CN117466907A - 一种超低体积收缩的丙烯酸酯类单体和应用 - Google Patents
一种超低体积收缩的丙烯酸酯类单体和应用 Download PDFInfo
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- CN117466907A CN117466907A CN202311495135.5A CN202311495135A CN117466907A CN 117466907 A CN117466907 A CN 117466907A CN 202311495135 A CN202311495135 A CN 202311495135A CN 117466907 A CN117466907 A CN 117466907A
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- Prior art keywords
- compound
- methyl
- volume shrinkage
- acrylate monomer
- reaction
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- 239000000178 monomer Substances 0.000 title claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 123
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 24
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- QNXIYXGRPXRGOB-UHFFFAOYSA-N oxolane;propan-2-one Chemical compound CC(C)=O.C1CCOC1 QNXIYXGRPXRGOB-UHFFFAOYSA-N 0.000 claims abstract description 8
- PYMYPHUHKUWMLA-VPENINKCSA-N aldehydo-D-xylose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-VPENINKCSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 18
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 238000000016 photochemical curing Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 23
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 abstract description 7
- -1 acrylic ester Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 abstract description 4
- 150000003997 cyclic ketones Chemical class 0.000 abstract description 4
- 150000002576 ketones Chemical class 0.000 abstract description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 15
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
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- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229940125877 compound 31 Drugs 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
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- 239000012074 organic phase Substances 0.000 description 5
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- HGOUNPXIJSDIKV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl 2-methylprop-2-enoate Chemical group CCC(CO)(CO)COC(=O)C(C)=C HGOUNPXIJSDIKV-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 2
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
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- 229940125878 compound 36 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229940126540 compound 41 Drugs 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000000976 ink Substances 0.000 description 1
- 238000005907 ketalization reaction Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
- C07D491/20—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/20—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
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Abstract
本发明涉及一种超低体积收缩的丙烯酸酯类单体,其特征在于,具有如下任意一类中的一种化学结构: 其中,R1为氢或甲基;R2与R3分别独立的是甲基、苯基中的一种,或者R2与R3构成环烷基、含氧杂环、含氮杂环中的一种。以上结构化合物以甘油、三羟甲基丙烷、季戊四醇、DL‑木糖、DL‑阿拉伯糖醇为原料,通过与不同结构的环状酮如环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N‑甲基‑4‑哌啶酮等,利用酮与羟基的酮叉反应,将多羟基中的部分羟基形成缩酮,剩余的羟基则通过酯化反应生成本发明一系列丙烯酸酯类单体。本发明获得的丙烯酸酯类单体在固化后具有较低体积收缩率。
Description
本申请是同一申请人的申请日为2023年5月31日、申请号为202310629496.8、发明名称为“一种超低体积收缩的丙烯酸酯类单体和应用”的中国发明专利申请的分案申请。
技术领域
本发明涉及丙烯酸酯类化合物技术领域,具体涉及一种超低体积收缩的丙烯酸酯类单体和应用。
背景技术
自由基光固化涂料、油墨、粘合剂由于以(甲基)丙烯酸酯为原料,(甲基)丙烯酸酯在聚合时由于分子间作用力从范德华力转化为碳碳单键,由此产生了分子体积大大缩小,导致体积收缩,固化后容易产生变形及附着力下降。为解决这一问题,目前商业(甲基)丙烯酸酯单体通常是通过降低双键密度,即增加分子量的方法来实现,但由此会产生一系列的问题,如成本提高、粘度增加、溶解度下降等等。(甲基)丙烯酸异冰片酯虽然体积收缩率较低,但成本高、气味大、合成方法复杂。因而开发超低体积收缩(甲基)丙烯酸酯单体是目前光固化领域的热点之一。
发明内容
为了解决现有技术中丙烯酸酯类单体化合物的固化时体积收缩大易产生变形的技术问题,而提供一种超低体积收缩的丙烯酸酯类单体和应用。本发明获得的丙烯酸酯类单体在固化后具有较低体积收缩率。
为了达到以上目的,本发明通过以下技术方案实现:
一种超低体积收缩的丙烯酸酯类单体,是单官或双官可光聚合的丙烯酸酯类单体,具有如下式Ⅰ-式IV任意一类中的一种化学结构:
其中,R1为氢或甲基;
R2与R3分别独立的是甲基、苯基中的一种,或者R2与R3构成环烷基、含氧杂环、含氮杂环中的一种。
优选地,式Ⅰ化学结构的单体包括如下化合物1至化合物10:
优选地,式Ⅱ化学结构的单体包括如下化合物10至化合物20:
优选地,式Ⅲ化学结构的单体包括如下化合物21至化合物30:
优选地,式Ⅳ化学结构的单体包括如下化合物31至化合物40:
优选地,式Ⅴ化学结构的单体包括如下化合物41至化合物50:
以上结构化合物可以甘油、三羟甲基丙烷、季戊四醇、DL-木糖、DL-阿拉伯糖醇等多羟基化合物为原料,通过与不同结构的环状酮如环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮等,利用酮与羟基的酮叉反应,将多羟基中的部分羟基形成缩酮,剩余的羟基则通过酯化反应生成本发明一系列丙烯酸酯类单体。
以上式Ⅰ化学结构的化合物1-10中一种的合成方法:将甘油中两个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含一个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得化合物1-10中的一种。
以上式Ⅱ化学结构的化合物11-20中一种的合成方法:将三羟甲基丙烷中两个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含一个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得化合物11-20中的一种。
以上式Ⅲ化学结构的化合物21-30中一种的合成方法:将DL-木糖中的三个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含一个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得化合物21-30中的一种。
以上式Ⅳ化学结构的化合物31-40中一种的合成方法:将季戊四醇中的两个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含两个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得化合物31-40中的一种。
以上式Ⅴ化学结构的化合物41-50中一种的合成方法:将DL-阿拉伯糖醇中的四个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含两个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得化合物41-50中的一种。
以上反应的用量关系根据优化实验可得知。
本发明另一方面提供上述超低体积收缩的丙烯酸酯类单体在光固化涂料、光固化油墨、或光固化粘合剂中的应用。
有益技术效果:
本发明通过酮叉反应以及酯化反应得到了具有较低羟基含量的一系列超低体积收缩的丙烯酸酯类单体,本发明结构单体具有降低固化体系中氢键的作用,使得固化体系的粘度大大降低;另外,由于酮叉反应生成一个五元环结构,同时环状酮也含有一个环结构,两个以上环结构有利于降低丙烯酸酯类单体固化后的体积收缩率大的问题;最后,由于原材料多羟基化合物在有机溶剂中的溶解度较差,因而(甲基)丙烯酸与其进行酯化反应是不容易发生的,但本发明通过缩酮化的酮叉反应,可以改变多羟基化合物的溶解性,有利于反应的发生,获得超低体积收缩、超低粘度的丙烯酸酯类单体。本发明一系列结构单体利用价格便宜的多元醇与环状酮进行酮叉反应,然后进行酯化获得,合成过程简便,且获得的单体粘度低,固化后体积收缩小。
具体实施方式
下面将结合本发明的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的,决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
除非另外具体说明,否则在这些实施例中阐述的数值不限制本发明的范围。对于相关领域普通技术人员已知的技术、方法可能不作详细讨论,但在适当情况下,所述技术、方法应当被视为说明书的一部分。在这里示出和讨论的所有示例中,任何具体值应被解释为仅仅是示例性的,而不是作为限制。因此,示例性实施例的其它示例可以具有不同的值。
以下实施例中未注明具体条件的实验方法,通常按照国家标准测定;若没有相应的国家标准,则按照通用的国际标准、或相关企业提出的标准要求进行。除非另有说明,否则所有的份数为重量份,所有的百分比为重量百分比。
实施例1
式Ⅰ化学结构化合物2及化合物7的合成:
(1)化合物2-iii的合成:在安装有搅拌机、分水器和温度计的三口瓶中,将化合物2-i(50g,0.51mol)、甘油(化合物2-ii,51.6g,0.56mol)、对甲基苯磺酸水合物(9.5g,0.05mol)和甲苯(500mL)混合,缓慢升温至回流并保持16小时,TLC显示原料消失;将反应液倒入饱和碳酸氢钠水溶液(500mL)中,有机相以饱和食盐水洗涤、无水硫酸钠干燥、活性炭脱色、浓缩除去溶剂后得到64.5g无色油状产物化合物2-iii,收率56wt%。
测试化合物2-iii的化学结构,核磁表征结果如下:
1HNMR(400MHz,CDCl3)δ:4.31-4.25(m,1H),4.05-3.95(t,1H),3.80-3.65(m,2H),3.61-3.45(m,1H),1.86(s,1H),1.69-1.50(m,8H),1.45-1.31(m,2H);
13C(400MHz,CDCl3)δ:110.9,76.9,66.6,63.2,35.9,26.2,16.2。
(2)化合物2的合成:在安装有搅拌机、恒压滴加漏斗和温度计的三口瓶中,将步骤(1)的化合物2-iii(50g,0.22mol)、三乙胺(26.7g,0.26mol)和三氯甲烷(500mL)混合,冰浴下缓慢滴加丙烯酰氯(化合物2-iv,22g,0.24mol),滴加完成后缓慢升至室温,继续搅拌2小时,TLC显示原料消失;将反应液倒入饱和碳酸氢钠水溶液中,有机相以饱和食盐水洗涤、无水硫酸钠干燥、活性炭脱色、浓缩除去溶剂后得到44g无色油状产物化合物2,收率89wt%。
测试化合物2的化学结构,核磁表征结果如下:
1HNMR(400MHz,CDCl3)δ:6.39-6.29(d,1H),6.11-6.05(m,1H),5.89-5.81(d,1H),4.44-4.35(m,1H),4.15-4.05(m,1H),3.90-3.75(m,1H),1.88(m,2H),1.58-1.49(m,4H),1.44-1.38(m,6H);
13C(400MHz,CDCl3)δ:166.5,130.2,128.3,113.9,78.7,69.1,65.2,36.9,28.8,16.2。
化合物7的合成方法与化合物2一致,以甲基丙烯酰氯替代丙烯酰氯,可制备得到化合物7。
实施例2
式Ⅰ化学结构化合物1及化合物6的合成如下:
化合物1的合成过程与实施例1相同:将环戊酮(化合物1-i)与甘油(化合物2-ii)反应得到化合物1-ii,然后与丙烯酰氯(化合物2-iv)进行反应,得到化合物1,化合物1的两步收率为60%;
化合物6的合成过程与化合物1相同,不同之处在于化合物1-ii与甲基丙烯酰氯(化合物2-iv)进行反应,得到化合物6,化合物6的两步收率为69%。
化合物1的核磁表征结果如下:
1H NMR(400MHz,CDCl3)δ:6.49-6.39(d,1H),6.18-6.15(m,1H),5.98-5.91(d,1H),4.45–4.37(m,1H),4.19-4.11(m,1H),4.00-3.98(m,1H),3.77-3.76(d,1H),3.74-3.71(d,1H),1.94-1.88(m,2H),1.69-1.55(m,6H)。
化合物6的核磁表征结果如下:
1H NMR(400MHz,CDCl3)δ:6.15(s,1H),5.58(s,1H),4.25-4.19(m,1H),4.1-4.01(m,2H),3.87-3.86(d,1H),3.81-3.79(d,1H),2.0(s,3H),1.99-1.89(m,2H),1.71-1.65(m,6H)。
实施例3
式Ⅰ化学结构化合物3(甲基苯基甲酮叉甘油丙烯酸酯)及化合物8(甲基苯基甲酮叉甘油甲基丙烯酸酯)的合成:
(1)化合物3-ii的合成:在安装有搅拌机、分水器和温度计的三口瓶中,将化合物3-i(10g,83.23mmol)、甘油(化合物2-ii,9.2g,99.9mmol)、对甲基苯磺酸水合物(1.5g,8mmol)和甲苯(100mL)混合,缓慢升至回流并保持48小时,将反应液倒入饱和碳酸氢钠水溶液(100mL)中,有机相以饱和食盐水洗涤、无水硫酸钠干燥、浓缩除去溶剂,柱层析分离后得9.3g无色油状产物化合物3-ii,收率45wt%;
测试化合物3-ii的化学结构,核磁表征结果如下:
1HNMR(400MHz,CDCl3)δ:7.49-7.22(m,5H),4.39-4.29(m,1H),4.20-4.01(m,2H),3.90-3.55(d,2H),1.69(d,3H)。
(2)化合物3的合成:化合物3-ii与丙烯酰氯反应,原料摩尔数与反应条件与实施例1步骤(2)相同,可得化合物3,经测试核磁表征,化合物3的测试结果如下:
1HNMR(400MHz,CDCl3)δ:7.50-7.23(m,5H),6.41-6.37(d,1H),6.21-6.15(m,1H),5.99-5.91(d,1H),4.41-4.3(m,1H),4.25-4.15(m,2H),3.96-3.59(d,2H),1.74(d,3H)。
将化合物3-ii与甲基丙烯酰氯反应,材料摩尔数与反应条件与实施例1步骤(2)的相同,得化合物8。
实施例4
式Ⅰ化学结构化合物4(四氢呋喃-3酮叉三羟甲基丙烷丙烯酸酯)及化合物9(四氢呋喃-3酮叉三羟甲基丙烷甲基丙烯酸酯)的合成:
(1)化合物4-ii的合成:在安装有搅拌机、分水器和温度计的三口瓶中,将化合物4-i(5g,50mmol)、甘油(化合物2-ii,9.2g,99.9mmol)、对甲基苯磺酸水合物(960mg,5mmol)和正己烷(50mL)混合,缓慢升至回流并保持48小时,将反应液倒入饱和碳酸氢钠水溶液(50mL)中,有机相以饱和食盐水洗涤、无水硫酸钠干燥、浓缩除去溶剂,柱层析分离后得3.6g无色油状产物化合物4-ii,收率41.5wt%;
测试化合物4-ii的化学结构,核磁表征结果如下:
1HNMR(400MHz,CDCl3)δ:4.31-4.19(m,2H),4.15-4.1(m,1H),3.98-3.55(m,6H),2.23-1.98(d,2H)。
(2)化合物4-ii与丙烯酰氯反应,原料摩尔数及反应条件与实施例1步骤(2)的相同,可得化合物4,经测试核磁表征,化合物4的测试结果如下:
1HNMR(400MHz,CDCl3)δ:6.36-6.3(d,1H),6.21-6.11(m,1H),5.99-5.85(d,1H),4.35-4.29(m,2H),4.19-4.11(m,1H),4.05-3.55(m,6H),2.29-2.05(d,2H)。
化合物4-ii与甲基丙烯酰氯反应,原料摩尔数及反应条件与实施例1步骤(2)的相同,可得化合物9。
实施例5
式Ⅰ化学结构化合物5(N-甲基-4-哌啶酮叉甘油丙烯酸酯)及化合物10(N-甲基-4-哌啶酮叉甘油甲基丙烯酸酯)的合成:
合成方法与化合物1-4类似(具体方法与实施例1步骤(1)相同),以N-甲基-4-哌啶酮(化合物5-i)为原料与甘油反应得到化合物5-ii,然后分别丙烯酰氯反应得到化合物5,具体制备路线如下:
测试化合物5的化学结构,核磁表征结果如下:
1HNMR(400MHz,CDCl3)δ:6.45-6.43(d,1H),6.10-6.05(m,1H),5.89-5.80(d,1H),4.49-4.45(m,1H),4.41-4.30(d,2H),4.19-4.11(m,2H),2.29-2.19(m,7H),1.88-1.63(m,4H)。
化合物5-ii与甲基丙烯酰氯反应,原料摩尔数及反应条件与实施例1步骤(2)的相同,得化合物10。
实施例6
式Ⅱ化学结构化合物11-15、化合物16-20的合成:
以化合物11为例:化合物11的合成与化合物1-5基本相同,以三羟甲基丙烷(化合物11-i)代替甘油与环戊酮(化合物1-i)进行酮叉反应,再以丙烯酰氯进行酯化,具体路线如下:
化合物11的核磁表征如下:
1H NMR(400MHz,CDCl3)δ:6.41-6.38(d,1H),6.05-6.0(m,1H),5.81-5.75(d,1H),4.11(s,2H),3.91-3.85(m,2H),3.67-3.61(m,2H),1.78-1.7(t,4H),1.51-1.5(m,4H),1.26-1.23(m,2H),0.95-0.9(t,3H)。
将化合物11-ii与甲基丙烯酰氯反应可制备化合物16。
三羟甲基丙烷(化合物11-i)分别与环己酮(化合物2-i)、苯乙酮(化合物3-i)、四氢呋喃酮(化合物4-i)、N-甲基-4-哌啶酮(化合物5-i)经酮叉反应,再进行丙烯酰氯或甲基丙烯酰氯酯化,可分别制备化合物12-15,及化合物17-20。
实施例7
式Ⅲ化学结构化合物21-25、化合物26-30的制备:
以DL-木糖(化合物21-i)为起始原料,分别先与环戊酮(化合物1-i)、环己酮(化合物2-i)、苯乙酮(化合物3-i)、四氢呋喃酮(化合物4-i)及N-甲基-4-哌啶酮(化合物5-i)进行酮叉反应,再与丙烯酰氯或甲基丙烯酰氯酯化,可分别制备化合物21-25、化合物26-30。
以化合物21的合成为例具体路线如下:
化合物21的核磁表征如下:
1H NMR(400MHz,CDCl3)δ:6.47-6.41(d,1H),6.15-6.1(m,1H),5.91-5.87(d,1H),6.22-6.15(m,1H),4.41-4.35(m,1H),4.11-3.81(m,2H),3.33-3.26(m,1H),2.35-2.10(m,2H),1.89-1.64(m,4H),1.51-1.46(m,4H)。
实施例8
式Ⅳ化学结构化合物31-40的制备:
以化合物31的合成为例:
(1)化合物31-ii的合成:在安装有搅拌机、分水器和温度计的三口瓶中,将化合物31-i(50g,0.367mol)、环戊酮(化合物1-i,27.8g,0.33mol)、对甲基苯磺酸水合物(5.8g,0.03mol)和甲苯(500mL)混合,缓慢升至回流并保持16小时,TLC显示原料消失;将反应液倒入饱和碳酸氢钠水溶液(500mL)中,有机相以饱和食盐水洗涤、无水硫酸钠干燥、活性炭脱色、浓缩除去溶剂及未反应的环戊酮后,得到40.7g无色油状产物化合物31-ii,收率61wt%。
(2)化合物31-ii与2当量的丙烯酰氯、2当量三乙胺作为缚酸剂进行酯化反应,反应条件与实施例1步骤(2)的相同,柱层析后可得化合物31,经测试核磁表征,化合物31的测试结果如下:
1HNMR(400MHz,CDCl3)δ:6.44-6.41(d,2H),6.15-6.07(m,2H),5.91-5.85(d,2H),4.07(s,4H),3.81(s,4H),1.77(t,4H),1.51(m,4H)。
化合物36:化合物31-ii与甲基丙烯酰氯反应,材料摩尔数与反应条件与化合物16步骤(2)的相同,经柱层析后即可得化合物36,核磁表征测试结果如下:
1HNMR(400MHz,CDCl3)δ:6.17(s,2H),5.61(s,2H),4.19(s,4H),3.88(s,4H),2.01(s,6H),1.80(t,4H),1.55(m,4H)。
化合物32-35,化合物37-40的合成与化合物31的制备过程相同,不同之处在于:将上述步骤(1)中的环戊酮(化合物1-i)分别替换为环己酮(化合物2-i)、苯乙酮(化合物3-i)、四氢呋喃酮(化合物4-i)、N-甲基-4-哌啶酮(化合物5-i),各物料比例及反应条件与化合物31相同,经酮叉、丙烯酰氯或甲基丙烯酰氯酯化即可得到化合物32-35,化合物37-40。
实施例9
式Ⅴ化学结构化合物41-50的制备与化合物31相同,以DL-阿拉伯糖醇(化合物41-i)为原料,分别与环戊酮(化合物1-i)、环己酮(化合物2-i)、苯乙酮(化合物3-i)、四氢呋喃酮(化合物4-i)、N-甲基-4-哌啶酮(化合物5-i)进行酮叉反应,再以丙烯酰氯或甲基丙烯酰氯酯化,可分别制备化合物41-50;以化合物41为例,具体路线如下:
试验例
分别取100重量份的上述化合物、与2重量份的UVI-1173混合均匀,均匀涂抹于玻璃片上,以高压汞灯(灯距5cm,光照强度I365nm=1mW/cm2)照射进行光固化,光固化后所得膜的性能见表1。
收缩率根据ISO 4216:2021热固性树脂和紫外光固化树脂固化收缩率连续测量法,测量结果与TPDGA对比,结果如表1所示。
表1 TPGDA及本发明部分单体粘度及光固化后所得膜体积收缩率
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由表1可知,本发明一系列单体光固化后形成的膜其体积收缩率在10%以内,相较于常规使用TPGDA的体积收缩率小。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种超低体积收缩的丙烯酸酯类单体,其特征在于,具有如下式Ⅲ化学结构:
其中,R1为氢或甲基;
R2与R3分别独立的是甲基、苯基中的一种,或者R2与R3构成环烷基、含氧杂环、含氮杂环中的一种。
2.根据权利要求1所述的一种超低体积收缩的丙烯酸酯类单体,其特征在于,式Ⅲ化学结构的单体包括如下化合物21至化合物30:
3.根据权利要求2所述的一种超低体积收缩的丙烯酸酯类单体,其特征在于,式Ⅲ化学结构的合成方法:将DL-木糖中的三个羟基与环戊酮、环己酮、四氢呋喃甲基酮、苯乙酮、N-甲基-4-哌啶酮中的一种进行酮叉反应得到含一个羟基的酮叉化合物,然后与丙烯酰氯或甲基丙烯酰氯进行酯化反应获得。
4.一种超低体积收缩的丙烯酸酯类单体在光固化涂料、光固化油墨、或光固化粘合剂中的应用。
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