CN113583211A - Polyurea acrylate oligomer and preparation method and application method thereof - Google Patents
Polyurea acrylate oligomer and preparation method and application method thereof Download PDFInfo
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- CN113583211A CN113583211A CN202110870234.1A CN202110870234A CN113583211A CN 113583211 A CN113583211 A CN 113583211A CN 202110870234 A CN202110870234 A CN 202110870234A CN 113583211 A CN113583211 A CN 113583211A
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- acrylate oligomer
- polyurea
- diisocyanate
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 46
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- SXQFCVDSOLSHOQ-UHFFFAOYSA-N lactamide Chemical group CC(O)C(N)=O SXQFCVDSOLSHOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CMDHNEAPXOZXBI-UHFFFAOYSA-N n-[4-[4-(hydroxyamino)phenyl]phenyl]hydroxylamine Chemical compound C1=CC(NO)=CC=C1C1=CC=C(NO)C=C1 CMDHNEAPXOZXBI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- 229950005308 oxymethurea Drugs 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- IXQBIOPGDNZYNA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC=C1C1=CC=CC=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1C1=CC=CC=C1C IXQBIOPGDNZYNA-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 9
- 238000001723 curing Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 Tert-butyl Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- LSZFFPVDPBVFRO-UHFFFAOYSA-N 2-(propan-2-ylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(C)NCCOC(=O)C(C)=C LSZFFPVDPBVFRO-UHFFFAOYSA-N 0.000 description 1
- WRJXGJVVKVFPBH-UHFFFAOYSA-N 2-(propan-2-ylamino)ethyl prop-2-enoate Chemical compound CC(C)NCCOC(=O)C=C WRJXGJVVKVFPBH-UHFFFAOYSA-N 0.000 description 1
- KDAKDBASXBEFFK-UHFFFAOYSA-N 2-(tert-butylamino)ethyl prop-2-enoate Chemical compound CC(C)(C)NCCOC(=O)C=C KDAKDBASXBEFFK-UHFFFAOYSA-N 0.000 description 1
- GMTJKMKNOIUGPG-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCCCC1 GMTJKMKNOIUGPG-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention discloses a polyurea acrylate oligomer, which can be dissociated to generate isocyanate groups under the heating condition and react with characteristic groups on side chains to form a cross-linked network, and has the following structure:
wherein R is1Is hydrogen or methyl, R2Being a sterically hindered group, R3Is a characteristic group which can react with isocyanate on a side chain. The invention also discloses a preparation method and an application method of the polyurea acrylate oligomer. After the polyurea acrylate oligomer provided by the invention is photocured, the molecular structure, the crosslinking density and other network structure characteristics of the polyurea acrylate oligomer can be changed through specific post-treatment, so that the corresponding thermodynamic performance of the polyurea acrylate oligomer can be controllably changed.
Description
Technical Field
The invention belongs to the field of photocuring oligomers, and particularly relates to a polyurea acrylate oligomer as well as a preparation method and an application method thereof.
Background
Photocuring usually uses visible or ultraviolet light as energy source, and initiates the process of rapidly converting a photoreactive liquid substance into a solid substance by free radical or cationic polymerization. The light curing technology has the characteristics of high efficiency, high speed, wide adaptability, low cost and good environmental protection performance. Therefore, the photocuring technology is widely applied to the fields of coatings, printing ink, adhesives, photoresists, emerging 3D printing and the like.
Generally, the light curing system mainly comprises an oligomer, a reactive diluent, a photoinitiator, a light absorber and the like. Wherein, the oligomer mainly comprises two categories of polyester acrylate and polyurethane/polyurea acrylate. For example, Chinese patent with publication number CN105111998A discloses an ultraviolet light curing adhesive, and Chinese patent with publication number CN113072678A discloses a polyurea acrylate oligomer, a preparation method and an application method thereof. The properties of the oligomer largely determine the properties of the cured material, including hardness, strength, toughness, transition temperature and other thermodynamic parameters. In general, the photo-curing results in a non-fusible and insoluble cross-linked network, the material properties of which cannot be changed, and the higher cross-linking density thereof results in poor mechanical properties, particularly brittle and poor toughness.
Therefore, if the oligomer prepared by a certain network molecule design can meet the requirement of rapid curing, and the molecular structure and the network topological structure of the photo-crosslinking network can be changed in a post-treatment manner to improve the mechanical property of the oligomer, the application range of the photo-curing technology can be further expanded.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide the polyurea acrylate oligomer, after photocuring, the molecular structure, the crosslinking density and other network structure characteristics of the polyurea acrylate oligomer can be changed through specific post-treatment, so that the corresponding thermodynamic property of the polyurea acrylate oligomer can be controllably changed. The invention also provides a preparation method of the polyurea acrylate oligomer.
The purpose of the invention is realized by the following technical route:
a polyurea acrylate oligomer which can be dissociated under heating to generate isocyanate groups and react with characteristic groups on side chains to form a cross-linked network has the following structure:
wherein R is1Is hydrogen or methyl, R2Being a sterically hindered group, R3Is a characteristic group which can react with isocyanate on a side chain.
The polyurea acrylate oligomer provided by the invention is characterized in that a urea bond is introduced on a main chain, and a characteristic group R is introduced on a side chain3. The urea bond is a dynamic covalent chemical bond, and can be dissociated at high temperature to generate an NCO group and hindered amine, and the NCO can react with a characteristic group on a side chain to generate a more stable chemical bond (urethane bond, amido bond or urea bond and the like). On one hand, the crosslinking density of the photo-crosslinked polymer network is reduced, and internal stress is released; on the other hand, the dissociated NCO group and the side chain group are crosslinked to form a polyurea structure, so that the mechanical property of the polymer is changed.
The R is2Tert-butyl, isopropyl, ethyl, methyl, piperidine, pyrazole, oxime and the like.
The R is3Characteristic groups that can react with isocyanates include hydroxyl, amino, phenol, carboxylic acid, anhydride, epoxy, urea, carbamate, amide, hydrazide, and the like.
The invention also provides a preparation method of the polyurea acrylate oligomer, which comprises the following steps:
1) the first step is to contain R3The polyfunctional monomer reacts with diisocyanate to obtain an intermediate product 1 with an end group of isocyanate;
reacting a diisocyanate with a compound containing R3The multifunctional monomer is reacted, group protection is realized by controlling reaction conditions, so that other two groups (hydroxyl or amino) participate in the reaction, and R3The reaction is not participated in, the reaction end point is judged by confirming the NCO value of the system by a di-n-butylamine method, and R in the system is confirmed by nuclear magnetism3The content of (a).
The diisocyanate and the compound containing R3The molar ratio of the polyfunctional monomer(s) is 1: 2-1: 2.01 (excluding unreacted R)3)。
Preferably, the diisocyanate is hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, 4 ' -diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, or the like.
Preferably, the compound contains R3The polyfunctional monomer is lactamide, dihydroxy benzidine, N' -dimethylol urea, 2-dimethylol propionic acid, diphenolic acid, 2-dimethylol butyric acid and the like.
2) In the second step, intermediates 1 and R2A group-substituted hindered amine acrylate reaction;
the molar ratio of the intermediate product 1 to the hindered amine acrylate is 1: 2-1: 2.01.
The hindered amine acrylate end-capped intermediate 1 may be: t-butylaminoethyl methacrylate, t-butylaminoethyl acrylate, isopropylaminoethyl methacrylate, isopropylaminoethyl acrylate, piperidinoethyl methacrylate, and the like.
The invention also provides an application method of the polyurea acrylate oligomer, which comprises the following specific steps:
1) mixing the polyurea acrylate oligomer with a specific reactive diluent, and adding a photoinitiator, a polymerization inhibitor and a light absorber;
2) curing the mixture using a light source matched with the initiator;
3) and (3) treating the cured sample at 80-120 ℃ for 1-10 hours.
The active diluent is 0.05-0.5 part by weight of polyurea acrylate oligomer; the photoinitiator is 0.01-0.05 part by weight of polyurea acrylate oligomer; the light absorber is 0.0001-0.001 weight part of polyurea acrylate oligomer; the polymerization inhibitor is 0.0005-0.015 weight part of polyurea acrylate oligomer.
The reactive diluent can be used for adjusting the viscosity of a resin system and the mechanical property of a sample after the resin system is cured, and the photoinitiator and the polymerization inhibitor can be used for adjusting the kinetics of photopolymerization. The reactive diluent may be a low viscosity mono-or multifunctional acrylate or methacrylate compound. The light source used should be compatible with the photoinitiator and may be an ultraviolet or visible light source.
The polyurea acrylate oligomer forms a cross-linked network after photo-initiated polymerization, and after the polymerization is carried out under a certain temperature condition, hindered urea bonds in the network are dissociated and further react with characteristic groups on side chains. On one hand, the crosslinking density of the photocrosslinking network is reduced, and partial curing internal stress is released; on the other hand, a cross-linked network of polyacrylate-polyurethane can be obtained through post-treatment, so that the mechanical property of the sample is obviously changed, and the toughness is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the crosslinking density of the photo-crosslinking network is reduced after post-treatment, and meanwhile, the crosslinking network of polyacrylate-polyurethane is generated, so that the toughness of the polymer can be improved;
2. the material characteristics of the cross-linked network of polyacrylate-polyurethane can be regulated and controlled by parameters such as the type and content of characteristic groups on side chains.
Drawings
FIG. 1 is a stress-strain plot of the polyurea acrylate oligomer prepared in example 1;
FIG. 2 is a stress-strain plot of the polyurea acrylate oligomer prepared in example 2.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, but rather should be construed in breadth and scope in accordance with the appended claims.
Example 1
1) 0.5mol of polytetrahydrofuran ether glycol (PTMG, M) is added into the reaction kettlew650) and 1mol of 4, 4' -diphenylmethane diisocyanate (HMDI, M)w262), controlling the temperature to be 50 ℃, and determining the reaction to be finished by sampling nuclear magnetic analysis to obtain an intermediate product 1;
2) then 0.3mol of lactamide is dripped into the reaction kettle through a constant pressure funnel, the temperature is controlled to be 50 ℃ during dripping, heat preservation is carried out after dripping is finished, reaction is continued, and the end of the reaction is determined through sampling nuclear magnetic analysis to obtain an intermediate product 2;
3) and continuously dropwise adding 0.4mol of tert-butylaminoethyl methacrylate into the reaction kettle through a constant pressure funnel, controlling the temperature to be 50 ℃ during dropwise adding, keeping the temperature after dropwise adding, continuously reacting, and determining the reaction to be finished through sampling nuclear magnetic analysis to obtain the polyurea acrylate oligomer.
Taking 10g of the polyurea acrylate oligomer, adding 5g of diluent isobornyl methacrylate, adding 0.1g of photoinitiator 819 and 0.02g of polymerization inhibitor p-hydroxyanisole, casting a sample strip meeting the ASTM D412 standard in a transparent mold, testing the uniaxial tension performance, and treating the sample strip at 120 ℃ for 8 hours to test the uniaxial tension performance. The elongation at break before treatment was 21%, and the breaking strength was 39 MPa; the elongation at break after the treatment was 95% and the breaking strength was 35MPa (FIG. 1).
Example 2
1) 0.5mol of polypropylene glycol (PPG, M) was added to the reactorw1000) and 1mol of hexamethylene diisocyanate (HDI, M)w168 deg.c), controlling the temperature to 50 deg.c, and determining the end of the reaction by sampling nuclear magnetic analysis to obtain intermediate product 1;
2) then, 0.25mol of 2, 2-dimethylolbutyric acid is dripped into the reaction kettle through a constant pressure funnel, the temperature is controlled to be 50 ℃ when dripping is carried out, heat preservation is carried out after dripping is finished, reaction is continued, and the end of the reaction is determined through sampling nuclear magnetic analysis to obtain an intermediate product 2;
3) and continuously dropwise adding 0.5mol of isopropyl aminoethyl acrylate into the reaction kettle through a constant-pressure funnel, controlling the temperature to be 50 ℃ during dropwise adding, keeping the temperature to continue reacting after the dropwise adding is finished, and determining the reaction to be finished through sampling nuclear magnetic analysis to obtain the polyurea acrylate oligomer.
10g of the polyurea acrylate oligomer, 0.1g of the photoinitiator 819, 0.02g of the polymerization inhibitor p-hydroxyanisole and a high-pressure mercury lamp as a light source are cast in a transparent mould to form a sample strip meeting the ASTM D412 standard, the uniaxial tensile property is tested, and the sample strip is treated at the temperature of 80 ℃ for 4 hours to test the uniaxial tensile property. The elongation at break before treatment is 120%, and the breaking strength is 2 MPa; the elongation at break after the treatment was 880% and the strength at break was 16MPa (FIG. 2).
Claims (8)
1. A polyurea acrylate oligomer that dissociates upon heating to form isocyanate groups and reacts with the pendant groups on the side chains to form a crosslinked network, the oligomer having the structure:
wherein R is1Is hydrogen or methyl, R2Being a sterically hindered group, R3Is a characteristic group which can react with isocyanate on a side chain.
2. The polyurea acrylate oligomer of claim 1 wherein R is2Is tert-butyl, isopropyl, ethyl, methyl, piperidine, pyrazole or oxime.
3. The polyurea acrylate oligomer of claim 1 wherein R is3Is a characteristic group that can react with isocyanate and is selected from hydroxyl, amino, phenol, carboxylic acid, anhydride, epoxy, urea, carbamate, amide or hydrazide.
4. A method for preparing the polyurea acrylate oligomer of claim 1, comprising the steps of:
1) NCO group-terminated and side chain containing R3Preparation of intermediate 1
Reacting a diisocyanate with a compound containing R3Wherein R is a polyfunctional monomer, wherein R is3Without participating in the reaction, intermediate 1 has the following structure:
2) intermediate 1 and R2Reacting the group-substituted hindered amine acrylate to obtain polyurea acrylate oligomer, R2The group-substituted hindered amine acrylate has the following structure:
5. process for the preparation of polyurea acrylate oligomers according to claim 4Characterized in that the diisocyanate is a mixture of a diisocyanate and a compound containing R3The molar ratio of the polyfunctional group monomer is 1: 2-1: 2.01; the molar ratio of the intermediate product 1 to the hindered amine acrylate is 1: 2-1: 2.01.
6. The method for preparing the polyurea acrylate oligomer according to claim 4, wherein the diisocyanate is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, 4 ' -diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and 3,3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate.
7. The method for preparing the polyurea acrylate oligomer according to claim 4, wherein the R-containing compound is3The polyfunctional monomer is selected from lactamide, dihydroxybenzidine, N' -dimethylol urea, 2-dimethylolpropionic acid, diphenolic acid or 2, 2-dimethylolbutyric acid:
8. the application method of the polyurea acrylate oligomer according to claim 1, which comprises the following specific steps:
1) mixing the polyurea acrylate oligomer with a specific reactive diluent, and adding a photoinitiator, a polymerization inhibitor and a light absorber;
2) curing the mixture by using a light source matched with an initiator to obtain a cured sample;
3) treating the cured sample for 1-10 hours at a certain temperature;
the active diluent is 0.05-0.5 part by weight of polyurea acrylate oligomer;
the photoinitiator is 0.01-0.05 part by weight of polyurea acrylate oligomer;
the light absorber is 0.0001-0.001 weight part of polyurea acrylate oligomer;
the polymerization inhibitor is 0.0005-0.015 weight part of polyurea acrylate oligomer.
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