CN114507347A - Preparation method of adhesive based on mercapto Michael addition reaction - Google Patents
Preparation method of adhesive based on mercapto Michael addition reaction Download PDFInfo
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- CN114507347A CN114507347A CN202210128274.3A CN202210128274A CN114507347A CN 114507347 A CN114507347 A CN 114507347A CN 202210128274 A CN202210128274 A CN 202210128274A CN 114507347 A CN114507347 A CN 114507347A
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- Prior art keywords
- bisphenol
- compound
- adhesive
- red solid
- addition reaction
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- 239000000853 adhesive Substances 0.000 title claims abstract description 72
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006845 Michael addition reaction Methods 0.000 title claims abstract description 10
- 125000003396 thiol group Chemical class [H]S* 0.000 title description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000012265 solid product Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 229930185605 Bisphenol Natural products 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- -1 bisphenol compound Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FIYYMXYOBLWYQO-UHFFFAOYSA-N ortho-iodylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1I(=O)=O FIYYMXYOBLWYQO-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 claims description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 claims description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 2
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 abstract description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 3
- 238000006957 Michael reaction Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000237536 Mytilus edulis Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000020638 mussel Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012462 polypropylene substrate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
-
- 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
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an adhesive based on a mercapto Michael addition reaction, which comprises the following steps: oxidation and purification of BPx: dissolving bisphenol compounds in an organic solvent, adding an oxidant, and stirring at room temperature to form a red solid; cooling and then carrying out vacuum filtration; re-dissolving the filter residue, and repeatedly performing suction filtration to remove unreacted reactants to obtain a red solid product; dissolving the red solid substance in an organic solvent, performing vacuum filtration, and performing rotary evaporation to remove the solvent in the filtrate to obtain a purified red solid product, wherein the purified red solid product is BQx; preparation of the adhesive based on the mercaptomichael addition reaction: BQx is dissolved in organic solvent, the solution of the biquinones compound is prepared by magnetic stirring, and the multi-sulfhydryl compound is added to react to obtain light yellow solution; purification of the adhesive based on the mercaptomichael addition reaction: and dripping a precipitator into the light yellow solution under the stirring state, and centrifuging at a high speed to separate a supernatant and a precipitate to obtain a yellow viscous compound serving as a final adhesive. The adhesive prepared by the preparation method has high adhesive strength and good underwater adhesion.
Description
Technical Field
The invention relates to the field of high polymer materials, belongs to the fields of chemical engineering, biomedical materials and marine industry, and particularly relates to a preparation method of an adhesive based on a mercapto Michael addition reaction.
Background
Polymer adhesive materials are widely used in various fields such as biomedicine, underwater equipment and marine industry. Polymer adhesives are now being put into commercial production. However, most adhesives currently only work on the surface of dry solids, forming a permanent or reversible bond with the dry surface. However, in many applications, adhesives that can bond to wet surfaces or surfaces submerged in aqueous media are needed, such as medical implantable devices, wound dressings, underwater sensors, and the like. And adhesives that have been put into commercial use today also suffer from the problem that the strength of adhesion does not achieve the desired target. Therefore, it is a breakthrough in this field to develop a new adhesive having high adhesive strength and suitable for use in underwater environments.
Most of the underwater adhesives developed today draw inspiration from the nature. For example, inspired by marine mussel organisms, permanent underwater adhesion is achieved using l-3, 4-Dihydroxyphenylalanine (DOPA), where the key contributing structure is the catechol group. In the past decade, inspired by this, significant progress has been made in the design and manufacture of new underwater adhesives. For example, chinese patent publication No. CN107916078A discloses a method for preparing a starch-based mussel-like adhesive based on a chemical-biological coupling method, which utilizes simple chemical reaction and laccase catalysis to generate reactive active quinones and other structures to prepare a novel functional material with starch as a macromolecular skeleton and dopa-containing side groups, and achieves the purpose of improving the starch bonding strength through biomimetic bonding. For example, chinese patent publication No. CN107625991A discloses a method for preparing a mussel-like functionalized fracture adhesive, which uses a catechol-containing structural polymer, hydroxyapatite and chitosan as raw materials, wherein the raw materials for preparing the catechol-containing structural polymer are polyethylene glycol, acrylic acid chloride and a catechol-containing structural compound, and the catechol-containing structural compound is dopamine hydrochloride. However, the research on the current adhesive is more dependent on the existing catechol group-containing compound, and the large-scale development and application of the catechol-containing adhesive cannot be realized, so that the development of a large amount of catechol-containing adhesive which can be chemically synthesized is the current research hotspot.
Bisphenols are compounds in which two hydroxyphenyl groups are bonded together by one or more carbon atoms, optionally a sulfur atom and an oxygen atom. Bisphenols are of great interest because of their endocrine disrupting properties. The bisphenol compound is introduced into a high molecular chain by chemical reaction and is possibly expanded into a substance with biological friendliness, the biological safety problem of the bisphenol compound monomer is solved, and the catechol group is obtained by the oxidation-reduction reaction of the bisphenol compound, so that the high adhesion of the adhesive material is facilitated.
The mercapto group is a negative monovalent functional group formed by connecting a sulfur atom and a hydrogen atom, the chemical formula is-SH, and the multi-mercapto compound refers to a compound containing two or more mercapto groups. The mercapto Michael addition reaction is a common method for growing carbon chains and is widely applied to polymer reactions. The mechanism is a conjugate addition reaction of a compound containing an electrophilic conjugate system as an electron acceptor with a nucleophilic mercapto group, i.e., an electron donor. The reaction system is efficient and rapid, and can generate a polymer chain segment with a certain connecting group.
Disclosure of Invention
The invention aims to provide a preparation method of an adhesive based on a mercapto Michael addition reaction, and the prepared adhesive has high adhesion strength.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a thiol michael addition reaction based adhesive comprising the steps of:
(1) oxidation and purification of bisphenol compound BPx: dissolving a bisphenol compound in an organic solvent, adding an oxidant, stirring at room temperature to form a red solid, cooling, performing vacuum filtration, taking filter residues for redissolving, and repeating the filtration step to remove unreacted reactants to obtain a red solid product; dissolving the red solid substance in an organic solvent, performing vacuum filtration, and performing rotary evaporation to remove the solvent in the filtrate to obtain a purified red solid product which is a biquinone compound BQx;
(2) preparation of the adhesive based on the mercaptomichael addition reaction: dissolving the biquinone compound BQx in an organic solvent, preparing a biquinone compound solution by magnetic stirring, and adding a multi-mercapto compound to react to obtain a light yellow solution;
(3) purification of the adhesive based on the mercaptomichael addition reaction: and dripping a precipitator into the obtained light yellow solution under the stirring state, and centrifuging at a high speed to separate a supernatant and a precipitate to obtain a yellow viscous compound serving as a final adhesive.
In the step (1), the bisphenol compound is selected from any one of bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, bisphenol AP, bisphenol AF, bisphenol BP and bisphenol PH.
In the step (1), the multi-mercapto compound is selected from any one of pentaerythritol tetramercaptoacetate, 2' - (1, 2-ethanediylbis oxo) bisethanethiol, 1, 2-ethanedithiol and 1, 4-butanediol bis (mercaptoacetate).
In the step (1), the oxidant is selected from any one of 2-iodoxybenzoic acid, potassium permanganate, potassium dichromate (acidic), manganese dioxide and sodium chlorate (acidic). 2-iodoxybenzoic acid is preferred.
In the step (1), the organic solvent for dissolving the red solid is selected from any one of acetone in N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, ethyl acetate and N, N-dimethylformamide. Preferably chloroform.
In the technical scheme, the concentration of the solution of the bisquinone compound prepared in the step (2) is 10-40 wt%, and preferably 22.6 wt%.
In step (2), the molar ratio of conjugated double bonds to mercapto functional groups (1-4) to (1-4), preferably 1: 1.
In the step (2), the organic solvent is selected from N-methylpyrrolidone, dimethyl sulfoxide, methanol, chloroform, tetrahydrofuran, ethanol, ethyl acetate, N-dimethylformamide or acetone. N-methylpyrrolidone is preferred.
In the step (3), the precipitant is a methanol solution or an ethanol solution with a concentration of 40-100%, and the dosage of the precipitant is 5-10 times. Preferably 60% methanol solution, and the amount of precipitant is preferably 8 times.
Preferably, the bisphenol compound is bisphenol A, the multi-mercapto compound is 2, 2' - (1, 2-ethanediylbis oxo) bis ethanethiol, the ratio of the two functional groups is 1:1, and the adhesive strength of the adhesive prepared is 1700-2500kPa, and the underwater adhesive strength is 400 kPa. The preparation method specifically comprises the following steps:
the method comprises the following steps: oxidation and purification of bisphenol A (BPA)
Bisphenol a (bpa) was dissolved in methanol, the oxidant 2-iodoxybenzoic acid (IBX) was added and stirred at room temperature for 15 minutes, and the formation of a red solid was observed. The solution was cooled in an ice bath for 10 minutes and filtered under reduced pressure. And re-dissolving the filter residue, and repeatedly performing suction filtration to remove unreacted reactants to obtain a red solid product. Dissolving the obtained red solid substance in chloroform, vacuum filtering, and removing solvent from the filtrate by rotary evaporator to obtain purified red solid product (bisquinone A (BQA)).
Step two: preparation of adhesives based on the mercaptoMichael addition reaction
Dissolving the bisquinone A (BQA) prepared in the step one in N-methyl pyrrolidone (NMP), placing on a magnetic stirrer, and preparing 22.6 wt% of the bisquinone A at a stirring speed of 200-500 r/min. Adding 2, 2' - (1, 2-ethanediylbis oxo) bisethanethiol with the amount of the same substances into the solution according to the molar ratio of the conjugated double bonds to the mercapto functional groups of 1:1, gradually lightening the brick red solution, and obtaining a light yellow solution after 15 minutes.
Step three: purification of adhesives based on the mercaptoMichael reaction
And (3) taking 60% methanol solution prepared from deionized water and methanol as a precipitator, slowly dripping the faint yellow solution obtained in the step two into the 60% methanol solution under the stirring state, and separating the supernatant and the precipitate by using a high-speed centrifuge to obtain a yellow viscous compound.
The oxidation mechanism is as follows:
the reaction mechanism of the adhesive based on the mercapto michael addition reaction is as follows:
specifically, the phenolic hydroxyl group on bisphenol A (BPA) is oxidized by an oxidant such as 2-iodoxybenzoic acid (IBX) to generate bisquinone A (BQA) with a conjugated carbonyl structure. Based on the mercapto Michael addition reaction, the mercapto group on the 2,2 '- (1, 2-ethanediylbis oxo) bisethanethiol and the carbonyl group on the bisquinone A are subjected to conjugate addition reaction, the 2, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and the bisquinone A are quickly and efficiently connected, and the benzoquinone group is reduced to the phenol group, so that the high-molecular polymer adhesive connected through the mercapto catechol connecting group is formed.
The invention also provides application of the adhesive prepared by the preparation method in the biomedical field, water-based energy equipment, underwater sensors, underwater repair and marine industry. The biomedical field may be in medical implant devices and wound dressings.
The invention overcomes the defects in the prior art, is biologically excited by mussels, utilizes the rich diversity of bisphenol compounds, can be oxidized by an oxidant to generate the biquinone compounds, and obtains the structure rich in catechol groups after reduction reaction. The bisquinone compound can be subjected to a mercaptoMichael type addition reaction with a polymercapto compound at room temperature to form a polymer binder having mercapto catechol group linkages. The catechol group obtained by reduction of the bisquinone compound gives the adhesive a high adhesive strength. And the method can be expanded to different bisphenol compounds and multi-sulfhydryl compounds.
The adhesive based on the mercaptomichael addition reaction of the present invention has the following advantageous effects:
1. the raw materials of bisphenol compounds and multi-sulfhydryl compounds selected by the preparation method provided by the invention have diversity.
2. The invention introduces the bisphenol compound to a macromolecular chain by utilizing the mercapto Michael reaction and possibly expands the bisphenol compound into a substance with biological friendliness, thereby solving the problem of biological safety of the bisphenol compound monomer. And the bisphenol compounds are rich in catechol groups after oxidation-reduction, which is more beneficial to the high adhesion of the prepared adhesive material.
3. The preparation method of the adhesive is simple and efficient, mild in condition and high in reaction rate.
4. The adhesive has high adhesive strength which is respectively 2500kPa and 1700kPa on an aluminum substrate and a polypropylene substrate.
5. The hydrogel adhesive has good underwater adhesion, has the underwater adhesion strength of up to 400kPa, and can be applied to the biomedical fields such as medical implantation equipment, wound dressings, water-based energy equipment, underwater sensors, underwater repair, marine industry and the like.
Drawings
FIG. 1 shows the NMR carbon spectrum of bisphenol A oxidized to obtain bisquinone A.
FIG. 2 shows the NMR spectrum of bisphenol A oxidized to obtain bisquinone A.
FIG. 3 is a schematic representation of an adhesive prepared with bisphenol A2, 2' - (1, 2-ethanediylbisixoxy) bisethanethiol of the present invention at a ratio of 1: 1.
FIG. 4 is a graph showing the adhesive strength of an adhesive prepared with bisphenol A2, 2' - (1, 2-ethanediylbisixoxy) bisethanethiol of the present invention at a ratio of 1: 1.
Detailed Description
The invention is further illustrated by the following specific figures and examples.
The drugs used in the examples are shown in the following table:
| medicine and food additive | Manufacturer of the product |
| Bisphenol A | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Pentaerythritol Tetramercaptoacetate | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| 2, 2' - (1, 2-ethanediylbis-oxo) bisethanethiol | Sigma-Aldrich |
| 2-iodoxybenzoic acid | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Methanol | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Trichloromethane | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| N-methyl pyrrolidone | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
The instruments used in the examples are shown in the following table:
| instrument for measuring the position of a moving object | Manufacturer of the product |
| Electronic analytical balance | German Sadolis group |
| Vacuum drying oven | SHANGHAI YIHENG INSTR Co.,Ltd. |
| 85-1 magnetic stirrer | Hangzhou David instruments & Equipment Co Ltd |
| DHG-9040A forced air drying oven | SHANGHAI YIHENG INSTR Co.,Ltd. |
| TG16.5 high-speed table type centrifugal machine | Changshan instrument centrifuge instruments Ltd |
| IMS-40 full-automatic ice maker | CHANGSHU XUEKE ELECTRIC Co.,Ltd. |
| Circulating water vacuum pump | Shanghai Lichen Bangxi Instrument science and technology Co Ltd |
| N-1300 rotary evaporator | Shanghai Ailang instruments Ltd |
Example 1
The preparation of the adhesive based on the mercaptoMichael reaction is illustrated by using 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) and 2, 2' - (1, 2-ethanediylbis-oxo) bisethanethiol (EDET) as starting materials in a feed ratio of 1: 1.
The method comprises the following steps: oxidation and purification of bisphenol A (BPA)
Bisphenol a (bpa) was dissolved in methanol, the oxidant 2-iodoxybenzoic acid (IBX) was added and stirred at room temperature for 15 minutes, and the formation of a red solid was observed. The solution was cooled in an ice bath for 10 minutes and filtered under reduced pressure. And re-dissolving the filter residue, and repeatedly performing suction filtration to remove the unreacted reactant to obtain a red solid product. Dissolving the red solid product in chloroform, vacuum filtering, and removing solvent from the filtrate with rotary evaporator to obtain purified red solid product bisquinone A (BQA).
Step two: preparation of Binders based on the mercapto Michael reaction
Dissolving the bisquinone A (BQA) prepared in the step one in N-methyl pyrrolidone (NMP), placing the solution on a magnetic stirrer, and preparing a 22.6 wt% bisquinone A solution at a stirring speed of 200-500 r/min. Adding 2, 2' - (1, 2-ethanediylbis oxo) bisethanethiol with the amount of the substances being equal to the amount of the conjugated double bonds and the mercapto functional groups in a feeding ratio of 1:1, namely the molar ratio of the conjugated double bonds to the mercapto functional groups of 1:1 into the solution, gradually lightening the brick red solution, and obtaining a light yellow solution after 15 minutes.
Step three: purification of adhesives based on the mercaptoMichael reaction
And (3) taking 60% methanol solution prepared from deionized water and methanol as a precipitator, slowly dripping the faint yellow solution obtained in the step two into the 60% methanol solution under the stirring state, and separating the supernatant and the precipitate by using a high-speed centrifuge to obtain a yellow viscous compound.
FIG. 1 shows the nuclear magnetic hydrogen spectrum of bisquinone A obtained by oxidation of bisphenol A, and it can be seen that-CH is present at 1.44ppm3The absorption peak of the upper hydrogen atom, 7.08ppm and 6.39ppm are the absorption peaks of the hydrogen atom on the six-membered ring, respectively, and the structure of BQA can be judged by nuclear magnetic hydrogen spectrum.
FIG. 2 is a nuclear magnetic carbon spectrum of diquinone A obtained by oxidation of bisphenol A, and it can be seen that at 24.14ppm and 43.43ppm, — CH is present respectively3The absorption peaks of carbon atoms, 126.24ppm, 130.07ppm, 139.88ppm, 155.74ppm and 179.64ppm, are absorption peaks of carbon atoms on the six-membered ring, and the structure of BQA can be judged by nuclear magnetic carbon spectrum.
FIG. 3 is a schematic representation of the adhesive prepared with bisphenol A2, 2' - (1, 2-ethanediylbis-oxo) bisethanethiol at a ratio of 1:1, the solution becoming slightly pale yellow from the original brick red.
FIG. 4 is a graph showing the adhesive strength of the adhesive prepared with bisphenol A2, 2' - (1, 2-ethanediylbisioxo) bisethanethiol at 1: 1. The adhesive strength is tested by using a lap shear method, and the specific operation steps are as follows: aluminum and polypropylene substrates (100 mm. times.10 mm) were cleaned with acetone and pre-treated with UV/ozone for 30 minutes. 100 mul of polymer adhesive solution (200mg/ml) was uniformly applied to the surface of a sheet substrate, the solvent was evaporated at room temperature, and the coated surfaces of the two samples were combined, the overlapping area was 10mm × 10mm, cured at 120 ℃ for 15min, and tested by a universal tensile tester, the tensile rate was fixed at 5mm/min, and the Adhesive Strength (AS) was calculated according to the following formula.
Where F is the maximum load (N) at which the lap specimen is stretched and S is the lap area (m)2)。
The adhesive strength of the adhesive prepared by the invention on an aluminum substrate and a polypropylene substrate is respectively as high as 2500kPa and 1700kPa, and the underwater adhesive strength is 400 kPa.
Example 2
The preparation of an adhesive based on the mercaptoMichael reaction is illustrated by taking as an example the starting materials 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) and pentaerythritol tetramercaptoacetate in a 2:1 feed ratio.
The method comprises the following steps: oxidation and purification of bisphenol A
Bisphenol a (bpa) was dissolved in methanol, the oxidant 2-iodoxybenzoic acid (IBX) was added and stirred at room temperature for 15 minutes, and the formation of a red solid was observed. The solution was cooled in an ice bath for 10 minutes and filtered under reduced pressure. And re-dissolving the filter residue, and repeatedly performing suction filtration to remove the unreacted reactant to obtain a red solid product. Dissolving the red solid product in chloroform, vacuum filtering, and removing solvent from the filtrate with rotary evaporator to obtain purified red solid product bisquinone A (BQA).
Step two: preparation of Binders based on the mercapto Michael reaction
Dissolving the bisquinone A (BQA) prepared in the step one in N-methylpyrrolidone (NMP), placing on a magnetic stirrer, and preparing a 22.6 wt% bisquinone A solution at a stirring speed of 200-500 r/min. Pentaerythritol tetramercaptoacetate with the amount of equal substances is added into the solution according to the feeding ratio of 2:1, namely the molar ratio of the conjugated double bond to the mercapto functional group is 1:1, the brick red solution becomes lighter gradually, and a light yellow solution is obtained after 15 minutes.
Step three: purification of adhesives based on the mercaptoMichael reaction
And (3) taking 60% methanol solution prepared from deionized water and methanol as a precipitator, slowly dripping the faint yellow solution obtained in the step two into the 60% methanol solution under the stirring state, and separating the supernatant and the precipitate by using a high-speed centrifuge to obtain a yellow viscous compound.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A method for preparing a mercapto michael addition reaction based adhesive, comprising the steps of:
(1) oxidation and purification of bisphenol compound BPx: dissolving a bisphenol compound in an organic solvent, adding an oxidant, stirring at room temperature to form a red solid, cooling, performing vacuum filtration, taking filter residues for redissolving, and repeating the filtration step to remove unreacted reactants to obtain a red solid product; dissolving the red solid substance in an organic solvent, performing vacuum filtration, and performing rotary evaporation to remove the solvent in the filtrate to obtain a purified red solid product which is a biquinone compound BQx;
(2) preparation of the adhesive based on the mercaptomichael addition reaction: dissolving the biquinone compound BQx in an organic solvent, preparing a biquinone compound solution by magnetic stirring, and adding a multi-mercapto compound to react to obtain a light yellow solution;
(3) purification of the adhesive based on the mercaptomichael addition reaction: and dripping a precipitator into the obtained light yellow solution under the stirring state, and centrifuging at a high speed to separate a supernatant and a precipitate to obtain a yellow viscous compound serving as a final adhesive.
2. The method of claim 1, wherein in step (1), the bisphenol compound is selected from any one of bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, bisphenol AP, bisphenol AF, bisphenol BP, and bisphenol PH.
3. The method of claim 1, wherein in step (1), the multi-mercapto compound is selected from any one of pentaerythritol tetramercaptoacetate, 2' - (1, 2-ethanediylbutoxy) bisethanethiol, 1, 2-ethanedithiol, and 1, 4-butanediol bis (mercaptoacetate).
4. The method for preparing an adhesive based on a mercaptomichael addition reaction according to claim 1, wherein in step (1), the oxidizing agent is selected from any one of 2-iodoxybenzoic acid, potassium permanganate, potassium dichromate, manganese dioxide and sodium chlorate.
5. The method of claim 1, wherein the organic solvent for re-dissolving the red solid is selected from any one of N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, ethyl acetate, N-dimethylformamide, and acetone.
6. The method of claim 1, wherein in the step (2), the organic solvent is selected from any one of N-methylpyrrolidone, dimethyl sulfoxide, methanol, chloroform, tetrahydrofuran, ethanol, ethyl acetate, N-dimethylformamide, and acetone.
7. The method for preparing an adhesive based on a mercaptoMichael reaction, according to claim 1, wherein the concentration of the solution of the bisquinone compound prepared in the step (2) is 10 to 40 wt%.
8. The method for preparing an adhesive based on a mercaptoMichael reaction, according to claim 1, wherein in the step (3), the precipitant is a methanol solution or an ethanol solution having a concentration of 40 to 100%; the dosage of the precipitant is 5-10 times.
9. The method of claim 1, wherein the bisphenol compound is bisphenol A, the multi-mercapto compound is 2, 2' - (1, 2-ethanediylbutoxy) bisethanethiol, and the ratio of the two functional groups is 1:1, whereby the adhesive strength is 1700-2500kPa, and the underwater adhesive strength is 400 kPa.
10. Use of the adhesive obtained by the process according to any one of claims 1 to 9 in biomedical fields, water-based energy equipment, underwater sensors, underwater repair and marine industries.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110101898A (en) * | 2019-04-04 | 2019-08-09 | 华南理工大学 | Bionical tissue adhesive of bi-component in-situ injection type poly-asparagine and preparation method thereof |
| CN112724415A (en) * | 2019-10-14 | 2021-04-30 | 天津大学 | Adhesive capable of realizing underwater strong adhesion and preparation method and application thereof |
| DE102020108099A1 (en) * | 2020-03-24 | 2021-09-30 | Humboldt-Universität Zu Berlin | Shell-inspired polymeric adhesives and methods of making them |
| CN113929910A (en) * | 2021-12-07 | 2022-01-14 | 郑州大学 | Hyperbranched polymer underwater adhesive based on polyfunctional group rigid hydrophobic component and preparation method and application thereof |
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|---|---|---|---|---|
| CN110101898A (en) * | 2019-04-04 | 2019-08-09 | 华南理工大学 | Bionical tissue adhesive of bi-component in-situ injection type poly-asparagine and preparation method thereof |
| CN112724415A (en) * | 2019-10-14 | 2021-04-30 | 天津大学 | Adhesive capable of realizing underwater strong adhesion and preparation method and application thereof |
| DE102020108099A1 (en) * | 2020-03-24 | 2021-09-30 | Humboldt-Universität Zu Berlin | Shell-inspired polymeric adhesives and methods of making them |
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