CN117210138B - Reusable acrylate adhesive - Google Patents
Reusable acrylate adhesive Download PDFInfo
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- CN117210138B CN117210138B CN202311305497.3A CN202311305497A CN117210138B CN 117210138 B CN117210138 B CN 117210138B CN 202311305497 A CN202311305497 A CN 202311305497A CN 117210138 B CN117210138 B CN 117210138B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 70
- 239000000853 adhesive Substances 0.000 title claims abstract description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 20
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- IIJAEVGPROJHIY-UHFFFAOYSA-N (10-methylanthracen-9-yl)methanol Chemical compound C1=CC=C2C(C)=C(C=CC=C3)C3=C(CO)C2=C1 IIJAEVGPROJHIY-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 3
- 239000003522 acrylic cement Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- -1 alcohol compound Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000002441 reversible effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- JCORDFBSOCALKC-UHFFFAOYSA-N 3-(1-carboxypropan-2-yldisulfanyl)butanoic acid Chemical compound OC(=O)CC(C)SSC(C)CC(O)=O JCORDFBSOCALKC-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 125000005577 anthracene group Chemical group 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 150000001454 anthracenes Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000005262 alkoxyamine group Chemical group 0.000 description 1
- 229940045799 anthracyclines and related substance Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of adhesives, and particularly discloses a reusable acrylate adhesive. The acrylate adhesive comprises anthracene-mercapto ester derivative, 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, bisphenol A glycerol dimethacrylate and photoinitiator. The invention also provides a preparation method of the composite. Compared with the prior art, the acrylate adhesive prepared by the invention has the advantages of good reusability, mild debonding effect, difficult residue, wide application range and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a reusable acrylate adhesive.
Background
An adhesive is defined as a functional chemical medium that binds two identical or different substances, the creation of which can be achieved by chemical bond bonding or physical adsorption. According to the bonding time of the adhesive to the substances, the bonding time can be divided into permanent bonding and temporary bonding, when the bonded sample is separated after the bonding, if the bonded sample is required to be bonded again under the action of external conditions, the reversible adhesive is formed. At present, the reusable adhesive has potential research and application values in the fields of biological organ lapping (especially tooth or bone connection), electronic component bonding, interior decoration and automobile assembly. Conventional structural adhesives suffer from difficult cleaning and poor reusability, and present significant environmental and resource challenges. Therefore, the development of the green recyclable adhesive has positive promotion effects on the aspects of new material development, environmental protection, resource conservation and the like.
The bonding mechanisms shown when the adhesives with different molecular structures bond different substances are different, the bonding mechanisms comprise different theories such as chemical bonds, mechanical locking, infiltration adsorption, electrostatic theory, weak boundary layers and the like, and even a plurality of reinforcing mechanisms exist in the same system condition, so that different driving modes exist in reversible bonding. But are mainly summarized in two general categories, namely non-covalent and covalent links, depending on the manner of reversible linking. Non-covalent linkages primarily contain van der Waals forces, hydrogen bonding, metal coordination, host-guest ligands, and charge interactions. Covalent bonding is achieved by dynamic reversible chemical bond bonding formed in molecules or among molecules, and the main structures of the covalent bonding are DIELS ALDER reaction, disulfide bond, acylhydrazone, alkoxyamine, boric acid ester bond, polytriazole and the like.
Chinese patent 201710457117.6 provides a high-strength heat reversible polytriazole adhesive and preparation and application thereof, wherein the adhesive is prepared from polytriazole polymer, and the chemical structural general formula of the polytriazole polymer is shown as (I); when the polytriazole adhesive film is prepared, the diyne monomer, the diazide monomer and the dihalide cross-linking agent are added into an organic solvent together, stirred and mixed, coated on a substrate, heat-preserved for 1-5 hours at 50-100 ℃, then heat-preserved for 1-8 hours at 120-180 ℃, cooled to room temperature, then soaked in deionized water, and the adhesive film is automatically peeled off from the substrate and dried; when the polytriazole liquid adhesive is prepared, the diacetylene monomer, the diazide monomer and the dihalide cross-linking agent are mixed, heated to 50-100 ℃, and fully stirred and uniformly mixed. Compared with the prior art, the adhesive has the advantages of high initial bonding strength, good reversible bonding property, simple construction process and good storage stability, and is suitable for application fields requiring high bonding strength, repeated bonding and adjustable bonding.
Chinese patent 202110311856.0 discloses a high-strength light reversible adhesive, a preparation method and application. The invention firstly epoxidizes the raw material of the compound containing anthracene group to prepare an epoxidation product containing anthracene, then mixes the epoxidation product with the mercapto-terminated alcohol compound and the accelerator, and carries out ring opening at room temperature to prepare the double-end hydroxyl compound containing anthracene group side chain. The double-end isocyanate compound and double-end hydroxyl polycaprolactone are adopted, an organotin catalyst is added, and chain extension reaction is carried out to form the chain extension double-end isocyanate compound with larger molecular weight. And finally, reacting the chain-extended double-end isocyanate compound with a double-end hydroxyl compound containing an anthracene side chain and a double-end hydroxyl compound not containing an anthracene side chain, and adding an organotin catalyst for catalytic reaction to obtain the high-strength light reversible adhesive. The adhesive of the invention is subjected to [4+4] cycloaddition reaction and solidification under the irradiation of ultraviolet light of 350-405 nm; decrosslinking under ultraviolet radiation of less than 300 nm.
However, repeatable adhesives generally require heating to high temperatures to break the corresponding dynamic covalent bonds to effect debonding, which is not friendly to electronic products and can cause irreversible damage to precision parts and even substrates, and thus the search for a more gentle debonding means to produce reusable adhesives would have greater utility.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a reusable acrylate adhesive.
The insertion of a photosensitive structure such as an anthracycline as a reversible covalent crosslinking center into a polymer network will enable the corresponding adhesive to heal precisely and rapidly and to fall off more easily under light assisted or other mild conditions. The [ 4pi+4pi ] cycloaddition based on the 9-bit substituted anthracene precursor has the advantages of low energy barrier, high reaction activity, high photoreaction rate and the like, and is favorable for stably and efficiently generating anthracene dimer in the photocuring process to construct a light reversible crosslinked network. However, the high reflectivity and weak penetration of the shorter wavelength uv tends to result in incomplete depolymerization and even failure of debonding, which results in the rejection of stacked or packaged electronic devices due to adhesive residues, and also in reduced adhesion if the adhesive is not cured, resulting in a substantial reduction in efficacy. According to the invention, the inventor obtains an anthracene-mercapto ester derivative through esterification and further cleavage of 9-hydroxymethyl-10-methylanthracene and 3- (1-carboxypropyl-2-yl disulfide acyl) butyric acid, and mixes the anthracene-mercapto ester derivative with 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, bisphenol A glycerol dimethacrylate and a photoinitiator to obtain an acrylic ester adhesive, and the acrylic ester adhesive is bonded through thiol-ene click reaction and polymerization and addition of [ 4pi+4pi ] rings of 9-substituted anthracene precursors under ultraviolet light, and the anthracene dimer depolymerizes under heating to realize debonding, so that a reusable effect is achieved, and a hydrogen bond network formed by hydroxyl groups in 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester is improved in crosslinking degree, so that the adhesive with good bonding force is obtained, and the adhesive is good in reusability, mild in debonding effect, not easy to remain, and wide in application range.
In order to achieve the aim, the invention provides a reusable acrylate adhesive which comprises anthracene-mercapto ester derivatives, 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, bisphenol A glycerol dimethacrylate and a photoinitiator.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 15-25 parts by weight of 9-hydroxymethyl-10-methylanthracene, 8-20 parts by weight of 3- (1-carboxyprop-2-yl disulfide acyl) butyric acid and 0.5-2 parts by weight of 4-dimethylaminopyridine into 200-400 parts by weight of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; 45-75 parts by weight of dicyclohexylcarbodiimide is added into 100-200 parts by weight of tetrahydrofuran to obtain a solution B; adding the solution B into the solution A at 0-5 ℃ under nitrogen atmosphere, stirring for 18-28 h at room temperature, cooling the mixed solution to 0-5 ℃, standing for 8-10 h, centrifugally separating, washing the lower precipitate with alcohol, and drying for the next step;
S2, adding the product obtained in the last step into 300-500 parts by weight of tetrahydrofuran aqueous solution (75% by volume), adding 8-15 parts by weight of 1, 4-dimercaptosuitol and 4-10 parts by weight of triethylamine, heating to 25-35 ℃, stirring for 16-26 hours under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, drying and concentrating an organic phase after liquid separation to obtain the anthracene-mercaptoester derivative.
Further, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
A preparation method of a reusable acrylate adhesive comprises the following steps:
15 to 35 weight parts of anthracene-mercapto ester derivative, 10 to 15 weight parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 5 to 10 weight parts of bisphenol A glycerol dimethacrylate and 0.5 to 2 weight parts of photoinitiator are mixed and stirred uniformly to obtain the acrylate adhesive.
The invention has the beneficial effects that:
1. the invention obtains anthracene-mercapto ester derivatives through esterification and further cleavage of 9-hydroxymethyl-10-methylanthracene and 3- (1-carboxypropyl-2-yl disulfide acyl) butyric acid, and can realize solidification under ultraviolet light and de-adhesion after heating when being applied to adhesives, thereby achieving the effect of repeated use;
2. The prepared acrylic ester adhesive can form a hydrogen bond network to achieve the improvement of crosslinking degree during crosslinking, so that the adhesive with better adhesive force is obtained, the adhesive has good reusability, mild debonding effect, difficult residue and wide application range.
Detailed Description
9-Hydroxymethyl-10-methylanthracene, 10-METHYLANTHRACEN-9-yl) methanol, CAS number: 71339-55-4.
3- (1-Carboxyprop-2-yldithioyl) butyric acid, 3- (1-carboxypropan-2-yldisulfanyl) butanoic acid, CAS number: 63684-27-5.
Comparative example 1
A preparation method of a reusable acrylate adhesive comprises the following steps:
And mixing 25g of anthracene-mercapto ester derivative, 12g of propyl-2-methyl-2-acrylic ester, 7.5g of bisphenol A glycerol dimethacrylate and 1.5g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring to obtain the acrylic ester adhesive.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 22g of 9-hydroxymethyl-10-methylanthracene, 15g of 3- (1-carboxyprop-2-yl disulfide yl) butyric acid and 1.2g of 4-dimethylaminopyridine into 300mL of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; dicyclohexylcarbodiimide 65g was added to 150mL of tetrahydrofuran to give solution B; adding the solution B into the solution A at 0 ℃ under nitrogen atmosphere, stirring for 20 hours at room temperature, cooling the mixed solution to 2 ℃, standing for 10 hours, centrifuging at 8500rpm for 10 minutes, washing the lower precipitate with alcohol, and drying for the next step;
s2, adding the product obtained in the last step into 400mL of tetrahydrofuran aqueous solution (75 v%), adding 10.5g of 1, 4-dimercaptosuccinol and 7.5g of triethylamine, heating to 30 ℃, stirring for 18h under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, separating the liquid, drying an organic phase, and concentrating at 35 ℃ and minus 0.9MPa to obtain the anthracene-mercaptoester derivative.
Example 1
A preparation method of a reusable acrylate adhesive comprises the following steps:
25g of anthracene-mercapto ester derivative, 12g of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 7.5g of bisphenol A glycerol dimethacrylate and 1.5g of 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed and stirred uniformly to obtain the acrylate adhesive.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 22g of 9-hydroxymethyl-10-methylanthracene, 15g of 3- (1-carboxyprop-2-yl disulfide yl) butyric acid and 1.2g of 4-dimethylaminopyridine into 300mL of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; dicyclohexylcarbodiimide 65g was added to 150mL of tetrahydrofuran to give solution B; adding the solution B into the solution A at 0 ℃ under nitrogen atmosphere, stirring for 20 hours at room temperature, cooling the mixed solution to 2 ℃, standing for 10 hours, centrifuging at 8500rpm for 10 minutes, washing the lower precipitate with alcohol, and drying for the next step;
s2, adding the product obtained in the last step into 400mL of tetrahydrofuran aqueous solution (75 v%), adding 10.5g of 1, 4-dimercaptosuccinol and 7.5g of triethylamine, heating to 30 ℃, stirring for 18h under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, separating the liquid, drying an organic phase, and concentrating at 35 ℃ and minus 0.9MPa to obtain the anthracene-mercaptoester derivative.
Example 2
A preparation method of a reusable acrylate adhesive comprises the following steps:
The acrylic ester adhesive is obtained by uniformly mixing and stirring 25g of anthracene-mercapto ester derivative, 12g of hydroxypropyl methacrylate, 7.5g of bisphenol A glycerol dimethacrylate and 1.5g of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 22g of 9-hydroxymethyl-10-methylanthracene, 15g of 3- (1-carboxyprop-2-yl disulfide yl) butyric acid and 1.2g of 4-dimethylaminopyridine into 300mL of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; dicyclohexylcarbodiimide 65g was added to 150mL of tetrahydrofuran to give solution B; adding the solution B into the solution A at 0 ℃ under nitrogen atmosphere, stirring for 20 hours at room temperature, cooling the mixed solution to 2 ℃, standing for 10 hours, centrifuging at 8500rpm for 10 minutes, washing the lower precipitate with alcohol, and drying for the next step;
s2, adding the product obtained in the last step into 400mL of tetrahydrofuran aqueous solution (75 v%), adding 10.5g of 1, 4-dimercaptosuccinol and 7.5g of triethylamine, heating to 30 ℃, stirring for 18h under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, separating the liquid, drying an organic phase, and concentrating at 35 ℃ and minus 0.9MPa to obtain the anthracene-mercaptoester derivative.
Example 3
A preparation method of a reusable acrylate adhesive comprises the following steps:
And mixing 25g of anthracene-mercapto ester derivative, 12g of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 5g of bisphenol A glycerol dimethacrylate and 1.5g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring to obtain the acrylate adhesive.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 22g of 9-hydroxymethyl-10-methylanthracene, 15g of 3- (1-carboxyprop-2-yl disulfide yl) butyric acid and 1.2g of 4-dimethylaminopyridine into 300mL of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; dicyclohexylcarbodiimide 65g was added to 150mL of tetrahydrofuran to give solution B; adding the solution B into the solution A at 0 ℃ under nitrogen atmosphere, stirring for 20 hours at room temperature, cooling the mixed solution to 2 ℃, standing for 10 hours, centrifuging at 8500rpm for 10 minutes, washing the lower precipitate with alcohol, and drying for the next step;
s2, adding the product obtained in the last step into 400mL of tetrahydrofuran aqueous solution (75 v%), adding 10.5g of 1, 4-dimercaptosuccinol and 7.5g of triethylamine, heating to 30 ℃, stirring for 18h under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, separating the liquid, drying an organic phase, and concentrating at 35 ℃ and minus 0.9MPa to obtain the anthracene-mercaptoester derivative.
Example 4
A preparation method of a reusable acrylate adhesive comprises the following steps:
And mixing 25g of anthracene-mercapto ester derivative, 12g of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 10g of bisphenol A glycerol dimethacrylate and 1.5g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring to obtain the acrylate adhesive.
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1, adding 22g of 9-hydroxymethyl-10-methylanthracene, 15g of 3- (1-carboxyprop-2-yl disulfide yl) butyric acid and 1.2g of 4-dimethylaminopyridine into 300mL of tetrahydrofuran, and stirring and mixing uniformly to obtain a solution A; dicyclohexylcarbodiimide 65g was added to 150mL of tetrahydrofuran to give solution B; adding the solution B into the solution A at 0 ℃ under nitrogen atmosphere, stirring for 20 hours at room temperature, cooling the mixed solution to 2 ℃, standing for 10 hours, centrifuging at 8500rpm for 10 minutes, washing the lower precipitate with alcohol, and drying for the next step;
s2, adding the product obtained in the last step into 400mL of tetrahydrofuran aqueous solution (75 v%), adding 10.5g of 1, 4-dimercaptosuccinol and 7.5g of triethylamine, heating to 30 ℃, stirring for 18h under a nitrogen atmosphere, concentrating the mixed solution to dryness, diluting with dichloromethane, washing with water and brine, separating the liquid, drying an organic phase, and concentrating at 35 ℃ and minus 0.9MPa to obtain the anthracene-mercaptoester derivative.
Test example 1
The adhesive strength of the acrylate adhesive is tested, the testing method refers to GB/T7124-2008 'determination of tensile shear strength of adhesive (rigid material to rigid material)', the adhesive is coated on a test piece, another test piece is covered on the test piece according to the length of a standard bonding surface, after curing for 5min under ultraviolet light (365 nm), tensile force is applied in the direction of a main axis of the test piece, and the shear stress of the bonding position of the overlap joint of the rigid material is measured, wherein the specific result is shown in Table 1.
Table 1 tensile shear strength test results table for adhesives
| Experimental protocol | Tensile shear Strength/MPa |
| Comparative example 1 | 2.10 |
| Example 1 | 3.82 |
| Example 2 | 2.65 |
| Example 3 | 3.41 |
| Example 4 | 3.32 |
The test results show that the tensile shear strength of the example 1 is highest, which is probably due to the rigid group and the hydroxyl group on the structure of the acrylate adhesive, the rigid group endows the adhesive with better mechanical property, the hydroxyl group in the polymer can form a hydrogen bond network during crosslinking, so that the crosslinking degree is improved, the adhesive force is improved, the shear strength is high, the propyl-2-methyl-2-acrylate of the comparative example 1 is high, the hydroxypropyl methacrylate of the example 2 is provided with only one hydroxyl group, the crosslinking degree of the adhesive film formed by the obtained acrylate adhesive is lower than that of the example 1, and the examples 3-4 prove that the proportion of the functional monomers influences the crosslinking degree, the crosslinking degree is insufficient when the proportion is too small, but the crosslinking is excessive when the proportion is too large, so that the tensile shear strength is influenced.
Test example 2
Determining the debonding temperature of the prepared adhesive and determining the bonding performance after repeated use, preparing the prepared adhesive into a test piece according to the method in test example 1, performing ultraviolet light curing, baking (80-150 ℃) for 10min at different temperatures after curing, observing whether debonding is performed or not, if debonding is performed, curing the debonded test piece again as 1 cycle, measuring the tensile shear strength again after 10 cycles (refer to test example 1), and if debonding is not performed, continuously baking for 10min at a gradient of 10 ℃ until debonding is performed, and recording the debonding temperature.
TABLE 2 debonding stability and reusable adhesive Properties of acrylate Adhesives
As can be seen from the debonding temperature, in comparative example 1, the debonding is advantageous because the degree of crosslinking of the acrylate is poor, if the acrylate is more easily catalyzed in the presence of acid in the system, and thus the ester bond is broken to cause debonding, whereas in comparative example and example, the adhesive film formed in example 1 has stronger adhesive force and thus the debonding is relatively higher in temperature, but does not exceed 100 ℃, which is advantageous for the product itself and is not easily damaged, because of the difference in debonding temperature due to the strength of the adhesive property. It can be seen from the tensile shear properties after 10 cycles that the debonding condition of example 1 is higher, but the reusable property is better, which is also closely related to the degree of crosslinking, so that the balance between maintaining the relatively mild debonding condition and the reusability is the best strategy.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (5)
1. The reusable acrylate adhesive is characterized by comprising the following raw materials in parts by weight: 15-35 parts of anthracene-mercapto ester derivative, 10-15 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 5-10 parts of bisphenol A glycerol dimethacrylate and 0.5-2 parts of photoinitiator;
The preparation method of the anthracene-mercapto ester derivative comprises the following steps:
S1 9-hydroxymethyl-10-methylanthracene, 3- (1-carboxypropan-2-yl disulfide acyl) butyric acid and 4-dimethylaminopyridine are stirred and mixed uniformly in A solvent to obtain A solution A; adding dicyclohexylcarbodiimide into a solvent to obtain a solution B; adding the solution B into the solution A at low temperature under inert atmosphere, stirring at room temperature, standing at low temperature, centrifuging, washing, and drying for the next step;
S2, mixing the product obtained in the last step with 1, 4-dimercaptosuccinol and triethylamine in a solvent, heating and stirring under inert atmosphere, concentrating the mixed solution to be dry, diluting, washing and carrying out aftertreatment to obtain the anthracene-mercapto ester derivative.
2. The adhesive of claim 1, wherein: the low temperature in the step S1 is in the range of 0-5 ℃.
3. The adhesive of claim 1, wherein: the heating temperature in the step S2 is 25-35 ℃.
4. The adhesive of claim 1, wherein: the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
5. A method of preparing an adhesive according to any one of claims 1 to 4, comprising the steps of:
and mixing the anthracene-mercapto ester derivative, 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, bisphenol A glycerol dimethacrylate and a photoinitiator, and uniformly stirring to obtain the acrylic adhesive.
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| KR100549574B1 (en) * | 1999-12-30 | 2006-02-08 | 주식회사 하이닉스반도체 | Organic anti-reflective coating polymers and preparation thereof |
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