CN112126395A - Thixotropic ultraviolet curing adhesive - Google Patents
Thixotropic ultraviolet curing adhesive Download PDFInfo
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- CN112126395A CN112126395A CN202010995843.5A CN202010995843A CN112126395A CN 112126395 A CN112126395 A CN 112126395A CN 202010995843 A CN202010995843 A CN 202010995843A CN 112126395 A CN112126395 A CN 112126395A
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- containing polycarbonate
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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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
- 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
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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
- C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- 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
Abstract
The invention discloses a preparation method and application of a thixotropic ultraviolet light adhesive. The ultraviolet curing adhesive comprises the following components in parts by weight: 20-40 parts of carbonate (methyl) acrylate, 10-35 parts of divinyl epoxy resin, 30-70 parts of reactive monomer, 3-5 parts of hydroxyl-terminated aliphatic hyperbranched polyester, 2-5 parts of initiator, 0.1-0.6 part of defoaming agent and 0.01-0.02 part of polymerization inhibitor. The ultraviolet curing adhesive has high transparency, good thixotropic property (thixotropic index is greater than 1.4) and very high bonding strength to polycarbonate or polyethylene terephthalate.
Description
Technical Field
The invention relates to the field of ultraviolet light curing adhesives, in particular to an adhesive application of an ultraviolet light curing adhesive with thixotropic property in the field of polycarbonate or polyethylene terephthalate transparent plastics.
Background
Thixotropy is a physical property related to the shearing history of materials, and is an important index for evaluating the service performance of the adhesive. After some needle-shaped (or rod-shaped) solid particles with neutral charges or layered and plate-shaped substances with negative charges (such as kaolin and montmorillonite) are uniformly dispersed in the polymer, a large number of weak bonds are formed between the particles and polymer molecules. When external force acts on the dispersion system, part of weak bonds are damaged by the external force, and the viscosity of the system is rapidly reduced; when the external force is removed, the broken weak bond structure is gradually recovered, and the viscosity of the system is continuously increased. The behavior of the material, which is related to the history of the external action, is called thixotropy, and is very important for the use of adhesives or the whole construction process. During gluing, the adhesive is low in viscosity under the action of shearing external force, and the flowing and leveling of the adhesive on the bonded surface are facilitated; after the glue application is finished, the microstructure in the adhesive is gradually recovered, and the viscosity of the adhesive is continuously increased, so that the glue keeps a better shape (no flowing or sagging) or uniform glue film thickness. Therefore, the thixotropy is used as an important index for evaluating the construction performance of the adhesive, and at the same time, the thixotropy is closely related to the final bonding strength of the adhesive.
In order to obtain the desired thixotropy, a certain amount of inorganic particles is generally added to the formulation, such as: montmorillonite, attapulgite, organic bentonite or gas phase nano-silica, etc. However, the addition of inorganic particles to the binder blocks the transmission of light, resulting in a decrease in light transmittance or even no light at all. For the ultraviolet light curing adhesive, higher transparency is needed, which is more beneficial to the transmission of ultraviolet light, and the initiator is activated to complete the processes of chain initiation, propagation and the like. Therefore, after the inorganic thixotropic particles are added into the system, the light transmittance of the ultraviolet curing adhesive is lost, so that the initiation link of the polymerization reaction fails and the bonding effect is finally lost. In order to solve the problem that the binder-inorganic particle dispersion is opaque due to a large difference in refractive index between the inorganic particles and the binder, organic thixotropic agents such as polyamide wax, modified polyurea compound, etc., which can form a microstructure, may be used. However, the polyamide wax and the modified polyurea compound have dark colors and strong absorption in the ultraviolet wavelength range, which not only affects the color of the adhesive, but also causes the curing efficiency of the adhesive to be reduced, the monomer conversion is incomplete, and the mechanical property is reduced. In addition, the structural difference between the polyamide wax, the modified polyurea compound and the ultraviolet light-curable adhesive monomer is large, resulting in limited compatibility between the two. The organic thixotropic agent is easy to separate out from the adhesive and form flocculent precipitates, so that the thixotropic property is lost.
Disclosure of Invention
In order to solve the defects in the prior art that an organic thixotropic agent has color, inorganic thixotropic particles cause poor transparency of an ultraviolet light adhesive and shield ultraviolet light, the invention provides the ultraviolet light curing adhesive with thixotropic property.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a thixotropic ultraviolet curing adhesive comprises the following components in parts by weight:
20-40 parts of carbonate (methyl) acrylate,
10-35 parts of divinyl epoxy resin,
30-70 parts of reactive monomer,
3-5 parts of hydroxyl-terminated aliphatic hyperbranched polyester,
2-5 parts of an initiator,
0.1 to 0.6 portion of defoaming agent,
0.01 to 0.02 portion of polymerization inhibitor,
wherein the content of the first and second substances,
the reaction monomer is one or a combination of more of glycidyl methacrylate, acryloyl morpholine, tetrahydrofuran acrylate, cyclotrimethylolpropane methylal acrylate, N-vinyl caprolactam and N-vinyl pyrrolidone;
the molecular weight of the aliphatic hyperbranched polyester is 500-1200 g/mol, and the average number of hydroxyl groups at the periphery of the molecule is 5-12;
the photoinitiator is benzoin dimethyl ether, isopropyl thioxanthone, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2-dimethyl-alpha-hydroxyacetophenone, alpha' -ethoxyacetophenone, 4- (N, N-dimethylamino) ethyl benzoate, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, methyl phthalate or 2,4, at least one of 6-trimethylbenzoylphenylphosphonic acid ethyl ester;
the defoaming agent is organic siloxane;
the polymerization inhibitor is one or a combination of more of hydroquinone, p-hydroxyanisole, p-benzoquinone, p-tert-butylcatechol, p-methylhydroquinone, p-tert-butylhydroquinone and 6-tert-butyl-2, 4-dimethylphenol.
Preferably, the carbonate (meth) acrylate is 1, 6-hexanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-containing polycarbonate dimethacrylate, 1, 5-pentanediol-containing polycarbonate diacrylate, 1, 5-pentanediol-containing polycarbonate dimethacrylate, 1, 5-butanediol-containing polycarbonate diacrylate, 1, 4-butanediol-containing polycarbonate dimethacrylate, 1, 4-cyclohexanedimethanol-containing polycarbonate diacrylate, 1, 4-cyclohexanedimethanol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 5-pentanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 5-pentanediol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 5-pentanediol, 1, 6-hexanediol-and 1, 4-butanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 4-butanediol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 4-cyclohexanedimethanol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 4-cyclohexanedimethanol-containing polycarbonate dimethacrylate;
and, its molecular weight is 2000-3200 g/mol, molecular weight distribution < 2.0.
Preferably, the divinyl epoxy resin has a molecular weight < 1000 g/mol.
A preparation method of a thixotropic ultraviolet light curing adhesive comprises the following steps:
preparing reactants according to the components of the thixotropic ultraviolet curing adhesive and the proportion of the components, and comprising the following steps:
s1, adding reactive monomers and a polymerization inhibitor into the reactor under the condition of stirring, and slowly heating to 45-55 ℃;
s2, adding carbonate (methyl) acrylate after the polymerization inhibitor is completely dissolved, and uniformly stirring; then adding a defoaming agent, aliphatic hyperbranched polyester resin and divinyl epoxy resin in sequence; cooling to below 30 deg.C, adding photoinitiator under the condition of keeping out of the sun, stirring, filtering, and packaging.
The key point of the thixotropic ultraviolet curing adhesive is that a large number of intermolecular hydrogen bonds can be formed between molecular chains by matching the carbonate acrylate with the aliphatic hyperbranched polyester and the divinyl epoxy resin, and when an external force acts, a hydrogen bond network is destroyed, so that the apparent viscosity of a system is reduced; when the external force is removed, the hydrogen bonds among the molecules are gradually recovered, and the apparent viscosity of the system is increased, namely the thixotropic property of the ultraviolet light adhesive is endowed through a large number of hydrogen bonds among the molecules.
Advantageous effects
The thixotropic ultraviolet curing adhesive has the advantages of colorless and transparent performance, and the higher transparency of the adhesive is beneficial to the transmission of ultraviolet light, so that the ultraviolet light can smoothly activate an initiator to complete the processes of chain initiation, growth and the like, and the excellent thixotropy is further embodied. The ultraviolet curing adhesive has high transparency, good thixotropic property (thixotropic index is greater than 1.4) and very high bonding strength to polycarbonate or polyethylene terephthalate.
Moreover, the thixotropic ultraviolet curing adhesive has better compatibility and stability.
The thixotropic ultraviolet curing adhesive disclosed by the invention overcomes the problems of dark color, poor compatibility with acrylate monomers and the like of the existing organic thixotropic agent.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an infrared spectrum of the product of example 1.
FIG. 2 is an infrared spectrum of the product of example 2.
FIG. 3 is an infrared spectrum of the product of example 3.
FIG. 4 shows the product of the present invention, the addition of polyurea modifications, the addition of gas phase SiO2Schematic representation of (a).
Detailed Description
The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
The present invention will be further described with reference to the following specific examples. Also, it should be noted that the thixotropic uv curable adhesive in the following examples is prepared as follows:
the reactants are prepared according to the components and the proportion of the components of the thixotropic ultraviolet curing adhesive in the example, and the method comprises the following steps:
s1, adding reactive monomers and a polymerization inhibitor into the reactor under the condition of stirring, and slowly heating to 45-55 ℃;
s2, adding carbonate (methyl) acrylate after the polymerization inhibitor is completely dissolved, and uniformly stirring; then adding a defoaming agent, aliphatic hyperbranched polyester resin and divinyl epoxy resin in sequence; cooling to below 30 deg.C, adding photoinitiator under the condition of keeping out of the sun, stirring, filtering, and packaging.
Example 1
A thixotropic ultraviolet curing adhesive comprises the following components in parts by weight: 20 parts of carbonate acrylate (the main chain structure of the carbonate is a 1, 6-hexanediol structure, the average molecular weight is about 3200 g/mol), 35 parts of divinyl bisphenol A epoxy resin (the molecular weight is about 440 g/mol), 42.9 parts of glycidyl methacrylate, 3 parts of aliphatic hyperbranched polyester (the molecular weight is about 500 g/mol, the average number of terminal hydroxyl groups is 5), 2 parts of 1-hydroxycyclohexyl phenyl ketone, 0.1 part of antifoaming agent tego931 and 0.01 part of hydroquinone.
The viscosity of the product of example 1 was measured at 25 ℃ and at two rotation speeds of 1 and 10 rpm with a brookfield viscometer, respectively, and the thixotropic properties were calculated. The viscosity was measured at 4200 and 2900 mPa.s at 1 and 10 rpm, respectively, and the thixotropic index was calculated to be 1.45.
A Polycarbonate (PC) plate having a thickness of 1 mm was cut into a test piece of 80 mm. times.20 mm, coated on one end of the test piece of example 1 with an overlapping area of 20 mm. times.20 mm, irradiated with 365 nm ultraviolet light for 20 seconds, cooled to room temperature, and tested for shear tensile strength (tensile speed of 1 mm/min using a universal tester). The tensile shear strength was measured to be 9.81 MPa.
Further, a polyethylene terephthalate (PET) film having a thickness of 0.5 mm was cut into a 60 mm. times.20 mm test piece, one end of the test piece was coated with example 1 with an overlapping area of 20 mm. times.20 mm, and the test piece was cooled to room temperature by irradiating with 365 nm ultraviolet light for 25 seconds, and the shear tensile strength to the PET film was measured (the stretching speed of a universal tester was 1 mm/min). The tensile shear strength was measured to be 8.75 MPa. The bonding performance between the PC and PET substrates shows that the ultraviolet curing adhesive disclosed by the invention has better thixotropy and also ensures excellent mechanical properties.
The above shows that the thixotropic ultraviolet curing adhesive of the invention shows obvious thixotropy for polycarbonate or polyethylene terephthalate transparent plastics. For analysis reasons, the thixotropic property of the present invention is that the carbonyl group of the carbonate (meth) acrylate and the hydroxyl group in the molecular structure of the aliphatic hyperbranched polyester or divinyl epoxy resin can form a large number of intermolecular hydrogen bonds, and these intermolecular hydrogen bonds play the same role as the temporary microstructure can be formed between the thixotropic agent and the polymer. Meanwhile, the active monomer contains rigid oxygen heterocycle, and also forms intermolecular hydrogen bond with hydroxyl in divinyl epoxy resin molecules, and the intermolecular hydrogen bond further improves the thixotropic property of the ultraviolet light adhesive. Furthermore, the active monomer containing the oxygen heterocyclic ring structure is a good solvent of the carbonate (methyl) acrylate, the aliphatic hyperbranched polyester and the divinyl epoxy resin, so that a polymer molecular chain can freely extend in the active monomer, and a material condition is provided for forming an intermolecular hydrogen bond network by the carbonate (methyl) acrylate, the active monomer, the aliphatic hyperbranched polyester and the divinyl epoxy resin.
To confirm the above analysis, the mixture of carbonate acrylate, aliphatic hyperbranched polyester and divinyl bisphenol a epoxy resin in this example was dissolved in an appropriate amount of tetrahydrofuran and mixed well. The tetrahydrofuran solution of the prepolymer was coated on a potassium bromide salt sheet, baked with an infrared lamp, and the tetrahydrofuran was volatilized. Then, at room temperature, the formation of hydrogen bond structures between polymer molecular chains was characterized by an infrared spectrometer, and the results are shown in FIG. 1. As shown in fig. 1: the electron clouds of the carbonyl groups of the mixed products were averaged, and the absorption peak of the carbonyl group was shifted red to 1700 cm-1The demonstration of the formation of hydrogen bonding structures confirms the mechanistic analysis of the present invention.
Example 2
A thixotropic ultraviolet curing adhesive comprises the following components in parts by weight: 40 parts of carbonate methacrylate (the main chain structure of the carbonate is a mixture of 1, 6-hexanediol and 1, 5-pentanediol, and the average molecular weight is about 2000 g/mol), 10 parts of divinyl bisphenol F epoxy resin (the molecular weight is about 400 g/mol), 5 parts of aliphatic hyperbranched polyester (the molecular weight is about 1200 g/mol, and the average number of hydroxyl end groups is 12), 70 parts of tetrahydrofuran acrylate, 5 parts of phenyl bis (2,4, 6-trimethylbenzoyl phosphine oxide), 0.4 part of defoaming agent BYK 055 and 0.02 part of p-hydroxyanisole.
The viscosity of the product of example 2 was measured with a Brookfield viscometer at two rotation speeds of 25 deg.C, 1 and 10 rpm, respectively, and the thixotropic properties were calculated. The viscosities measured at 1 and 10 rpm were 7900 and 4300 mPa.s, respectively, and the thixotropic index calculated to be 1.84. The bonding performance of the PC and PET substrates shows that the ultraviolet curing adhesive has good thixotropy and excellent mechanical property.
A Polycarbonate (PC) plate having a thickness of 1 mm was cut into a test piece of 80 mm. times.20 mm, coated on one end of the test piece of example 2 with an overlapping area of 20 mm. times.20 mm, irradiated with 365 nm ultraviolet light for 20 seconds, cooled to room temperature, and tested for shear tensile strength (tensile speed of 1 mm/min using a universal tester). The tensile shear strength was measured to be 9.27 MPa.
Further, a polyethylene terephthalate (PET) film having a thickness of 0.5 mm was cut into a 60 mm. times.20 mm test piece, one end of the test piece was coated with example 2 with an overlapping area of 20 mm. times.20 mm, irradiated with 365 nm ultraviolet light for 20 seconds, cooled to room temperature, and tested for shear tensile strength to the PET film (tensile speed of 1 mm/min by a universal tester). The tensile shear strength was measured to be 8.31 MPa.
In the embodiment, the mixture of the carbonate acrylate, the aliphatic hyperbranched polyester and the divinyl bisphenol F type epoxy resin is dissolved in a proper amount of tetrahydrofuran and is uniformly mixed. The tetrahydrofuran solution of the prepolymer was coated on a potassium bromide salt sheet, baked with an infrared lamp, and the tetrahydrofuran was volatilized. Then, at room temperature, the formation of hydrogen bond structures between polymer molecular chains was characterized by an infrared spectrometer, and the results are shown in fig. 2. The carbonyl absorption peak is shifted red to 1705 cm-1Here, it can be confirmed that a hydrogen bond structure is formed between the compounds.
Example 3
A thixotropic ultraviolet curing adhesive comprises the following components in parts by weight: 30 parts of carbonate acrylate (carbonate with a main chain structure of a mixed structure of 1, 6-hexanediol and 1, 4-butanediol and an average molecular weight of about 2400 g/mol), 25 parts of divinyl bisphenol A epoxy resin (with a molecular weight of about 440 g/mol), 50 parts of trimethylolpropane formal acrylate, 4 parts of aliphatic hyperbranched polyester (with a molecular weight of about 800 g/mol and an average number of terminal hydroxyl groups of 7), 3.5 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 0.2 part of an EFKA2720 defoaming agent, and 0.02 part of p-tert-butyl catechol) to obtain a product of example 3.
The viscosity of the product of example 3 was measured with a Brookfield viscometer at two speeds of 25 deg.C, 1 and 10 rpm, respectively, and the thixotropic properties were calculated. The viscosity was measured at 3300 and 2300 mPa.s at 1 and 10 rpm, respectively, and the thixotropic index was calculated to be 1.42.
A Polycarbonate (PC) plate having a thickness of 1 mm was cut into a test piece of 80 mm. times.20 mm, coated on one end of the test piece with the overlapping area of 20 mm. times.20 mm by example 3, irradiated with 365 nm ultraviolet light for 25 seconds, cooled to room temperature, and tested for shear tensile strength (tensile speed of 1 mm/min by a universal tester). The tensile shear strength was measured to be 8.83 MPa.
Further, a polyethylene terephthalate (PET) film having a thickness of 0.5 mm was cut into a 60 mm. times.20 mm test piece, one end of the test piece was coated with example 3, and the test piece was overlapped with an area of 20 mm. times.20 mm, irradiated with 365 nm ultraviolet light for 20 seconds, cooled to room temperature, and tested for shear tensile strength to the PET film (tensile speed of a universal tester was 1 mm/min). The measured tensile shear strength is 8.57 MPa, and the bonding performance of the adhesive on the PC and PET substrates shows that the ultraviolet curing adhesive has good thixotropy and excellent mechanical properties.
In this example, a mixture of carbonate acrylate, aliphatic hyperbranched polyester, and divinyl bisphenol a epoxy resin was dissolved in a suitable amount of tetrahydrofuran and mixed uniformly. The tetrahydrofuran solution of the prepolymer was coated on a potassium bromide salt sheet, baked with an infrared lamp, and the tetrahydrofuran was volatilized. Then, at room temperature, the formation of hydrogen bond structures between polymer molecular chains was characterized by an infrared spectrometer, and the results are shown in fig. 3. Carbonyl absorption peak from 1720cm-1Is moved to red to 1702 cm-1Here, it can be confirmed that a hydrogen bond structure is formed between the compounds.
The product of example 1 of the present invention, the polyurea modified product, and the gas phase SiO2The product of (a) is shown in fig. 4, wherein, left side: the product of example 1; the middle part: adding a polyurea modification; right side: addition of gas phase SiO2. As shown by fig. 4: the product of example 1Light color and high transmittance; the sample added with the polyurea modifier has high transparency but dark color (the sample is yellow brown, and the yellow brown can not be obviously expressed after black-white treatment according to the requirements of patent specifications); by gas-phase SiO2The modified sample was poor in transparency.
The ultraviolet curing adhesive has high transparency, good thixotropic property (thixotropic index is greater than 1.4) and very high bonding strength to polycarbonate or polyethylene terephthalate. The above examples demonstrate that the thixotropic UV-curable adhesive of the present invention has excellent thixotropy, and exhibits high mechanical properties after being used for transparent plastics such as polycarbonate or polyethylene terephthalate. The thixotropic ultraviolet-curing adhesive provided by the invention overcomes the problems of dark color, poor compatibility with acrylate monomers and the like of the existing organic thixotropic agent, and can be effectively applied to daily construction scenes as a thixotropic ultraviolet-curing adhesive.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (4)
1. A thixotropic ultraviolet light curing adhesive is characterized in that,
the weight parts of the raw materials are as follows:
20-40 parts of carbonate (methyl) acrylate,
10-35 parts of divinyl epoxy resin,
30-70 parts of reactive monomer,
3-5 parts of hydroxyl-terminated aliphatic hyperbranched polyester,
2-5 parts of an initiator,
0.1 to 0.6 portion of defoaming agent,
0.01 to 0.02 portion of polymerization inhibitor,
wherein the content of the first and second substances,
the reaction monomer is one or a combination of more of glycidyl methacrylate, acryloyl morpholine, tetrahydrofuran acrylate, cyclotrimethylolpropane methylal acrylate, N-vinyl caprolactam and N-vinyl pyrrolidone;
the aliphatic hyperbranched polyester resin has the molecular weight of 500-1200 g/mol and the average number of hydroxyl groups at the periphery of the molecule is 5-12;
the photoinitiator is benzoin dimethyl ether, isopropyl thioxanthone, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2-dimethyl-alpha-hydroxyacetophenone, alpha' -ethoxyacetophenone, 4- (N, N-dimethylamino) ethyl benzoate, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, methyl phthalate or 2,4, at least one of 6-trimethylbenzoylphenylphosphonic acid ethyl ester,
the defoaming agent is organic siloxane, and the defoaming agent is organic siloxane,
the polymerization inhibitor is one or a combination of more of hydroquinone, p-hydroxyanisole, p-benzoquinone, p-tert-butylcatechol, p-methylhydroquinone, p-tert-butylhydroquinone and 6-tert-butyl-2, 4-dimethylphenol.
2. The thixotropic UV-curable adhesive according to claim 1,
the carbonate (meth) acrylate is 1, 6-hexanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-containing polycarbonate dimethacrylate, 1, 5-pentanediol-containing polycarbonate diacrylate, 1, 5-pentanediol-containing polycarbonate dimethacrylate, 1, 5-butanediol-containing polycarbonate diacrylate, 1, 4-butanediol-containing polycarbonate dimethacrylate, 1, 4-cyclohexanedimethanol-containing polycarbonate diacrylate, 1, 4-cyclohexanedimethanol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 5-pentanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 5-pentanediol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 5-pentanediol, 1, 6-hexanediol-and 1, 4-butanediol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 4-butanediol-containing polycarbonate dimethacrylate, 1, 6-hexanediol-and 1, 4-cyclohexanedimethanol-containing polycarbonate diacrylate, 1, 6-hexanediol-and 1, 4-cyclohexanedimethanol-containing polycarbonate dimethacrylate;
and, its molecular weight is 2000-3200 g/mol, molecular weight distribution < 2.0.
3. The thixotropic UV-curable adhesive according to claim 1,
the divinyl epoxy resin has a molecular weight < 1000 g/mol.
4. A preparation method of a thixotropic ultraviolet curing adhesive is characterized in that,
the preparation of reactants according to the components and the proportion of the components of the thixotropic UV-curable adhesive of claim 1, comprising the steps of:
s1, adding reactive monomers and a polymerization inhibitor into the reactor under the condition of stirring, and slowly heating to 45-55 ℃;
s2, adding carbonate (methyl) acrylate after the polymerization inhibitor is completely dissolved, and uniformly stirring; then adding a defoaming agent, aliphatic hyperbranched polyester resin and divinyl epoxy resin in sequence; cooling to below 30 deg.C, adding photoinitiator under the condition of keeping out of the sun, stirring, filtering, and packaging.
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| CN113088239A (en) * | 2021-05-24 | 2021-07-09 | 烟台大学 | Ultraviolet light chain initiated self-reaction low-viscosity high-thickness full-curing glue |
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| CN112126395B (en) | 2022-01-11 |
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