CN115368528B - Potting adhesive for polyurethane (methyl) acrylic ester and low-temperature printed circuit board - Google Patents

Potting adhesive for polyurethane (methyl) acrylic ester and low-temperature printed circuit board Download PDF

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CN115368528B
CN115368528B CN202211220158.0A CN202211220158A CN115368528B CN 115368528 B CN115368528 B CN 115368528B CN 202211220158 A CN202211220158 A CN 202211220158A CN 115368528 B CN115368528 B CN 115368528B
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methyl
acrylate
polyurethane
diisocyanate
hydroxy
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CN115368528A (en
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郑耀臣
乔程辉
张金凤
刘滟苓
吴兰
郝瑞悦
张新涛
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Yantai University
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Yantai University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses polyurethane (methyl) acrylic ester and potting adhesive for a low-temperature printed circuit board. The polyurethane (methyl) acrylic ester is obtained by the addition reaction of hydroxyl olefin containing different reactive carbon-carbon double bonds and isocyanate. After the polyurethane (methyl) acrylic ester, the monomer and the photoinitiator are matched, the quick curing glue which can be used for detecting a Printed Circuit Board (PCB) is prepared. The molecular structure of the ultraviolet light curing polyurethane (methyl) acrylic resin synthesized by the invention contains two carbon-carbon double bonds (C=C) with different reactivity, under the action of a photoinitiator, the (methyl) acrylic double bond and the vinyl double bond in the polyurethane (methyl) acrylic ester are subjected to free radical polymerization reaction successively, the heat release is relaxed in the polymerization reaction process, and the cured test block has good transparency and high hardness, so that the ultraviolet light curing polyurethane (methyl) acrylic resin is particularly suitable for the encapsulation detection application of metallographic cold mosaic PCB.

Description

Potting adhesive for polyurethane (methyl) acrylic ester and low-temperature printed circuit board
Technical Field
The invention belongs to the field of organic polymer packaging materials, and particularly relates to ultraviolet light curing polyurethane (methyl) acrylate, a synthesis method thereof and application of ultraviolet light curing glue in the field of metallographic cold mosaic, in particular to polyurethane (methyl) acrylate and potting glue for a low-temperature printed circuit board.
Background
And the rationality of the technological parameters set in the PCB manufacturing process is evaluated by detecting the quality of the PCB microscopic circuit, and whether the technological parameters are corrected or regulated is determined. Therefore, a rapid and efficient curing process is needed to more easily obtain samples that can be used for microstructure detection. In the currently adopted PCB sample preparation method, compared with the traditional two-component epoxy resin (which can be shortened to 2 h) and unsaturated polyester resin (which can shorten the curing period to 1-2 h), the ultraviolet light curing sample preparation method has the advantages of short curing time, high reaction efficiency (15-20 min) and relatively more convenient use. At present, not all ultraviolet curing systems can be applied to cold packaging application of PCB detection. The main reasons are as follows: 1) The size of the sample block for packaging the PCB is large (the diameter is about 30 mm), and the height is 30-35mm (the dosage is about 20 g). The curing depth of the ultraviolet curing glue is usually less than or equal to 2mm, and a sample block with the thickness of 30-35mm is difficult to cure; 2) The ultraviolet light curing glue reacts rapidly in a short time in the polymerization process, so that the concentrated heat release amount (heat release amount in unit time) is large, and when severe, the small molecular monomers are vaporized to generate a large amount of bubbles in the cured sample, and the problem of core burning of the ultraviolet light curing sample is sometimes caused. Therefore, the problem of concentrated heat release of the glue in the ultraviolet curing process is effectively reduced, and the method has important significance for reducing sample defects and popularizing ultraviolet curing PCB cold packaging glue.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides polyurethane (methyl) acrylate and potting adhesive for a low-temperature printed circuit board, in particular to polyurethane (methyl) acrylate and a preparation method thereof, and the potting adhesive for the low-temperature ultraviolet light printed circuit board.
In order to achieve one of the above objects, the technical scheme of the polyurethane (meth) acrylate is as follows:
polyurethane (meth) acrylate, characterized by the formula (I):
wherein R is 1 Is that Any one of the followingThe seed number is that m is more than or equal to 5 and less than or equal to 10, n is more than or equal to 5 and less than or equal to 10;
R 2 is that Any one or a mixture of at least two of them;
R 3 is H or CH 3 ；
R 4 Is H or CH 3 。
In order to achieve the second object, the technical scheme of the preparation method of polyurethane (methyl) acrylic ester is as follows:
the preparation method of the polyurethane (methyl) acrylic ester comprises the following steps:
1) Feeding polyester or polyether glycol and diisocyanate according to a molar ratio of 1:2, and adding a dibutyltin dilaurate catalyst accounting for 0.01% of the mass of the materials participating in the reaction; then heating to 60-90 ℃ under the condition of nitrogen protection and stirring, then reacting for 2-8h,
wherein the polyester or polyether glycol is at least one of polytetrahydrofuran glycol, polyethylene glycol adipate glycol, polyethylene glycol succinate glycol, polycarbonate glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-polypropylene glycol copolymer,
the diisocyanate is at least one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 3-m-xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate or 1, 3-cyclohexyldimethylene diisocyanate,
2) Adding hydroxyl compound with the same molar weight as the diisocyanate, and adding polymerization inhibitor with the mass of 0.01-0.05% of all materials; then under the protection of nitrogen and under the reaction condition of 60-90 ℃, reacting until the isocyanate group completely disappears, thus obtaining the catalyst;
wherein the hydroxyl compound is at least one of 2-hydroxy-2-methyl-5 (-isopropenyl) cyclohexyl methyl acrylate, 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl methyl acrylate, 2-hydroxy-5 (-isopropenyl) cyclohexyl methyl acrylate, 2-hydroxy-5 (-vinyl) cyclohexyl methyl acrylate, 2-hydroxy-2-methyl-5 (-isopropenyl) cyclohexyl acrylate, 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl acrylate, 2-hydroxy-5 (-isopropenyl) cyclohexyl acrylate, and 2-hydroxy-5 (-vinyl) cyclohexyl acrylate.
Preferably, the polymerization inhibitor is one or more of hydroquinone, p-hydroxyanisole, p-benzoquinone, p-tert-butylcatechol, phenothiazine, p-tert-butylhydroquinone, 6-tert-butyl-2, 4-dimethylphenol and p-methylhydroquinone.
In order to achieve the third purpose of the invention, the technical scheme of the potting adhesive for the low-temperature ultraviolet light printed circuit board is as follows:
the potting adhesive for the low-temperature printed circuit board comprises the following components in parts by mass:
(meth) acrylate monomer: 70-89.5 parts;
polyurethane (meth) acrylate: 10-30 parts of a lubricant;
0.5-3.0 parts of photoinitiator;
the components are uniformly mixed under the light-shielding condition, and the potting adhesive for the low-temperature printed circuit board is obtained.
Preferably, the monofunctional (meth) acrylate is any one or a mixture of at least two of isobornyl acrylate, isobornyl methacrylate, o-phenylphenoxyethyl acrylate, o-phenylphenoxyethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, phenoxyethyl acrylate and phenoxyethyl methacrylate;
the photoinitiator is any one or a mixture of at least two of 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-morpholinophenyl) 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 diphenyl phosphine oxide, methyl o-benzoate, methyl o-benzoyl benzoate or ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate.
When the potting adhesive for the low-temperature printed circuit board is used, the curing thickness of the ultraviolet curing adhesive is not more than 35mm, and the power of the ultraviolet lamp is 45-2000W.
Compared with the prior art, the invention has the beneficial effects that: 1. the main resin of the glue can be subjected to polymerization reaction in a grading manner (the acrylic ester or methacrylic ester double bond with high activity is subjected to polymerization reaction first, and the vinyl double bond with low reactivity is polymerized later), so that the reaction rate is effectively controlled, and the concentrated heat release of a polymerization system is avoided. 2. The polyurethane (methyl) acrylic ester has various dihydric alcohols, and can screen polyester/polyether dihydric alcohols with different structures and different molecular weights according to the needs, and adjust the reaction speed, the hardness and the polishing performance. 3. By adjusting R 3 And R is 4 The type of the (hydrogen atom or methyl) group adjusts the substituent of the double bond, and the activity of the double bond can be further adjusted, so that the polymerization reaction speed and the performance of the cured rubber block can be adjusted.
The molecular structure of the ultraviolet light curing polyurethane (methyl) acrylic ester synthesized by the invention contains two carbon-carbon double bonds (C=C) with different reactivity, under the action of a photoinitiator, the (methyl) acrylic ester double bonds and vinyl double bonds in the polyurethane (methyl) acrylic ester are subjected to free radical polymerization reaction successively, the heat release is relaxed in the polymerization reaction process, and the cured test block has good transparency and high hardness, so that the ultraviolet light curing polyurethane (methyl) acrylic ester is especially suitable for the encapsulation detection application of metallographic cold mosaic PCB.
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 and do not limit the invention.
FIG. 1. IR spectrum of urethane acrylate resin obtained in example 1.
Fig. 2. Example 1 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
FIG. 3. IR spectrum of polyurethane methacrylate resin obtained in example 2.
Fig. 4. Example 2 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
Fig. 5. Example 3 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
Fig. 6. Example 4 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
Fig. 7. Example 5 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
Fig. 8. Example 6 shows the reaction time-gel temperature profile of uv curable glue formulated with resin.
Detailed Description
The present invention will be described in more detail below, wherein preferred embodiments of the invention are shown, it being understood that those skilled in the art can modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description is to be construed as broadly known to those skilled in the art and not as limiting the invention.
Example 1
1) Into a 100ml reaction flask were charged 30.00g (0.02 mol) of polytetrahydrofuran diol, 8.89g (0.04 mol) of isophorone diisocyanate, and 0.039g of dibutyltin dilaurate (catalyst). The mixture was reacted for 8 hours at 60℃under nitrogen blanket with stirring.
2) 8.40g (0.04)mol) methyl 2-hydroxy-2-methyl-5- (vinyl) cyclohexyl acrylate, 4.7mg (0.01%) hydroquinone are added. And (3) reacting for 24 hours under the protection of nitrogen and at the temperature of 60 ℃ until the isocyanate groups completely disappear, thus obtaining the target product. The chemical structure of the product obtained in example 1 was measured by an infrared spectrometer, and the results are shown in FIG. 1. The product was at 3337cm -1 The absorption peak at the place is the characteristic peak of-N-H in polyurethane group, at 1733cm -1 The absorption peak appearing is a characteristic telescopic vibration absorption peak of c=c; the absorption peak of isophorone diisocyanate (IPDI) in the starting material should be 2270cm -1 The absorption peak at this point after the reaction had disappeared, indicating that-NCO reacted completely with-OH, indicating successful synthesis of the target product.
27 parts of example 1 product, 45 parts of isobornyl acrylate, 25 parts of phenoxyethyl methacrylate, 2.0 parts of benzoin dimethyl ether as a photoinitiator and 1.0 part of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
Weighing, mixing, standing and defoaming the components according to the mass composition. It was poured into a polyethylene mold having a diameter of 30mm and a height of 35mm, and the actual height of the poured glue was controlled to be 30mm. Under the irradiation of 2000W mercury lamp (wavelength 350-450 nm), the temperature at the center of the glue block is measured by a thermocouple, and the temperature of the glue surface is measured by a hand-held infrared thermometer. The curve of the reaction time and the temperature change of the center of the glue block in the curing reaction process of the tested glue is shown in fig. 2. The inset is a photo cured after the center temperature of the ultraviolet curing glue is tested by the thermocouple. As can be seen from the photo, no bubble exists in the glue block after the glue is solidified, and the glue block is clear and transparent.
As can be seen from FIG. 2, the glue reaches the highest peak (121.7 ℃) at around 139 s. In the process of testing and curing by using a handheld infrared thermometer, the highest temperature of the surface of the glue block is 97.5 ℃, which indicates that the pouring sealant is cured in a grading way, the pouring sealant reduces the reaction heat generated in unit time through the grading curing, avoids the problems of bubble generation caused by vaporization of small monomer molecules and core burning caused by heat release concentration, and simultaneously reduces the heat shrinkage rate of the glue block in the curing process.
And irradiating with ultraviolet light for 5min, taking out the rubber block, and testing the hardness of the rubber block to 80D (Shore hardness).
Example 2
1) 30.00g (0.03 mol) of polyethylene glycol adipate diol, 10.10g (0.06 mol) of hexamethylene diisocyanate, 0.04g of dibutyltin dilaurate (catalyst) were added to a 100ml reaction flask. The mixture was reacted for 2 hours at 90℃under nitrogen blanket with stirring.
2) 12.01g (0.06 mol) of 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl acrylate are added, 26.5mg of p-hydroxyanisole are added. Under the protection of nitrogen and the reaction condition of 90 ℃, reacting for 10 hours until the isocyanate group completely disappears, and obtaining the target product.
The product obtained in example 2 was measured for chemical structure by infrared spectrometer, and the results are shown in FIG. 3. The product was at 3337cm -1 The absorption peak at 1739cm is the characteristic peak of-N-H in polyurethane group -1 The absorption peak appearing is a characteristic telescopic vibration absorption peak of c=c; at the same time, isophorone diisocyanate (IPDI) has an absorption peak of 2270cm -1 The absorption peak at this point after the reaction had disappeared, indicating that-NCO reacted completely with-OH, indicating successful synthesis of the target product.
10.0 parts of the product of example 2, 19.5 parts of hexafluorobutyl methacrylate, 60.0 parts of isobornyl methacrylate, 10.0 parts of o-phenylphenoxyethyl acrylate and 0.5 part of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Weighing, mixing, standing and defoaming the components. Then, it was poured into a polyethylene mold having a diameter of 30mm and a height of 35mm, and the actual height of the poured glue was controlled not to exceed 35mm. Under the irradiation of 1000W mercury lamp (wavelength is 350-450 nm), the temperature at the center of the glue block is measured by a thermocouple, and the temperature of the glue surface is measured by a handheld infrared thermometer. The reaction time and the temperature change curve of the center of the glue block in the curing reaction process of the tested glue are shown in fig. 4.
As can be seen from FIG. 4, the glue reached the highest temperature (117.3℃) at around 174 s. In the process of testing and curing by using a handheld infrared thermometer, the highest temperature of the surface of the glue block is 97.7 ℃, and the center temperature and the surface temperature of the glue block of the encapsulated PCB are lower, so that the problem of thermal deformation of the PCB is solved, and the problems of bubble generation, core burning and the like caused by overhigh local temperature of the glue block are avoided.
And irradiating with ultraviolet light for 20min, taking out the rubber block, and testing the hardness of the rubber block to 80D (Shore hardness).
The excellent glue hardness indicates that double bonds react and are converted into saturated carbon-carbon single bonds in the staged curing process of the glue, so that the crosslinking density and the glue hardness of the glue are improved. The method is very beneficial to the subsequent grinding, polishing and observing of the glue block, namely the construction performance of the glue block is not changed after the glue is solidified in a grading way.
Example 3
1) Into a 100ml reaction flask were charged 30.0g (0.02 mol) of polybutylene adipate diol, 10.49g (0.04 mol) of dicyclohexylmethane diisocyanate, and 0.045g of dibutyltin dilaurate (catalyst). The mixture was reacted for 4 hours at 80℃under nitrogen protection and stirring.
2) 9.12g (0.04 mol) of 2-hydroxy-5 (-isopropenyl) cyclohexyl acrylate are added, and 14.9mg of p-tert-butylcatechol are added. And (3) reacting for 12 hours under the protection of nitrogen and at the temperature of 80 ℃ until the isocyanate groups completely disappear, thus obtaining the target product.
Example 3 product 30 parts, isobornyl methacrylate 40 parts, o-phenylphenoxyethyl methacrylate 20 parts, trifluoroethyl acrylate 9 parts, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate 0.5 parts, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 0.5 parts.
Weighing, mixing, standing and defoaming the components according to the mass composition. It is poured into a polyethylene mould with the diameter of 30mm and the height of 35mm, and the actual height of the poured glue is controlled to be not more than 30mm. Under the irradiation of 45W LED lamp tubes (5 9W LED lamp tubes with the wavelength of 350-400 nm), the temperature at the center of the glue block is measured by a thermocouple, and the temperature of the glue surface is measured by a handheld infrared thermometer. The reaction time and the temperature change curve of the center of the glue block in the curing reaction process of the tested glue are shown in fig. 5.
As can be seen from FIG. 5, the glue reached the maximum peak at about 207.1s at a glue block temperature of 107.4 ℃. In the curing process of the test by using a handheld infrared thermometer, the highest temperature of the surface of the rubber block is 90.0 ℃.
And (3) irradiating the rubber block for 20min by ultraviolet light, and taking out the rubber block, wherein the hardness of the rubber block is tested to be 81D (Shore hardness).
Example 4
1) Into a 100ml reaction flask were charged 20.0g (0.02 mol) of polytetrahydrofuran diol, 10.0g (0.01 mol) of polycarbonate diol (T5651, asahi chemical Co., ltd.), 13.34g (0.06 mol) of isophorone diisocyanate, and 0.043g of dibutyltin dilaurate (catalyst). The mixture was reacted for 8 hours at 70℃under nitrogen blanket with stirring.
2) 14.29g (0.06 mol) of methyl 2-hydroxy-2-methyl-5 (-isopropenyl) cyclohexyl acrylate are added, and 23.0mg of p-tert-butylhydroquinone are added. And (3) reacting for 24 hours under the protection of nitrogen and at the temperature of 70 ℃ until the isocyanate groups completely disappear, thus obtaining the target product.
Example 4 product 23.5 parts, phenoxyethyl methacrylate 47.0 parts, o-phenylphenoxyethyl methacrylate 25 parts, hexafluorobutyl methacrylate 3.0 parts, 2-dimethyl- α -hydroxyacetophenone 1.0 parts, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate 0.5 parts.
Weighing, mixing, standing and defoaming the components according to the mass composition. It is poured into a polyethylene mould with the diameter of 30mm and the height of 35mm, and the actual height of the poured glue is controlled to be not more than 30mm. Under the irradiation of 90WLED lamp tubes (10 9W LED lamp tubes with the wavelength of 350-400 nm), the temperature at the center of the glue block is measured by a thermocouple, and the temperature of the glue surface is measured by a handheld infrared thermometer. The reaction time and the temperature change curve of the center of the glue block in the curing reaction process of the tested glue are shown in fig. 6. As can be seen from FIG. 6, the glue reached the highest temperature (106.5 ℃ C.) at around 165 s. In the curing process of the test by using a handheld infrared thermometer, the highest temperature of the surface of the rubber block is 90.3 ℃.
And (3) irradiating the rubber block for 20min by ultraviolet light to take out the rubber block, wherein the hardness of the rubber block is tested to be 83D (Shore hardness).
Example 5
1) 10.0g (0.01 mol) of polyethylene succinate glycol, 10.00g (0.02 mol) of polytetrahydrofuran ether glycol, 10.49g (0.04 mol) of dicyclohexylmethane diisocyanate, 4.45g (0.02 mol) of isophorone diisocyanate, and 0.04g of dibutyltin dilaurate (catalyst) are charged into a 100ml reaction flask. The mixture was reacted for 4 hours at 80℃under nitrogen protection and stirring.
2) 5.89g (0.03 mol) of 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl acrylate, 7.14g (0.03 mol) of methyl 2-hydroxy-5 (-isopropenyl) cyclohexyl acrylate were added to 14.39mg of p-hydroxyanisole, 4.8mg (0.01%) of p-benzoquinone. And (3) reacting for 16 hours under the protection of nitrogen and at the temperature of 80 ℃ until the isocyanate groups completely disappear, thus obtaining the target product.
25 parts of the product of example 5, 15 parts of phenoxyethyl methacrylate, 25 parts of isobornyl acrylate, 15 parts of isobornyl methacrylate, 18 parts of trifluoroethyl methacrylate, 1.5 parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.5 part of benzoin dimethyl ether.
Weighing, mixing, standing and defoaming the components according to the mass composition. It is poured into a polyethylene mould with the diameter of 30mm and the height of 35mm, and the actual height of the poured glue is controlled to be not more than 30mm. Under the irradiation of 180W LED lamp tubes (20 9W LED lamp tubes with the wavelength of 350-400 nm), the surface temperature of the glue is measured by using a handheld infrared thermometer. The highest surface temperature of the glue in the curing process is 87.1 ℃. As can be seen from FIG. 7, the glue reached the highest temperature (109.5 ℃ C.) at around 187 s.
And (3) irradiating the rubber block for 20min by ultraviolet light, and taking out the rubber block, wherein the hardness of the rubber block reaches 82D (Shore hardness).
Example 6
1) 10.0g (0.01 mol) of polyethylene succinate glycol, 10.00g (0.02 mol) of polytetrahydrofuran ether glycol, 10.49g (0.04 mol) of dicyclohexylmethane diisocyanate, 4.45g (0.02 mol) of isophorone diisocyanate, and 0.04g of dibutyltin dilaurate (catalyst) are charged into a 100ml reaction flask. The mixture was reacted for 4 hours at 80℃under nitrogen protection and stirring.
2) 7.85g (0.04 mol) of methyl 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl acrylate, 4.75g (0.02 mol) of methyl 2-hydroxy-5 (-isopropenyl) cyclohexyl acrylate, 4.7mg of p-methylhydroquinone, 4.7mg of p-hydroxyanisole, 4.7mg of hydroquinone were charged to a round bottom flask. And (3) reacting for 8 hours under the protection of nitrogen and at the reaction condition of 90 ℃ until the isocyanate groups completely disappear, thus obtaining the target product.
30 parts of the product of example 6, 20 parts of phenoxyethyl methacrylate, 40 parts of isobornyl methacrylate, 7 parts of trifluoroethyl acrylate, 2.0 parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 1.0 part of 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-propanone.
Weighing, mixing, standing and defoaming the components according to the mass composition. Slowly pouring the glue into a polyethylene mould with the diameter of 30mm and the height of 35mm, and controlling the actual height of the poured glue not to exceed 30mm. Under the irradiation of 90W LED lamp tubes (10 9W LED lamp tubes with the wavelength of 350-400 nm), the surface temperature of the glue is measured by using a handheld infrared thermometer. The highest surface temperature of the glue during the curing process is 91.3 ℃. As can be seen from FIG. 8, the glue reached the highest temperature (113.6 ℃) at around 202 s.
And (5) irradiating the rubber block for 25min by ultraviolet light, and taking out the rubber block, wherein the hardness of the rubber block reaches 82D (Shore hardness).
Because the molecular structure of the graded curing polyurethane (methyl) acrylic ester resin contains two different reactive carbon-carbon double bonds, namely, two pairs of high-reactivity (methyl) acrylic ester double bonds and low-reactivity vinyl double bonds, under the action of a photoinitiator, the two double bonds sequentially undergo free radical polymerization according to different reactivity, thereby artificially prolonging the curing reaction period, namely, the (methyl) acrylic ester double bonds and the vinyl double bonds in the polyurethane (methyl) acrylic ester sequentially undergo free radical polymerization, slowing down the concentrated heat release of a polymerization system, reducing the internal temperature of a curing glue block, avoiding the problem that a large number of bubbles are generated in the cured sample block by vaporization and ultraviolet light curing the core burning of the sample block sometimes. In addition, the synthesized polyurethane (methyl) acrylic resin has 4 functionalities, can be cured in a grading way, and the cured rubber block has good transparency and high hardness.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various equivalent changes can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the equivalent changes belong to the protection scope of the present invention. In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (5)

1. A polyurethane (meth) acrylate, wherein the structural formula of the polyurethane (meth) acrylate is shown in formula (I):
wherein R is 1 Is that M is more than or equal to 5 and less than or equal to 10, n is more than or equal to 5 and less than or equal to 10;
R 2 is that
Any one or a mixture of at least two of them;
R 3 is H or CH 3 ；
R 4 Is H or CH 3 。
2. A process for the preparation of the polyurethane (meth) acrylate according to claim 1, characterized by the steps of:
1) Feeding polyester or polyether glycol and diisocyanate according to a molar ratio of 1:2, and adding a dibutyltin dilaurate catalyst accounting for 0.01% of the mass of the reacted materials; then heating to 60-90 ℃ under the condition of nitrogen protection and stirring, then reacting for 2-8h,
wherein the polyester or polyether glycol is at least one of polytetrahydrofuran glycol, polyethylene glycol adipate glycol, polyethylene glycol succinate glycol, polycarbonate glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-polypropylene glycol copolymer,
the diisocyanate is at least one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 3-m-xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate or 1, 3-cyclohexyldimethylene diisocyanate,
2) Adding hydroxyl compound of the material with the same molar weight as the diisocyanate, and adding polymerization inhibitor accounting for 0.01-0.05% of the mass of all the materials participating in the reaction; then under the protection of nitrogen and under the reaction condition of 60-90 ℃, reacting until the isocyanate group completely disappears, thus obtaining the catalyst;
wherein the hydroxyl compound is at least one of 2-hydroxy-2-methyl-5 (-isopropenyl) cyclohexyl methyl acrylate, 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl methyl acrylate, 2-hydroxy-5 (-isopropenyl) cyclohexyl methyl acrylate, 2-hydroxy-5 (-vinyl) cyclohexyl methyl acrylate, 2-hydroxy-2-methyl-5 (-isopropenyl) cyclohexyl acrylate, 2-hydroxy-2-methyl-5 (-vinyl) cyclohexyl acrylate, 2-hydroxy-5 (-isopropenyl) cyclohexyl acrylate, and 2-hydroxy-5 (-vinyl) cyclohexyl acrylate.
3. The preparation method according to claim 2, wherein the polymerization inhibitor is one or more of benzene diphenol, p-hydroxyanisole, p-benzoquinone, p-tert-butyl catechol, phenothiazine, p-tert-butyl hydroquinone, 6-tert-butyl-2, 4-dimethylphenol and p-methyl hydroquinone.
4. The potting adhesive for the low-temperature printed circuit board is characterized by comprising the following components in parts by mass:
(meth) acrylic acid esters: 70-89.5 parts;
the polyurethane (meth) acrylate of claim 1: 10-30 parts of a lubricant;
0.5-3.0 parts of photoinitiator;
the components are uniformly mixed under the light-shielding condition, and the potting adhesive for the low-temperature printed circuit board is obtained.
5. The potting adhesive for low temperature printed circuit board according to claim 4, wherein the (meth) acrylic acid ester is any one or a mixture of at least two of isobornyl acrylate, isobornyl methacrylate, o-phenylphenoxyethyl acrylate, o-phenylphenoxyethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate;
the photoinitiator is any one or a mixture of at least two of 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-morpholinophenyl) 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 diphenyl phosphine oxide, methyl o-benzoate, methyl o-benzoyl benzoate or ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate.
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