile machine (XLW, jinan Languano electric machine technology Limited). Coating the nano adhesive on a PET film with the length of 100mm and the width of 25mm, carrying out ultraviolet light curing, and then adhering the cured adhesive film on a special steel plate for peeling test, wherein the peeling speed is 300mm/min, and the test temperature is 25 ℃.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3
Initial tack 10 13 13 12 18 15 13 15 7 9 5
Permanent adhesive force (h) 15 26 27 25 32 28 33 13 11 10 3
180 degree peel strength (N/25 mm) 12 18 21 19 25 20 14 16 9 13 8
As can be seen from Table 1, the super-strong adhesive nanometer glue for the automobile is obtained by adopting specific types of acrylate, tackifying resin and reactive diluent and adding carbon nano tube loaded zirconia through the interaction of the raw materials, so that the super-strong adhesive nanometer glue has excellent adhesive property.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.

Claims (8)

1. The super-strong-viscosity nano glue for the automobiles is characterized by comprising the following raw materials in parts by weight: 30-60 parts of polybutadiene acrylate; 1-15 parts of tackifying resin; 30-60 parts of reactive diluent; 0.5-5 parts of carbon nano tube-loaded zirconia; 1-20 parts of a photoinitiator;
the photoinitiator comprises a first photoinitiator and a second photoinitiator, wherein the first photoinitiator and the second photoinitiator are both 2-hydroxy-2-methyl-1-phenyl acetone;
the preparation method of the super-strong-viscosity nano-adhesive for the automobile comprises the following steps:
(1) Mixing polybutadiene acrylate, a reactive diluent and a first photoinitiator for 1-2h, controlling the temperature to be 40-60 ℃, wherein the addition amount of the first initiator is 0.5-1wt% of the total amount of the polybutadiene acrylate and the reactive diluent; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400mPa.s-600mPa.s to obtain a prepolymer for later use;
(2) Mixing the prepolymer obtained in the step (1) with tackifying resin, carbon nano tube loaded zirconia and a second photoinitiator for 0.5-2h, controlling the temperature to be 45-70 ℃, wherein the addition amount of the second photoinitiator is 3-4wt% of the mass of the prepolymer, so as to obtain super-strong viscous nano-gel;
step (2) also adds coupling agent KH550, coupling agent KH560 and/or coupling agent KH570;
antioxidant 168 and/or antioxidant 1010 are/is also added in the step (2).
2. The super-strong-viscosity nano-gel for the automobile according to claim 1, wherein the polybutadiene acrylate is prepared by anionic reaction of hydroxyl-terminated polybutadiene and acryloyl chloride compound; the acryloyl chloride compound is one or a mixture of more of acryloyl chloride, methacryloyl chloride, 2-ethyl acryloyl chloride or 2-propyl acryloyl chloride.
3. The super-adhesive nano-size for automobiles according to claim 1, wherein the tackifying resin is at least one selected from rosin resin, petroleum resin, coumarone resin, terpene resin, and oil-soluble phenol aldehyde.
4. The super-high-viscosity nano-adhesive for the automobiles according to claim 1, wherein the tackifying resin is one or more selected from hydrogenated carbon five resin, carbon five aliphatic petroleum resin, carbon five alicyclic petroleum resin and carbon five modified resin.
5. Super-adhesive nano-gel for automobiles according to claim 1, wherein the reactive diluent is one or more of hydroxypropyl methacrylate (HPMA), 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), isobornyl methacrylate (IBOA), tetrahydrofuran acrylate (THFA), methyl laurate acrylate (LMA), and ethoxyethoxyethyl acrylate (EOEA).
6. The super-viscous nano-gel for the automobile according to claim 1, wherein the reactive diluent is a mixture of 1:0.5-0.8:1-1.2 of isobornyl methacrylate (IBOA), trimethylolpropane triacrylate (TMPTA) and ethoxyethoxyethyl acrylate (EOEOEA).
7. The super-viscous nano-adhesive for the automobile as claimed in claim 1, wherein the surface of the carbon nanotube-loaded zirconia is modified by a silane coupling agent;
the silane coupling agent is any one or more than two of a coupling agent KH550, a coupling agent KH560 or a coupling agent KH 570.
8. The super-adhesive nano-gel for the automobile according to claim 1, wherein the raw materials for preparing the nano-gel further comprise one or more of a stabilizer, a plasticizer, a light transmission modifier, a compatilizer or an antifogging agent.
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