CN107189730A - A kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane and preparation method thereof - Google Patents
A kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane and preparation method thereof Download PDFInfo
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- CN107189730A CN107189730A CN201710472005.8A CN201710472005A CN107189730A CN 107189730 A CN107189730 A CN 107189730A CN 201710472005 A CN201710472005 A CN 201710472005A CN 107189730 A CN107189730 A CN 107189730A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- 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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Abstract
The present invention provides a kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane and preparation method thereof, and specific preparation method is：IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, it is stirred at room temperature, PCDL reaction is first added dropwise, end hydroxy polyether modified silicon oil is added dropwise again, temperature reaction, is then added dropwise dihydromethyl propionic acid reaction, and hydroxyethyl methacrylate and the reaction of 4 metoxyphenols is finally added dropwise, Di PE reactions are eventually adding, hyperbranched aqueous polyurethane is prepared；The acrylic monomers and initiator for reaction of hydroxyl will be added in hyperbranched aqueous polyurethane, obtain acrylic acid modified hyperbranched aqueous polyurethane；Mixed again with epoxy acrylate, add acrylic acid, benzene sulfonyl hydrazide, saccharin, light trigger and stabilizer, stirred in planetary mixer, isopropyl benzene hydroperoxide initiator is added dropwise again, it is stirred under vacuum, lucifuge packaging obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
Description
Technical field
The invention belongs to UV glue material technical fields, and in particular to a kind of based on acrylic acid modified hyperbranched aqueous poly- ammonia
Double UV curing glue of ester and preparation method thereof.
Background technology
Ultraviolet photo-curing cementing agent is also referred to as UV glue, refers under appropriate wavelength and the UV of intensity irradiation, light printing machine triggers
Polymerisation occurs for each component in system, ultimately forms the solidfied material of solid netted cross-linked structure.With traditional heat cure
Adhesive is compared with moisture-curable adhesive, and ultraviolet photo-curing cementing agent has in unique advantage, such as solidification process without molten
Agent is volatilized and the small, form stable that generates heat, light fastness aging and resistance to humid-ageing exposure are good, using technique is simple, solidification rate is fast and
Cubical contraction is small etc. after solidification, therefore, is used widely in the precision instruments such as electronics, optics, medical treatment and automobile field.
Ultraviolet photo-curing cementing agent is typically made up of UV-Curable Prepolymer, light trigger, reactive diluent and auxiliary agent etc., is passed through
The optimal adhesive of solidification effect can be made in different material proportions.Ultraviolet photo-curing cementing agent is largely acrylate at present
System.A kind of polyacrylate UV glue and preparation method thereof disclosed in Chinese patent CN105315929A, polyacrylate UV
Contain polyacrylate, reactive diluent, light trigger, stabilizer, adhesive promoter, pigment, thixotropic agent, levelling in glue
Agent, age resister, PTFE and chromium oxide, are that the polyacrylate UV glue prepared has preferable anti-wear performance.Chinese patent
UV glue, urethane acrylate oligomer and preparation method thereof disclosed in CN103980456B, by phenyl glycidyl ether and
Propylene acid reaction produces intermediate product A, adds IPDI and reacts to form intermediate product B, by the double of 10EO
Phenol A APEOs and 20EO bisphenol A polyethenoxy ether reaction generation intermediate product C, by intermediate product B and intermediate product C
Reaction, adds reactive diluent, and vacuum distillation obtains urethane acrylate oligomer, polyurethane propylene prepared by this method
The preparation method of acid esters oligomer is simple, modest viscosity, with higher refraction index, is adapted for use in the painting of prismatic lens surface
Layer.Current acrylatcs systems curing mechanism is radical polymerization, and feature is that cure shrinkage is big, typically more than 5%, solidification
During high shrinkage can cause to produce internal stress in adhesive member, reduce adhesive strength, and the chi of the accurate bonding of influence
Very little stability, or even can the local situation for producing cracking warpage.Therefore, it is necessary to solidify to polyacrylate base ultraviolet light gluing
Agent is modified to reduce its cure shrinkage.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of double based on acrylic acid modified hyperbranched aqueous polyurethane
UV curing glue and preparation method thereof, acrylic acid modified hyperbranched aqueous polyurethane is combined with epoxy acrylate, will be poly-
Urethane, epoxy resin select hyperbranched aqueous polyurethane together with the sets of advantages of polyacrylate, make the double of preparation
The drawbacks of UV curing glue solves to solidify at different conditions, makes storage stabilization, the application method of the product of preparation convenient and solidification
Efficiency is good.
In order to solve the above technical problems, the technical scheme is that：
A kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane, it is described based on acrylic acid modified
Double UV curing glue of hyperbranched aqueous polyurethane are included based on acrylic acid modified hyperbranched aqueous polyurethane, epoxy acrylic
Ester, adhesion promoter, accelerator, kicker, light trigger, stabilizer and initiator, the adhesion promoter are third
Olefin(e) acid, the accelerator is benzene sulfonyl hydrazide, and the primary accelerator is saccharin, and the stabilizer is EDTA, and the initiator is different
Cumene hydroperoxide.
As the preferred of above-mentioned technical proposal, described is hyperbranched water based on acrylic acid modified hyperbranched aqueous polyurethane
The acrylic monomers of the polyurethane grafted hydroxyl of property is obtained.
The present invention also provides a kind of preparation side of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane
Method, comprises the following steps：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane；
(2) hyperbranched aqueous polyurethane for preparing step (1) is placed in four-hole boiling flask, is added pH adjusting agent, is warming up to
80 DEG C, the acrylic monomers and initiator of hydroxyl are added, 3h is reacted, obtains acrylic acid modified hyperbranched aqueous polyurethane；
(3) the acrylic acid modified hyperbranched aqueous polyurethane for preparing step (2) is mixed with epoxy acrylate, is added
Acrylic acid, benzene sulfonyl hydrazide, saccharin, light trigger and stabilizer, stir 1-2h, then isopropylbenzene peroxide is added dropwise in planetary mixer
Change hydrogen initiator, be stirred under vacuum, lucifuge packaging obtains double UV curings based on acrylic acid modified hyperbranched aqueous polyurethane
Glue.
As the preferred of above-mentioned technical proposal, in the step (1), the component in hyperbranched aqueous polyurethane, by weight
Percentages, including IPDI 15-16%, dibutyl tin laurate 3.5-4%, PCDL
22-30%, end hydroxy polyether modified silicon oil 5-15%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate 2.5%, Di-
PE 0.35%, surplus is 4- metoxyphenols.
As the preferred of above-mentioned technical proposal, in the step (2), initiator is isopropyl benzene hydroperoxide.
As the preferred of above-mentioned technical proposal, in the step (2), the acrylic acid of hyperbranched aqueous polyurethane and hydroxyl
The mass ratio 1 of monomer:5-8.
As the preferred of above-mentioned technical proposal, in the step (2), the acrylic monomers and initiator of hydroxyl are added
Time is 2-3h.
As the preferred of above-mentioned technical proposal, in the step (3), acrylic acid modified hyperbranched aqueous polyurethane and ring
The mass ratio of oxypropylene acid esters is 1:1-2.
As the preferred of above-mentioned technical proposal, in the step (3), light trigger is Irgacure1173.
As the preferred of above-mentioned technical proposal, in the step (3), stabilizer is 0.02mol/L EDTA solution.
Compared with prior art, the invention has the advantages that：
(1) double UV curing glue prepared by the present invention mainly include acrylic acid modified hyperbranched aqueous polyurethane and epoxy third
Olefin(e) acid ester, wherein acrylic acid modified hyperbranched aqueous polyurethane is a kind of highly branched three-D space structure, substantial amounts of work
Property end, solubility is excellent, and rheological characteristic is good, and viscosity is low, then acrylic acid is modified to hyperbranched aqueous polyurethane, improves hyperbranched
The heat-resisting quantity and water resistance of aqueous polyurethane, improve anti-wear performance, mechanical performance and the weather resistance of UV glue, epoxy acrylic
Ester has excellent water resistance, heat resistance, caking property and toughness, the present invention by acrylic acid modified hyperbranched aqueous polyurethane with
Epoxy acrylate is combined, by polyurethane, epoxy resin together with the sets of advantages of polyacrylate, and from over-expense
Change aqueous polyurethane, make the drawbacks of double UV curing glue of preparation solve to solidify at different conditions, make the storage of the product of preparation
Stablize, application method is convenient and curing efficiency is good.
(2) acrylic acid is all contained in the primary raw material in double UV curing glue prepared by the present invention, thus it is acrylic acid modified
The compatibility of hyperbranched aqueous polyurethane and epoxy acrylate preferably, and can be well by polyurethane, acrylic acid and epoxy
Resin is mutually gathered, and on the basis of original polyacrylic acid UV solidification glue performances are retained, the features such as assigning its small viscosity, anaerobism carries
The high combination property of UV glue, is conducive to raising to use scope.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, adds Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, hyperbranched aqueous polyurethane
In component, by weight percentage, including IPDI 15%, dibutyl tin laurate 3.5%, poly- carbon
Acid esters dihydric alcohol 22%, end hydroxy polyether modified silicon oil 5%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate 2.5%,
Di-PE0.35%, surplus is 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:5, will be hyperbranched aqueous poly-
Urethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene peroxide of hydroxyl
Change hydrogen initiator, the addition time is 2h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethane and 20 parts of epoxy acrylic
Ester is mixed, acrylic acid, 1 part of benzene sulfonyl hydrazide, 1.5 parts of saccharin, 1.5 parts of the Irgacure1173 light triggers of 3 parts of addition
With 0.1 part of 0.02mol/L EDTA solution, 1h is stirred in planetary mixer, then 3 parts of isopropyl benzene hydroperoxide is added dropwise draw
Agent is sent out, is stirred under vacuum, lucifuge packaging obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
Embodiment 2：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, it is hyperbranched aqueous poly-
Component in urethane, by weight percentage, including IPDI 16%, dibutyl tin laurate 4%, gather
Carbonic ester dihydric alcohol 30%, end hydroxy polyether modified silicon oil 15%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate
2.5%, Di-PE0.35%, surplus are 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:8, will be hyperbranched aqueous poly-
Urethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene peroxide of hydroxyl
Change hydrogen initiator, the addition time is 3h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethane and 40 parts of epoxy acrylic
Ester is mixed, acrylic acid, 2 parts of benzene sulfonyl hydrazide, 2 parts of saccharin, 2 parts of the Irgacure1173 light triggers and 0.5 of 5 parts of addition
Part 0.02mol/L EDTA solution, stir 2h in planetary mixer, then be added dropwise 4 parts of isopropyl benzene hydroperoxide initiator,
It is stirred under vacuum, lucifuge packaging obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
Embodiment 3：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, it is hyperbranched aqueous poly-
Component in urethane, by weight percentage, including IPDI 15.5%, dibutyl tin laurate
3.9%, PCDL 28%, end hydroxy polyether modified silicon oil 14%, dihydromethyl propionic acid 3.5%, methacrylic acid
Hydroxyl ethyl ester 2.5%, Di-PE0.35%, surplus is 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:7, will be hyperbranched aqueous poly-
Urethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene peroxide of hydroxyl
Change hydrogen initiator, the addition time is 2.5h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethanes and 35 parts of epoxy acrylate
Mixing, acrylic acid, 1.5 parts of benzene sulfonyl hydrazide, 1.8 parts of saccharin, 1.9 parts of the Irgacure1173 of 3.5 parts of addition is light-initiated
Agent and 0.3 part of 0.02mol/L EDTA solution, stir 1.5h, then 3.5 parts of isopropylbenzene peroxide is added dropwise in planetary mixer
Change hydrogen initiator, be stirred under vacuum, lucifuge packaging obtains double UV curings based on acrylic acid modified hyperbranched aqueous polyurethane
Glue.
Embodiment 4：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, it is hyperbranched aqueous poly-
Component in urethane, by weight percentage, including IPDI 15%, dibutyl tin laurate 4%, gather
Carbonic ester dihydric alcohol 25%, end hydroxy polyether modified silicon oil 10%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate
2.5%, Di-PE0.35%, surplus are 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:6.5, will be hyperbranched aqueous
Polyurethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene mistake of hydroxyl
Hydrogen oxide initiator, the addition time is 2h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethane and 35 parts of epoxy acrylic
Ester is mixed, acrylic acid, 2 parts of benzene sulfonyl hydrazide, 2 parts of saccharin, 2 parts of the Irgacure1173 light triggers and 0.3 of 4 parts of addition
Part 0.02mol/L EDTA solution, stir 2h in planetary mixer, then be added dropwise 3 parts of isopropyl benzene hydroperoxide initiator,
It is stirred under vacuum, lucifuge packaging obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
Embodiment 5：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, adds Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, hyperbranched aqueous polyurethane
In component, by weight percentage, including IPDI 16%, dibutyl tin laurate 3.5%, poly- carbon
Acid esters dihydric alcohol 27%, end hydroxy polyether modified silicon oil 8%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate 2.5%,
Di-PE0.35%, surplus is 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:7, will be hyperbranched aqueous poly-
Urethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene peroxide of hydroxyl
Change hydrogen initiator, the addition time is 3h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethane and 40 parts of epoxy acrylic
Ester mix, add 3 parts acrylic acid, 1 part of benzene sulfonyl hydrazide, 2 parts of saccharin, 1.5 parts of Irgacure1173 light triggers and
0.3 part of 0.02mol/L EDTA solution, stirs 2h, then 4 parts of isopropyl benzene hydroperoxide initiation is added dropwise in planetary mixer
Agent, is stirred under vacuum, lucifuge packaging, obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
Embodiment 6：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly,
Nitrogen protection is passed through, 50 DEG C are progressively warming up to, PCDL reaction 2h is first added dropwise, then end hydroxy polyether modified silicon is added dropwise
Oil, is warming up to 75 DEG C of reaction 2h, and dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- first is finally added dropwise
Epoxide phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane, wherein, it is hyperbranched aqueous poly-
Component in urethane, by weight percentage, including IPDI 15.5%, dibutyl tin laurate
3.5%, PCDL 26%, end hydroxy polyether modified silicon oil 13%, dihydromethyl propionic acid 3.5%, methacrylic acid
Hydroxyl ethyl ester 2.5%, Di-PE0.35%, surplus is 4- metoxyphenols.
(2) according to the mass ratio 1 of hyperbranched aqueous polyurethane and the acrylic monomers of hydroxyl:7, will be hyperbranched aqueous poly-
Urethane is placed in four-hole boiling flask, adds pH adjusting agent, is warming up to 80 DEG C, adds the acrylic monomers and isopropylbenzene peroxide of hydroxyl
Change hydrogen initiator, the addition time is 3h, reacts 3h, obtains acrylic acid modified hyperbranched aqueous polyurethane.
(3) by weight, by 20 parts of acrylic acid modified hyperbranched aqueous polyurethane and 25 parts of epoxy acrylic
Ester is mixed, and acrylic acid, 1.5 parts of benzene sulfonyl hydrazide, 2 parts of saccharin, 1.5 parts of the Irgacure1173 of 4.5 parts of addition are light-initiated
Agent and 0.5 part of 0.02mol/L EDTA solution, stir 1h, then 3 parts of isopropyl benzene hydroperoxide is added dropwise in planetary mixer
Initiator, is stirred under vacuum, lucifuge packaging, obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
After testing, double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane that prepared by embodiment 1-6
Hardening time, shear strength, breakdown torque intensity, result it is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Positioning time (s) | 60 | 80 | 65 | 70 | 75 | 65 |
| Hardening time (s) | 40 | 50 | 45 | 42 | 41 | 43 |
| Shear strength (MPa) | 16 | 18.5 | 18 | 17.5 | 17 | 17.5 |
| Breakdown torque intensity (Nm) | 32 | 31 | 30 | 31 | 32 | 30 |
| Bin stability | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged |
| Cure shrinkage (%) | 3.2 | 3.5 | 3.4 | 3.6 | 3.3 | 3.4 |
| Water contact angle (°) after film forming | 103 | 106 | 102 | 104 | 103 | 105 |
As seen from the above table, double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane that prepared by the present invention
The UAN of good mechanical property, hardening time and positioning time, storage stablize, and cure shrinkage is reduced, also with certain water-fast
Property.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane, it is characterised in that：It is described to be based on third
The double UV curing glue for the hyperbranched aqueous polyurethane that olefin(e) acid is modified are included based on acrylic acid modified hyperbranched aqueous polyurethane, ring
Oxypropylene acid esters, adhesion promoter, accelerator, kicker, light trigger, stabilizer and initiator, the attachment are made every effort to promote
Enter agent for acrylic acid, the accelerator is benzene sulfonyl hydrazide, the primary accelerator is saccharin, and the stabilizer is EDTA, described to draw
Hair agent is isopropyl benzene hydroperoxide.
2. a kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 1, its
It is characterised by：Described is the third of hyperbranched aqueous polyurethane grafting hydroxyl based on acrylic acid modified hyperbranched aqueous polyurethane
Acrylic monomer is obtained.
3. a kind of preparation method of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane, it is characterised in that
Comprise the following steps：
(1) IPDI and dibutyl tin laurate are fitted into four-hole boiling flask, are stirred at room temperature uniformly, are passed through
Nitrogen is protected, and is progressively warming up to 50 DEG C, and PCDL reaction 2h is first added dropwise, then is added dropwise end hydroxy polyether modified silicon oil,
75 DEG C of reaction 2h are warming up to, dihydromethyl propionic acid reaction 3h is then added dropwise, hydroxyethyl methacrylate and 4- methoxies is finally added dropwise
Base phenol reactant 3h, is eventually adding Di-PE reaction 4h, prepares hyperbranched aqueous polyurethane；
(2) hyperbranched aqueous polyurethane for preparing step (1) is placed in four-hole boiling flask, is added pH adjusting agent, is warming up to 80 DEG C,
The acrylic monomers and initiator of hydroxyl are added, 3h is reacted, obtains acrylic acid modified hyperbranched aqueous polyurethane；
(3) the acrylic acid modified hyperbranched aqueous polyurethane for preparing step (2) is mixed with epoxy acrylate, adds propylene
Acid, benzene sulfonyl hydrazide, saccharin, light trigger and stabilizer, stir 1-2h, then isopropyl benzene hydroperoxide is added dropwise in planetary mixer
Initiator, is stirred under vacuum, lucifuge packaging, obtains double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane.
4. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (1), the component in hyperbranched aqueous polyurethane, by weight percentage, including
IPDI 15-16%, dibutyl tin laurate 3.5-4%, PCDL 22-30%, hold hydroxyl
Base polyether modified silicon oil 5-15%, dihydromethyl propionic acid 3.5%, hydroxyethyl methacrylate 2.5%, Di-PE 0.35% is remaining
Measure as 4- metoxyphenols.
5. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (2), initiator is isopropyl benzene hydroperoxide.
6. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (2), the mass ratio of the acrylic monomers of hyperbranched aqueous polyurethane and hydroxyl
1:5-8。
7. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (2), the time of the acrylic monomers and initiator that add hydroxyl is 2-3h.
8. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (3), acrylic acid modified hyperbranched aqueous polyurethane and epoxy acrylate
Mass ratio is 1:1-2.
9. a kind of system of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation Method, it is characterised in that：In the step (3), light trigger is Irgacure1173.
10. a kind of double UV curing glue based on acrylic acid modified hyperbranched aqueous polyurethane according to claim 3
Preparation method, it is characterised in that：In the step (3), stabilizer is 0.02mol/L EDTA solution.
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| CN110066400A (en) * | 2019-04-26 | 2019-07-30 | 深圳职业技术学院 | A kind of highly-water-soluble modified epoxy acrylate resin and preparation method thereof |
| CN115181539A (en) * | 2022-09-08 | 2022-10-14 | 拓迪化学(上海)有限公司 | UV (ultraviolet) light-cured glue for battery and application thereof |
| CN118027843A (en) * | 2024-02-22 | 2024-05-14 | 宁波启合新材料科技有限公司 | Thermal reaction adhesive tape and preparation method thereof |
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| CN110066400A (en) * | 2019-04-26 | 2019-07-30 | 深圳职业技术学院 | A kind of highly-water-soluble modified epoxy acrylate resin and preparation method thereof |
| CN110066400B (en) * | 2019-04-26 | 2021-08-24 | 深圳职业技术学院 | A kind of highly water-soluble modified epoxy acrylic resin and preparation method thereof |
| CN115181539A (en) * | 2022-09-08 | 2022-10-14 | 拓迪化学(上海)有限公司 | UV (ultraviolet) light-cured glue for battery and application thereof |
| CN118027843A (en) * | 2024-02-22 | 2024-05-14 | 宁波启合新材料科技有限公司 | Thermal reaction adhesive tape and preparation method thereof |
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| CN107189730B (en) | 2020-11-24 |
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