CN114656458A - Oxetane-modified isocyanurate compound, curing composition and application - Google Patents
Oxetane-modified isocyanurate compound, curing composition and application Download PDFInfo
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- CN114656458A CN114656458A CN202011536241.XA CN202011536241A CN114656458A CN 114656458 A CN114656458 A CN 114656458A CN 202011536241 A CN202011536241 A CN 202011536241A CN 114656458 A CN114656458 A CN 114656458A
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- Prior art keywords
- oxetane
- modified isocyanurate
- isocyanurate compound
- compound
- curing composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- -1 Oxetane-modified isocyanurate compound Chemical class 0.000 title claims abstract description 31
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 238000001723 curing Methods 0.000 description 26
- 239000002994 raw material Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000002921 oxetanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RXDCRQDAOBLOSZ-UHFFFAOYSA-N 3-[1-(oxiran-2-ylmethoxy)propyl]oxetane Chemical compound C(C1CO1)OC(CC)C1COC1 RXDCRQDAOBLOSZ-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 238000005259 measurement 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
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Abstract
The invention provides an oxetane modified isocyanurate compound, a curing composition and application. The oxetane-modified isocyanurate compound has a structure shown in the following structural general formula (I),
wherein R is1、R2And R3Each independently selected from H,
Any one of (1), R1、R2And R3Not simultaneously being H or R4Is composed of
-any one of OH and R1、R2And R3R of (A) to (B)4Not simultaneously being-OH, and R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Each independently selected from C1‑C20Linear alkylene of (2), C3‑C20N is 1, 2 or 3. When the compound with the structural general formula (I) is applied to a curing composition, the hardness and the flexibility of a cured product of the curing composition can be improved, and the advantage of excellent adhesion of an oxetane compound can be maintained.
Description
Technical Field
The invention relates to the field of curing materials, and particularly relates to an oxetane modified isocyanurate compound, a curing composition and application.
Background
The oxetane product has similar ring tension and higher alkalinity, but also shows longer induction period and low overall polymerization degree, and has the characteristics of small shrinkage rate during curing, mechanical property, heat resistance, weather resistance and excellent transparency. In view of such excellent characteristics, applications of oxetane compounds in the fields of coatings, paints, inks, adhesives, films, optical materials, sealants and the like have been reported. However, the hardness and flexibility of oxetane products have yet to be improved.
The isocyanurate compound has good thermal stability, flame retardance and chemical resistance. Widely used for the preparation of polyurethane rigid foams, medicines and as polyurethane coatings, curing agents for mastic agents, and variously modified isocyanurate-modified compounds have been reported, and for example, CN105073810A, CN109749045A, CN108884082A and the like report the use of variously modified isocyanurate compounds as polymers or oligomers of resist underlayer film forming compositions and the like, rigid foam raw materials and the like.
Disclosure of Invention
The invention mainly aims to provide an oxetane modified isocyanurate compound, a curing composition and application, so as to improve the hardness and flexibility of oxetane products.
In order to achieve the above object, according to one aspect of the present invention, there is provided an oxetane-modified isocyanurate compound having a structure represented by the following general structural formula (I),
wherein R is1、R2And R3Each independently selected from H,
Any one of (1), R1、R2And R3Not simultaneously being H or R4Is composed of
-OH and R1、R2And R3R of (A) to (B)4Not simultaneously being-OH, and R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Each independently selected from C1-C20Linear alkylene of (2), C3-C20Any one of the branched alkylene groups of (1), and R6In the main chain-CH2-is optionally substituted by-O-, aryl, provided that two-O-are not directly connected, n is 1 or 2 or 3; r7Selected from ethylene,
Any one of them.
Further, the above R1、R2And R3Each independently selected from
Any one of them.
Further, the oxetane-modified isocyanurate compound has any one of the structures represented by the general structural formulae (II) to (IV),
further, the above R5Each independently of the other being methyl or ethyl, preferably R5Each independently is ethyl.
Further, the above R6Each independently selected from C1-C10Linear alkylene of (2), C3-C10Any one of the branched alkylene groups of (1), and R6In the main chain-CH2-optionally substituted by-O-, aryl, preferably at least R6Second position in the main chain-CH2-is substituted by-O-.
Further, the above R7Selected from ethylene,
Any one of them.
According to another aspect of the present invention there is provided a curing composition comprising a monomer comprising one or more oxetane-modified isocyanurate compound of any of the above, an initiator.
Further, the curing composition is a photo-curing composition or a thermal-curing composition, and the initiator is a photo-initiator or a thermal initiator.
According to another aspect of the present invention, there is provided a resin product obtained by curing a curing composition, which is any one of the above-mentioned curing compositions.
Further, the resin product is any one of paint, ink, adhesive, optical device, sealing material and photoresist.
By applying the technical scheme of the invention, when the compound with the structural general formula (I) is applied to a curing composition, the hardness and flexibility of a cured product of the curing composition can be improved, and the advantage of excellent adhesive force of the oxetane compound can be maintained. The above-mentioned oxetane-modified isocyanurate compound of the present application can be cured by photo-curing or thermal curing polymerization according to the application environment requirements.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background of the present application, there is room for improvement in hardness and flexibility of oxetane products, and in order to improve hardness and flexibility of oxetane products, oxetane-modified isocyanurate compounds, curing compositions and uses thereof are provided.
In a typical embodiment of the present application, there is provided an oxetane-modified isocyanurate compound having a structure represented by the following general structural formula (I),
wherein R is1、R2And R3Each independently selected from H,
Any one of (1), R1、R2And R3Not simultaneously being H or R4Is composed of
-any one of OH and R1、R2And R3R of (A) to (B)4Not simultaneously being-OH, and R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Each independently selected from C1-C20Linear chain of (2)Alkylene radical, C3-C20Any one of the branched alkylene groups of (1), and R6In the main chain-CH2-is optionally substituted by-O-, aryl, provided that two-O-are not directly connected, n is 1 or 2 or 3; r7Selected from ethylene,
Any one of them.
When the compound with the structural general formula (I) is applied to a curing composition, the hardness and the flexibility of a cured product of the curing composition can be improved, and the advantage of excellent adhesion of an oxetane compound can be maintained. The above-mentioned oxetane-modified isocyanurate compound of the present application can be cured by photo-curing or thermal curing polymerization according to the application environment requirements.
In order to simplify the preparation of the above-mentioned oxetane-modified isocyanurate compound, the above-mentioned R is preferable1、R2And R3Each independently selected from
Any one of them.
In some embodiments, the oxetane-modified isocyanurate-based compound has any one of the structures represented by the general structural formulae (II) to (IV),
in some embodiments, to facilitate oxetane formationModification of isocyanurate with alkane compound, preferably R5Each independently being methyl or ethyl, preferably said R5Each independently is ethyl.
Further, R is preferred for facilitating the modification of isocyanurates with oxetanes6Each independently selected from C1-C10Linear alkylene of (2), C3-C10Any one of the branched alkylene groups of (1), and R6In the main chain-CH2-optionally substituted by-O-, aryl.
Similarly, R is preferably the above-mentioned7Selected from ethylene,
Any one of them.
The oxetane-modified isocyanurate compound of the present invention may be a single compound or a plurality of compounds having the above general formula may be present at the same time, and in order to facilitate obtaining the above compound by those skilled in the art, an exemplary method for producing the compound is provided below, and the following description is only an exemplary description, and does not mean that the compound of the present invention can be produced by only the following production method.
The compounds of the present application are prepared by reference to the following general scheme:
in the above-mentioned production methods, the raw materials used are all known compounds in the prior art, and the type of the solvent used is not particularly limited as long as the raw materials can be dissolved and the reaction is not adversely affected, and dichloroethane, acetonitrile, benzene, toluene, xylene, dimethylformamide (N, N-dimethylformamide) and the like are preferable.
The person skilled in the art can further obtain compounds with different substituents in the general structural formula (I) according to the difference between the raw material b and the raw material c.
The isocyanurate can be modified and substituted to different degrees by adjusting the amount of the raw material b relative to the raw material a, and the molar ratio of the raw material b to the raw material a is preferably 1.0-4.0: 1, in the above range.
Further, the substituent R can be adjusted by adjusting the amount of the raw material c relative to the raw material b5、R6And R7The molar ratio of the raw material c to the raw material b is preferably 1.0-2.0: 1, in the above range.
Furthermore, the compounds of the general structural formulae (II), (III) or (IV) and their mutual proportions can be obtained by adjusting the amount of starting material b relative to starting material c.
The reaction is carried out in two stages, wherein the temperature of the first stage is preferably 80-150 ℃ for 1-5 hours, and the temperature of the second stage is 20-60 ℃ for 10-18 hours.
After the reaction is completed, the resulting reaction solution may be subjected to, for example, solvent extraction or the like, and then the compound of the present invention is isolated. If necessary, it can be purified by washing with a solvent such as water, treating with activated carbon, silica gel chromatography or the like.
The raw material b may be a compound containing a plurality of oxa-functionalities as described below
R9Is a m-valent radical selected from C1-C20Straight or branched alkyl of (2), C2-C20Alkenyl of (C)2-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of C4-C40Optionally, one or more hydrogen atoms of these groups may be independently substituted by a group selected from alkyl, phenyl, halo, nitro, alkoxy, carbonyl; r is8Is represented by C1-C20Alkylene of (a) which is-CH in the main chain2-can renOptionally substituted by an oxygen atom, provided that two-O-groups are not directly attached, optionally one or more hydrogen atoms in these groups may be independently substituted by a group selected from alkyl, halogen, nitro; m is any integer of 1-8.
In another exemplary embodiment of the present application, there is provided a curing composition comprising a monomer comprising one or more oxetane-modified isocyanurate-based compounds of any of the above, an initiator.
When the compound with the structural general formula (I) is applied to a curing composition, the hardness and the flexibility of a cured product of the curing composition can be improved, and the advantage of excellent adhesion of an oxetane compound can be maintained.
The above-mentioned oxetane-modified isocyanurate compound of the present application can be cured by photo-curing or thermal curing polymerization according to the application environment requirements. Thus, the above-mentioned curing composition is a photocurable composition or a thermosetting composition, and the initiator is a photoinitiator or a thermal initiator. The skilled person can select from the initiators used for the conventional initiation of polymerization of oxetanes and will not be described in detail here.
In another exemplary embodiment of the present application, there is provided a resin product obtained by curing a curing composition, which is any one of the above curing compositions. The cured compositions of the present application form resin products having improved hardness and flexibility, thereby improving the application properties of the resin products.
Depending on the properties of the oxetanyl group and the isocyanurate, the above resin product can be applied as any of a coating, an ink, an adhesive, an optical device, a sealing material, and a photoresist.
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
1-1 preparation:
N2under protection: adding 12.9g of isocyanuric acid, 61.6g of 1-ethyl (3-oxetanyl) methyl glycidyl ether and 50mL of toluene into a 250mL four-neck flask, heating and refluxing at 100 ℃ for 2h, then cooling to room temperature, dropwise adding 30.0g of succinic anhydride, stirring at room temperature overnight, pouring the product system into 50mL of deionized water, stirring and layering to obtain an organic phase and an aqueous phase, then washing the organic phase with water (50 mL multiplied by 5 times) to obtain a washing solution, extracting and combining the washing solution and the aqueous phase with toluene, and after rotary evaporation of the extract, recrystallizing acetonitrile to obtain 45.4g of a light yellow liquid. MS (M/z) 946(M +1)+，1H-NMR(CDCl3，500MHz):δ11.89-11.28(s,3H),5.91-5.54(m,9H),4.24-4.14(m,12H),3.90-3.35(m,12H),2.76-2.50(t,12H),1.70-1.65(m，6H)，0.89(t,9H)。
1-2 preparation:
the preparation method is the same as the above, the amount of succinic anhydride is changed to 20.0g, and the pale yellow liquid is obtained after recrystallization by 38.5 g. MS (M/z):846(M +1)+，1H-NMR(CDCl3，500MHz):δ12.09-11.78(s,2H),5.93-5.46(m,9H),4.38-4.15(m,13H),3.84-3.36(m,12H),2.77-2.53(m,8H),1.72-1.66(m，6H)，0.91(t,9H)。
1-3 preparation:
the preparation method is the same as the above, the amount of succinic anhydride is changed to 10.0g, and the light yellow liquid 36.5g is obtained after recrystallization. MS (M/z) 746(M +1)+，1H-NMR(CDCl3，500MHz):δ12.03-11.66(s,1H),5.93-5.46(m,9H),4.43-4.16(m,14H),3.76-3.38(m,12H),2.77-2.53(m,4H),1.72-1.67(m，6H)，0.85(t,9H)。
Example 2:
2-1 preparation:
N2under protection: in a 250mL four-neck flask, 12.9g of isocyanuric acid and 3-ethyl-3- [ [ 3-methoxy ] are added2- (oxyethylene-2-methoxy) propane]Methyl radical]78.0g of oxetane and 50mL of toluene are heated and refluxed at 105 ℃ for 4h, then the temperature is reduced to room temperature, 44.4g of phthalic anhydride is added dropwise, the mixture is stirred at the room temperature overnight, the obtained product system is poured into 50mL of deionized water and stirred and layered to obtain an organic phase and an aqueous phase, then the organic phase is washed with water (50 mL multiplied by 5 times) to obtain a washing solution, the washing solution and the aqueous phase are extracted and combined by toluene, and after the extract is evaporated in a rotary manner, acetonitrile is recrystallized to obtain 42.5g of light yellow liquid. MS (M/z):1396(M +1)+，1H-NMR(CDCl3，500MHz):δ13.27-12.89(s,3H),8.20-7.81(m，12H),5.56-5.45(m,3H),4.39-4.14(m,12H),3.92-3.36(m,33H),3.25-3.26(s，9H)，1.71-1.68(m，12H)，0.87(t,9H)。
2-2 preparation:
the preparation method is the same as the above, the amount of the phthalic anhydride is changed to 29.6g, and 42.3g of light yellow liquid is obtained after recrystallization. MS (M/z):1248(M +1)+，1H-NMR(CDCl3，500MHz):δ12.79-13.55(s,2H),7.83-8.22(m，8H),5.54-5.40(m,3H),4.38-4.12(m,13H),3.92-3.35(m,33H),3.27-3.25(s，9H)，1.71-1.68(m，12H)，0.86(t,9H)。
2-3 preparation:
the preparation method is the same as the above, the amount of the phthalic anhydride is changed to 14.8g, and the light yellow liquid is obtained after recrystallization, wherein the weight of the light yellow liquid is 38.7 g. MS (M/z):1085(M +1)+，1H-NMR(CDCl3，500MHz):δ12.79-13.55(s,1H),7.86-8.25(m，4H),5.48-5.37(m,3H),4.38-4.12(m,14H),3.92-3.35(m,33H),3.26-3.23(s，9H)，1.71-1.68(m，12H)，0.87(t,9H)。
Further, the reaction can be carried out by using different raw materials and different reaction conditions, thereby obtaining compounds with different structures or mixtures in different proportions, but the method is not limited to the following, and the raw materials of examples 3 to 8 are shown in Table 1.
TABLE 1
Performance evaluation:
preparation of photocured product
TABLE 2
Resin compositions prepared according to the formulations in examples 9 to 16 and comparative examples 1 to 4 were coated on a glass plate and subjected to a track exposure treatment with a mercury lamp (energy 1000 mj/cm)2) And observing the curing condition, evaluating by a finger touch method, heating to 150 ℃, keeping the temperature for 30min, and testing the application performance of the composition.
Preparation of a thermoset product
TABLE 3
The resin compositions prepared according to the formulations of examples 17 to 24 and comparative examples 5 to 8 were stirred at room temperature, coated on a glass substrate, heated at 80 ℃ and observed for the time required for curing, and the application properties of the compositions were tested.
(3) Measurement of hardness
Reference GB T6739-.
(4) Flexibility test
The T-bend performance is tested with reference to GB/T30791-2014.
The evaluation results are recorded in table 4.
TABLE 4
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: when the oxetane cycloisocyanurate compound of the present invention is used as a raw material of a photocurable compound together with a thermosetting compound, the curing performance is relatively excellent as compared with the case of using a conventional oxetane compound. Further, the cured product obtained from the resin composition has a high crosslinking density and sufficient hardness and flexibility.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An oxetane-modified isocyanurate compound characterized by having a structure represented by the following general structural formula (I),
wherein R is1、R2And R3Each independently selected from H,
Any one of (1), R1、R2And R3Not simultaneously being H, R4Is composed of
-any one of OH and R1、R2And R3R of (A)4Not simultaneously being-OH, and R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Each independently selected from C1-C20Linear alkylene of (2), C3-C20Any one of the branched alkylene groups of (1), andR6in the main chain-CH2-is optionally substituted by-O-, aryl, provided that two-O-are not directly connected, n is 1 or 2 or 3;
R7selected from ethylene group,
Any one of them.
2. The oxetane-modified isocyanurate compound of claim 1, wherein R is1、R2And R3Each independently selected from
Any one of them.
3. The oxetane-modified isocyanurate compound of claim 1 or 2, which has any one of the structures represented by general structural formulae (II) to (IV),
4. the oxetane-modified isocyanurate compound of any one of claims 1 to 3, wherein R is5Each independently being methyl or ethyl, preferably said R5Each independently is ethyl.
5. An oxa according to any one of claims 1 to 4A cyclobutane-modified isocyanurate compound, wherein R is6Each independently selected from C1-C10Linear alkylene of (2), C3-C10Any one of the branched alkylene groups of (1), and said R6In the main chain-CH2-optionally substituted by-O-, aryl, preferably at least said R6Second position in the main chain-CH2-is substituted by-O-.
6. The oxetane-modified isocyanurate compound of any one of claims 1 to 5, wherein R is7Selected from ethylene,
Any one of them.
7. A curing composition comprising a monomer, an initiator, wherein the monomer comprises one or more oxetane-modified isocyanurate compound of any of claims 1 to 6.
8. The cured composition of claim 7, wherein the cured composition is a photocurable composition or a thermally curable composition, and the initiator is a photoinitiator or a thermal initiator.
9. A resin product cured with a curing composition, characterized in that the curing composition is the curing composition according to claims 7 and 8.
10. The resin product according to claim 9, wherein the resin product is any one of a paint, an ink, an adhesive, an optical device, a sealing material, and a photoresist.
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| CN202011536241.XA CN114656458B (en) | 2020-12-22 | 2020-12-22 | Oxetane-modified isocyanurate compound, curing composition and application |
| PCT/CN2021/138911 WO2022135275A1 (en) | 2020-12-22 | 2021-12-16 | Oxetane-modified isocyanurate compounds, curing composition, and use thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163653A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2013163651A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2013163654A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2017132751A (en) * | 2016-01-21 | 2017-08-03 | 四国化成工業株式会社 | Isocyanurate compound having oxetane ring, method for synthesizing the same and use of the isocyanurate compound |
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- 2020-12-22 CN CN202011536241.XA patent/CN114656458B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163653A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2013163651A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2013163654A (en) * | 2012-02-10 | 2013-08-22 | Shikoku Chem Corp | Isocyanurate compound having oxetane ring |
| JP2017132751A (en) * | 2016-01-21 | 2017-08-03 | 四国化成工業株式会社 | Isocyanurate compound having oxetane ring, method for synthesizing the same and use of the isocyanurate compound |
Non-Patent Citations (1)
| Title |
|---|
| ANNBY, ULF ET AL: "synthesis of new monofunctional and oligofunctional oxetane acetals", 《JOURNAL OF POLYMER SCIENCE, PART A:POLYMER CHEMISTRY》, vol. 39, no. 5, XP055945396, DOI: 10.1002/1099-0518(20010301)39:5<613::AID-POLA1032>3.0.CO;2-0 * |
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