WO2022135275A1 - 氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用 - Google Patents
氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用 Download PDFInfo
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- WO2022135275A1 WO2022135275A1 PCT/CN2021/138911 CN2021138911W WO2022135275A1 WO 2022135275 A1 WO2022135275 A1 WO 2022135275A1 CN 2021138911 W CN2021138911 W CN 2021138911W WO 2022135275 A1 WO2022135275 A1 WO 2022135275A1
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- Prior art keywords
- oxetane
- modified isocyanurate
- isocyanurate compound
- modified
- cured composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 38
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title abstract description 18
- 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 8
- 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
- -1 oxetane-modified isocyanurate compound Chemical class 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000976 ink Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 150000002921 oxetanes Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 18
- 238000001723 curing Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 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
- 239000008346 aqueous phase Substances 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
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229940014800 succinic anhydride Drugs 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
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 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
- 102000001708 Protein Isoforms Human genes 0.000 description 1
- 108010029485 Protein Isoforms Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000743 hydrocarbylene group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 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
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
Definitions
- the present invention relates to the field of curing materials, in particular to an oxetane-modified isocyanurate compound, a curing composition and applications.
- the rings of oxetane-based products have similar ring tension and higher basicity, but also exhibit longer induction period and low overall degree of polymerization, together with low shrinkage on cure, mechanical properties, resistance to Heat resistance, weather resistance, and excellent transparency.
- the application of oxetane-containing compounds in the fields of coatings, paints, inks, adhesive materials, films, optical materials, sealing materials and the like has been continuously reported.
- the hardness and flexibility of oxetane products need to be improved.
- Isocyanurate compounds have good thermal stability, flame retardancy and chemical resistance. Widely used in the preparation of polyurethane rigid foams, medicine and as a curing agent for polyurethane coatings, glue-boosting agents, and different modified isocyanurate-modified compounds have been reported, such as CN105073810A, CN109749045A, CN108884082A et al. reported the use of variously modified isocyanurate compounds as polymers or oligomers of resist underlayer film-forming compositions and the like, raw materials for rigid foams, and the like.
- the main purpose of the present invention is to provide an oxetane-modified isocyanurate compound, a cured composition and an application, so as to improve the hardness and flexibility of oxetane-based products.
- an oxetane-modified isocyanurate compound having the following Structure shown in general formula (I),
- R 1 , R 2 and R 3 are each independently selected from H, Any one of, R 1 , R 2 and R 3 are not H at the same time, and R 4 is Any one of -OH and R 4 of R 1 , R 2 and R 3 is not -OH at the same time, and R 5 is each independently a hydrogen atom, methyl or ethyl;
- R 6 is each independently selected from C 1 - Any one of C 20 straight-chain alkylene, C 3 -C 20 branched alkylene, and -CH 2 - in the main chain of R 6 can be optionally substituted by -O-, aryl , the substitution condition is that two -O- are not directly connected, n is 1 or 2 or 3;
- R 7 is selected from ethylene, any of the .
- a resin product which is obtained by curing a curing composition, wherein the curing composition is any one of the above-mentioned curing compositions.
- the compound having the above-mentioned general structural formula (I) when applied in the cured composition, the hardness and flexibility of the cured product of the cured composition can be improved, and the excellent properties of the oxetane compounds can be maintained. the advantage of adhesion.
- the above-mentioned oxetane-modified isocyanurate compounds of the present application can be cured by photocuring or thermal curing polymerization according to the needs of the application environment.
- the hardness and flexibility of oxetane products still have room for improvement.
- the application provides a kind of oxetane. Alkane-modified isocyanurates, curing compositions and applications.
- an oxetane-modified isocyanurate compound is provided, and the oxetane-modified isocyanurate compound has the following structure The structure shown in general formula (I),
- R 1 , R 2 and R 3 are each independently selected from H, Any one of, R 1 , R 2 and R 3 are not H at the same time, and R 4 is Any one of -OH and R 4 of R 1 , R 2 and R 3 is not -OH at the same time, and R 5 is each independently a hydrogen atom, methyl or ethyl;
- R 6 is each independently selected from C 1 - Any one of C 20 straight-chain alkylene, C 3 -C 20 branched alkylene, and -CH 2 - in the main chain of R 6 can be optionally substituted by -O-, aryl , the substitution condition is that two -O- are not directly connected, n is 1 or 2 or 3;
- R 7 is selected from ethylene, any of the .
- the hardness and flexibility of the cured product of the cured composition can be improved, and the advantages of excellent adhesion of oxetane compounds can be maintained.
- the above-mentioned oxetane-modified isocyanurate compounds of the present application can be cured by photocuring or thermal curing polymerization according to the needs of the application environment.
- R 1 , R 2 and R 3 are each independently selected from any of the .
- the above-mentioned oxetane-modified isocyanurate compound has any one of the structures represented by the general structural formulas (II) to (IV),
- each of the above R 5 is independently methyl or ethyl, and preferably each of the R 5 is independently ethyl.
- R 6 is each independently selected from C 1 -C 10 straight-chain alkylene, C 3 -C 10 branched-chain alkylene Any of the alkyl groups, and -CH 2 - in the main chain of R 6 can be optionally substituted by -O-, aryl groups.
- R 7 is selected from ethylene, any of the .
- the above-mentioned oxetane-modified isocyanurate compounds in the present application may be a single compound, or may be a plurality of compounds with the above general formula coexisting, in order to facilitate those skilled in the art to obtain
- an exemplary preparation method of the compound is provided below. The following description is only an exemplary description, and does not mean that the compound of the present application can only be prepared by the following preparation method.
- the raw materials used are all known compounds in the prior art, and the type of solvent used is not particularly limited, as long as the raw materials can be dissolved and there is no adverse effect on the reaction, preferably dichloroethane, acetonitrile, Benzene, toluene, xylene, dimethylformamide (N,N-dimethylformamide) and the like.
- 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.
- the molar ratio of the raw material b to the raw material a is in the range of 1.0 to 4.0:1.
- the ratio of different substituents in the substituents R 5 , R 6 and R 7 can be adjusted by adjusting the amount of raw material c relative to raw material b, preferably the molar ratio of raw material c and raw material b is in the range of 1.0-2.0:1 Inside.
- the compounds of the general structural formula (II), (III) or (IV) and their mutual ratios can be obtained by adjusting the amount of the raw material b relative to the raw material c.
- the above reaction is carried out in two stages, the temperature of the first stage is preferably 80-150°C and the time is 1-5h, and the temperature of the second stage is 20-60°C and the time is 10-18h.
- the compound of the present invention can be isolated after completion by, for example, solvent extraction or the like. If necessary, it can be purified by washing with a solvent such as water, treatment with activated carbon, chromatography on silica gel, and the like.
- the above-mentioned raw material b may also be the following compound containing a plurality of oxa functionalities
- R 9 is an m-valent group selected from C 1 -C 20 straight or branched chain alkyl, C 2 -C 20 alkenyl, C 2 -C 20 cycloalkyl, C 4 -C 20 Cycloalkylalkyl, C4 - C20 alkylcycloalkyl, C4 - C40 heteroalkyl or heterocyclyl, phenyl, biphenyl, naphthyl or heteroaryl, optionally, One or more hydrogen atoms in these groups may be independently substituted by groups selected from alkyl, phenyl, halogen, nitro, alkoxy, carbonyl; R 8 represents a C 1 -C 20 hydrocarbylene group , the -CH 2 - in its main chain can be optionally substituted by an oxygen atom, provided that the two -O- are not directly connected, optionally, one or more hydrogen atoms in these groups can be independently selected Substituted from groups of alkyl, halogen and nitro;
- a curing composition comprising a monomer and an initiator, the monomer comprising one or more of the above-mentioned oxetane-modified isoforms Cyanurate compounds.
- the hardness and flexibility of the cured product of the cured composition can be improved, and the advantages of excellent adhesion of oxetane compounds can be maintained.
- the above-mentioned oxetane-modified isocyanurate compounds of the present application can be cured by photocuring or thermal curing polymerization according to the needs of the application environment. Therefore, the above-mentioned curing composition is a photo-curing composition or a thermal-curing composition, and the initiator is a photo-initiator or a thermal-initiator. Those skilled in the art can choose from the initiators used for the polymerization initiation of conventional oxetane compounds, which will not be repeated here.
- a resin product which is obtained by curing a curing composition, and the curing composition is any one of the above-mentioned curing compositions.
- the hardness and flexibility of the resin product formed by the cured composition of the present application are improved, thus improving the application performance of the resin product.
- the above resin products can be used as any one of coatings, inks, adhesives, optical devices, sealing materials, and photoresists.
- the resin compositions were prepared according to the above-mentioned formulations in Examples 9-16 and Comparative Examples 1-4, and the resin compositions were coated on a glass plate, subjected to mercury lamp crawler exposure treatment (energy 691.4 mj/cm 2 ), and the curing conditions were observed. Evaluation was carried out by touch method, the temperature was set at 150 °C, and the temperature was maintained for 30 min to test the application performance of the composition.
- the resin compositions were prepared according to the formulations in the above-mentioned Examples 17-24 and Comparative Examples 5-8, and the resin compositions were coated on a glass substrate with stirring at room temperature, heated at 80°C, and the time required for curing was observed to test the application properties of the compositions. .
- the oxetane ring isocyanurate compound of the present invention is used as a raw material for a photocurable compound together with a thermosetting compound
- the curing performance is relatively excellent compared with the case of using a conventional oxetane compound.
- the cured product obtained from the resin composition has a high crosslinking density and sufficient hardness and flexibility.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Plural Heterocyclic Compounds (AREA)
- Epoxy Compounds (AREA)
Abstract
本发明提供了一种氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用。该氧杂环丁烷改性的异氰脲酸酯类化合物具有以下结构通式(I)所示结构，其中，R1、R2和R3各自独立地选自H、式(II)、式(III)中的任意一种，R1、R2和R3不同时为H，R4为式(IV)、 -OH中的任意一种且R1、R2和R3的R4不同时为-OH，且R5各自独立为氢原子、甲基或乙基；R6各自独立地选自C1-C20的直链亚烷基、C3-C20的支链亚烷基中的任意一种，n为1或2或3。具有上述结构通式(I)的化合物在固化组合物中应用时，可以改善固化组合物固化产品的硬度和柔韧性，且可以保持氧杂环丁烷类化合物的优异的附着力的优势。
Description
交叉引用：
本申请是以CN申请号为202011536241.X，申请日为2020年12月22日的中国申请为基础，并主张其优先权，该CN申请的公开内容再次作为整体引入本申请中。
本发明涉及固化材料领域，具体而言，涉及一种氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用。
氧杂环丁烷类产品的环具有相似的环张力和更高的碱度，但同时也表现出更长的诱导期和低的整体聚合度，同时具有固化时收缩率小、机械性能、耐热性、耐候性，透明性优异的特点。鉴于这样的优良的特性，含有氧杂环丁烷化合物在涂料、油漆、油墨、粘合材料、薄膜、光学材料、密封材料等领域的应用不断被报道。但是氧杂环丁烷类产品的硬度和柔韧性还有待提高。
异氰脲酸酯类化合物具有良好的热稳定性、阻燃性和耐化学品性。广泛用于制备聚氨醋硬质泡沫塑料、医药及作为聚氨醋涂料，胶勃剂的固化剂，不同改性的异氰脲酸酯改性的化合物已被报道，如CN105073810A、CN109749045A、CN108884082A等报道了不同改性的异氰脲酸酯化合物作为抗蚀剂下层膜形成用组合物等的聚合物或低聚物、硬质泡沫体原料等的用途。
发明内容
本发明的主要目的在于提供一种氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用，以提高氧杂环丁烷类产品的硬度和柔韧性。
为了实现上述目的，根据本发明的一个方面，提供了一种氧杂环丁烷改性的异氰脲酸酯类化合物，该氧杂环丁烷改性的异氰脲酸酯类化合物具有以下结构通式(I)所示结构，
其中，R
1、R
2和R
3各自独立地选自H、
中的任意一种，R
1、R
2和R
3不同时为H，R
4为
-OH中的任意一种且R
1、R
2和R
3的R
4不同时为-OH，且R
5各自独立为氢原子、甲基或乙基；R
6各自独立地选自C
1-C
20的直链亚烷基、C
3-C
20的支链亚烷基中的任意一种，且R
6主链中的-CH
2-可任选地被-O-、芳基所取代，取代条件是两个-O-不直接相连，n为1或2或3；R
7选自亚乙基、
中的任意一种。
根据本发明的另一方面，提供了一种树脂产品，采用固化组合物固化而成，该固化组合物为上述任一种的固化组合物。
应用本发明的技术方案，具有上述结构通式(I)的化合物在固化组合物中应用时，可以改善固化组合物固化产品的硬度和柔韧性，且可以保持氧杂环丁烷类化合物的优异的附着力的优势。本申请的上述氧杂环丁烷改性的异氰脲酸酯类化合物可以根据应用环境需要通过光固化或热固化聚合固化。
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
如本申请背景技术所记载的，氧杂环丁烷类产品的硬度和柔韧性还具有改进空间，为了提高氧杂环丁烷类产品的硬度和柔韧性，本申请提供了种氧杂环丁烷改性的异氰脲酸酯类化合物、固化组合物及应用。
在本申请一种典型的实施方式中，提供了一种氧杂环丁烷改性的异氰脲酸酯类化合物，该氧杂环丁烷改性的异氰脲酸酯类化合物具有以下结构通式(I)所示结构，
其中，R
1、R
2和R
3各自独立地选自H、
中的任意一种，R
1、R
2和R
3不同时为H，R
4为
-OH中的任意一种且R
1、R
2和R
3的R
4不同时为-OH，且R
5各自独立为氢原子、甲基或乙基；R
6各自独立地选自C
1-C
20的直链亚烷基、C
3-C
20的支链亚烷基中的任意一种，且R
6主链中的-CH
2-可任选地被-O-、芳基所取代，取代条件是两个-O-不直接相连，n为1或2或3；R
7选自亚乙基、
中的任意一种。
具有上述结构通式(I)的化合物在固化组合物中应用时，可以改善固化组合物固化产品的硬度和柔韧性，且可以保持氧杂环丁烷类化合物的优异的附着力的优势。本申请的上述氧杂环丁烷改性的异氰脲酸酯类化合物可以根据应用环境需要通过光固化或热固化聚合固化。
为了简化上述氧杂环丁烷改性的异氰脲酸酯类化合物的制备，优选上述R
1、R
2和R
3各自独立地选自
中的任意一种。
在一些实施例中，上述氧杂环丁烷改性的异氰脲酸酯类化合物具有结构通式(II)至(IV)所示结构的任意一种，
在一些实施例中，为了便于氧杂环丁烷类化合物对异氰脲酸酯的修饰，优选上述R
5各自独立为甲基或乙基，优选所述R
5各自独立为乙基。
进一步地，为了便于氧杂环丁烷类化合物对异氰脲酸酯的修饰，优选R
6各自独立地选自C
1-C
10的直链亚烷基、C
3-C
10的支链亚烷基中的任意一种，且R
6主链中的-CH
2-可任选地被-O-、芳基所取代。
同样地，优选上述R
7选自亚乙基、
中的任意一种。
本申请上述的氧杂环丁烷改性的异氰脲酸酯类化合物可以为单独的一种化合物，也可以是多种具有上述通式的多种化合物同时存在，为了便于本领域技术人员得到上述化合物，以下提供该化合物的一种示例性的制备方法，以下说明仅是示例性说明，并不表示本申请的化合物仅可以采用以下制备方法制备而成。
参考以下合称路线制备本申请的化合物：
上述制备方法中，使用的原料均是现有技术中的已知化合物，对使用的溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，优选二氯乙烷、乙腈、苯、甲苯、二甲苯、二甲基甲酰胺(N，N-二甲基甲酰胺)等。
本领域技术人员可以根据原料b和原料c的不同进而得到结构通式(I)中不同取代基的化合物。
另外，可以通过调整原料b相对于原料a的量对异氰脲酸酯进行不同程度的修饰取代，优选原料b与原料a的摩尔比在1.0～4.0：1的范围内。
进一步的，可以通过调整原料c相对于原料b的量，调整取代基R
5、R
6和R
7中不同取代基的比例，优选原料c和原料b的摩尔比在1.0～2.0：1的范围内。
另外，可以通过调整原料b相对于原料c的量获得结构通式(II)、(III)或(IV)的化合物及相互的比例。
上述反应分两个阶段进行，第一阶段的温度优选为80～150℃，时间为1～5h，第二阶段的温度为20～60℃，时间为10～18h。
在反应完成之后所得反应溶液，可通过例如溶剂萃取或类似方法完成之后，分离出本发明的化合物。如果需要，可以通过用水等溶剂洗涤，活性炭处理，硅胶色谱法等方法纯化。
此外，上述原料b亦可为下述含有多个氧杂官能度的化合物
R
9为m价基团，选自C
1-C
20的直链或支链烷基、C
2-C
20的链烯基、C
2-C
20的环烷基、C
4-C
20的环烷基烷基、C
4-C
20的烷基环烷基，C
4-C
40的杂烷基或杂环基、苯基、联苯基、萘基或杂芳基，任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团所取代；R
8表示C
1-C
20的亚烃基，其主链中的-CH
2-可任选地被氧原子取代，条件是两个-O-不直接相连，任选地，这些基团中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团所取代；m为1～8的任意一个整数。
在本申请另一种典型的实施方式中，提供了一种固化组合物，包括单体、引发剂，该单体包括一种或多种上述任一种的氧杂环丁烷改性的异氰脲酸酯类化合物。
具有上述结构通式(I)的化合物在固化组合物中应用时，可以改善固化组合物固化产品的硬度和柔韧性，且可以保持氧杂环丁烷类化合物的优异的附着力的优势。
本申请的上述氧杂环丁烷改性的异氰脲酸酯类化合物可以根据应用环境需要通过光固化或热固化聚合固化。因此上述固化组合物为光固化组合物或热固化组合物，引发剂为光引发剂或热引发剂。本领域技术人员可以在常规的氧杂环丁烷类化合物聚合引发所用引发剂中进行选择，在此不再一一赘述。
在本申请另一种典型的实施方式中，提供了一种树脂产品，采用固化组合物固化而成，该固化组合物为上述任一种的固化组合物。本申请的固化组合物形成的树脂产品的硬度、柔韧性都有所提高，因此提高了该树脂产品的应用性能。
根据氧杂环丁烷基团和异氰脲酸酯的性能，可以使上述树脂产品作为涂料、油墨、粘合剂、光学器件、密封材料、光刻胶中的任意一种来应用。
以下将结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。
制备实施例
实施例1
1-1的制备：
N
2保护下：在250mL四口烧瓶中加入异氰脲酸12.9g、1-乙基(3-氧杂环丁烷基)甲基缩水甘油醚61.6g，甲苯50mL，100℃加热回流2h，后降至室温，滴加30.0g丁二酸酐，常温搅拌过夜，将所的产物体系倒入50mL去离子水中搅拌分层得有机相和水相，接着用水(50毫升×5次)洗涤有机相得到洗涤液，采用甲苯萃取合并洗涤液和水相，萃取物旋蒸后乙腈重结晶得淡黄色液体45.4g。MS(m/z):946(M+1)
+，
1H-NMR(CDCl
3，500MHz):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的制备：
制备方法同上，将丁二酸酐的量换成20.0g，重结晶后得淡黄色液体38.5g。MS(m/z):846(M+1)
+，
1H-NMR(CDCl
3，500MHz):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的制备：
制备方法同上，将丁二酸酐的量换成10.0g，重结晶后得淡黄色液体36.5g。MS(m/z):746(M+1)
+，
1H-NMR(CDCl
3，500MHz):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)。
实施例2：
2-1的制备：
N
2保护下：在250mL四口烧瓶中加入异氰脲酸12.9g、3-乙基-3-[[3-甲氧基-2-(氧化乙烯-2-甲氧基)丙烷]甲基]氧杂环丁烷78.0g，甲苯50mL，105℃加热回流4h，后降至室温，滴加44.4g苯酐，常温搅拌过夜，将所的产物体系倒入50mL去离子水中搅拌分层得有机相和水相，接着用水(50毫升×5次)洗涤有机相得到洗涤液，采用甲苯萃取合并洗涤液和水相，萃取物旋蒸后乙腈重结晶得淡黄色液体42.5g。MS(m/z):1396(M+1)
+，
1H-NMR(CDCl
3，500MHz):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的制备：
制备方法同上，将苯酐的量换成29.6g，重结晶后得淡黄色液体42.3g。MS(m/z):1248(M+1)
+，
1H-NMR(CDCl
3，500MHz):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的制备：
制备方法同上，将苯酐的量换成14.8g，重结晶后得淡黄色液体38.7g。MS(m/z):1085(M+1)
+，
1H-NMR(CDCl
3，500MHz):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)。
进一步的，可选用不同的原料进行反应及不同的反应条件，从而得到不同结构的化合物或不同比例的混合物，但不限于如此，以下实施例3至8的原料见表1。
表1
性能评价：
光固化产品的制备
表2
按上述的实施例9-16和比较例1～4中的配方制备树脂组合物涂布在玻璃板上，汞灯履带式曝光处理(能量691.4mj/cm
2)，观察其固化情况，采用指触法进行评价，升温置150℃，保温30min，测试其组合物的应用性能。
热固化产品的制备
表3
按上述的实施例17-24和比较例5～8中的配方制备树脂组合物常温搅拌涂布于玻璃基板上，80℃下加热，观察其固化所需要的时间，测试其组合物的应用性能。
(3)硬度的测量
参考GB T 6739-1996，测试固化膜的硬度。
(4)柔韧性测试
参考GB/T 30791-2014，T弯性能进行测试。
评价结果记录在表4中。
表4
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：具有本发明的氧杂环丁烷环异氰脲酸酯化合物，作为光固化性化合物的原料和热固性化合物一起使用时，与使用以往的氧杂环丁烷化合物的情况相比，固化性能相对优异。此外，由该树脂组合物得到的固化产物具有高交联密度和足够的硬度和柔韧性。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
- 一种氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述氧杂环丁烷改性的异氰脲酸酯类化合物具有以下结构通式(I)所示结构，
其中，R 1、R 2和R 3各自独立地选自H、中的任意一种，R 1、R 2和R 3不同时为H，R 4为
-OH中的任意一种且R 1、R 2和R 3的R 4不同时为-OH，且R 5各自独立为氢原子、甲基或乙基；R 6各自独立地选自C 1-C 20的直链亚烷基、C 3-C 20的支链亚烷基中的任意一种，且所述R 6主链中的-CH 2-可任选地被-O-、芳基所取代，取代条件是两个-O-不直接相连，n为1或2或3；
R 7选自亚乙基、
中的任意一种。
- 根据权利要求1所述的氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述R 1、R 2和R 3各自独立地选自中的任意一种。
- 根据权利要求1或2所述的氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述氧杂环丁烷改性的异氰脲酸酯类化合物具有结构通式(II)至(IV)所示结构的任意一种，
- 根据权利要求1至3中任一项所述的氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述R 5各自独立为甲基或乙基，优选所述R 5各自独立为乙基。
- 根据权利要求1至4中任一项所述的氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述R 6各自独立地选自C 1-C 10的直链亚烷基、C 3-C 10的支链亚烷基中的任意一种，且所述R 6主链中的-CH 2-可任选地被-O-、芳基所取代，优选至少所述R 6主链中的第二位-CH 2-被-O-所取代。
- 根据权利要求1至5中任一项所述的氧杂环丁烷改性的异氰脲酸酯类化合物，其特征在于，所述R 7选自亚乙基、
中的任意一种。
- 一种固化组合物，包括单体、引发剂，其特征在于，所述单体包括一种或多种权利要求1至6中任一项所述的氧杂环丁烷改性的异氰脲酸酯类化合物。
- 根据权利要求7所述的固化组合物，其特征在于，所述固化组合物为光固化组合物或热固化组合物，所述引发剂为光引发剂或热引发剂。
- 一种树脂产品，采用固化组合物固化而成，其特征在于，所述固化组合物为权利要求7和8所述的固化组合物。
- 根据权利要求9所述的树脂产品，其特征在于，所述树脂产品为涂料、油墨、粘合剂、光学器件、密封材料、光刻胶中的任意一种。
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