CN110627961A - Preparation method of photocuring resin integrated with hydrogen bonds and dynamic covalent bonds - Google Patents
Preparation method of photocuring resin integrated with hydrogen bonds and dynamic covalent bonds Download PDFInfo
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- CN110627961A CN110627961A CN201911036722.1A CN201911036722A CN110627961A CN 110627961 A CN110627961 A CN 110627961A CN 201911036722 A CN201911036722 A CN 201911036722A CN 110627961 A CN110627961 A CN 110627961A
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- acrylate
- mixture
- dynamic covalent
- bonds
- resin
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- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001408 amides Chemical group 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000006276 transfer reaction Methods 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 40
- 238000001723 curing Methods 0.000 claims description 16
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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 8
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 5
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 4
- NCAVPEPBIJTYSO-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.OCCCCOC(=O)C=C NCAVPEPBIJTYSO-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- RBMWDBHKRZTOMB-UHFFFAOYSA-N 2-ethoxy-1-phenylethanone Chemical compound CCOCC(=O)C1=CC=CC=C1 RBMWDBHKRZTOMB-UHFFFAOYSA-N 0.000 claims 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 claims 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000010146 3D printing Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003848 UV Light-Curing Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical class C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a photocuring resin integrated with hydrogen bonds and dynamic covalent bonds, and belongs to the technical field of polymer material preparation. The light-cured resin consists of the following components in percentage by weight: 20 to 40 percent of dicarboxylic acid, 15 to 30 percent of acrylic glycidyl ether or ester, 0 to 40 percent of hydrogen bond leading-in body, 10 to 50 percent of light-cured monomer, 0.05 to 5 percent of photoinitiator, 0.05 to 5 percent of ester exchange reaction catalyst and 0.05 to 5 percent of phase transfer reaction catalyst. Firstly, synthesizing acrylate resin to obtain acrylate resin containing dynamic covalent bonds, then carrying out ester exchange reaction, introducing amide functional groups and adding a photoinitiator to prepare uniform prepolymer, and finally placing the prepolymer into a mould and carrying out UV curing to prepare the light-cured resin integrating hydrogen bonds and dynamic covalent bonds. The light-cured resin prepared by the method has good tensile strength, can effectively prolong the service life of the material, and is particularly suitable for the technical fields of 3D printing and the like.
Description
The technical field is as follows:
the invention belongs to the technical field of polymer material preparation, and particularly relates to a preparation method of a photocuring resin integrated with hydrogen bonds and dynamic covalent bonds, which can be used in the fields of 3D printing and the like.
Background art:
the photocuring material has the characteristics of energy conservation, emission reduction, pollution reduction, strong adaptability and the like, is a green environment-friendly material, and meets the environment-friendly requirement advocated by the state. The material prepared by taking the acrylate resin as the prepolymer can perform photopolymerization or photocrosslinking reaction under the irradiation of ultraviolet light, has high curing speed, is one of the most applied photosensitive resins in the ultraviolet light curing material, and has the advantages of light color, high transparency, chemical corrosion resistance, strong adhesive force and the like. However, the acrylate resin has certain defects in specific occasions, such as incapability of recycling, insufficient mechanical properties, high hardness, solvent resistance, high cost and the like, and further application of the acrylate resin is limited.
The acrylate resin and other monomers are polymerized to obtain a thermosetting material. Conventional thermosetting materials are widely used in daily life due to their chemical and heat resistance. But the thermoset material cannot be remodeled due to the irreversible covalently crosslinked network. This is in sharp contrast to thermoplastic materials, which can be reshaped after being softened or heated. The non-recyclability of conventional thermoset materials causes environmental pollution. Dynamic covalent bonds are introduced into the cross-linked network, so that the thermosetting material can be recycled. Dynamic covalent bonds are those that undergo reversible fragmentation and recombination under certain conditions. The polymer cross-linked network based on the dynamic covalent bond triggers reversible reaction under external stimulation, thereby realizing the topological structure rearrangement of the cross-linked network and endowing the material with reprocessing and adaptability. Although the introduction of dynamic covalent bonds imparts the properties of processability, removability and recyclability to conventional covalently crosslinked materials, the good superplasticity and mechanical properties of the materials are often not compatible. To enhance the mechanical properties of the material, it is common practice to add nanofillers. However, the addition of nanofillers greatly limits the mobility of the chains, hindering the rearrangement of the network topology, and thus reducing the dynamic properties of the material.
In order to prepare the light-cured resin which is chemically crosslinked, can be reshaped and has increased strength, epoxy groups in acrylic glycidyl ether or ester are firstly reacted with carboxyl groups of dicarboxylic acid to generate beta-hydroxy ester, namely, the acrylate resin containing dynamic covalent bonds is prepared, the material is endowed with the plasticity of the light-cured resin, acrylamide is additionally added, hydrogen bonds are introduced into a crosslinking network and are used as sacrificial bonds, the covalent bonds are broken first, and reversible breaking and reforming are carried out under the action of external force, so that huge energy is consumed, the problem of poor mechanical property of the acrylate resin is solved, and the problem that the plasticity and the mechanical property of the thermosetting material are not easy to combine is solved. The method is simple and easy to operate, energy-saving and environment-friendly, and the resin prepared by the method has a great application prospect in 3D printing.
The invention content is as follows:
the invention provides a preparation method of a photocuring resin integrating hydrogen bonds and dynamic covalent bonds aiming at the non-recyclability and non-processability of the traditional thermosetting resin. The method of the invention can give the traditional thermosetting resin plasticity and reprocessing performance by introducing dynamic covalent bond; aiming at the problems that the mechanical property of the acrylate resin is poor and the material has poor plasticity and mechanical strength, the amide functional group is introduced to form hydrogen bonds, so that the strength of the material is obviously improved, and the stability of the dynamic property of the material is ensured.
The invention provides a preparation method of a light-cured resin integrating hydrogen bonds and dynamic covalent bonds, which comprises the following components in percentage by weight: 20-40% of dicarboxylic acid, 15-30% of glycidyl acrylate or glycidyl acrylate, 0-40% of hydrogen bond lead-in body, 10-50% of light curing monomer, 0.05-5% of photoinitiator, ester exchange reaction catalyst and phase transfer reaction catalyst; the preparation method of the photocuring resin integrating hydrogen bonds and dynamic covalent bonds comprises the following specific steps:
(1) synthesis of acrylate resin: mixing acrylic glycidyl ether or ester with a certain proportion and dicarboxylic acid, adding a phase transfer reaction catalyst, placing the mixture of the acrylic glycidyl ether or ester and the dicarboxylic acid into a three-neck flask, condensing and refluxing the mixture for 3-5 hours in a 105 ℃ constant-temperature oil bath, washing the product for 3-5 times, and then freeze-drying the product for 18-28 hours to obtain the acrylic resin containing the dynamic covalent bond.
(2) Addition of transesterification catalyst: and (2) adding a transesterification catalyst into the acrylate resin containing the dynamic covalent bond obtained in the step (1), and stirring at 60-90 ℃ for 10-30min to uniformly mix to prepare a mixture after transesterification.
(3) Introduction of amide functional group: and (3) respectively adding a photocuring monomer and a hydrogen bond introduction body into the mixture obtained in the step (2) after the ester exchange reaction in a certain proportion, stirring for 10-30min at normal temperature, and then stirring for 10-30min at 50-90 ℃ to uniformly mix, thus preparing the mixture containing the amide functional group.
(4) Addition of the photoinitiator: and (3) adding a photoinitiator into the mixture containing the amide functional group obtained in the step (3), uniformly mixing the mixture by stirring the mixture under vacuum at normal temperature for 10-30min to prepare a uniform prepolymer, and vacuumizing the prepolymer for 1-3 times to remove bubbles.
(5) Curing treatment: and (3) putting the prepared prepolymer into a mold, and then curing for 1-3min by ultraviolet light to prepare the light-cured resin integrating the hydrogen bond and the dynamic covalent bond.
The phase transfer reaction catalyst comprises one or a mixture of more than two of tetrabutylammonium bromide (TBAB), triethylamine, triethanolamine, N-dimethylformamide and hexadecyltrimethylammonium chloride (CTMAC).
The glycidyl acrylate or glycidyl acrylate comprises any one or a mixture of more than two of 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether and glycidyl methacrylate.
The dicarboxylic acid comprises any one or a mixture of more than two of suberic acid, sebacic acid, adipic acid, azelaic acid, isophthalic acid and terephthalic acid.
The photo-curing monomer comprises any one or a mixture of more than two of isodecyl acrylate, lauryl acrylate, butyl acrylate, ethoxyethoxyethyl acrylate, hydroxyethyl methacrylate, caprolactone acrylate, 2-phenoxyethyl acrylate, ethoxylated tetrahydrofuran acrylate, tetrahydrofurfuryl methacrylate and tetrahydrofuran acrylate (THFA).
The hydrogen bond introducers comprise any one or a mixture of more than two of acrylamide, N-methylolacrylamide and N-isopropylacrylamide.
The ester exchange reaction catalyst comprises one or a mixture of more than two of gamma-chloropropyl methyl dimethoxy silane (TBD), anhydrous zinc acetate, zinc acetylacetonate, triphenylphosphine and copper chloride.
The photoinitiator comprises 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexyl phenyl ketone (184), 2-dimethoxy-phenyl acetophenone (DMPA), alpha，-ethoxyacetophenone (DEAP), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl]Any one or a mixture of more than two of (E) -1-butanone, ethyl 2,4, 6-trimethylbenzoylphosphonate, (HMP) and Methyl Benzoylformate (MBF).
The invention has the following technical characteristics:
1. the invention adopts the photocuring technology and has the advantages of energy conservation, emission reduction and environmental protection.
2. The photocuring resin prepared by the method has the characteristics of simple operation, high reaction rate, mild conditions and high product yield. The preparation method of the invention is simple and efficient.
3. The polymer prepared by the method contains beta-hydroxy ester, and ester bonds can generate exchange reaction under the action of a catalyst at high temperature, so that the utilization rate of the material can be effectively improved.
4. The resin containing hydrogen bonds and dynamic covalent bonds prepared by the method has good tensile strength, can effectively prolong the service life of the material, and is particularly suitable for the field of 3D printing.
The specific implementation mode is as follows:
the principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Comparative example 1:
the components are prepared according to the comparative example 1 in the table 1, 4-hydroxy butyl acrylate glycidyl ether, octanediol and tetrabutylammonium bromide are subjected to oil bath magnetic stirring at 60 ℃ for 3 hours until the reaction is complete, and the uniformly mixed acrylate resin is obtained. Washing acrylate resin with distilled water for 3-5 times, removing TBAB, freeze drying in freeze drier for 24 hr, and removing distilled water. Then adding TBD into acrylate resin, and magnetically stirring for 30min at 90 ℃ to uniformly mix to prepare a uniform mixture. Then adding THFA into the mixture, stirring at room temperature for 30min to mix uniformly, adding N-isopropyl acrylamide, and magnetically stirring at 65 deg.C for 30min to mix uniformly. And (3) cooling to room temperature, adding a photoinitiator TPO, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the comparative example material.
Comparative example 2:
the components are prepared according to the comparative example 2 in the table 1, and the allyl glycidyl ether, the octanediamine and the N, N-dimethylformamide are stirred in an oil bath under the temperature of 55 ℃ by magnetic stirring for 3 hours until the reaction is complete, so that the acrylate resin with uniform mixing is obtained. Washing the acrylate resin with distilled water for 3-5 times, removing N, N-dimethylformamide, freeze-drying in a freeze dryer for 24h, and removing distilled water. Then adding anhydrous zinc acetate into acrylate resin, and magnetically stirring for 30min at 130 ℃ to uniformly mix to prepare a uniform mixture. Adding caprolactone acrylate into the mixture, stirring at room temperature for 30min to mix uniformly, adding N-hydroxymethyl acrylamide, and magnetically stirring at 75 deg.C for 30min to mix uniformly. And (3) cooling to room temperature, adding a photoinitiator TPO, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the comparative example material.
Example 1:
the components were prepared as described in table 1 for example 1, and glycidyl methacrylate, suberic acid and tetrabutylammonium bromide were magnetically stirred in an oil bath at 105 ℃ for 3 hours until the reaction was complete to give a uniformly mixed acrylate resin. Washing acrylate resin with distilled water for 3-5 times, removing TBAB, freeze drying in freeze drier for 24 hr, and removing distilled water. Then adding TBD into acrylate resin, and magnetically stirring for 30min at 90 ℃ to uniformly mix to prepare a uniform mixture. Adding THFA into the mixture, stirring at room temperature for 30min to mix, adding acrylamide, and magnetically stirring at 70 deg.C for 30min to mix. And (3) cooling to room temperature, adding a photoinitiator HMPP, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
Example 2:
the components were prepared as described in Table 1 for example 2 at 105 deg.C, allyl glycidyl ether, sebacic acid and tetrabutylammonium bromide were magnetically stirred in an oil bath at 117 deg.C for 3h until the reaction was complete, yielding a uniformly mixed acrylate resin. Washing the acrylate resin with distilled water for 3-5 times, removing TBAB, freeze-drying in a freeze dryer for 24h, removing distilled water, adding anhydrous zinc acetate into the acrylate resin, and stirring for 30min to obtain a uniform mixture. Adding the ethoxylated tetrahydrofuran acrylate into the mixture, stirring for 30min at normal temperature to mix uniformly, adding acrylamide, and magnetically stirring for 30min at 90 ℃ to mix uniformly. And cooling to room temperature, adding the photoinitiator 184, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
Example 3:
the components were prepared as described in table 1 for example 3, and glycidyl methacrylate, octanediol and tetrabutylammonium bromide were magnetically stirred in an oil bath at 60 ℃ for 3 hours until the reaction was complete, to obtain a uniformly mixed acrylate resin. Washing the acrylate resin with distilled water for 3-5 times, removing TBAB, freeze-drying in a freeze dryer for 24h, removing distilled water, adding triphenylphosphine into the acrylate resin, and magnetically stirring at 85 ℃ for 30min to obtain a uniform mixture. And adding tetrahydrofurfuryl methacrylate into the mixture, stirring for 30min at normal temperature to uniformly mix, adding acrylamide, and magnetically stirring for 30min at 90 ℃ to uniformly mix. And (3) cooling to room temperature, adding a photoinitiator TPO, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
Example 4:
the components were prepared as in table 1 for example 4, and the glycidyl methacrylate, octanediamine and tetrabutylammonium bromide oil baths were magnetically stirred at 55 ℃ for 3 hours until the reaction was complete to give well-mixed acrylate resins. Washing acrylate resin with distilled water for 3-5 times, removing TBAB, freeze drying in a freeze drier for 24 hr, removing distilled water, adding zinc acetylacetonate into acrylate resin, and stirring at 120 deg.C to obtain uniform mixture. And adding tetrahydrofurfuryl methacrylate into the mixture, stirring for 30min at normal temperature to uniformly mix, adding acrylamide, and magnetically stirring for 30min at 70 ℃ to uniformly mix. And (3) cooling to room temperature, adding a photoinitiator TPO, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
Example 5:
the components were prepared as described in table 1 for example 5, and glycidyl methacrylate, terephthalic acid and cetyltrimethylammonium chloride were magnetically stirred in an oil bath at 90 ℃ for 3 hours until the reaction was complete, to give a uniformly mixed acrylate resin. Washing acrylate resin with distilled water for 3-5 times, removing hexadecyl trimethyl ammonium chloride, freeze-drying in a freeze dryer for 24h, removing distilled water, adding copper chloride into acrylate resin, and stirring at 100 deg.C to obtain a uniform mixture. Then adding THFA into the mixture, stirring at room temperature for 30min to mix uniformly, adding acrylamide, and magnetically stirring at 70 deg.C for 30min to mix uniformly. And cooling to room temperature, adding the photoinitiator 184, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
Example 6:
the components were prepared as described in table 1 for example 6, and allyl glycidyl ether, suberic acid and tetrabutylammonium bromide were magnetically stirred in an oil bath at 105 ℃ for 3 hours until the reaction was complete, to give a uniformly mixed acrylate resin. Washing acrylate resin with distilled water for 3-5 times, removing TBAB, freeze drying in a freeze dryer for 24h, removing distilled water, adding TBD into acrylate resin, stirring at 90 deg.C for 30min, and preparing to obtain uniform mixture. And adding tetrahydrofurfuryl methacrylate into the mixture, stirring for 30min at normal temperature to uniformly mix, adding N-isopropyl acrylamide, and magnetically stirring for 30min at 65 ℃ to uniformly mix. And (3) cooling to room temperature, adding a photoinitiator TPO, and stirring at room temperature for 30min to obtain a uniform prepolymer. And finally, vacuumizing the prepared prepolymer, and curing for 2min by using a UV mercury lamp to obtain the photocuring resin integrated with hydrogen bonds and dynamic covalent bonds.
TABLE 1 weight percent of the components of each comparative and example
Table 2 tensile and remodeling test results obtained for each comparative example and example
As can be seen from table 2, the present invention can greatly improve the mechanical strength of the remodelable material by introducing hydrogen bonds into the resin containing dynamic covalent bonds, and can be applied to 3D printing.
Claims (8)
1. A preparation method of a light-cured resin integrating hydrogen bonds and dynamic covalent bonds is characterized in that the light-cured resin integrating hydrogen bonds and dynamic covalent bonds is composed of the following components in percentage by weight: 20-40% of dicarboxylic acid, 15-30% of glycidyl acrylate or glycidyl acrylate, 0-40% of hydrogen bond lead-in body, 10-50% of light curing monomer, 0.05-5% of photoinitiator, ester exchange reaction catalyst and phase transfer reaction catalyst; the preparation method of the photocuring resin integrating hydrogen bonds and dynamic covalent bonds comprises the following specific steps:
(1) synthesis of acrylate resin: mixing acrylic glycidyl ether or ester with a certain proportion and dicarboxylic acid, adding a phase transfer reaction catalyst, placing the mixture of the acrylic glycidyl ether or ester and the dicarboxylic acid into a three-neck flask, condensing and refluxing the mixture for 3-5 hours in a 105 ℃ constant-temperature oil bath, washing the product for 3-5 times, and then freeze-drying the product for 18-28 hours to obtain acrylic resin containing dynamic covalent bonds;
(2) addition of transesterification catalyst: adding a transesterification catalyst into the acrylate resin containing the dynamic covalent bond obtained in the step (1), stirring at 60-90 ℃ for 10-30min, and uniformly mixing to prepare a mixture after transesterification;
(3) introduction of amide functional group: respectively adding a photocuring monomer and a hydrogen bond introduction body into the mixture obtained in the step (2) after the ester exchange reaction in a certain proportion, stirring for 10-30min at normal temperature, and then stirring for 10-30min at 50-90 ℃ to uniformly mix to prepare a mixture containing the amide functional group;
(4) addition of the photoinitiator: adding a photoinitiator into the mixture containing the amide functional group obtained in the step (3), uniformly mixing the mixture by stirring the mixture for 10 to 30 minutes at normal temperature in vacuum to prepare a uniform prepolymer, and vacuumizing the prepolymer for 1 to 3 times to remove bubbles;
(5) curing treatment: and (3) putting the prepared prepolymer into a mold, and then curing for 1-3min by ultraviolet light to prepare the light-cured resin integrating the hydrogen bond and the dynamic covalent bond.
2. The method of claim 1, wherein the phase transfer reaction catalyst comprises one or a mixture of more than two of tetrabutylammonium bromide, triethylamine, triethanolamine, N-dimethylformamide and cetyltrimethylammonium chloride.
3. The method for preparing photocurable resin integrating hydrogen bond and dynamic covalent bond as claimed in claim 1, wherein the glycidyl acrylate or glycidyl acrylate comprises any one or a mixture of two or more of 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether and glycidyl methacrylate.
4. The method for preparing photocurable resin integrating hydrogen bond and dynamic covalent bond as claimed in claim 1, wherein said dicarboxylic acid comprises any one or a mixture of two or more of suberic acid, sebacic acid, adipic acid, azelaic acid, isophthalic acid and terephthalic acid.
5. The method of claim 1, wherein the photo-curable monomer comprises at least one of isodecyl acrylate, lauryl acrylate, butyl acrylate, ethoxyethoxyethyl acrylate, hydroxyethyl methacrylate, caprolactone acrylate, 2-phenoxyethyl acrylate, ethoxylated tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and tetrahydrofurfuryl acrylate.
6. The method for preparing a photocurable resin integrating hydrogen bonding and dynamic covalent bonding according to claim 1, wherein the hydrogen bond-introducing substance comprises any one or a mixture of two or more of acrylamide, N-methylolacrylamide and N-isopropylacrylamide.
7. The method for preparing photocuring resin integrating hydrogen bonds and dynamic covalent bonds as claimed in claim 1, wherein the transesterification catalyst comprises one or a mixture of more than two of gamma-chloropropylmethyldimethoxysilane, anhydrous zinc acetate, zinc acetylacetonate, triphenylphosphine and copper chloride.
8. The method of claim 1, wherein the photoinitiator comprises 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-phenyl acetophenone, α，Ethoxyacetophenone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl]Any one or a mixture of more than two of (E) -1-butanone, ethyl 2,4, 6-trimethylbenzoylphosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl benzoylformate.
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| CN113248654A (en) * | 2021-05-14 | 2021-08-13 | 西北工业大学 | Dynamic ester exchange glass body high polymer material and preparation method thereof |
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