CN112111062A - Silicon-containing monomer containing dioxygen heterocycle and preparation and application thereof - Google Patents
Silicon-containing monomer containing dioxygen heterocycle and preparation and application thereof Download PDFInfo
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- CN112111062A CN112111062A CN201910544043.9A CN201910544043A CN112111062A CN 112111062 A CN112111062 A CN 112111062A CN 201910544043 A CN201910544043 A CN 201910544043A CN 112111062 A CN112111062 A CN 112111062A
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- 239000000178 monomer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052710 silicon Inorganic materials 0.000 title abstract description 9
- 239000010703 silicon Substances 0.000 title abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 297
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000000016 photochemical curing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 129
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 63
- 239000003054 catalyst Substances 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 33
- 150000002367 halogens Chemical class 0.000 claims description 33
- 150000003254 radicals Chemical class 0.000 claims description 31
- 230000008014 freezing Effects 0.000 claims description 30
- 238000007710 freezing Methods 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 8
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 5
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- -1 polysiloxane chain Polymers 0.000 description 115
- 239000002904 solvent Substances 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
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- 239000005457 ice water Substances 0.000 description 16
- 239000012535 impurity Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229940125782 compound 2 Drugs 0.000 description 10
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 125000000466 oxiranyl group Chemical group 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
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- 229940125904 compound 1 Drugs 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012433 hydrogen halide Substances 0.000 description 5
- 229910000039 hydrogen halide Inorganic materials 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 125000003566 oxetanyl group Chemical group 0.000 description 5
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- 238000001953 recrystallisation Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010626 work up procedure Methods 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- UKLWXKWTXHHMFK-UHFFFAOYSA-N 3-(chloromethyl)-3-ethyloxetane Chemical compound CCC1(CCl)COC1 UKLWXKWTXHHMFK-UHFFFAOYSA-N 0.000 description 3
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012663 cationic photopolymerization Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- VQVGJEIVVJBMCV-UHFFFAOYSA-N (4-octoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 VQVGJEIVVJBMCV-UHFFFAOYSA-N 0.000 description 1
- 125000004643 (C1-C12) haloalkoxy group Chemical group 0.000 description 1
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- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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Abstract
The application relates to a silicon-containing monomer containing a dioxygen heterocycle, and preparation and application thereof. The invention relates to compounds of the formulae (I) and (II), where the variables n, m, z, p', R2、R3、R4、R5、R6、R7And R8As defined in the specification. The compound of the formula (I) has the advantages of good tensile property after photocuring, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, good heat resistance, high curing speed and easy adjustment of performance, thereby widening the application range of a photocuring system. The invention also relates to the preparation of compounds of formulae (I) and (II), to photocurable compositions comprising compounds of formulae (I) and/or (II) and to photocurable materials obtained by photocuring of the photocurable compositions.
Description
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to a silicon-containing monomer containing a dioxygen heterocycle. The present invention also relates to a process for preparing the monomer, a photocurable composition comprising the monomer and a photocurable material obtained by photocuring the photocurable composition.
Background
Ultraviolet curing refers to a process in which a photoinitiator is excited to become a radical or a cation under the irradiation of ultraviolet rays, thereby initiating a polymerization curing reaction between monomers to form a high molecular polymer. Compared with thermal curing, the ultraviolet curing technology has the advantages of small environmental pollution, high coating quality, low energy consumption and the like, so the ultraviolet curing technology is widely applied to the fields of photo-curing coatings, adhesives, ink printing and the like. And with the stricter emission control of the organic volatile components, the ultraviolet curing technology has wider development prospect. Compared with free radical photopolymerization systems, cationic photopolymerization systems have the advantages of insensitivity to oxygen, small volume shrinkage, strong adhesion, post-curing capability and the like, so that the cationic photopolymerization systems occupy irreplaceable important positions in the field of photopolymerization.
The oxirane monomer can be used for cationic photocuring and is a main raw material of a cationic photocuring product, and the system has the advantages of low viscosity, low toxicity, high polymerization speed, and excellent thermal stability and mechanical properties. However, ultraviolet light curing has been rapidly developed with the advantages of energy saving, environmental protection, high efficiency, etc., and simultaneously, higher requirements are put forward on the aspects of heat resistance, water repellency, surface contamination resistance, corrosion resistance, fingerprint resistance, etc. of the light curing material. Consumers increasingly demand the appearance of products, and in addition to beautiful color and comfortable hand feeling, the products also require the surfaces to have fingerprint resistance and stain resistance, so that the product surface is not easy to leave fingerprints and other marks when in use, or the marks are easy to wipe. Currently, there are fewer types of photo-curable cationic monomers that can meet the aforementioned requirements, and there is a need to develop more types of cationically curable monomers.
Disclosure of Invention
In view of the above-mentioned situation in the prior art, the inventors of the present invention conducted extensive and intensive studies on an oxacyclic cationically photopolymerizable monomer to find a novel oxacyclic cationically photocurable monomer which has advantages of fast photocuring speed, good tensile properties after curing, excellent hydrophobic properties, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, and the like. The present inventors have found that the silicon-containing monomer containing a dioxyheterocycle obtained by introducing an oxirane group into both ends of a polysiloxane chain has the aforementioned advantages.
Accordingly, it is an object of the present invention to provide a silicon-containing dioxyheterocycle-containing monomer which contains not only a cationically photocurable oxacycloalkyl group but also a polysiloxane chain. The oxacyclic monomer with the structure has the advantages of high photocuring speed, good tensile property after curing, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and good heat resistance.
Another object of the present invention is to provide a method for preparing the silicon-containing dioxyheterocycle-containing monomer of the present invention. The preparation process is simple and feasible, the conditions are mild, the raw materials are easy to obtain, and the price is low.
It is a further object of the present invention to provide a photocurable composition comprising a dioxyheterocycle-containing silicon-containing monomer according to the present invention.
It is a final object of the present invention to provide a photocurable material obtained by photocuring the photocurable composition of the present invention.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. compounds of the following formulae (I) and/or (II):
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An alkyl group; and
R8is H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group.
2. The compound according to item 1, wherein
n is an integer of 1 to 15, preferably an integer of 1 to 12; and/or
m is an integer of 1 to 6, preferably an integer of 2 to 4; and/or
z is an integer from 1 to 6, preferably an integer from 0 to 3; and/or
p and p' are the same or different and are each independently an integer of 1 to 4, preferably 1 to 3; and/or
R2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs H or C1-C4Alkyl, preferably, R2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs H or C1-C4An alkyl group; and/or
R8Is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group; preferably R8Is H or C1-C4An alkyl group.
3. The compound according to item 1, wherein
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
R2、R3、R4、R5、R6、R7are the same or different and are independently C1-C4An alkyl group; and
R8is H or C1-C4An alkyl group.
4. The compound according to item 1, which is one or more compounds selected from the group consisting of compounds 1 to 5.
5. A process for the preparation of a compound of formula (I) according to any one of items 1 to 4, comprising:
(1) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of formula (IV) to give a compound of formula (I)
Wherein p and R8As defined for any one of items 1 to 4, and X is halogen, for example chlorine, bromine or iodine.
6. The method according to item 5, wherein in step (1),
the reaction of the compound of formula (III) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:2 to 1: 10; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2 to 1: 2.4; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
7. A process for the preparation of a compound of formula (II) according to any one of items 1 to 4, comprising:
(a) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of the formula (IV),
wherein p and R8As defined for any one of items 1 to 4 and X is halogen, for example chlorine, bromine or iodine, to give a compound of formula (V),
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for any one of items 1 to 4; and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Wherein p' is as defined for any one of items 1 to 4 and Y is halogen, for example chlorine, bromine or iodine.
8. The method according to item 7, wherein in step (a),
the reaction of the compound of formula (III) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
9. The method according to item 7 or 8, wherein in step (b),
the reaction of the compound of formula (V) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (V) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V) and the compound of formula (VI) is firstly carried out at the freezing temperature, and then the temperature is raised to 25-60 ℃, preferably 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
10. A process for the preparation of a compound of formula (II) according to any one of items 1 to 4, comprising:
(i) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4,
with a compound of the formula (VI),
wherein p' is as defined for any one of items 1 to 4 and Y is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V-a),
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for any one of items 1 to 4;
and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Wherein p and R8As defined for any one of items 1 to 4, and X is halogen, for example chlorine, bromine or iodine.
11. The method according to item 10, wherein in step (i),
the reaction of the compound of formula (III) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (VI) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
12. The method according to item 10 or 11, wherein in step (ii),
the reaction of the compound of formula (V-a) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (V-a) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V-a) and the compound of formula (IV) is firstly carried out at the freezing temperature, then the temperature is raised to 25-60 ℃, and preferably the temperature is raised to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
13. Any one of claims 5-12, wherein X is chlorine and Y is bromine.
14. A photocurable composition comprising a compound of formula (I) and/or (II) according to any one of items 1 to 4 as polymerized monomer.
15. A photocurable material obtained by photocuring the photocurable composition according to item 14.
Drawings
FIG. 1 is a graph of quaternary oxirane conversion versus exposure time for compound 1 prepared in example 1.
FIG. 2 is a graph of quaternary oxirane conversion versus exposure time for Compound 2 prepared in example 2.
FIG. 3 is a graph of ternary oxirane conversion versus exposure time for Compound 2 prepared in example 2.
Detailed Description
According to one aspect of the present invention, there is provided a compound of the following formula (I) and/or (II):
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6; r2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An alkyl group; and
R8is H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group.
In the present invention, the compounds of the formulae (I) and (II) contain both a cationically photocurable oxygen heterocyclic structure and a polysiloxane moiety. The compound with the structure can be subjected to cationic photocuring, and has the advantages of high photocuring speed, good tensile property after curing, excellent hydrophobic property, contamination resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance and the like. In addition, the compounds of the formulae (I) and (II) according to the invention have less volume shrinkage, better adhesion and faster polymerization rates than compounds which contain oxirane rings at both ends.
In the present invention, the prefix "Cn-Cm"in each case tableThe number of carbon atoms contained in the group is shown to be n-m.
"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises fluorine, chlorine or a combination thereof.
The term "C" as used hereinn-CmAlkyl "means a monovalent branched or unbranched saturated hydrocarbon radical having n to m, for example 1 to 12, preferably 1 to 6, particularly preferably 1 to 4, carbon atoms. As Cn-CmAs examples of alkyl groups, there may be mentioned methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-dimethylbutyl, 1, 3-dimethylbutyl, 3-ethylbutyl, 1,1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof.
The term "C" as used herein6-CmAryl "refers to monocyclic, bicyclic or higher ring aromatic hydrocarbon radicals containing from 6 to m carbon atoms, for example from 6 to 10 carbon atoms. As C6-CmAs examples of the aryl group, there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylbenzyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and the like; phenyl or naphthyl, especially phenyl, is preferred.
The term "C" as used hereinn-CmAlkoxy "means at Cn-CmOpen chain C corresponding to alkyln-CmC having an oxygen atom as a linking group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C12Alkoxy, more preferably C1-C6Alkoxy, particularly preferably C1-C4An alkoxy group. AsCn-CmAs examples of the alkoxy group, there may be mentioned methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy and isomers thereof.
The term "C" as used hereinn-CmHaloalkyl "means C substituted by one or more halogen atoms which may be the same or differentn-CmAlkyl radicals, e.g. C1-C12Haloalkyl, preferably C1-C6Haloalkyl, particularly preferably C1-C4A haloalkyl group. As examples of the haloalkyl group herein, mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl, 1-chloromethylpropyl, 2-chloromethylpropyl, 1-dichloromethylethyl, monochloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1-dichloromethylpropyl, 1, 2-dichloromethylpropyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1-dichloromethylbutyl, 1, 2-dichloromethylbutyl, 1, 3-dichloromethylbutyl, dichloromethylbutyl, 2, 2-dichloromethylbutyl, 2, 3-dichloromethylbutyl, 3-dichloromethylbutyl, 1-chloroethylbutyl, 2-chloroethylbutyl, 1, 2-trichloromethylpropyl, 1,2, 2-trichloromethylpropyl, 1-chloroethyl-1-methylpropyl, 1-ethyl-2-chloromethylpropyl and isomers thereof.
The term "C" as used hereinn-CmHaloalkoxy "means C substituted by one or more of the same or different halogen atomsn-CmAlkoxy radicals, e.g. C1-C12Haloalkoxy, more preferably C1-C6Haloalkoxy, particularly preferably C1-C4A haloalkoxy group. As Cn-CmAs examples of the haloalkoxy group, there may be mentioned monochlorooxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2-chloroisopropoxy group, 4-chloro-n-butoxy group, 3-chloro-sec-butoxy group, 2-chloro-tert-butoxy group, 5-chloropentyloxy group, 4-chloropentyloxy group, 6-chlorohexyloxy group and isomers thereof.
The term "C" as used hereinn-CmHydroxyalkyl "means at Cn-CmOpen chain C corresponding to alkyln-CmC having a hydroxy group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C6Hydroxyalkyl, particularly preferably C1-C4Hydroxyalkyl radicals, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and isomers thereof.
In the compounds of the invention, n is generally an integer from 1 to 50, preferably an integer from 1 to 15, particularly preferably an integer from 1 to 12, for example 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12.
In the compounds of the invention, m is generally an integer from 1 to 10, preferably an integer from 1 to 6, particularly preferably an integer from 2 to 4, for example 2,3 or 4, in particular 2.
In the compounds of the invention, z is generally an integer from 0 to 10, preferably an integer from 1 to 6, particularly preferably an integer from 0 to 3, for example 0, 1,2 or 3, in particular 1.
In the compounds of the invention, p and p' are identical or different and are each independently of the other usually an integer from 1 to 6, preferably an integer from 1 to 4, particularly preferably an integer from 1 to 3, for example 1,2 or 3, in particular 1.
In the compounds of the formulae (I) and (II) according to the invention, R2、R3、R4、R5、R6、R7Are identical or different and are usually independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or two carbon atoms between which one or more are independently selected from NRbO, S C of hetero atom1-C12Alkyl radical, wherein RbIs H or C1-C4An alkyl group. Preferably, R is2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs H or C1-C4An alkyl group. It is particularly preferred that R2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs H or C1-C4An alkyl group. Especially R2、R3、R4、R5、R6、R7Are the same or different and are independently C1-C4An alkyl group. For example, R2、R3、R4、R5、R6、R7The same or different and are independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy.
In the compounds of the formulae (I) and (II) according to the invention, R8Usually H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group. Preferably, R is8Is H, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4A haloalkoxy group. It is particularly preferred that R8Is H or C1-C4An alkyl group. For example, R8Can be H, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy-tert-butyl.
In some preferred embodiments of the compounds of formulae (I) and (II) of the present invention,
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
R2、R3、R4、R5、R6、R7are the same or different and are independently C1-C4An alkyl group; and
R8is H or C1-C4An alkyl group.
In another embodiment of the present invention, the compounds of formula (I) and formula (II) are compounds selected from the group consisting of:
according to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the invention which comprises:
(1) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compounds of formula (I),
with a compound of formula (IV) to give a compound of formula (I)
Wherein p and R8As defined for compounds of formula (I) and X is halogen, for example chlorine, bromine or iodine.
In step (1), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:2 to 1: 10. The reaction of the compound of formula (III) with the compound of formula (IV) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (III), the compound of formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (IV), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (I). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 0.5 to 3 times the total weight of the compound of formula (III) and the compound of formula (IV). The compound of formula (IV) and the compound of formula (III) are generally used in a molar ratio of about twice the molar amount. Advantageously, the compound of formula (III) and the compound of formula (IV) are used in a molar ratio of from 1:2 to 1: 2.4. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (I) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
According to a third aspect of the present invention there is provided a process for the preparation of a compound of formula (II) of the present invention comprising:
(a) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compound of formula (II),
with a compound of the formula (IV),
wherein p and R8As defined for the compounds of formula (II) and X is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V),
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for compounds of formula (II); and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Wherein p' is as defined for the compound of formula (II) and Y is halogen, for example chlorine, bromine or iodine.
In step (a), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (IV) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (III) with the compound of formula (IV) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (III), the compound of formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (IV), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (V). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional, and in general, the amount of solvent is 0.5 to 3 times the total weight of the compound of formula (III) and the compound of formula (IV). The molar ratio of the compound of the formula (IV) to the compound of the formula (III) is generally approximately equimolar. Advantageously, the compound of formula (III) and the compound of formula (IV) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (V) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In step (b), the reaction of the terminal hydroxyl group in the compound of formula (V) with the halogen in the compound of formula (VI) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (V) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (V) with the compound of formula (VI) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (V), the compound of formula (VI) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (V) and the compound of formula (VI), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (II). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional and is generally 0.5 to 3 times the total weight of the compound of formula (V) and the compound of formula (VI). The molar ratio of the compound of the formula (VI) to the compound of the formula (V) is generally approximately equimolar. Advantageously, the compound of formula (V) and the compound of formula (VI) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (V) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (VI) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (II) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
According to a fourth aspect of the present invention there is provided a process for the preparation of a compound of formula (II) of the present invention comprising:
(i) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for the compound of formula (II),
with a compound of the formula (VI),
wherein p' is as defined for the compound of formula (II) and Y is halogen, for example chlorine, bromine or iodine,
to obtain the compound of the formula (V-a),
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for compounds of formula (II); and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Wherein p and R8As defined for compounds of formula (II) and X is halogen, for example chlorine, bromine or iodine.
In step (i), the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (VI) is of a type known in the art, and the reaction produces a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (III) with the compound of formula (VI) is generally carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (III), the compound of formula (VI) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of formula (III) and the compound of formula (VI), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of formula (V-a). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of solvent is also conventional and is generally 0.5 to 3 times the total weight of the compound of formula (III) and the compound of formula (VI). The molar ratio of the compound of the formula (VI) to the compound of the formula (III) is generally approximately equimolar. Advantageously, the compound of formula (III) and the compound of formula (VI) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (III) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (VI) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (V-a) is obtained by conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In step (ii), the reaction of the terminal hydroxyl group in the compound of formula (V-a) with the halogen in the compound of formula (IV) is of a type known in the art, the reaction producing a hydrogen halide. Generally, the reaction is carried out in the presence of a basic catalyst. As basic catalysts suitable for this reaction, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixtures thereof may be mentioned. The amount of catalyst used is also conventional. Generally, the molar ratio of the compound of formula (V-a) to the basic catalyst is from 1:1 to 1: 5. The reaction of the compound of formula (V-a) with the compound of formula (IV) is usually carried out in a solvent. As the type of the solvent, there is no particular limitation as long as the compound of the formula (V-a), the compound of the formula (IV) and the corresponding basic catalyst can be dissolved and do not participate in the reaction between the compound of the formula (V-a) and the compound of the formula (IV), and it is preferable that the solvent also contributes to precipitation of the product, i.e., the compound of the formula (II). As the solvent, an organic solvent is generally used, and toluene, acetone, butanone, toluene, tetrahydrofuran, cyclohexane, 1, 4-dioxane, dichloromethane, acetonitrile, or any mixture thereof is preferably used. The amount of the solvent is also conventional, and in general, the amount of the solvent is 0.5 to 3 times the total weight of the compound of formula (V-a) and the compound of formula (IV). The compound of the formula (IV) and the compound of the formula (V-a) are usually used in a molar ratio of approximately equimolar amounts. Advantageously, the compound of formula (V-a) and the compound of formula (IV) are used in a molar ratio of from 1:1 to 1: 1.2. To achieve the above reaction, the compound of formula (V-a) and the basic catalyst are generally dissolved in a solvent, the temperature is reduced to the freezing point (about 0 ℃), then the compound of formula (IV) is added, and after the addition is completed, the resulting reaction mixture is stirred at the freezing point (about 0 ℃) for 0.5 to 3 hours, preferably 0.5 to 1 hour, then heated to 25 to 60 ℃, preferably 35 to 60 ℃, and the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours. The reaction is, of course, advantageously carried out with stirring. After the reaction is finished, the compound of the formula (II) is obtained through conventional post-treatment. This work-up generally comprises extraction or washing (for example with water, which is then advantageously freed from water using an absorbent compound such as magnesium sulfate or sodium sulfate), filtration or centrifugation to remove solid impurities, rotary evaporation to remove the solvent, and distillation under reduced pressure to further remove the solvent. If a higher purity product is to be obtained, impurities may also be isolated by recrystallization or column chromatography.
In some preferred embodiments of the invention, wherein X is chlorine and Y is bromine.
The compound of the formula (I) and the compound of the formula (II) are silicon-containing monomers containing dioxygen heterocycle, the monomers have high curing speed, better stretching performance after curing, excellent hydrophobic performance, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance. The synthesis method is simple and easy, and the conditions are mild; the raw materials are easy to obtain and the price is low.
Thus, according to a third aspect of the present invention, there is provided a photocurable composition comprising as polymerized monomers the compounds of formula (I) and/or (II) of the present invention. The photocurable composition may contain, in addition to the compound of formula (I) and the compound of formula (II) of the present invention, a ring-opening polymerization photoinitiator (a photoinitiator capable of initiating cationic polymerization) and other monomers and oligomers having a cationically photocurable group such as a vinyl ether double bond, an alicyclic epoxy group, an oxirane group, or an oxetane group, for example, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221).
The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, or the like. After the composition is cured, the cured product has the advantages of good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance and strong aging resistance.
As the cationic photoinitiator for ring-opening polymerization, iodonium salts and sulfonium salts are generally used. Advantageously, the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulae (A) and (B), respectively
Wherein
Ra、Rb、Rc、Rd、ReEach independently is unsubstituted C6-C10Aryl, or selected from halogen, nitro, carbonyl, C1-C12Alkyl radical, C1-C12Alkoxy, thiophenyl, phenyl and substituted phenyl substituents substituted C6-C10Aryl, preferably phenyl or naphthyl, or selected from halogen, nitro, C1-C6Phenyl or naphthyl substituted with alkyl and substituted phenyl substituents, wherein said substituted phenyl comprisesThe substituent is one or more selected from halogen, nitro and C1-C6Alkyl and C1-C6A group of alkoxy groups; and
y, Z are non-nucleophilic anions, e.g. triflate, BF4 —、ClO4 —、PF6 —、AsF6 —、SbF6 —。
For example, as the photoinitiator, one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate (810), 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl 4' -methylphenylidium hexafluorophosphate, and mixtures thereof, 4-isobutylphenyl 4' -methylphenyliodilium hexafluoroantimonate, bis (4-dodecylbenzene) iodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate, 2-Isopropylthioxanthone (ITX).
For the purposes of the present invention, the amounts of photoinitiator are conventional. The photoinitiator is generally present in an amount of 0.5 to 5%, preferably 1 to 3%, based on the photocurable composition of the present invention.
According to a final aspect of the present invention, there is provided a photocurable material obtained by photocuring the photocurable composition of the present invention. The photocuring material has the advantages of good tensile property, excellent hydrophobic property, stain resistance, fingerprint resistance, chemical corrosion resistance, strong aging resistance, good heat resistance and the like due to the fact that the photocuring material contains the compound shown in the formula (I) and/or (II) as the photocuring monomer.
Examples
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
In a three-necked flask with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotating speed of 300r/min, adding 8.92g (160mmol) of potassium hydroxide, then slowly dropwise adding 5.65g (44mmol) of 3-ethyl-3-chloromethyl oxetane, reacting for 30min at the temperature of the ice-water bath after dropwise adding, then removing the ice-water bath, reacting for 24 h in an oil bath at 60 ℃, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. Characterized by nuclear magnetic hydrogen spectroscopy, identified as compound 1 below, which is sometimes referred to as BOSi.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Example 2
In a three-necked flask with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at a rotation speed of 300r/min, adding 4.46g (80mmol) of potassium hydroxide, slowly adding 2.83g (22mmol) of 3-ethyl-3-chloromethyl oxetane dropwise, and finishing dropwise addingAnd then reacting for 30min at the temperature of the ice-water bath, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 hours again, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is characterized by nuclear magnetic hydrogen spectrum and is determined as the following compound 2 a.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.61(t,J＝7.0Hz,4H),0.83(t,J＝7.5Hz,3H),1.42(m,4H),1.69(q,J＝7.5Hz,2H),3.35(m,4H),3.52(m,6H),3.70(m,2H),3.79(s,2H),4.39-4.14(m,1H),5.4(m,1H).
20.56g (20mmol) of Compound 2a and 30mL of toluene were put into a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, stirred in an ice-water bath at a rotation speed of 300r/min, 4.46g (80mmol) of potassium hydroxide powder was added, 3.01g (22mmol) of epibromohydrin was slowly dropped thereinto, and after 30min of reaction, the ice-water bath was removed, and the reaction was carried out in an oil bath at 60 ℃ for 24 hours again to terminate the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. Characterized by nuclear magnetic hydrogen spectroscopy, identified as compound 2 below, which is sometimes designated as BOTSi.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.58(t,J＝7.0Hz，4H),0.92(t,J＝7.5Hz,3H),1.56(m,4H),1.87(q,J＝7.5Hz,2H),2.61-2.38(m,2H),2.74(m,H),3.61-3.36(m,16H),3.79(s,4H),4.44-4.14(m,4H).
Example 3
In a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to formula (III))Wherein n-8, m-2, z-1, and R2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotation speed of 300r/min, adding 4.46g (80mmol) of potassium hydroxide powder, then slowly dropwise adding 3.01g (22mmol) of epoxy bromopropane, reacting at the temperature of the ice-water bath for 30min after the dropwise adding is finished, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 h, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is identified as the following compound 2b by nuclear magnetic hydrogen spectrum characterization.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.61(t,J＝7.0Hz，4H),1.56(m,4H),2.61-2.38(m,2H),2.74(m,H),3.70-3.38(m,14H),5.4(m,1H).
19.72g (20mmol) of the compound 2b and 30mL of toluene were put into a three-necked flask equipped with a dropping funnel, a temperature probe and a reflux condenser, stirred in an ice-water bath at a rotation speed of 300r/min, 42.23g (40mmol) of potassium hydroxide powder was added, 2.83g (22mmol) of 3-ethyl-3-chloromethyloxetane was slowly dropped thereinto, and after 30 minutes of reaction, the ice-water bath was removed, and the reaction was completed after further 24 hours in an oil bath at 60 ℃. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with a rotary evaporator, and distilling the solution at 300Pa and 40 deg.C under reduced pressure to obtain the final product. The compound is determined to be a compound 2 by nuclear magnetic hydrogen spectrum characterization
Example 4
Example 1 was repeated, but the bishydroxy silicone oil in example 1 was replaced by a bishydroxy silicone oil corresponding to a compound of formula (III) wherein n is 1, m is 2, z is 1, and R is2、R3、R4、R5、R6And R7Is methyl. The final product obtained isThe nuclear magnetic hydrogen spectrum is characterized and determined as the following compound 3.1H NMR(400MHz,CDCl3):0.07-0.17(m,12H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Example 5
Example 1 was repeated, but the bishydroxy silicone oil in example 1 was replaced by a bishydroxy silicone oil corresponding to a compound of formula (III) wherein n-15, m-2, z-1, and R2、R3、R4、R5、R6And R7Is methyl. The obtained final product was characterized by nuclear magnetic hydrogen spectrum and identified as the following compound 4.1H NMR(400MHz,CDCl3):0.07-0.17(m,102H),0.56(m,4H),0.92(t,J＝7.5Hz,6H),1.76-1.50(m,4H),1.87(q,J＝7.5Hz,4H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Example 6
In a three-necked flask with dropping funnel, temperature probe and reflux condenser, 18.6g (20mmol) of bishydroxy silicone oil (corresponding to the compound of formula (III) wherein n is 8, m is 2, z is 1, and R is added2、R3、R4、R5、R6And R7Methyl) and 30mL of toluene, stirring in an ice-water bath at the rotating speed of 300r/min, adding 8.92g (160mmol) of potassium hydroxide, then slowly dropwise adding 3.87g (44mmol) of 3-hydroxymethyl oxetane, reacting at the temperature of the ice-water bath for 30min after the dropwise adding is finished, then removing the ice-water bath, carrying out oil bath at 60 ℃ for reacting for 24 h again, and finishing the reaction. The reaction was washed repeatedly with distilled water, and the supernatant was collected and centrifuged to remove solid impurities. Removing most of the solvent by rotary evaporation at 45 deg.C and 0.1MPa with rotary evaporator, and removing the solutionDistilling under reduced pressure at 300Pa and 40 ℃ to obtain the product. The compound is characterized by nuclear magnetic hydrogen spectrum and is determined as the following compound 5.1H NMR(400MHz,CDCl3):0.07-0.17(m,60H),0.56(m,4H),1.76-1.50(m,4H),,2.92(s,2H),3.46(t,J＝7.0Hz,4H),3.58-3.54(m,4H),3.77-3.73(m,4H),3.82(s,4H),4.44(s,8H).
Example 7
This example is intended to illustrate the photopolymerizability of the compounds 1 and 3 to 5 according to the invention.
The photopolymerization performance of the compounds 1 and 3-5 at different initiator concentrations is tested by a real-time infrared (RT-IR) method by taking a mixture of a photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-Isopropylthioxanthone (ITX) in a mass ratio of 2:1 as a photoinitiation system. The peak of the absorption of the C-O-C bond asymmetric deformation vibration of the oxetanyl group was found to be 980cm-1As the curing reaction proceeds, the C-O-C bond is broken by ring opening, and the absorption peak area at the corresponding position is reduced. The conversion rate of the quaternary oxygen heterocyclic ring can be calculated by monitoring the change of the area size of an infrared absorption peak through RT-IR. The light source is a high-pressure mercury lamp, the emission wavelength is 365nm, and the light intensity is 60mW/cm2. The results for compound 1 are shown in figure 1. FIG. 1 is a graph of oxetane ring conversion as a function of irradiation time. The results show that compound 1 has good photopolymerization performance. In addition, each of the compounds 3-5 has four initiating systems of 0.75% 810+ 0.38% ITX, 1.50% 810+ 0.75% ITX, 3.00% 810+ 1.50% ITX, 4.50% 810+ 2.25% ITX, and after 600 seconds of high-pressure mercury lamp irradiation, the conversion rate of the monomer with the four-membered oxygen heterocycle increases with the increase of the initiator concentration, and the maximum conversion rate of the four-membered oxygen heterocycle reaches at least 53%. Wherein the respective concentrations of 810 and ITX are based on the respective weights of compounds 1 and 3-5. Therefore, the compound of the invention has good photopolymerization performance.
Example 8
This example is intended to illustrate the photopolymerization performance of compound 2 prepared in example 2.
A mixture of a photoinitiator diphenyl iodonium hexafluorophosphate (810) and 2-Isopropyl Thioxanthone (ITX) in a mass ratio of 2:1 is used as a photoinitiation system, and the photopolymerization performance of the compound 2 at different initiator concentrations is tested by a real-time infrared method. The peak of the absorption of the C-O-C bond asymmetric deformation vibration of the oxetanyl group was found to be 980cm-1The vibration absorption peak of the C-O-C bond asymmetric deformation of the three-membered oxygen heterocycle is positioned at 910cm-1As the curing reaction proceeds, the C-O-C bond is broken by ring opening, and the absorption peak area at the corresponding position is reduced. The conversion rates of the quaternary oxygen heterocycle and the ternary oxygen heterocycle can be respectively calculated by monitoring the change of the area size of an infrared absorption peak through RT-IR. The light source is a high-pressure mercury lamp, the emission wavelength is 365nm, and the light intensity is 60mW/cm2. The results for compound 2 are shown in figures 2 and 3. FIG. 2 is a graph showing the change in the conversion of oxetane ring with irradiation time, and FIG. 3 is a graph showing the change in the conversion of oxirane ring with irradiation time. The result shows that the ternary heterocycle can promote the polymerization of the quaternary oxygen heterocycle, and the compound 2 has good photopolymerization performance.
Example 9
The present example is intended to demonstrate that the compounds of the present invention can improve the surface hydrophobicity of a photocurable film.
Reacting each of compounds 1-5 with 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (E4221) epoxy monomer at a molar ratio of 5: 95, and 3.0 wt% 810 and 1.5 wt% ITX based on the total weight of the compounds 1 to 5 and E44221, respectively, as an initiator, and uniformly mixing to obtain the photosensitive solution. Uniformly spreading the obtained photosensitive solution in a silica gel mold with the thickness of 70mm multiplied by 8mm multiplied by 6mm at the concentration of 60mW/cm2The film was exposed to light for 900 seconds under a high-pressure mercury lamp to obtain a completely cured film. Then, the surface hydrophobicity of each cured film was measured by using a water contact angle measuring instrument model OCA20 (model OCA20, daphysics, germany) at a measurement temperature of 25 ℃. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method.
The results show that when the E4221 polymerization system is not added with the compound of the present invention, the water contact angle of the cured film is 62.5 °, and the contact angles reach 81.5 ° and 87.4 ° after the additional addition of compound 1 or 2, respectively. In addition, the contact angles of the cured films obtained by additionally adding one of the compounds 3 to 5 were each over 78.6 °. Therefore, the compound of the invention can remarkably improve the surface hydrophobicity of the cured film, thereby resisting contamination and fingerprints.
Example 10
The purpose of this example is to demonstrate that each of the compounds 1 and 2 prepared in examples 1-2 can improve the heat resistance of the cured film.
Each of the cured films of the compounds 1 to 2 was obtained in the same manner as described in example 9. Then, the heat resistance of each photocurable film was measured by a thermal gravimetric analyzer model TGA 550 (TGA 550, watt & ltd., usa). The test conditions were: under the protection of nitrogen, the temperature range is 25-800 ℃, and the heating speed is 10 ℃/min. Meanwhile, a blank E4221 cured film was prepared as a reference using the same method. The results are shown in Table 1.
The results show that, after addition of the compounds 1 or 2, the initial decomposition temperature (T) of the cured film5％) And maximum temperature T of thermal weight lossmax1And Tmax2The heat resistance is improved remarkably.
TABLE 1
Claims (15)
1. Compounds of the following formulae (I) and/or (II):
wherein
n is an integer of 1 to 50;
m is an integer of 1 to 10;
z is an integer from 0 to 10;
p and p' are the same or different and are integers from 1 to 6;
R2、R3、R4、R5、R6、R7are the same or different and are independently C6-C10Aryl radical, C1-C12Alkyl radical, C1-C12Alkoxy or C having two carbon atoms interrupted by one or more heteroatoms independently selected from N, O, S1-C12An alkyl group; and
R8is H, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Hydroxyalkyl radical, C1-C6Alkoxy or C1-C6A haloalkoxy group.
2. A compound according to claim 1, wherein
n is an integer of 1 to 15, preferably an integer of 1 to 12; and/or
m is an integer of 1 to 6, preferably an integer of 2 to 4; and/or
z is an integer from 1 to 6, preferably an integer from 0 to 3; and/or
p and p' are the same or different and are each independently an integer of 1 to 4, preferably 1 to 3; and/or
R2、R3、R4、R5、R6、R7Are the same or different and are independently C6-C10Aryl radical, C1-C6Alkyl radical, C1-C6Alkoxy or two carbon atoms between which one or more members selected from NRbO, S C of hetero atom1-C6Alkyl radical, wherein RbIs H or C1-C4Alkyl, preferably, R2、R3、R4、R5、R6、R7Identical or different and independently of one another are phenyl, C1-C4Alkyl radical, C1-C4Alkoxy or two carbon atoms between which one or more are independently selected from NRbO, S C of hetero atom1-C4Alkyl radical, wherein RbIs H or C1-C4An alkyl group; and/or
R8Is H, halogen,C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Hydroxyalkyl radical, C1-C4Alkoxy or C1-C4Haloalkoxy, preferably R8Is H or C1-C4An alkyl group.
3. A compound according to claim 1, wherein
n is an integer of 1 to 12;
m is 2,3 or 4;
z is 0, 1,2 or 3;
p and p' are the same and are 1,2 or 3;
R2、R3、R4、R5、R6、R7are the same or different and are independently C1-C4An alkyl group; and
R8is H or C1-C4An alkyl group.
4. The compound according to claim 1, which is one or more compounds selected from the group consisting of:
5. a process for the preparation of a compound of formula (I) according to any one of claims 1 to 4, comprising:
(1) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7Reaction with a compound of formula (IV) as defined in any one of claims 1 to 4 to give a compound of formula (I)
Wherein p and R8As defined for any one of claims 1-4, and X is halogen, such as chlorine, bromine, or iodine.
6. The method according to claim 5, wherein in step (1),
the reaction of the compound of formula (III) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:2 to 1: 10; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2 to 1: 2.4; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
7. A process for the preparation of a compound of formula (II) according to any one of claims 1 to 4, comprising:
(a) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any of claims 1 to 4, with a compound of formula (IV),
wherein p and R8As defined for any one of claims 1 to 4 and X is halogen, such as chlorine, bromine or iodine,
to obtain the compound of the formula (V),
wherein n, m, z, R2、R3、R4、R5、R6、R7And R8As defined for any one of claims 1-4; and
(b) reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II)
Wherein p' is as defined for any one of claims 1 to 4 and Y is halogen, such as chlorine, bromine or iodine.
8. The method according to claim 7, wherein in step (a),
the reaction of the compound of formula (III) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (IV) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
9. The method according to claim 7 or 8, wherein in step (b),
the reaction of the compound of formula (V) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (V) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V) and the compound of formula (VI) is firstly carried out at the freezing temperature, and then the temperature is raised to 25-60 ℃, preferably 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
10. A process for the preparation of a compound of formula (II) according to any one of claims 1 to 4, comprising:
(i) reacting a compound of formula (III)
Wherein n, m, z, R2、R3、R4、R5、R6And R7As defined for any of claims 1 to 4, with a compound of the formula (VI),
wherein p' is as defined for any one of claims 1 to 4 and Y is halogen, such as chlorine, bromine or iodine, to give a compound of formula (V-a),
wherein n, m, z, p', R2、R3、R4、R5、R6And R7As defined for any one of claims 1-4; and
(ii) reacting a compound of formula (V-a) with a compound of formula (IV) to give a compound of formula (II)
Wherein p and R8As defined for any one of claims 1-4, and X is halogen, such as chlorine, bromine, or iodine.
11. The method according to claim 10, wherein in step (i),
the reaction of the compound of formula (III) with the compound of formula (VI) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (III) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (III) to the compound of formula (VI) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (III) and the compound of formula (VI) is firstly carried out at the freezing point temperature, and then the temperature is raised to 25-60 ℃, preferably to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
12. The method according to claim 10 or 11, wherein in step (ii),
the reaction of the compound of formula (V-a) with the compound of formula (IV) is carried out in the presence of a basic catalyst, preferably sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, more preferably, the molar ratio of the compound of formula (V-a) to the basic catalyst is from 1:1 to 1: 5; and/or
The molar ratio of the compound of formula (V-a) to the compound of formula (IV) is 1:1 to 1: 1.2; and/or
The reaction between the compound of formula (V-a) and the compound of formula (IV) is firstly carried out at the freezing temperature, then the temperature is raised to 25-60 ℃, and preferably the temperature is raised to 35-60 ℃ for reaction; preferably, the reaction is carried out at freezing temperature for 0.5 to 3 hours, preferably 0.5 to 1 hour; and/or, after the temperature is raised, the reaction is continued for 6 to 24 hours, preferably 8 to 24 hours.
13. Any of claims 5-12, wherein X is chloro and Y is bromo.
14. Photocurable composition comprising as polymerized monomers compounds of the formula (I) and/or (II) according to any of claims 1 to 4.
15. A photocurable material obtained by photocuring the photocurable composition according to claim 14.
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|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416447A (en) * | 2000-02-18 | 2003-05-07 | 罗狄亚化学公司 | Plastic material surface treatment with polymerisable and/or crosslinkable organic compsn. having reactive functions |
| CN1418912A (en) * | 2001-11-13 | 2003-05-21 | 住友化学工业株式会社 | Composition containing cationic polymerized composition and coating obtained from same |
| CN1727378A (en) * | 2004-07-29 | 2006-02-01 | 国家淀粉及化学投资控股公司 | Siloxane resins with oxetane functionality |
| WO2006013863A1 (en) * | 2004-08-04 | 2006-02-09 | Toagosei Co., Ltd. | Polyorganosiloxane and curable composition containing same |
| CN106188548A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof |
-
2019
- 2019-06-21 CN CN201910544043.9A patent/CN112111062A/en active Pending
-
2020
- 2020-06-19 WO PCT/CN2020/097174 patent/WO2020253838A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416447A (en) * | 2000-02-18 | 2003-05-07 | 罗狄亚化学公司 | Plastic material surface treatment with polymerisable and/or crosslinkable organic compsn. having reactive functions |
| CN1418912A (en) * | 2001-11-13 | 2003-05-21 | 住友化学工业株式会社 | Composition containing cationic polymerized composition and coating obtained from same |
| CN1727378A (en) * | 2004-07-29 | 2006-02-01 | 国家淀粉及化学投资控股公司 | Siloxane resins with oxetane functionality |
| WO2006013863A1 (en) * | 2004-08-04 | 2006-02-09 | Toagosei Co., Ltd. | Polyorganosiloxane and curable composition containing same |
| CN106188548A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张雅静等: "《光致阳离子聚合单体的进展》", 《信息记录材料》 * |
Cited By (2)
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|---|---|---|---|---|
| CN113416208A (en) * | 2021-06-21 | 2021-09-21 | 湖北固润科技股份有限公司 | Eugenol bio-based silicon-containing oxetane monomer and preparation method thereof |
| WO2022267989A1 (en) * | 2021-06-21 | 2022-12-29 | 湖北固润科技股份有限公司 | Eugenol bio-based silicon-containing oxetane monomer and preparation method therefor |
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