WO2021135377A1 - Graphene uv pressure-sensitive adhesive and preparation method therefor - Google Patents

Graphene uv pressure-sensitive adhesive and preparation method therefor Download PDF

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Publication number
WO2021135377A1
WO2021135377A1 PCT/CN2020/114655 CN2020114655W WO2021135377A1 WO 2021135377 A1 WO2021135377 A1 WO 2021135377A1 CN 2020114655 W CN2020114655 W CN 2020114655W WO 2021135377 A1 WO2021135377 A1 WO 2021135377A1
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Prior art keywords
graphene
pressure
sensitive adhesive
general formula
acrylate
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PCT/CN2020/114655
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French (fr)
Chinese (zh)
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蒋路谣
华永军
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苏州桐力光电股份有限公司
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Publication of WO2021135377A1 publication Critical patent/WO2021135377A1/en

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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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the technical field of adhesive materials, and relates to a graphene UV pressure-sensitive adhesive and a preparation method thereof.
  • Acrylic acid and acrylate oligomers are composed of unsaturated double bonds such as acryloxy, vinyl and allyl groups and esterified groups such as epoxy, polyurethane, polysiloxane and polyether.
  • the hybrid structure of unsaturated oligomers makes free radical light-curable materials have the properties of epoxy, polyurethane, polysiloxane, polyether, acrylic acid and acrylic ester, impact resistance, weather resistance, and chemical resistance. Properties and excellent physical strength make acrylic light-curable materials increasingly prominent, making it easier to meet the requirements of high-speed assembly line operations and efficient industrial production.
  • Light-curing pressure-sensitive adhesive is a distinctive branch of acrylic light-curing material application field.
  • Graphene is a honeycomb hexagonal lattice two-dimensional carbon nano-plane monoatomic layer material formed by carbon atoms in SP 2 hybrid mode. It is the basic structural unit of all carbon crystals except diamond. Graphene has excellent optical, electrical and thermal properties, which is of special significance to the basic research of materials science and is a revolutionary material in the future. The absorption rate of graphene in a wide wavelength range is about 2.3%. The unusual low-energy electronic structure enables the optical response of graphene nanoribbons to be tuned to the terahertz range. Under intensive laser illumination, graphene often exhibits a nonlinear phase. The optical nonlinear Kerr effect of shifting.
  • Adding graphene to the acrylic matrix resin has high line resolution, suitable for fine lead spacing and high-density assembly, and meets the requirements of lightweight and miniaturized microelectronic products for high-speed flow packaging, and achieves simultaneous electromagnetic and thermal shielding
  • the performance and the synergistic effect of each component make the acrylic light-curable material have good heat resistance and fatigue resistance, strong adhesion with various substrates, strong peeling force, and stable and reliable electronic and electrification performance.
  • the purpose of the present invention is to provide a graphene UV pressure-sensitive adhesive and a preparation method.
  • a graphene UV pressure-sensitive adhesive including the following raw materials in mass percentages:
  • R 1 represents tolyl, diphenylmethane or xylylene;
  • R 3 represents hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane or xylylene; the viscosity is 500-1000mPa ⁇ s at 25°C.
  • polysiloxane acrylate is at least one of the compounds conforming to the general formula E, the general formula F and the general formula G:
  • R 2 stands for hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane, benzene two Methylene has a viscosity of 500 to 50,000 mPa ⁇ s at 25°C.
  • the reactive diluent is alkoxylated tetrahydrofuran acrylate, ethoxylated nonylphenol acrylate, alkoxylated nonylphenol acrylate, alkoxylated lauryl acrylate, isodecyl acrylate, isodecyl acrylate, At least one of tridecyl acrylate, ethylated nonylphenol acrylate, and propoxylated neopentyl glycol diacrylate.
  • the tackifying resin is rosinane-8,11,13-triene-7-ol, 12-ethyl-13-methoxy-8,11,13-podnatriene- At least one of 7-ketone, 13-methoxy-6-hydroxybenzidine-5,8,11,13-tetraene-7-one, and 13-hydroxy-8(14)-rosinene.
  • the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2 -At least one of phenylbenzyl-dimethylamine-4-morpholinopropyl phenyl ketone and 1-hydroxycyclohexyl phenyl ketone.
  • the stabilizer is tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, hydroxyanisole, hydroquinone, p-benzoquinone and 2,6-di-tert-butyl At least one of -4-methylphenol.
  • the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; and the graphene loose packing density is 0.01-0.05 g/cm Within 3 , the tap density is 0.05 ⁇ 0.1g/cm 3 .
  • the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers and a length of 0.1-2 micrometers, The wall thickness of 1 gram is 10 13 -10 15 PCS.
  • the carbon interface treatment agent is at least one of diborane, pentaborane, decaborane and carborane.
  • the silane coupling agent is a compound conforming to the following general formula:
  • Y represents an amino group, a mercapto group, a long-chain alkyl group, an epoxy group, a cyano group and a methacryloxy group
  • R represents an alkylene group
  • X represents a hydrolyzable group
  • n 0 or 1.
  • the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.
  • the hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction.
  • R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy).
  • R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group.
  • the functional additive is polyether modified dimethyl polysiloxane copolymer, foam-breaking polysiloxane non-aqueous emulsion, non-ionic polysiloxane copolymer, electrically neutral polysiloxane At least one of amide and polyester copolymer, low-molecular-weight unsaturated carboxylic acid polymer, block copolymer containing acidic group alkane ammonium salt, and micronized modified high-density polyethylene wax mixture.
  • the technical solution provided by the present invention is: a method for preparing graphene UV pressure-sensitive adhesive: It is characterized in that it includes the following steps:
  • Step 1 Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
  • Step 2 Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
  • Step 3 In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
  • Step 4 Take out the glue sample, irradiate it under 500-1000 millijoule ultraviolet light for 10-60 seconds, and then perform the test. After reaching the standard requirements, the material is discharged to make graphene UV pressure-sensitive adhesive.
  • the negative pressure condition is that the vacuum degree is -0.08 ⁇ -0.1MPa.
  • the physical properties of the graphene UV pressure-sensitive adhesive not only achieve the performance of simultaneous electromagnetic and thermal shielding, but also the weight ratio and volume ratio are properly controlled, the curing rate and the curing degree are good, and the components are synergistic. It has achieved excellent mechanical strength and reliable stability.
  • the conductivity of the graphene pressure-sensitive adhesive is 10 3 ⁇ 10 4 S/m
  • the electromagnetic shielding efficiency is 20 ⁇ 40dB at 10KHz
  • the thermal conductivity is 1.5 ⁇ 2.0W/(m ⁇ K)
  • the thermal conductivity is at 14.5°C.
  • Neutron capture cross-section 0.01 ⁇ 0.1mbar; three-point bending elastic modulus 0.2 ⁇ 1Mpa; PC/PC shear strength 4 ⁇ 5Mpa, pullout strength 5 ⁇ 7MPa; glass/glass shear strength 7 ⁇ 8MPa, pullout strength 8 ⁇ 10MPa; After 1000 hours of'double 85' aging test, the loss rate of electromagnetic and thermal shielding effectiveness is within 10%, and the loss rate of mechanical strength is within 25%.
  • Example 1 A graphene UV pressure-sensitive adhesive and its preparation method
  • a graphene UV pressure-sensitive adhesive which is characterized by comprising the following components and weight percentages:
  • the aliphatic urethane acrylate is a compound conforming to the general formula C:
  • R 1 represents hexamethylene
  • the glass transition temperature (Tg, °C) is controlled within -30 ⁇ 30.
  • the polysiloxane acrylate conforms to the structural formula:
  • the reactive diluent is alkoxy tetrahydrofuran acrylate; surface tension (Dyne/cm, 20°C) is within 20-40; glass transition temperature (Tg,°C) is controlled within -60-40.
  • the tackifying resin is a tricyclic diterpenoid compound.
  • the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • the stabilizer is tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
  • the graphene is a single-layer graphene.
  • the diameter of carbon nanotubes is within 0.5-2 nanometers, the length is within 0.1-2 microns, and the wall thickness of 1 gram is 10 13 ⁇ 10 15 PCS.
  • the carbon interface treatment agent is diborane.
  • the hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction.
  • R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy).
  • R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group. This embodiment is specifically propyl.
  • the functional additive is polyether modified dimethyl polysiloxane copolymer.
  • a method for preparing graphene UV pressure-sensitive adhesive includes the following steps:
  • the high speed is 50r/min; the low speed is 15r/min; the negative pressure condition is that the vacuum degree is -0.09MPa.
  • Example 2 A graphene UV pressure-sensitive adhesive and its preparation method
  • a graphene UV pressure-sensitive adhesive including the following mass percentages of raw materials:
  • aromatic urethane acrylate is a mixture of compounds conforming to the general formula A and the general formula B in a mass ratio of 1:1:
  • aliphatic urethane acrylate is a mixture of compounds conforming to the general formula C and the general formula D in a mass ratio of 1:1:
  • polysiloxane acrylate is a mixture of compounds conforming to the general formula E, the general formula F and the general formula G in a mass ratio of 1:2:1:
  • the reactive diluent is a mixture of alkoxylated tetrahydrofuran acrylate and ethoxylated nonylphenol acrylate in a mass ratio of 1:1.
  • the tackifying resin is rosinane-8,11,13-triene-7-ol, 12-ethyl-13-methoxy-8,11,13-podrobanines- A mixture of 7-ketones in a mass ratio of 1:1.
  • the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide according to 1. : A mixture composed of a mass ratio of 1.
  • a preferred embodiment is that the stabilizer is a mixture of hydroxyanisole and hydroquinone in a mass ratio of 1:1.
  • the graphene is a mixture of single-layer graphene and double-layer graphene in a mass ratio of 1:2; the graphene loose packing density is within 0.04 g/cm 3 and the tap density is 0.08g/cm 3 .
  • the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:2, and the carbon nanotubes have a diameter of 0.5-2 nanometers and a length of 0.1- 2 microns, 1 gram wall thickness is 10 13 -10 15 PCS.
  • the carbon interface treatment agent is a mixture of diborane and pentaborane in a mass ratio of 1:5.
  • Y represents a mercapto group
  • R represents an alkylene group
  • X represents a hydrolyzable group
  • n 1.
  • the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and this embodiment is specifically a butylene group.
  • the hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction.
  • R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolysis of a hydrolyzable group. In this example, it is specifically a halogen.
  • the functional additive is a mixture of polyether modified dimethyl polysiloxane copolymer and foam-breaking polysiloxane non-aqueous emulsion in a mass ratio of 1:2.
  • the method of preparing graphene UV pressure-sensitive adhesive includes the following steps:
  • Step 1 Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
  • Step 2 Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
  • Step 3 In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
  • Step 4 Take out the glue sample, irradiate it under 500 millijoule ultraviolet light for 60 seconds, and then perform the test. After reaching the standard requirements, the graphene UV pressure-sensitive adhesive will be made from the material after discharge.
  • a preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.00.1 MPa.
  • Example 3 A graphene UV pressure-sensitive adhesive and its preparation method
  • a graphene UV pressure-sensitive adhesive including the following mass percentages of raw materials:
  • polysiloxane acrylate is a compound conforming to the general formula G:
  • R 2 represents isophorone dicyclohexylmethane tolyl, and the viscosity is 500-50000 mPa ⁇ s at 25°C.
  • the reactive diluent is a mixture of tridecyl acrylate and ethylated nonylphenol acrylate in a mass ratio of 1:2.
  • the tackifying resin is 13-methoxy-6-hydroxy-undecane-5,8,11,13-tetraene-7-one and 13-hydroxy-8(14)-rosin A mixture of olefins in a mass ratio of 1:1.
  • the photoinitiator is 2-phenylbenzyl-dimethylamine-4-morpholinopropyl phenyl ketone.
  • a preferred embodiment is that the stabilizer is 2,6-di-tert-butyl-4-methylphenol.
  • the graphene is a multilayer graphene; the graphene has a loose packing density of 0.05 g/cm 3 or less, and a tap density of 0.1 g/cm 3 .
  • the carbon nanotubes are single-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers, a length of 0.1-2 micrometers, and a wall thickness of 10 13 -10 15 PCS per gram.
  • the carbon interface treatment agent is decaborane.
  • Y represents amino group, mercapto group, long-chain alkyl group, epoxy group, cyano group and methyl propionyloxy group
  • R represents propylene group
  • X represents -OCH 3
  • n 0.
  • the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.
  • the hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction.
  • -OR, -OCOR, -ON CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms, etc., preferably -OR (ie alkane Oxy).
  • R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group.
  • a preferred embodiment is that the functional additive is a copolymer of electrically neutral polyamide and polyester.
  • the method of preparing graphene UV pressure-sensitive adhesive includes the following steps:
  • Step 1 Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
  • Step 2 Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
  • Step 3 In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
  • Step 4 Take out the glue sample, irradiate it under 1000 millijoule ultraviolet light for 10 seconds, and then perform the test. After reaching the standard requirement, the graphene UV pressure-sensitive adhesive will be made out of the material.
  • the negative pressure condition is that the vacuum degree is -0.1 MPa.
  • Example 4 A graphene UV pressure-sensitive adhesive and its preparation method
  • R 1 represents a tolyl group
  • the viscosity is 500-1000 mPa ⁇ s at 25°C.
  • R 1 represents hexamethylene; at 25°C, the viscosity is 500-1000 mPa ⁇ s.
  • polysiloxane acrylate is at least one of the compounds conforming to the general formula E, the general formula F and the general formula G:
  • m 10; at 25°C, the viscosity is 500 to 50,000 mPa ⁇ s.
  • a preferred embodiment is that the reactive diluent is lauryl alkoxide acrylate.
  • tackifying resin is 13-hydroxy-8(14)-rosinene.
  • a preferred embodiment is that the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • a preferred embodiment is that the stabilizer is tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.
  • the graphene is a double-layer graphene; the graphene has a loose packing density of 0.02 g/cm 3 or less, and a tap density of 0.08 g/cm 3 .
  • the carbon nanotubes are single-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers, a length of 0.1-2 micrometers, and a wall thickness of 10 13 -10 15 PCS per gram.
  • a preferred embodiment is that the carbon interface treatment agent is diborane.
  • Y represents an amino group, a mercapto group, a long-chain alkyl group, an epoxy group, a cyano group, and a methylpropionyloxy group
  • R represents a methylene group
  • X represents a hydrolyzable group
  • n 1.
  • the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.
  • the hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction.
  • -OR, -OCOR, -O-N CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy).
  • R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolysis of a hydrolyzable group. In this example, it is specifically an isopropyl group.
  • the functional additive is a polyether modified dimethyl polysiloxane copolymer.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

A graphene UV pressure-sensitive adhesive and a preparation method therefor. The graphene UV pressure-sensitive adhesive has a formula comprising the following raw materials: aromatic carbamate acrylate, aliphatic carbamate acrylate, polysiloxane acrylate, a reactive diluent, a tackifying resin, a photosensitive initiator, a stabilizer, graphene, a carbon nanotube, a carbon interface treating agent, a silane coupling agent, and a functional additive. The graphene UV pressure-sensitive adhesive is light in weight, viscoelastic, fine and uniform in cross-section foam pores, is firm in bonding with a base material due to the interaction between a graphene nanometer thin film and an organic silicon material base body, excellent in compression resistance, impact resistance and thermal stability, and applicable to lightweight application scenes such as sealing shock absorption, microwave absorption, electromagnetic shielding, and heat dissipation protection. Compared with the prior art, the graphene UV pressure-sensitive adhesive has the following physical properties: the electromagnetic and thermal simultaneous shielding performance is achieved, the weight ratio and volume ratio are properly controlled, the curing rate and curing degree are good, and the excellent mechanical strength and reliable stability are achieved by means of the synergistic effect of the components.

Description

一种石墨烯UV压敏胶及其制备方法Graphene UV pressure-sensitive adhesive and preparation method thereof 技术领域Technical field
本发明属于胶粘材料技术领域，涉及一种石墨烯UV压敏胶及其制备方法。The invention belongs to the technical field of adhesive materials, and relates to a graphene UV pressure-sensitive adhesive and a preparation method thereof.
背景技术Background technique
丙烯酸及丙烯酸酯类低聚物由丙烯酰氧基、乙烯基和烯丙基等不饱和双键和环氧、聚氨基甲酸酯、聚硅氧烷和聚醚等酯化的基团构成，不饱和低聚物的杂化结构使自由基光固化材料兼备环氧、聚氨基甲酸酯、聚硅氧烷、聚醚和丙烯酸及丙烯酸酯的性能，耐冲击性、耐候性、耐药品性和优异的物理强度使丙烯酸光固化材料日益突出，更容易满足高速的流水线作业和高效的工业生产要求。光固化压敏胶是丙烯酸光固化材料应用领域与众不同的分支部分，它的特点在于高速高效、高柔韧性、低收缩性、低弹性模量和对多种基材具有优异的粘基力等，广泛应用于各类电子元器件的粘结、密封和保护等，作业环境常介于机械频率1000HZ到机器作业的最高频率之间，粘基力基本不变，特殊的压敏胶甚至能承受200HZ到800OHZ的机械频率的循环冲击，且作业性稳定可靠。Acrylic acid and acrylate oligomers are composed of unsaturated double bonds such as acryloxy, vinyl and allyl groups and esterified groups such as epoxy, polyurethane, polysiloxane and polyether. The hybrid structure of unsaturated oligomers makes free radical light-curable materials have the properties of epoxy, polyurethane, polysiloxane, polyether, acrylic acid and acrylic ester, impact resistance, weather resistance, and chemical resistance. Properties and excellent physical strength make acrylic light-curable materials increasingly prominent, making it easier to meet the requirements of high-speed assembly line operations and efficient industrial production. Light-curing pressure-sensitive adhesive is a distinctive branch of acrylic light-curing material application field. It is characterized by high speed and efficiency, high flexibility, low shrinkage, low elastic modulus and excellent adhesion to a variety of substrates. It is widely used in the bonding, sealing and protection of various electronic components. The operating environment is often between the mechanical frequency of 1000HZ and the highest frequency of machine operation. The base force is basically unchanged. Special pressure-sensitive adhesives can even Withstand the cyclic impact of mechanical frequency from 200HZ to 800OHZ, and the workability is stable and reliable.
随着电子元器件轻量微型化和密度集中化的迅速发展，相应的封装材料线分辨率、电气化程度和使用工艺等性能显得尤为关键。为了满足丙烯酸光固化材料在电子工业各领域的应用，常用功能化填料即金属和金属氧化物等糅合丙烯酸基体树脂，经过光固化和收缩，丙烯酸材料内部的功能化填料形成闭路和导通，实现电子电气化性能和敏感元器件的功能化连接。传统的金属和金属氧化物等电子电气化功能单一，作用有限，低量填充无法形成有效闭路和导通，高量填充在丙烯酸基体树脂占据庞大体积比和重量比，易迁移、沉降和分层，严重影响丙烯酸光固化材料的固化速率和固化程度，固化缺陷越来越明显，常出现固化不均匀、多孔和固化层与基材附着力弱等问题。大量功能化填料使得丙烯酸光固化压敏胶表面张力增加，粘弹性和粘基力消失，弹性模量升高，压缩量和抗疲劳性严重降低，作业时对电子元件产生机械应力，破坏敏感元器件。且功能化金属和金属氧化物与丙烯酸复合材料作业稳定性差，在湿热等特殊环境中，作用力和功能性随时间延长逐渐消失，可靠性受到严重影响。所以如何降低和优化功能化填料在丙烯酸基体树脂中体积比与重量比，如何丰富和提高丙烯酸光固化材料的电子电气化性能，成为丙烯酸材料研究领域的重要方向之一。With the rapid development of light-weight miniaturization and density concentration of electronic components, the line resolution, electrification degree and use process of the corresponding packaging materials are particularly critical. In order to meet the application of acrylic light-curable materials in various fields of the electronics industry, commonly used functionalized fillers, such as metals and metal oxides, are combined with acrylic matrix resins. After light curing and shrinkage, the functionalized fillers inside the acrylic material form a closed circuit and conduction. Electronic performance and functional connection of sensitive components. The traditional electronic and electrification functions such as metals and metal oxides are single and limited. Low-volume filling cannot form an effective closed circuit and conduction. High-volume filling of acrylic matrix resin occupies a huge volume ratio and weight ratio, and is easy to migrate, settle and delamination. Seriously affect the curing rate and curing degree of acrylic light-curing materials, curing defects are becoming more and more obvious, and problems such as uneven curing, porous and weak adhesion between the cured layer and the substrate often occur. A large number of functional fillers increase the surface tension of acrylic light-curing pressure-sensitive adhesives, disappear viscoelasticity and base force, increase elastic modulus, severely reduce compression and fatigue resistance, generate mechanical stress on electronic components during operation, and damage sensitive elements. Device. In addition, functionalized metals and metal oxides and acrylic composites have poor operational stability. In special environments such as heat and humidity, the force and functionality gradually disappear with time, and reliability is seriously affected. Therefore, how to reduce and optimize the volume ratio and weight ratio of the functional filler in the acrylic matrix resin, and how to enrich and improve the electronic and electrical properties of acrylic light-curable materials have become one of the important directions in the research field of acrylic materials.
石墨烯是一种由碳原子以SP 2杂化方式形成的蜂窝状六角型晶格二维碳纳米平面单原子层材料，是除金刚石外所有碳晶体的基本结构单元。石墨烯具有优异的光学、电学和热学特性，对材料学基础研究有着特殊意义，是一种未来革命性的材料。石墨烯在较宽波长范围内吸收率约为2.3％，不寻常低能电子结构使石墨烯纳米带的光学响应可调谐至太赫兹范围，在密集的激光照明下，石墨烯时常出现一个非线性相移的光学非线性克尔效应。优异的光学性能，以及适宜得当的体积比和重量比，几乎不影响丙烯酸光固化材料的固化速率和固化程度。石墨烯在辐射下稳定，不产生高能量射线或只产生低能量射线，热中子吸收截面小，优异的高能量射线衰减和热中子吸收慢化性能有效减弱辐射能量进入电子工业设备，保护敏感元件不致因吸收辐射能量产生大量热量引起巨大的热应力而损坏。不仅如此，石墨烯中的载流子遵循一种特殊的量子隧道效应，即使在碰到杂质时也不会产生背反射，超高的载流子迁移率和超强的局域导电性导致电磁感应在石墨烯上产生反向电磁场和涡流，减弱和抵消干扰电磁波的作用，达到最佳的电磁屏蔽效果。将石墨烯加入丙烯酸基体树脂中，线分辨率高，适用于精细的引线间距和高密度组装，符合轻量化、微型化的微电子产品高速流水作业封装需求，且达到了电磁和热同时屏蔽的性能，各组分协同作用，致使丙烯酸光固化材料具有良好的耐热性和抗疲劳性，与各种基材粘结牢固，剥离力强大，电子电气化性能稳定可靠。 Graphene is a honeycomb hexagonal lattice two-dimensional carbon nano-plane monoatomic layer material formed by carbon atoms in SP 2 hybrid mode. It is the basic structural unit of all carbon crystals except diamond. Graphene has excellent optical, electrical and thermal properties, which is of special significance to the basic research of materials science and is a revolutionary material in the future. The absorption rate of graphene in a wide wavelength range is about 2.3%. The unusual low-energy electronic structure enables the optical response of graphene nanoribbons to be tuned to the terahertz range. Under intensive laser illumination, graphene often exhibits a nonlinear phase. The optical nonlinear Kerr effect of shifting. Excellent optical properties, and appropriate volume ratio and weight ratio, hardly affect the curing rate and degree of curing of acrylic light-curing materials. Graphene is stable under radiation, does not generate high-energy rays or only low-energy rays, has a small thermal neutron absorption cross-section, and has excellent high-energy ray attenuation and thermal neutron absorption slowing performance, which effectively reduces the radiation energy entering electronic industrial equipment and protects Sensitive components will not be damaged due to huge thermal stress caused by a large amount of heat generated by absorbing radiant energy. Not only that, the carriers in graphene follow a special quantum tunneling effect, even when it encounters impurities, there will be no back reflection, ultra-high carrier mobility and ultra-strong local conductivity lead to electricity Magnetic induction produces reverse electromagnetic fields and eddy currents on the graphene to weaken and offset the effect of interference electromagnetic waves to achieve the best electromagnetic shielding effect. Adding graphene to the acrylic matrix resin has high line resolution, suitable for fine lead spacing and high-density assembly, and meets the requirements of lightweight and miniaturized microelectronic products for high-speed flow packaging, and achieves simultaneous electromagnetic and thermal shielding The performance and the synergistic effect of each component make the acrylic light-curable material have good heat resistance and fatigue resistance, strong adhesion with various substrates, strong peeling force, and stable and reliable electronic and electrification performance.
发明内容Summary of the invention
本发明的目的在于提供一种石墨烯UV压敏胶及制备方法。The purpose of the present invention is to provide a graphene UV pressure-sensitive adhesive and a preparation method.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种石墨烯UV压敏胶，包括下列质量百分比的原料：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a graphene UV pressure-sensitive adhesive, including the following raw materials in mass percentages:
Figure PCTCN2020114655-appb-000001
Figure PCTCN2020114655-appb-000001
Figure PCTCN2020114655-appb-000002
Figure PCTCN2020114655-appb-000002
优选的技术方案为：所述芳香族氨基甲酸酯丙烯酸酯为符合通式A和通式B的化合物中的至少一种：The preferred technical solution is that the aromatic urethane acrylate is at least one of the compounds conforming to the general formula A and the general formula B:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                                 通式A；General formula A;
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 3NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 3 NHCOOCH 2 CH 2 OOCCHCH 2
                                   通式B；General formula B;
其中R 1代表甲苯基、二苯基甲烷或苯二亚甲基；其中R 2代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝1～10，m＝1～5；R 3代表六亚甲基、异佛尔酮、二环己基甲烷甲苯基、二苯基甲烷或苯二亚甲基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents tolyl, diphenylmethane or xylylene; where R 2 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O]m [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=1～10, m=1～5; R 3 represents hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane or xylylene; the viscosity is 500-1000mPa·s at 25°C.
优选的技术方案为：所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C和通式D的化合物中的至少一种：The preferred technical solution is that the aliphatic urethane acrylate is at least one of the compounds conforming to the general formula C and the general formula D:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                                        通式C；General formula C;
R 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2            通式D； R 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula D;
其中R 1代表六亚甲基、异佛尔酮和二环己基甲烷；其中R 2代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝1～10，m＝1～5；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents hexamethylene, isophorone and dicyclohexylmethane; where R 2 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O] m[CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=1～10, m=1～5; At 25°C, the viscosity is 500 to 1000 mPa·s.
优选的技术方案为：所述聚硅氧烷丙烯酸酯为符合通式E、通式F和通式G的化合物中的至少一种：The preferred technical solution is that the polysiloxane acrylate is at least one of the compounds conforming to the general formula E, the general formula F and the general formula G:
CH 2CHCOOCH 2CH 2O[Si(CH 3)O] nCH 2CH 2OOCCHCH 2      通式E； CH 2 CHCOOCH 2 CH 2 O[Si(CH 3 )O] n CH 2 CH 2 OOCCHCH 2 general formula E;
CH 2CHCOOR[Si(CH 3) 2O] nSi(CH 3) 2ROOCCHCH 2(n＝20～80)      通式 F； CH 2 CHCOOR[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 ROOCCHCH 2 (n=20～80) General formula F;
CH 2CHCOOCH 2CH 2OOCNHR 2NHCOOR 1[Si(CH 3) 2O]Si(CH 3) 2R 1OOCNHR 2NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 2 NHCOOR 1 [Si (CH 3) 2 O] Si (CH 3) 2 R 1 OOCNHR 2 NHCOOCH 2 CH 2 OOCCHCH 2
通式G；General formula G;
R 1代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝20-80；R 2代表六亚甲基、异佛尔酮二环己基甲烷甲苯基、二苯基甲烷、苯二亚甲基，在25℃时，粘度为500～50000mPa·s。 R 1 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O]m[CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=20-80; R 2 stands for hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane, benzene two Methylene has a viscosity of 500 to 50,000 mPa·s at 25°C.
优选的技术方案为：所述活性稀释剂为烷氧化四氢呋喃丙烯酸酯、乙氧化壬基苯酚丙烯酸酯、烷氧化壬基苯酚丙烯酸酯、烷氧化丙烯酸月桂酯、丙烯酸异癸酯、丙烯酸异癸酯、丙烯酸十三烷基酯、乙基化壬基苯酚丙烯酸酯和丙氧化新戊二醇二丙烯酸酯中的至少一种。The preferred technical solution is: the reactive diluent is alkoxylated tetrahydrofuran acrylate, ethoxylated nonylphenol acrylate, alkoxylated nonylphenol acrylate, alkoxylated lauryl acrylate, isodecyl acrylate, isodecyl acrylate, At least one of tridecyl acrylate, ethylated nonylphenol acrylate, and propoxylated neopentyl glycol diacrylate.
优选的技术方案为：所述增粘树脂为松香烷-8,11,13-三烯-7-醇、12-乙基-13-甲氧基-8,11,13-罗汉松三烯-7-酮、13-甲氧基-6-羟基钩勿烷-5,8,11,13-四烯-7-酮和13-羟基-8(14)-松香烯中的至少一种。The preferred technical solution is: the tackifying resin is rosinane-8,11,13-triene-7-ol, 12-ethyl-13-methoxy-8,11,13-podnatriene- At least one of 7-ketone, 13-methoxy-6-hydroxybenzidine-5,8,11,13-tetraene-7-one, and 13-hydroxy-8(14)-rosinene.
优选的技术方案为：所述光敏引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-苯基苄-二甲基胺-4-吗啉代丙基苯基酮和1-羟基环已基苯基甲酮中的至少一种。The preferred technical solution is: the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2 -At least one of phenylbenzyl-dimethylamine-4-morpholinopropyl phenyl ketone and 1-hydroxycyclohexyl phenyl ketone.
优选的技术方案为：所述稳定剂为三(N-亚硝基-N-苯基羟胺)铝盐、羟基苯甲醚、对苯二酚、对苯醌和2,6-二叔丁基-4-甲基苯酚中的至少一种。The preferred technical solution is: the stabilizer is tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, hydroxyanisole, hydroquinone, p-benzoquinone and 2,6-di-tert-butyl At least one of -4-methylphenol.
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯、少层石墨烯和多层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm 3以内，振实密度为0.05～0.1g/cm 3。 The preferred technical solution is: the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; and the graphene loose packing density is 0.01-0.05 g/cm Within 3 , the tap density is 0.05～0.1g/cm 3 .
优选的技术方案为：所述碳纳米管为单壁碳纳米管和多壁碳纳米管中的一种或两种，所述碳纳米管直径为0.5-2纳米，长度为0.1-2微米，1克壁厚为10 13-10 15PCS。 The preferred technical solution is: the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers and a length of 0.1-2 micrometers, The wall thickness of 1 gram is 10 13 -10 15 PCS.
优选的技术方案为：所述碳界面处理剂为乙硼烷、戊硼烷、癸硼烷和碳硼烷中的至少一种。The preferred technical solution is that the carbon interface treatment agent is at least one of diborane, pentaborane, decaborane and carborane.
优选的技术方案为：所述硅烷偶联剂为符合通式下列通式的化合物：The preferred technical solution is: the silane coupling agent is a compound conforming to the following general formula:
YR nSiX 3-n YR n SiX 3-n
其中Y代表氨基、巯基、长链烷基、环氧基、氰基和甲基丙乙烯酰氧基，R 代表亚烷基，X代表能够水解的基团，n＝0或1。亚烷基为碳原子数2～20的取代或非取代的亚烷基。能够水解的基团是指能够通过水解反应从化合物的主骨架上脱离的基团。例如：-OR、-OCOR、-O－N＝CR2、-NR2、－NHR、卤素，这些式中，R表示取代或非取代的碳原子数1～4的烷基等，优选为-OR(即烷氧基)。R的例子包括甲基、乙基、丙基、异丙基、正丁基、异丁基等非取代烷基；氯甲基等取代烷基。这些之中，优选烷基、特别是非取代烷基，更优选为甲基或乙基。羟基没有特别限定，可以为能够水解的基团发生水解而生成的羟基。Wherein Y represents an amino group, a mercapto group, a long-chain alkyl group, an epoxy group, a cyano group and a methacryloxy group, R represents an alkylene group, X represents a hydrolyzable group, and n=0 or 1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group.
优选的技术方案为：所述功能型添加剂为聚醚改性二甲基聚硅氧烷共聚物、破泡聚硅氧烷非水乳液、非离子型聚硅氧烷共聚物、电中性聚酰胺与聚酯共聚物、低分子量不饱和羧酸聚合物、含酸性基团的嵌段共聚物烷烃基铵盐和微粉化改性高密度聚乙烯蜡混合物中的至少一种。The preferred technical solution is: the functional additive is polyether modified dimethyl polysiloxane copolymer, foam-breaking polysiloxane non-aqueous emulsion, non-ionic polysiloxane copolymer, electrically neutral polysiloxane At least one of amide and polyester copolymer, low-molecular-weight unsaturated carboxylic acid polymer, block copolymer containing acidic group alkane ammonium salt, and micronized modified high-density polyethylene wax mixture.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯UV压敏胶的方法：其特征在于：包括下列步骤：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a method for preparing graphene UV pressure-sensitive adhesive: It is characterized in that it includes the following steps:
步骤1：向反应釜中依次加入芳香族氨基丙烯酸酯、脂肪族氨基丙烯酸酯、聚硅氧烷丙烯酸酯、活性稀释剂、增粘树脂和稳定剂，在负压条件下，搅拌分散均匀；Step 1: Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
步骤2：向反应釜中加入石墨烯、碳纳米管、碳界面处理剂和硅烷偶联剂，在负压条件下，搅拌分散均匀；Step 2: Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
步骤3：在黄光环境下，向反应釜中加入光敏引发剂，在负压条件下，搅拌分散均匀；Step 3: In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
步骤4：取出胶样，在500～1000毫焦紫外光下照射10～60秒，然后进行测试，达到标准要求后，出料即制成石墨烯UV压敏胶。Step 4: Take out the glue sample, irradiate it under 500-1000 millijoule ultraviolet light for 10-60 seconds, and then perform the test. After reaching the standard requirements, the material is discharged to make graphene UV pressure-sensitive adhesive.
优选的技术方案为：：负压条件为真空度为-0.08～-0.1MPa。The preferred technical solution is: the negative pressure condition is that the vacuum degree is -0.08～-0.1MPa.
由于上述技术方案运用，本发明与现有技术相比具有的优点是：Due to the application of the above technical solutions, the advantages of the present invention compared with the prior art are:
本发明与现有技术相比，石墨烯UV压敏胶的物理性质，不仅达到了电磁和热同时屏蔽的性能，而且重量比和体积比控制适当，固化速率和固化程度良好，各组分协同作用，达到了优秀的力学强度和可靠稳定性。通过测试，该石墨烯压敏胶的电导率在10 3～10 4S/m，在10KHz处电磁屏蔽效能20～40dB；导热率1.5～2.0W/(m·K)，在14.5℃时热中子俘获截面0.01～0.1mbar；三点弯弹性模量0.2～1Mpa；PC/PC剪切强度4～5Mpa，拉拔强度5～7MPa；玻璃/玻璃剪切强度7～8MPa，拉 拔强度8～10MPa；经过1000个小时的‘双85’老化测试，电磁和热屏蔽效能损耗率在10％以内，力学强度损耗率在25％以内。 Compared with the prior art, the physical properties of the graphene UV pressure-sensitive adhesive not only achieve the performance of simultaneous electromagnetic and thermal shielding, but also the weight ratio and volume ratio are properly controlled, the curing rate and the curing degree are good, and the components are synergistic. It has achieved excellent mechanical strength and reliable stability. Through the test, the conductivity of the graphene pressure-sensitive adhesive is 10 3 ～10 4 S/m, the electromagnetic shielding efficiency is 20～40dB at 10KHz; the thermal conductivity is 1.5～2.0W/(m·K), and the thermal conductivity is at 14.5℃. Neutron capture cross-section 0.01～0.1mbar; three-point bending elastic modulus 0.2～1Mpa; PC/PC shear strength 4～5Mpa, pullout strength 5～7MPa; glass/glass shear strength 7～8MPa, pullout strength 8 ~10MPa; After 1000 hours of'double 85' aging test, the loss rate of electromagnetic and thermal shielding effectiveness is within 10%, and the loss rate of mechanical strength is within 25%.
具体实施方式Detailed ways
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The following specific examples illustrate the implementation of the present invention. Those familiar with the technology can easily understand the other advantages and effects of the present invention from the content disclosed in this specification.
实施例1：一种石墨烯UV压敏胶及制备方法Example 1: A graphene UV pressure-sensitive adhesive and its preparation method
一种石墨烯UV压敏胶，其特征在于，包括以下组分及重量百分数：A graphene UV pressure-sensitive adhesive, which is characterized by comprising the following components and weight percentages:
Figure PCTCN2020114655-appb-000003
Figure PCTCN2020114655-appb-000003
所述的芳香族氨基甲酸酯丙烯酸酯符合结构式的化合物The compound of the aromatic urethane acrylate conforming to the structural formula
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2                  通式A； CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula A;
其中R 1代表甲苯基；其中R 2代表[CH 2CH 2O]m[CH 2CHO(CH 3)]n，n＝5，m＝2；25℃时，粘度在500～1000mPa·s以内，分子量在1000～2000以内，玻璃化温度(Tg,℃)控制在-30～30以内。 Wherein R 1 represents tolyl; where R 2 represents [CH 2 CH 2 O]m[CH 2 CHO(CH 3 )]n, n=5, m=2; at 25℃, the viscosity is within 500～1000mPa·s , The molecular weight is within 1000-2000, and the glass transition temperature (Tg, ℃) is controlled within -30-30.
所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C的化合物：The aliphatic urethane acrylate is a compound conforming to the general formula C:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2                 通式C； CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula C;
其中R 1代表六亚甲基；其中R 2代表[CH 2CH 2O]n，n＝5；在25℃时，25℃时，粘度在500～1000mPa·s以内，分子量在1000～2000以内，玻璃化温度(Tg,℃)控制在-30～30以内。 Wherein R 1 represents hexamethylene; where R 2 represents [CH 2 CH 2 O]n, n=5; at 25℃, at 25℃, the viscosity is within 500～1000mPa·s and the molecular weight is within 1000～2000 , The glass transition temperature (Tg, ℃) is controlled within -30～30.
所述的聚硅氧烷丙烯酸酯符合结构式为：The polysiloxane acrylate conforms to the structural formula:
A)CH 2CHCOOCH 2CH 2O[Si(CH 3)O] nCH 2CH 2OOCCHCH 2，n＝60。 A) CH 2 CHCOOCH 2 CH 2 O[Si(CH 3 )O] n CH 2 CH 2 OOCCHCH 2 , n=60.
所述的活性稀释剂为烷氧化四氢呋喃丙烯酸酯；表面张力(Dyne/cm,20℃)在20～40以内；玻璃化温度(Tg,℃)控制在-60～40以内。The reactive diluent is alkoxy tetrahydrofuran acrylate; surface tension (Dyne/cm, 20°C) is within 20-40; glass transition temperature (Tg,°C) is controlled within -60-40.
所述的增粘树脂为三环二萜类化合物。The tackifying resin is a tricyclic diterpenoid compound.
所述的光敏引发剂为2-羟基-2-甲基-1-苯基-1-丙酮。The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
所述的稳定剂为三(N-亚硝基-N-苯基羟胺)铝盐。The stabilizer is tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
所述的石墨烯为单层石墨烯。碳纳米管直径在0.5～2纳米以内，长度在0.1～2微米以内，1克壁厚在10 13～10 15PCS。 The graphene is a single-layer graphene. The diameter of carbon nanotubes is within 0.5-2 nanometers, the length is within 0.1-2 microns, and the wall thickness of 1 gram is 10 13 ～10 15 PCS.
所述的碳界面处理剂为乙硼烷。The carbon interface treatment agent is diborane.
所述的硅烷偶联剂符合结构通式YR nSiX 3-n其中Y代表有机官能团，R代表亚烷基，X代表能够水解的基团，n＝0～3；的功能性添加剂；n＝1，Y为氨基；亚烷基为碳原子数2～20的取代或非取代的亚烷基，本实施例具体为亚甲基。能够水解的基团是指能够通过水解反应从化合物的主骨架上脱离的基团。例如：-OR、-OCOR、-O－N＝CR2、-NR2、－NHR、卤素，这些式中，R表示取代或非取代的碳原子数1～4的烷基等，优选为-OR(即烷氧基)。R的例子包括甲基、乙基、丙基、异丙基、正丁基、异丁基等非取代烷基；氯甲基等取代烷基。这些之中，优选烷基、特别是非取代烷基，更优选为甲基或乙基。羟基没有特别限定，可以为能够水解的基团发生水解而生成的羟基。本实施例具体为丙基。 The silane coupling agent meets the general structural formula YR n SiX 3-n, where Y represents an organic functional group, R represents an alkylene group, X represents a hydrolyzable group, n=0 to 3; functional additives; n= 1, Y is an amino group; the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and this embodiment is specifically a methylene group. The hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group. This embodiment is specifically propyl.
所述的功能型添加剂为聚醚改性二甲基聚硅氧烷共聚物。The functional additive is polyether modified dimethyl polysiloxane copolymer.
一种石墨烯UV压敏胶的制备方法，包括以下步骤：A method for preparing graphene UV pressure-sensitive adhesive includes the following steps:
(1)向反应釜中依次加入芳香族氨基丙烯酸酯、脂肪族氨基丙烯酸酯、聚硅氧烷丙烯酸酯、活性稀释剂、的增粘树脂(80℃下溶解至无颗粒)和稳定剂，在负压条件下高速搅拌，至分散均匀；(1) Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin (dissolved to no particles at 80°C) and stabilizer in sequence into the reactor, Stir at high speed under negative pressure until the dispersion is even;
(2)继续向反应釜中加入配方总重量石墨烯、碳纳米管、碳界面处理剂和硅烷偶联剂，先低速搅拌，再在负压条件下，高速搅拌，至分散均匀；(2) Continue to add the total formula weight graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, first stir at low speed, and then stir at high speed under negative pressure until the dispersion is uniform;
(3)在黄光环境下，向反应釜中加入配方总重量光敏引发剂，在负压条件下高速搅拌，至分散均匀；(3) In a yellow light environment, add the total weight of the photoinitiator to the reaction kettle, stir at high speed under negative pressure, until the dispersion is uniform;
(4)取出胶样，在750毫焦紫外光下照射35秒，然后进行测试，达到标准要求后，出料，即制成石墨烯UV压敏胶。(4) Take out the glue sample, irradiate it under 750 millijoule ultraviolet light for 35 seconds, and then perform the test. After reaching the standard requirements, the material is discharged, and the graphene UV pressure-sensitive adhesive is made.
步骤(1)～(4)中所述高速为50r/min；低速为15r/min；负压条件为真空 度为-0.09MPa。In steps (1) to (4), the high speed is 50r/min; the low speed is 15r/min; the negative pressure condition is that the vacuum degree is -0.09MPa.
实施例2：一种石墨烯UV压敏胶及制备方法Example 2: A graphene UV pressure-sensitive adhesive and its preparation method
一种石墨烯UV压敏胶，包括下列质量百分比的原料：A graphene UV pressure-sensitive adhesive, including the following mass percentages of raw materials:
Figure PCTCN2020114655-appb-000004
Figure PCTCN2020114655-appb-000004
优选的实施方式为：所述芳香族氨基甲酸酯丙烯酸酯为符合通式A和通式B的化合物按照1：1的质量比例构成的混合物：A preferred embodiment is that the aromatic urethane acrylate is a mixture of compounds conforming to the general formula A and the general formula B in a mass ratio of 1:1:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                          通式A；General formula A;
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 3NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 3 NHCOOCH 2 CH 2 OOCCHCH 2
                         通式B；Formula B;
其中R 1代表苯二亚甲基；其中R 2代表[CH 2CH 2O]n，n＝10；R 3代表苯二亚甲基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents xylylene; where R 2 represents [CH 2 CH 2 O]n, n = 10; R 3 represents xylylene; at 25° C., the viscosity is 500-1000 mPa·s.
优选的实施方式为：所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C和通式D的化合物按照1：1的质量比例构成的混合物：A preferred embodiment is that the aliphatic urethane acrylate is a mixture of compounds conforming to the general formula C and the general formula D in a mass ratio of 1:1:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2         通式C； CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula C;
R 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2      通式D； R 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula D;
其中R 1代表六亚甲基；其中R 2代表[CH 2CH 2O]n，n＝10；在25℃时，粘度 为500～1000mPa·s。 Wherein R 1 represents hexamethylene; where R 2 represents [CH 2 CH 2 O]n, n=10; at 25° C., the viscosity is 500-1000 mPa·s.
优选的实施方式为：所述聚硅氧烷丙烯酸酯为符合通式E、通式F和通式G的化合物按照1：2：1的质量比例构成的混合物：A preferred embodiment is that the polysiloxane acrylate is a mixture of compounds conforming to the general formula E, the general formula F and the general formula G in a mass ratio of 1:2:1:
CH 2CHCOOCH 2CH 2O[Si(CH 3)O] nCH 2CH 2OOCCHCH 2       通式E； CH 2 CHCOOCH 2 CH 2 O[Si(CH 3 )O] n CH 2 CH 2 OOCCHCH 2 general formula E;
CH 2CHCOOR[Si(CH 3) 2O] nSi(CH 3) 2ROOCCHCH 2(n＝20～80)    通式F； CH 2 CHCOOR[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 ROOCCHCH 2 (n=20～80) General formula F;
CH 2CHCOOCH 2CH 2OOCNHR 2NHCOOR 1[Si(CH 3) 2O]Si(CH 3) 2R 1OOCNHR 2NHCOOCH 2CH 2OOCCHCH 2         通式G； CH 2 CHCOOCH 2 CH 2 OOCNHR 2 NHCOOR 1 [Si (CH 3) 2 O] Si (CH 3) 2 R 1 OOCNHR 2 NHCOOCH 2 CH 2 OOCCHCH 2 Formula G;
R 1代表[CH 2CH 2O]n，n＝30；R 2代表苯二亚甲基，在25℃时，粘度为500～50000mPa·s。 R 1 represents [CH 2 CH 2 O]n, n=30; R 2 represents xylylene, and the viscosity is 500 to 50,000 mPa·s at 25°C.
优选的实施方式为：所述活性稀释剂为烷氧化四氢呋喃丙烯酸酯、乙氧化壬基苯酚丙烯酸酯按照1：1的质量比例构成的混合物。A preferred embodiment is that the reactive diluent is a mixture of alkoxylated tetrahydrofuran acrylate and ethoxylated nonylphenol acrylate in a mass ratio of 1:1.
优选的实施方式为：所述增粘树脂为松香烷-8,11,13-三烯-7-醇、12-乙基-13-甲氧基-8,11,13-罗汉松三烯-7-酮按照1：1的质量比例构成的混合物。A preferred embodiment is: the tackifying resin is rosinane-8,11,13-triene-7-ol, 12-ethyl-13-methoxy-8,11,13-podrobanines- A mixture of 7-ketones in a mass ratio of 1:1.
优选的实施方式为：所述光敏引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦按照1：1的质量比例构成的混合物。The preferred embodiment is: the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide according to 1. : A mixture composed of a mass ratio of 1.
优选的实施方式为：所述稳定剂为羟基苯甲醚、对苯二酚按照1：1的质量比例构成的混合物。A preferred embodiment is that the stabilizer is a mixture of hydroxyanisole and hydroquinone in a mass ratio of 1:1.
优选的实施方式为：所述石墨烯为单层石墨烯、双层石墨烯按照1：2的质量比例构成的混合物；所述石墨烯松装密度为0.04g/cm 3以内，振实密度为0.08g/cm 3。 A preferred embodiment is: the graphene is a mixture of single-layer graphene and double-layer graphene in a mass ratio of 1:2; the graphene loose packing density is within 0.04 g/cm 3 and the tap density is 0.08g/cm 3 .
优选的实施方式为：所述碳纳米管为单壁碳纳米管和多壁碳纳米管按照1：2的质量比例构成的混合物，所述碳纳米管直径为0.5-2纳米，长度为0.1-2微米，1克壁厚为10 13-10 15PCS。 A preferred embodiment is that the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:2, and the carbon nanotubes have a diameter of 0.5-2 nanometers and a length of 0.1- 2 microns, 1 gram wall thickness is 10 13 -10 15 PCS.
优选的实施方式为：所述碳界面处理剂为乙硼烷、戊硼烷按照1：5的质量比例构成的混合物。A preferred embodiment is that the carbon interface treatment agent is a mixture of diborane and pentaborane in a mass ratio of 1:5.
优选的实施方式为：所述硅烷偶联剂为符合通式下列通式的化合物：A preferred embodiment is that the silane coupling agent is a compound conforming to the following general formula:
YR nSiX 3-n YR n SiX 3-n
其中Y代表巯基，R代表亚烷基，X代表能够水解的基团，n＝1。亚烷基为碳原子数2～20的取代或非取代的亚烷基，本实施例具体为亚丁基。能够水解的基团是指能够通过水解反应从化合物的主骨架上脱离的基团。例如：-OR、-OCOR、-O－N＝CR2、-NR2、－NHR、卤素，这些式中，R表示取代或非取 代的碳原子数1～4的烷基等，优选为-OR(即烷氧基)。R的例子包括甲基、乙基、丙基、异丙基、正丁基、异丁基等非取代烷基；氯甲基等取代烷基。这些之中，优选烷基、特别是非取代烷基，更优选为甲基或乙基。羟基没有特别限定，可以为能够水解的基团发生水解而生成的羟基，本实施例具体为卤素。Where Y represents a mercapto group, R represents an alkylene group, X represents a hydrolyzable group, and n=1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and this embodiment is specifically a butylene group. The hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolysis of a hydrolyzable group. In this example, it is specifically a halogen.
优选的实施方式为：所述功能型添加剂为聚醚改性二甲基聚硅氧烷共聚物、破泡聚硅氧烷非水乳液按照1：2的质量比例构成的混合物。A preferred embodiment is: the functional additive is a mixture of polyether modified dimethyl polysiloxane copolymer and foam-breaking polysiloxane non-aqueous emulsion in a mass ratio of 1:2.
制备石墨烯UV压敏胶的方法：包括下列步骤：The method of preparing graphene UV pressure-sensitive adhesive includes the following steps:
步骤1：向反应釜中依次加入芳香族氨基丙烯酸酯、脂肪族氨基丙烯酸酯、聚硅氧烷丙烯酸酯、活性稀释剂、增粘树脂和稳定剂，在负压条件下，搅拌分散均匀；Step 1: Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
步骤2：向反应釜中加入石墨烯、碳纳米管、碳界面处理剂和硅烷偶联剂，在负压条件下，搅拌分散均匀；Step 2: Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
步骤3：在黄光环境下，向反应釜中加入光敏引发剂，在负压条件下，搅拌分散均匀；Step 3: In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
步骤4：取出胶样，在500毫焦紫外光下照射60秒，然后进行测试，达到标准要求后，出料即制成石墨烯UV压敏胶。Step 4: Take out the glue sample, irradiate it under 500 millijoule ultraviolet light for 60 seconds, and then perform the test. After reaching the standard requirements, the graphene UV pressure-sensitive adhesive will be made from the material after discharge.
优选的实施方式为：负压条件为真空度为-0.00.1MPa。A preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.00.1 MPa.
实施例3：一种石墨烯UV压敏胶及制备方法Example 3: A graphene UV pressure-sensitive adhesive and its preparation method
一种石墨烯UV压敏胶，包括下列质量百分比的原料：A graphene UV pressure-sensitive adhesive, including the following mass percentages of raw materials:
Figure PCTCN2020114655-appb-000005
Figure PCTCN2020114655-appb-000005
优选的实施方式为：所述芳香族氨基甲酸酯丙烯酸酯为符合通式B的化合物：A preferred embodiment is that the aromatic urethane acrylate is a compound conforming to the general formula B:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 3NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 3 NHCOOCH 2 CH 2 OOCCHCH 2
                            通式B；Formula B;
其中R 1代表甲苯基；其中R 2代表[CH 2CH 2O]m[CH 2CHO(CH 3)]n，n＝2，m＝3；R 3代表六亚甲基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents tolyl; where R 2 represents [CH 2 CH 2 O]m[CH 2 CHO(CH 3 )]n, n=2, m=3; R 3 represents hexamethylene; at 25℃ , The viscosity is 500～1000mPa·s.
优选的实施方式为：所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C化合物：A preferred embodiment is that the aliphatic urethane acrylate is a compound conforming to the general formula C:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2            通式C； CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula C;
其中R 1代表六亚甲基；其中R 2代表[CH 2CH 2CH 2CH 2O]n，n＝5；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents hexamethylene; where R 2 represents [CH 2 CH 2 CH 2 CH 2 O]n, n=5; at 25° C., the viscosity is 500-1000 mPa·s.
优选的实施方式为：所述聚硅氧烷丙烯酸酯为符合通式G的化合物：A preferred embodiment is: the polysiloxane acrylate is a compound conforming to the general formula G:
C)CH 2CHCOOCH 2CH 2OOCNHR 2NHCOOR 1[Si(CH 3) 2O]Si(CH 3) 2R 1OOCNHR 2NHCOOCH 2CH 2OOCCHCH 2           通式G； C) CH 2 CHCOOCH 2 CH 2 OOCNHR 2 NHCOOR 1 [Si (CH 3) 2 O] Si (CH 3) 2 R 1 OOCNHR 2 NHCOOCH 2 CH 2 OOCCHCH 2 Formula G;
R 1代表[CH 2CH 2O]n，n＝20；R 2代表异佛尔酮二环己基甲烷甲苯基，在25℃时，粘度为500～50000mPa·s。 R 1 represents [CH 2 CH 2 O]n, n=20; R 2 represents isophorone dicyclohexylmethane tolyl, and the viscosity is 500-50000 mPa·s at 25°C.
优选的实施方式为：所述活性稀释剂为丙烯酸十三烷基酯、乙基化壬基苯酚丙烯酸酯按照1：2的质量比例构成的混合物。A preferred embodiment is that the reactive diluent is a mixture of tridecyl acrylate and ethylated nonylphenol acrylate in a mass ratio of 1:2.
优选的实施方式为：所述增粘树脂为13-甲氧基-6-羟基钩勿烷-5,8,11,13-四烯-7-酮和13-羟基-8(14)-松香烯按照1：1的质量比例构成的混合物。The preferred embodiment is: the tackifying resin is 13-methoxy-6-hydroxy-undecane-5,8,11,13-tetraene-7-one and 13-hydroxy-8(14)-rosin A mixture of olefins in a mass ratio of 1:1.
优选的实施方式为：所述光敏引发剂为2-苯基苄-二甲基胺-4-吗啉代丙基苯基酮。A preferred embodiment is: the photoinitiator is 2-phenylbenzyl-dimethylamine-4-morpholinopropyl phenyl ketone.
优选的实施方式为：所述稳定剂为2,6-二叔丁基-4-甲基苯酚。A preferred embodiment is that the stabilizer is 2,6-di-tert-butyl-4-methylphenol.
优选的实施方式为：所述石墨烯为多层石墨烯；所述石墨烯松装密度为0.05g/cm 3以内，振实密度为0.1g/cm 3。 A preferred embodiment is: the graphene is a multilayer graphene; the graphene has a loose packing density of 0.05 g/cm 3 or less, and a tap density of 0.1 g/cm 3 .
优选的实施方式为：所述碳纳米管为单壁碳纳米管，所述碳纳米管直径为0.5-2纳米，长度为0.1-2微米，1克壁厚为10 13-10 15PCS。 A preferred embodiment is that the carbon nanotubes are single-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers, a length of 0.1-2 micrometers, and a wall thickness of 10 13 -10 15 PCS per gram.
优选的实施方式为：所述碳界面处理剂为癸硼烷。In a preferred embodiment, the carbon interface treatment agent is decaborane.
优选的实施方式为：所述硅烷偶联剂为符合通式下列通式的化合物：A preferred embodiment is that the silane coupling agent is a compound conforming to the following general formula:
YR nSiX 3-n YR n SiX 3-n
其中Y代表氨基、巯基、长链烷基、环氧基、氰基和甲基丙乙烯酰氧基，R代表亚丙基，X代表代表-OCH 3，n＝0。 Wherein Y represents amino group, mercapto group, long-chain alkyl group, epoxy group, cyano group and methyl propionyloxy group, R represents propylene group, X represents -OCH 3 , and n=0.
亚烷基为碳原子数2～20的取代或非取代的亚烷基。能够水解的基团是指能够通过水解反应从化合物的主骨架上脱离的基团。例如：-OR、-OCOR、-O-N＝CR2、-NR2、－NHR、卤素，这些式中，R表示取代或非取代的碳原子数1～4的烷基等，优选为-OR(即烷氧基)。R的例子包括甲基、乙基、丙基、异丙基、正丁基、异丁基等非取代烷基；氯甲基等取代烷基。这些之中，优选烷基、特别是非取代烷基，更优选为甲基或乙基。羟基没有特别限定，可以为能够水解的基团发生水解而生成的羟基。The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -ON=CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms, etc., preferably -OR (ie alkane Oxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolyzing a hydrolyzable group.
优选的实施方式为：所述功能型添加剂为电中性聚酰胺与聚酯共聚物。A preferred embodiment is that the functional additive is a copolymer of electrically neutral polyamide and polyester.
制备石墨烯UV压敏胶的方法：包括下列步骤：The method of preparing graphene UV pressure-sensitive adhesive includes the following steps:
步骤1：向反应釜中依次加入芳香族氨基丙烯酸酯、脂肪族氨基丙烯酸酯、聚硅氧烷丙烯酸酯、活性稀释剂、增粘树脂和稳定剂，在负压条件下，搅拌分散均匀；Step 1: Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
步骤2：向反应釜中加入石墨烯、碳纳米管、碳界面处理剂和硅烷偶联剂，在负压条件下，搅拌分散均匀；Step 2: Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
步骤3：在黄光环境下，向反应釜中加入光敏引发剂，在负压条件下，搅拌分散均匀；Step 3: In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
步骤4：取出胶样，在1000毫焦紫外光下照射10秒，然后进行测试，达到标准要求后，出料即制成石墨烯UV压敏胶。Step 4: Take out the glue sample, irradiate it under 1000 millijoule ultraviolet light for 10 seconds, and then perform the test. After reaching the standard requirement, the graphene UV pressure-sensitive adhesive will be made out of the material.
优选的实施方式为：：负压条件为真空度为-0.1MPa。The preferred embodiment is as follows: the negative pressure condition is that the vacuum degree is -0.1 MPa.
实施例4：一种石墨烯UV压敏胶及制备方法Example 4: A graphene UV pressure-sensitive adhesive and its preparation method
其它实施措施同实施例3，不同之处在于：Other implementation measures are the same as in Example 3, the difference lies in:
优选的实施方式为：所述芳香族氨基甲酸酯丙烯酸酯为符合通式A和通式B的化合物中的至少一种：A preferred embodiment is that the aromatic urethane acrylate is at least one of the compounds conforming to the general formula A and the general formula B:
CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                              通式A；General formula A;
其中R 1代表甲苯基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents a tolyl group; the viscosity is 500-1000 mPa·s at 25°C.
优选的实施方式为：所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C和通式D的化合物中的至少一种：A preferred embodiment is that the aliphatic urethane acrylate is at least one of the compounds conforming to the general formula C and the general formula D:
R 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2       通式D； R 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula D;
其中R 1代表六亚甲基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents hexamethylene; at 25°C, the viscosity is 500-1000 mPa·s.
优选的实施方式为：所述聚硅氧烷丙烯酸酯为符合通式E、通式F和通式G的化合物中的至少一种：A preferred embodiment is that the polysiloxane acrylate is at least one of the compounds conforming to the general formula E, the general formula F and the general formula G:
CH 2CHCOOCH 2CH 2O[Si(CH 3)O] nCH 2CH 2OOCCHCH 2     通式E； CH 2 CHCOOCH 2 CH 2 O[Si(CH 3 )O] n CH 2 CH 2 OOCCHCH 2 general formula E;
m＝10；在25℃时，粘度为500～50000mPa·s。m=10; at 25°C, the viscosity is 500 to 50,000 mPa·s.
优选的实施方式为：所述活性稀释剂为烷氧化丙烯酸月桂酯。A preferred embodiment is that the reactive diluent is lauryl alkoxide acrylate.
优选的实施方式为：所述增粘树脂为13-羟基-8(14)-松香烯。A preferred embodiment is that the tackifying resin is 13-hydroxy-8(14)-rosinene.
优选的实施方式为：所述光敏引发剂为2-羟基-2-甲基-1-苯基-1-丙酮。A preferred embodiment is that the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
优选的实施方式为：所述稳定剂为三(N-亚硝基-N-苯基羟胺)铝盐。A preferred embodiment is that the stabilizer is tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.
优选的实施方式为：所述石墨烯为双层石墨烯；所述石墨烯松装密度为0.02g/cm 3以内，振实密度为0.08g/cm 3。 A preferred embodiment is: the graphene is a double-layer graphene; the graphene has a loose packing density of 0.02 g/cm 3 or less, and a tap density of 0.08 g/cm 3 .
优选的实施方式为：所述碳纳米管为单壁碳纳米管，所述碳纳米管直径为0.5-2纳米，长度为0.1-2微米，1克壁厚为10 13-10 15PCS。 A preferred embodiment is that the carbon nanotubes are single-walled carbon nanotubes, the carbon nanotubes have a diameter of 0.5-2 nanometers, a length of 0.1-2 micrometers, and a wall thickness of 10 13 -10 15 PCS per gram.
优选的实施方式为：所述碳界面处理剂为乙硼烷。A preferred embodiment is that the carbon interface treatment agent is diborane.
优选的实施方式为：所述硅烷偶联剂为符合通式下列通式的化合物：A preferred embodiment is that the silane coupling agent is a compound conforming to the following general formula:
YR nSiX 3-n YR n SiX 3-n
其中Y代表氨基、巯基、长链烷基、环氧基、氰基和甲基丙乙烯酰氧基，R代表亚甲基，X代表能够水解的基团，n＝1。Wherein Y represents an amino group, a mercapto group, a long-chain alkyl group, an epoxy group, a cyano group, and a methylpropionyloxy group, R represents a methylene group, X represents a hydrolyzable group, and n=1.
亚烷基为碳原子数2～20的取代或非取代的亚烷基。能够水解的基团是指能够通过水解反应从化合物的主骨架上脱离的基团。例如：-OR、-OCOR、-O－N＝CR2、-NR2、－NHR、卤素，这些式中，R表示取代或非取代的碳原子数1～4的烷基等，优选为-OR(即烷氧基)。R的例子包括甲基、乙基、丙基、异丙基、正丁基、异丁基等非取代烷基；氯甲基等取代烷基。这些之中，优选烷基、特别是非取代烷基，更优选为甲基或乙基。羟基没有特别限定，可以为能够水解的基团发生水解而生成的羟基，本实施例具体为异丙基。The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The hydrolyzable group refers to a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen, in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, etc., preferably -OR( Namely alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group generated by hydrolysis of a hydrolyzable group. In this example, it is specifically an isopropyl group.
优选的实施方式为：所述功能型添加剂为聚醚改性二甲基聚硅氧烷共聚物。A preferred embodiment is: the functional additive is a polyether modified dimethyl polysiloxane copolymer.
以上所述者仅为用以解释本发明之较佳实施例，并非企图具以对本发明做任 何形式上之限制，是以，凡有在相同之发明精神下所作有关本发明之任何修饰或变更，皆仍应包括在本发明意图保护之范畴。The above descriptions are only used to explain the preferred embodiments of the present invention, and are not intended to restrict the present invention in any form. Therefore, any modification or alteration related to the present invention is made under the same spirit of the invention. , Should still be included in the scope of the present invention's intended protection.

Claims (15)

  1. 一种石墨烯UV压敏胶，其特征在于：所述石墨烯UV压敏胶的原料配方包括下列质量百分比的原料：A graphene UV pressure-sensitive adhesive, characterized in that: the raw material formula of the graphene UV pressure-sensitive adhesive includes the following raw materials in mass percentages:
    Figure PCTCN2020114655-appb-100001
    Figure PCTCN2020114655-appb-100001
  2. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述芳香族氨基甲酸酯丙烯酸酯为符合通式A和通式B的化合物中的至少一种：The graphene UV pressure-sensitive adhesive according to claim 1, wherein the aromatic urethane acrylate is at least one of the compounds conforming to the general formula A and the general formula B:
    CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                   通式A；General formula A;
    CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 3NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 3 NHCOOCH 2 CH 2 OOCCHCH 2
                   通式B；Formula B;
    其中R 1代表甲苯基、二苯基甲烷或苯二亚甲基；其中R 2代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝1～10，m＝1～5；R 3代表六亚甲基、异佛尔酮、二环己基甲烷甲苯基、二苯基甲烷或苯二亚甲基；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents tolyl, diphenylmethane or xylylene; where R 2 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O]m [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=1～10, m=1～5; R 3 represents hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane or xylylene; the viscosity is 500-1000mPa·s at 25°C.
  3. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述脂肪族氨基甲酸酯丙烯酸酯为符合通式C和通式D的化合物中的至少一种：The graphene UV pressure-sensitive adhesive according to claim 1, wherein the aliphatic urethane acrylate is at least one of the compounds conforming to the general formula C and the general formula D:
    CH 2CHCOOCH 2CH 2OOCNHR 1NHCOOR 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2 CH 2 CHCOOCH 2 CH 2 OOCNHR 1 NHCOOR 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2
                   通式C；General formula C;
    R 2OOCNHR 1NHCOOCH 2CH 2OOCCHCH 2  通式D； R 2 OOCNHR 1 NHCOOCH 2 CH 2 OOCCHCH 2 general formula D;
    其中R 1代表六亚甲基、异佛尔酮和二环己基甲烷；其中R 2代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝1～10，m＝1～5；在25℃时，粘度为500～1000mPa·s。 Wherein R 1 represents hexamethylene, isophorone and dicyclohexylmethane; where R 2 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O] m[CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=1～10, m=1～5; At 25°C, the viscosity is 500 to 1000 mPa·s.
  4. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述聚硅氧烷丙烯酸酯为符合通式E、通式F和通式G的化合物中的至少一种：The graphene UV pressure-sensitive adhesive according to claim 1, wherein the polysiloxane acrylate is at least one compound in accordance with the general formula E, the general formula F and the general formula G:
    CH 2CHCOOCH 2CH 2O[Si(CH 3)O] nCH 2CH 2OOCCHCH 2  通式E； CH 2 CHCOOCH 2 CH 2 O[Si(CH 3 )O] n CH 2 CH 2 OOCCHCH 2 general formula E;
    CH 2CHCOOR[Si(CH 3) 2O] nSi(CH 3) 2ROOCCHCH 2(n＝20～80)  通式F； CH 2 CHCOOR[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 ROOCCHCH 2 (n=20～80) General formula F;
    CH 2CHCOOCH 2CH 2OOCNHR 2NHCOOR 1[Si(CH 3) 2O]Si(CH 3) 2R 1OOCNHR 2NHCOOCH 2CH 2OOCCHCH 2  通式G； CH 2 CHCOOCH 2 CH 2 OOCNHR 2 NHCOOR 1 [Si (CH 3) 2 O] Si (CH 3) 2 R 1 OOCNHR 2 NHCOOCH 2 CH 2 OOCCHCH 2 Formula G;
    R 1代表[CH 2CH 2O]n、[CH 2CHO(CH 3)]n、[CH 2CH 2O]m[CH 2CHO(CH 3)]n、[CH 2CH 2CH 2CH 2O]n或[OCH 2CH 2CH 2CH 2CO]n，n＝20～80；R 2代表六亚甲基、异佛尔酮二环己基甲烷甲苯基、二苯基甲烷、苯二亚甲基，在25℃时，粘度为500～50000mPa·s。 R 1 represents [CH 2 CH 2 O]n, [CH 2 CHO(CH 3 )]n, [CH 2 CH 2 O]m[CH 2 CHO(CH 3 )]n, [CH 2 CH 2 CH 2 CH 2 O]n or [OCH 2 CH 2 CH 2 CH 2 CO]n, n=20～80; R 2 stands for hexamethylene, isophorone, dicyclohexylmethane tolyl, diphenylmethane, benzene two Methylene has a viscosity of 500 to 50,000 mPa·s at 25°C.
  5. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述活性稀释剂为烷氧化四氢呋喃丙烯酸酯、乙氧化壬基苯酚丙烯酸酯、烷氧化壬基苯酚丙烯酸酯、烷氧化丙烯酸月桂酯、丙烯酸异癸酯、丙烯酸异癸酯、丙烯酸十三烷基酯、乙基化壬基苯酚丙烯酸酯和丙氧化新戊二醇二丙烯酸酯中的至少一种。The graphene UV pressure-sensitive adhesive according to claim 1, wherein the reactive diluent is alkoxylated tetrahydrofuran acrylate, ethoxylated nonylphenol acrylate, alkoxylated nonylphenol acrylate, alkoxylated acrylic laurel At least one of ester, isodecyl acrylate, isodecyl acrylate, tridecyl acrylate, ethylated nonylphenol acrylate, and propylene oxide neopentyl glycol diacrylate.
  6. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述增粘树脂为松香烷-8,11,13-三烯-7-醇、12-乙基-13-甲氧基-8,11,13-罗汉松三烯-7-酮、13-甲氧基-6-羟基钩勿烷-5,8,11,13-四烯-7-酮和13-羟基-8(14)-松香烯中的至少一种。The graphene UV pressure-sensitive adhesive according to claim 1, wherein the tackifying resin is rosinane-8,11,13-triene-7-ol, 12-ethyl-13-methoxy -8,11,13-Podoxin-7-one, 13-Methoxy-6-Hydroxybenzidine-5,8,11,13-Tetraene-7-one and 13-Hydroxy-8( 14)-At least one of rosinene.
  7. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述光敏引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-苯基苄-二甲基胺-4-吗啉代丙基苯基酮和1-羟基环已基苯基甲酮中的至少一种。The graphene UV pressure-sensitive adhesive according to claim 1, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4,6-trimethyl At least one of benzoyl-diphenylphosphine oxide, 2-phenylbenzyl-dimethylamine-4-morpholinopropyl phenyl ketone, and 1-hydroxycyclohexyl phenyl ketone.
  8. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述稳定剂为三(N-亚硝基-N-苯基羟胺)铝盐、羟基苯甲醚、对苯二酚、对苯醌和2,6-二叔丁基-4-甲基苯酚中的至少一种。The graphene UV pressure-sensitive adhesive of claim 1, wherein the stabilizer is tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, hydroxyanisole, hydroquinone, At least one of p-benzoquinone and 2,6-di-tert-butyl-4-methylphenol.
  9. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述石墨烯为单层石墨烯、双层石墨烯、少层石墨烯和多层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm 3以内，振实密度为0.05～0.1g/cm 3。 The graphene UV pressure-sensitive adhesive according to claim 1, wherein the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; The bulk density of graphene is within 0.01-0.05g/cm 3 , and the tap density is 0.05-0.1g/cm 3 .
  10. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述碳纳米管为单壁碳纳米管和多壁碳纳米管中的一种或两种，所述碳纳米管直径为0.5-2纳米，长度为0.1-2微米，1克壁厚为10 13-10 15PCS。 The graphene UV pressure-sensitive adhesive according to claim 1, wherein the carbon nanotubes are one or two of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the diameter of the carbon nanotubes is 0.5-2 nanometers, the length is 0.1-2 microns, and the wall thickness of 1 gram is 10 13 -10 15 PCS.
  11. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述碳界面处理剂为乙硼烷、戊硼烷、癸硼烷和碳硼烷中的至少一种。The graphene UV pressure-sensitive adhesive according to claim 1, wherein the carbon interface treatment agent is at least one of diborane, pentaborane, decaborane and carborane.
  12. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述硅烷偶联剂为符合通式下列通式的化合物：The graphene UV pressure-sensitive adhesive according to claim 1, wherein the silane coupling agent is a compound conforming to the following general formula:
    YR nSiX 3-n YR n SiX 3-n
    其中Y代表氨基、巯基、长链烷基、环氧基、氰基和甲基丙乙烯酰氧基，R代表亚烷基，X代表能够水解的基团，n＝0或1。Wherein Y represents an amino group, a mercapto group, a long-chain alkyl group, an epoxy group, a cyano group, and a methylpropionyloxy group, R represents an alkylene group, X represents a hydrolyzable group, and n=0 or 1.
  13. 根据权利要求1所述的石墨烯UV压敏胶，其特征在于：所述功能型添加剂为聚醚改性二甲基聚硅氧烷共聚物、破泡聚硅氧烷非水乳液、非离子型聚硅氧烷共聚物、电中性聚酰胺与聚酯共聚物、低分子量不饱和羧酸聚合物、含酸性基团的嵌段共聚物烷烃基铵盐和微粉化改性高密度聚乙烯蜡混合物中的至少一种。The graphene UV pressure-sensitive adhesive according to claim 1, wherein the functional additive is polyether modified dimethyl polysiloxane copolymer, foam-breaking polysiloxane non-aqueous emulsion, non-ionic Type polysiloxane copolymers, electrically neutral polyamide and polyester copolymers, low molecular weight unsaturated carboxylic acid polymers, block copolymers containing acidic groups, alkanyl ammonium salts and micronized modified high-density polyethylene At least one of the wax mixture.
  14. 一种制备权利要求1-13任一所述的石墨烯UV压敏胶的方法：其特征在于：包括下列步骤：A method for preparing the graphene UV pressure-sensitive adhesive according to any one of claims 1-13, characterized in that it comprises the following steps:
    步骤1：向反应釜中依次加入芳香族氨基丙烯酸酯、脂肪族氨基丙烯酸酯、聚硅氧烷丙烯酸酯、活性稀释剂、增粘树脂和稳定剂，在负压条件下，搅拌分散均匀；Step 1: Add aromatic amino acrylate, aliphatic amino acrylate, polysiloxane acrylate, reactive diluent, tackifying resin and stabilizer to the reaction kettle in sequence, and stir and disperse uniformly under negative pressure;
    步骤2：向反应釜中加入石墨烯、碳纳米管、碳界面处理剂和硅烷偶联剂，在负压条件下，搅拌分散均匀；Step 2: Add graphene, carbon nanotubes, carbon interface treatment agent and silane coupling agent to the reaction kettle, stir and disperse uniformly under negative pressure;
    步骤3：在黄光环境下，向反应釜中加入光敏引发剂，在负压条件下，搅拌分散均匀；Step 3: In a yellow light environment, add a photoinitiator to the reaction kettle, stir and disperse evenly under negative pressure;
    步骤4：取出胶样，在500～1000毫焦紫外光下照射10～60秒，然后进行测试，达到标准要求后，出料即制成石墨烯UV压敏胶。Step 4: Take out the glue sample, irradiate it under 500-1000 millijoule ultraviolet light for 10-60 seconds, and then perform the test. After reaching the standard requirements, the material is discharged to make graphene UV pressure-sensitive adhesive.
  15. 根据权利要求14所述的方法，其特征在于：负压条件为真空度为-0.08～-0.1MPa。The method according to claim 14, wherein the negative pressure condition is that the degree of vacuum is -0.08 to -0.1 MPa.
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CN111909634A (en) * 2020-08-12 2020-11-10 苏州诺斯鲁精密科技有限公司 Graphene nano material UV pressure-sensitive adhesive and preparation method thereof
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