WO2022135348A1 - 氧杂环丁烷改性的异氰脲酸酯、其制备方法、能量固化组合物及应用 - Google Patents
氧杂环丁烷改性的异氰脲酸酯、其制备方法、能量固化组合物及应用 Download PDFInfo
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- WO2022135348A1 WO2022135348A1 PCT/CN2021/139776 CN2021139776W WO2022135348A1 WO 2022135348 A1 WO2022135348 A1 WO 2022135348A1 CN 2021139776 W CN2021139776 W CN 2021139776W WO 2022135348 A1 WO2022135348 A1 WO 2022135348A1
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- Prior art keywords
- oxetane
- modified isocyanurate
- group
- raw material
- substituent
- Prior art date
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 125000001424 substituent group Chemical group 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 4
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 150000002921 oxetanes Chemical class 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 230000006698 induction Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012662 bulk polymerization Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 isocyanurate compound Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-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
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000016 photochemical curing 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 231100000989 no adverse effect Toxicity 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
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention relates to the field of photocuring, in particular, to an oxetane-modified isocyanurate, a preparation method thereof, an energy-curable composition and applications.
- Isocyanurate compounds have good thermal stability, flame retardancy and chemical resistance, and are widely used in the preparation of polyurethane rigid foams, medicines and as curing agents for polyurethane coatings and glue-boosting agents.
- Differently modified isocyanurate-modified compounds have been reported, such as CN105073810A, CN109749045A, CN108884082A, etc. have reported differently modified isocyanurate compounds as polymers of resist underlayer film-forming compositions, etc. Or oligomers, rigid foam raw materials, etc.
- the main purpose of the present invention is to provide an oxetane-modified isocyanurate, its preparation method, energy curing composition and application, so as to solve how to further improve the curing performance of isocyanurate compounds , hardness and adhesion performance issues.
- one aspect of the present invention provides a method for preparing an oxetane-modified isocyanurate, the preparation method comprising: performing a first polymerization reaction on raw material a and raw material b to obtain a first Polymerization product system; The second polymerization reaction is carried out with the first polymerization product system and raw material c to obtain an oxetane-modified isocyanurate, and the structural formulas of raw material a and raw material c are as follows:
- X is a halogen element
- R 1 is selected from a hydrogen atom, a C 1 -C 10 alkyl group
- R 2 is selected from a C 1 -C 10 straight-chain or branched alkylene group, or one or more -CH 2 -
- R 3 is selected from C 1 -C 10 alkyl groups
- R 4 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 cycloalkyl alkyl, C 4 ⁇ C20 alkylcycloalkyl, C4 ⁇ C40 heteroalkyl or heterocyclyl, phenyl, biphenyl, naphthyl or heteroaryl, or one or more hydrogen atoms in the above groups
- Another aspect of the present application also provides an oxetane-modified isocyanurate, which is prepared by the preparation method provided in the present application.
- Yet another aspect of the present application also provides an energy-curable composition
- a matrix resin comprising a reactive monomer and an initiator, where the reactive monomer includes the oxetane-modified isocyanurate provided by the present application.
- Another aspect of the present application also provides an application of the oxetane-modified isocyanurate provided by the present application in the field of curing.
- a macromolecular substituent containing oxetane is introduced into triazonitrile through the first polymerization reaction, and then the product of the first polymerization reaction and the alkenyl halide are prepared through the second polymerization reaction Oxetane-modified isocyanurate.
- the rings in the above-mentioned oxetanes have similar ring tension and higher basicity, and show longer induction period and low overall degree of polymerization, they also have small shrinkage during curing, mechanical Due to the characteristics of excellent performance, heat resistance, weather resistance and transparency, the use of oxetane compounds with the above structure to modify isocyanurate is beneficial to improve the curing performance and hardness of isocyanurate. , heat resistance and weather resistance, and at the same time, due to the introduction of heteroatoms, the modified isocyanurate has better adhesion to the substrate after curing.
- the present application provides a preparation method of an oxetane-modified isocyanurate, the preparation method comprising: subjecting a raw material a and a raw material b to a first polymerization reaction to obtain a first polymerization Product system; The second polymerization reaction is carried out with the first polymerization product system and raw material c to obtain an oxetane-modified isocyanurate, and the structural formula of raw material a and raw material c is as follows:
- R 1 is selected from a hydrogen atom, a C 1 -C 10 alkyl group
- R 2 is selected from a C 1 -C 10 straight-chain or branched alkylene group, or one or more -CH 2 -
- R 3 is selected from C 1 -C 10 alkyl groups
- R 4 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 cycloalkyl alkyl, C 4 ⁇ C20 alkylcycloalkyl, C4 ⁇ C40 heteroalkyl or heterocyclyl, phenyl, biphenyl, naphthyl or heteroaryl, or one or more hydrogen atoms in the above groups
- the macromolecular substituent containing oxetane is introduced into the triazonitrile by the first polymerization reaction, and then the product of the first polymerization reaction and the alkenyl halide are prepared by the second polymerization reaction to obtain the oxetane.
- Cyclobutane-modified isocyanurate is introduced into the triazonitrile by the first polymerization reaction, and then the product of the first polymerization reaction and the alkenyl halide are prepared by the second polymerization reaction to obtain the oxetane.
- the rings in the above-mentioned oxetanes have similar ring tension and higher basicity, and show longer induction period and low overall degree of polymerization, they also have small shrinkage during curing, mechanical Due to the characteristics of excellent performance, heat resistance, weather resistance and transparency, the use of oxetane compounds with the above structure to modify isocyanurate is beneficial to improve the curing performance and hardness of isocyanurate. , heat resistance and weather resistance, and at the same time, due to the introduction of heteroatoms, the modified isocyanurate has better adhesion to the substrate after curing.
- R1 is selected from hydrogen atom, C1 - C5 alkyl
- R2 is selected from C1 - C5 linear or branched alkylene, or one of the above groups or The first substituent formed by multiple -CH 2 - being substituted by -O- or aryl, and the two -O- in the first substituent are not directly connected
- R 3 is selected from C 1 -C 5 alkyl
- R 4 is an m-valent group, selected from C 1 -C 10 linear or branched chain alkyl, C 2 -C 10 alkenyl, C 2 -C 10 cycloalkyl, C 4 -C 10 ring Alkylalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 20 heteroalkyl or heterocyclyl, phenyl, biphenyl
- the raw material b includes but is not limited to
- the oxetane-modified isocyanurate prepared by the above preparation method is a mixture of isocyanurates with an allyl substitution number of 1-3.
- the desired target product can be obtained by adjusting the ratio of the raw material a, the raw material b and the raw material c as required.
- the ratio of the moles of raw material a, raw material b and raw material c is 1:(1-4.0):(1-2.0).
- the ratio of moles of raw material a, raw material b and raw material c includes but is not limited to the above range, and limiting it within the above range is beneficial to further improve the yield of oxetane-modified isocyanurate.
- the first polymerization reaction and the second polymerization reaction are carried out in the presence of an organic solvent.
- the type of solvent used is not particularly limited, as long as it can dissolve the raw materials and has no adverse effect on the reaction, and dichloroethane, acetonitrile, benzene, toluene, xylene and dimethylformamide (N,N-dichloroethane) are preferred. one or more of the group consisting of methylformamide).
- the reaction product system usually also contains some unreacted raw materials or other impurities.
- the above-mentioned oxetane-modified isocyanide further comprises: after successively subjecting the product system of the second polymerization reaction to phase separation, water washing, rotary evaporation of the extractant and recrystallization, the oxetane-modified isocyanurate is obtained.
- the temperature of the first polymerization reaction is 80-200° C., and the reaction time is 1-5 h.
- the reaction temperature and reaction time within the above ranges is beneficial to improve the yield of the first polymerization product. More preferably, the boiling reflux treatment is carried out at the above temperature, which can reduce the loss of the solvent while increasing the reaction temperature, thereby saving the process cost.
- the temperature of the second polymerization reaction is -5 to 40° C., and the reaction time is 6 to 20 h.
- Another aspect of the present application also provides an oxetane-modified isocyanurate, which is prepared by the preparation method provided in the present application. Because the rings in the above-mentioned oxetanes have similar ring tension and higher basicity, and show longer induction period and low overall degree of polymerization, they also have small shrinkage during curing, mechanical Due to the characteristics of excellent performance, heat resistance, weather resistance and transparency, the use of oxetane compounds with the above structure to modify isocyanurate is beneficial to improve the curing performance and hardness of isocyanurate. , heat resistance and weather resistance, and at the same time, due to the introduction of heteroatoms, the modified isocyanurate has better adhesion to the substrate after curing.
- the oxetane-modified isocyanurate has the structure shown in (I), (II) or (III):
- each R 1 , each R 2 , and each R 3 have the same definitions as above.
- Yet another aspect of the present application also provides an energy-curable composition
- a matrix resin comprising a reactive monomer and an initiator, where the reactive monomer includes the oxetane-modified isocyanurate provided by the present application.
- the isocyanurate provided by the present application has better curing performance, hardness, heat resistance, weather resistance and adhesion. Therefore, the energy cured product containing the above-mentioned oxetane-modified isocyanurate has more excellent comprehensive properties.
- the curing methods of the above-mentioned energy-curable compositions include, but are not limited to, photocuring and thermal curing.
- Another aspect of the present application also provides an application of the oxetane-modified isocyanurate provided by the present application in the field of curing.
- the application of the energy-curable composition provided by the present invention is not particularly limited. In view of its excellent comprehensive properties, it has a good application prospect in the curing field, including but not limited to coatings, inks, adhesives, optical materials, optical materials devices, sealing materials, etc.
- the preparation method is the same as above, except that the amount of acryloyl chloride is changed to 9.0g (0.10mol), and after recrystallization, 30.0g of light yellow liquid is obtained, the yield is 42.4wt%, and the purity is 98.8%.
- Photocured products were prepared with the compositions shown in Table 2.
- the resin compositions prepared in the above-mentioned Examples 9 to 16 and Comparative Examples 1 to 4 were coated on a glass plate, subjected to mercury lamp crawler exposure treatment (energy 1000 mj/cm 2 ), and the curing conditions were observed, using the finger touch method. Evaluate. The temperature was raised to 150°C, and the temperature was kept for 30 minutes to test the application performance of the composition.
- Heat cured products were prepared with the compositions shown in Table 3.
- H means hardness, it is divided into H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H grades, and the hardness increases in turn.
- the oxetane ring isocyanurate compound of the present invention when used as a raw material for a photocurable compound and a thermosetting compound is used together, it is different from the case where a conventional oxetane compound is used. In contrast, the curing performance is relatively excellent. Furthermore, the cured product obtained from the resin composition has a high crosslinking density and sufficient hardness and adhesion.
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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)
- Plural Heterocyclic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
提供了一种氧杂环丁烷改性的异氰脲酸酯、其制备方法、能量固化组合物及应用。该制备方法包括：以原料a 和原料b 进行第一聚合反应，得到第一聚合产物体系；将第一聚合产物体系和原料c 进行第二聚合反应，得到氧杂环丁烷改性的异氰脲酸酯。由于上述氧杂环丁烷类化合物中的环具有相似的环张力和更高的碱度，且表现出更长的诱导期和低的整体聚合度，同时其还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，因而采用具有上述结构的氧杂环丁烷类化合物对异氰脲酸酯进行改性有利于提高异氰脲酸酯的固化性能、硬度、耐热性和耐候性，同时由于杂原子的引入使得改性后的异氰脲酸酯固化后与基材具有更好的附着力。
Description
本发明涉及光固化领域，具体而言，涉及一种氧杂环丁烷改性的异氰脲酸酯、其制备方法、能量固化组合物及应用。
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。为了进一步提高异氰脲酸酯酯的综合性能，需要开发一种在固化性能、硬度和附着力方面性能更加优异的异氰脲酸酯类化合物。
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、其制备方法、能量固化组合物及应用，以解决应如何进一步提升异氰脲酸酯类化合物在固化性能、硬度和附着力等方面的性能的问题。
为了实现上述目的，本发明一方面提供了一种氧杂环丁烷改性的异氰脲酸酯的制备方法，该制备方法包括：使原料a和原料b进行第一聚合反应，得到第一聚合产物体系；将第一聚合产物体系和原料c进行第二聚合反应，得到氧杂环丁烷改性的异氰脲酸酯，原料a和原料c的结构式如下：
原料b的结构式如下：
R
1选自氢原子、C
1～C
10的烷基；R
2选自C
1～C
10的直链或支链亚烷基，或上述基团中的一个或多个-CH
2-被-O-或芳基取代形成的第一取代基，且第一取代基中两个-O-不直接相连；R
3选自C
1～C
10的烷基；R
4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，或上述基团中的一个或多个氢原子被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团取代后形成的第二取代基；R
5选自C
1～C
20的亚烃基，或上述基团的主链中的一个或多个-CH
2-被氧原子取代形成的第三取代基，第三取代基中两个-O-不直接相连，或第三取代基中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团取代形成的第四取代基；m为1～8的整数。
本申请的另一方面还提供了一种氧杂环丁烷改性的异氰脲酸酯，采用本申请提供的制备方法制得。
本申请的又一方面还提供了一种能量固化组合物，包括基体树脂、活性单体和引发剂，活性单体包括本申请提供的氧杂环丁烷改性的异氰脲酸酯。
本申请的再一方面还提供了一种本申请提供的氧杂环丁烷改性的异氰脲酸酯在固化领域的应用。
应用本发明的技术方案，通过第一聚合反应在三氮腈中引入含氧杂环丁烷的大分子取代基，然后将第一聚合反应的产物与烯基酰卤通过第二聚合反应制得氧杂环丁烷改性的异氰脲酸酯。由于上述氧杂环丁烷类化合物中的环具有相似的环张力和更高的碱度，且表现出更长的诱导期和低的整体聚合度，同时其还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，因而采用具有上述结构的氧杂环丁烷类化合物对异氰脲酸酯进行改性有利于提高异氰脲酸酯的固化性能、硬度、耐热性和耐候性，同时由于杂原子的引入使得改性后的异氰脲酸酯固化后与基材具有更好的附着力。
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。
正如背景技术所描述的，本领域需要进一步提升异氰脲酸酯类化合物在固化性能、硬度和附着力等方面的性能的问题。为了解决上述技术问题，本申请提供了一种氧杂环丁烷改性 的异氰脲酸酯的制备方法，该制备方法包括：使原料a和原料b进行第一聚合反应，得到第一聚合产物体系；将第一聚合产物体系和原料c进行第二聚合反应，得到氧杂环丁烷改性的异氰脲酸酯，原料a和原料c的结构式如下：
原料b的结构式如下：
R
1选自氢原子、C
1～C
10的烷基；R
2选自C
1～C
10的直链或支链亚烷基，或上述基团中的一个或多个-CH
2-被-O-或芳基取代形成的第一取代基，且第一取代基中两个-O-不直接相连；R
3选自C
1～C
10的烷基；R
4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，或上述基团中的一个或多个氢原子被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团取代后形成的第二取代基；R
5选自C
1～C
20的亚烃基，或上述基团的主链中的一个或多个-CH
2-被氧原子取代形成的第三取代基，第三取代基中两个-O-不直接相连，或第三取代基中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团取代形成的第四取代基；m为1～8的整数。
上述制备方法中，通过第一聚合反应在三氮腈中引入含氧杂环丁烷的大分子取代基，然后将第一聚合反应的产物与烯基酰卤通过第二聚合反应制得氧杂环丁烷改性的异氰脲酸酯。由于上述氧杂环丁烷类化合物中的环具有相似的环张力和更高的碱度，且表现出更长的诱导期和低的整体聚合度，同时其还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，因而采用具有上述结构的氧杂环丁烷类化合物对异氰脲酸酯进行改性有利于提高异氰脲酸酯的固化性能、硬度、耐热性和耐候性，同时由于杂原子的引入使得改性后的异氰脲酸酯固化后与基材具有更好的附着力。
为了提高其聚合反应的容易程度，可以对原料a、b、c中的取代基进行优选。在一种优选的实施例中，R1选自氢原子、C
1～C
5烷基；R
2选自C
1～C
5的直链或支链亚烷基，或上述基团中的一个或多个-CH
2-被-O-或芳基取代形成的第一取代基，且第一取代基中两个-O-不直接相连；R
3选自C
1～C
5的烷基；R
4为m价基团，选自C
1～C
10的直链或支链烷基、C
2～C
10的 链烯基、C
2～C
10的环烷基、C
4～C
10的环烷基烷基、C
4～C
10的烷基环烷基，C
4～C
20的杂烷基或杂环基、苯基、联苯基、萘基或杂芳基，或上述基团中的一个或多个氢原子被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团取代后形成的第二取代基；R
5选自C
1～C
10的亚烃基，或上述基团的主链中的一个或多个-CH
2-被氧原子取代形成的第三取代基，第三取代基中两个-O-不直接相连，或第三取代基中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团取代形成的第四取代基；m为1～5的整数。
为了进一步提高氧杂环丁烷改性的异氰脲酸酯的固化性能、硬度和与基材的附着力，更优选地，原料b包括但不限于
采用上述制备方法制得的氧杂环丁烷改性的异氰脲酸酯为烯丙基取代数为1-3的异氰脲酸酯的混合物。实际生产过程中，可以根据需要通过调整原料a、原料b和原料c的比例，获得所需的目标产物。在一种优选的实施例中，原料a、原料b和原料c的摩尔数之比为1：(1～4.0)：(1～2.0)。原料a、原料b和原料c的摩尔数之比包括但不限于上述范围，而将其限定在上述范围内有利于进一步提高氧杂环丁烷改性的异氰脲酸酯的收率。
为了使反应更加充分，优选地，第一聚合反应和第二聚合反应在有机溶剂的存在下进行。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，优选为二氯乙烷、乙腈、苯、甲苯、二甲苯和二甲基甲酰胺(N，N-二甲基甲酰胺)组成的组中的一种或多种。
反应结束之后，反应产物体系中通常还含有部分未反应的原料或其它杂质，为了进一步提高目标产物的纯度，更优选地，在第二聚合反应之后，上述氧杂环丁烷改性的异氰脲酸酯的制备方法还包括：将第二聚合反应的产物体系依次进行分相、水洗、萃取剂旋蒸及重结晶处理后，得到氧杂环丁烷改性的异氰脲酸酯。
在一种优选的实施例中，第一聚合反应的温度为80～200℃，反应时间为1～5h。
第一聚合反应中，将反应温度和反应时间限定在上述范围内有利于提高第一聚合产物的收率。更优选地，在上述温度下进行沸腾回流处理，这能够实现在提高反应温度的同时，减少溶剂的损耗，从而节约工艺成本。
为了进一步提高目标产物的收率，优选地，第二聚合反应的温度为-5～40℃，反应时间为6～20h。
本申请的另一方面还提供了一种氧杂环丁烷改性的异氰脲酸酯，采用本申请提供的制备方法制得。由于上述氧杂环丁烷类化合物中的环具有相似的环张力和更高的碱度，且表现出更长的诱导期和低的整体聚合度，同时其还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，因而采用具有上述结构的氧杂环丁烷类化合物对异氰脲酸酯进行改性有利于提高异氰脲酸酯的固化性能、硬度、耐热性和耐候性，同时由于杂原子的引入使得改性后的异氰脲酸酯固化后与基材具有更好的附着力。
更优选地，氧杂环丁烷改性的异氰脲酸酯具有(I)、(Ⅱ)或(Ⅲ)所示的结构：
其中，各R
1、各R
2、各R
3与前文具有相同的定义。
本申请的又一方面还提供了一种能量固化组合物，包括基体树脂、活性单体和引发剂，活性单体包括本申请提供的氧杂环丁烷改性的异氰脲酸酯。
相比于现有的异氰脲酸酯，本申请提供的异氰脲酸酯具有更好的固化性能、硬度、耐热性和耐候性及附着力。因而含有上述氧杂环丁烷改性的异氰脲酸酯的能量固化物具有更加优异的综合性能。上述能量固化组合物的固化方式包括但不限于光固化和热固化。
本申请的再一方面还提供了一种本申请提供的氧杂环丁烷改性的异氰脲酸酯在固化领域的应用。
本发明提供的能量固化组合物的应用没有特别的限制，鉴于其优异的综合性能，因而其在固化领域具有较好的应用前景，包括但不限于涂料、油墨、粘合剂、光学材料、光学器件、密封材料等。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
制备实施例
实施例1
1-1的制备：
在250mL四口烧瓶中加入异氰脲酸12.9g(0.1mol)、1-乙基(3-氧杂环丁烷基)甲基缩水甘油醚61.6g(0.36mol)，甲苯50mL，100℃加热回流2h，得到第一聚合产物体系；
将上述第一聚合产物体系降至室温后，滴加27.0g丙烯酰氯(0.30mol)，常温搅拌过夜后倒入50mL去离子水中搅拌分层，接着用水(50毫升×5次)洗涤，甲苯萃取后旋蒸，乙腈重结晶得淡黄色液体32.1g，收率为39.5wt％，纯度为98.7％。MS(m/z)为808(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.83-0.84(s,9H),1.66-1.74(m,6H),3.47-3.67(m,12H)，4.14-4.40(m,12H),5.47-5.49(t,3H),5.84-6.40(m,15H)。
1-2的制备：
制备方法同上，区别在于：将丙烯酰氯的量换成18.0g(0.20mol)，重结晶后得淡黄色液体31.5g，收率为41.5wt％，纯度为98.9％。MS(m/z):754(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.83-0.84(s,9H),1.67-1.73(m,9H),3.25-3.71(m,13H)，4.15-4.42(m,15H),5.83-6.42(m,9H)。
1-3的制备：
制备方法同上，区别在于：将丙烯酰氯的量换成9.0g(0.10mol)，重结晶后得淡黄色液体30.0g，收率为42.4wt％，纯度为98.8％。MS(m/z):700(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.85-0.89(s,9H),1.69-1.73(m,6H),3.26-3.75(m,12H)，4.16-4.42(m,14H),5.53-6.50(m,12H)。
实施例2
2-1的制备：
在250mL四口烧瓶中加入异氰脲酸12.9g(0.1mol/L)、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(0.46mol)，甲苯50mL，105℃加热回流4h，得到第一聚合产物体系；
将上述第一聚合产物体系降至室温后，滴加27.0g丙烯酰氯(0.30mol)，常温搅拌过夜，后倒入50mL去离子水中搅拌分层，接着用水(50毫升×5次)洗涤，甲苯萃取后旋蒸，乙腈重结晶得淡黄色液体42.2g，收率为37.6wt％，纯度为96.8％。MS(m/z):1114(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.86-0.89(s,9H),1.64-1.74(m,12H),3.23-3.80(m,42H)，4.17-4.43(m,12H),5.52-6.48(m,12H)。
2-2的制备：
制备方法同上，将丙烯酰氯的量换成18.0g(0.25mol)，重结晶后得淡黄色液体37.1g，收率为33.4wt％，纯度为97.1％。MS(m/z):1059(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.84-0.88(s,9H),1.69-1.75(m,12H),3.23-3.78(m,42H)，4.14-4.45(m,13H),5.53-6.48(m,9H)。
2-3的制备：
制备方法同上，将丙烯酰氯的量换成9.0g(0.13mol)，重结晶后得淡黄色液体35.7g，收率为35.7wt％，纯度为97.5％。MS(m/z):992(M+1)
+。核磁氢谱数据为
1H NMR(400MHz,CDCl
3)δ0.84-0.89(s,9H),1.70-1.74(m,12H),3.26-3.75(m,42H)，4.16-4.42(m,14H),5.53-6.50(m,6H)。按照实施例1中的方法，可选用不同的原料实施实施例3至8，实施例3至8的反应原料及产物见表1。
表1
应用实施例：
(1)光固化产品的制备
按表2中所示的组成制备光固化产品。
表2
将上述的实施例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1000mj/cm
2)，观察其固化情况，采用指触法进行评价。升温至150℃，保温30min，测试其组合物的应用性能。
指触法评价：
1-油，不固；2-表面油，底层固化；3-表面粘，手触后指纹较重；
4-基本表干，手触后略发涩，淡指纹；5-完全固化，表面光滑，手触后无指纹。
(2)热固化产品的制备
按表3中所示的组成制备热固化产品。
表3
将上述实施例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，在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，H表示硬度，分为H、2H、3H、4H、5H、6H、7H、8H、9H个等级，且硬度依次增大。
(4)附着力测试
参考GB 1720-1979，测试固化膜的附着力。
评价结果记录在表4中。
表4
从表4中数据可知，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附着力。
需要说明的是，本申请的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的术语在适当情况下可以互换，以便这里描述的本申请的实施方式例如能够以除了在这里描述的那些以外的顺序实施。
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的制备方法，其特征在于，所述制备方法包括：使原料a和原料b进行第一聚合反应，得到第一聚合产物体系；将所述第一聚合产物体系和原料c进行第二聚合反应，得到所述氧杂环丁烷改性的异氰脲酸酯，所述原料a和所述原料c的结构式如下：所述X为卤元素；
所述原料b的结构式如下：其中
所述R 1选自氢原子、C 1～C 10的烷基；所述R 2选自C 1～C 10的直链或支链亚烷基，或上述基团中的一个或多个-CH 2-被-O-或芳基取代形成的第一取代基，且所述第一取代基中两个-O-不直接相连；所述R 3选自C 1～C 10的烷基；所述R 4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，或上述基团中的一个或多个氢原子被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团取代后形成的第二取代基；所述R 5选自C 1～C 20的亚烃基，或上述基团的主链中的一个或多个-CH 2-被氧原子取代形成的第三取代基，所述第三取代基中两个-O-不直接相连，或所述第三取代基中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团取代形成的第四取代基；所述m为1～8的整数。 - 根据权利要求1所述的氧杂环丁烷改性的异氰脲酸酯的制备方法，其特征在于，所述R1选自氢原子、C 1～C 5烷基；所述R 2选自C 1～C 5的直链或支链亚烷基，或上述基团中的一个或多个-CH 2-被-O-或芳基取代形成的第一取代基，且所述第一取代基中两个-O-不直接相连；所述R 3选自C 1～C 5的烷基；所述R 4为m价基团，选自C 1～C 10的直链或支链烷基、C 2～C 10的链烯基、C 2～C 10的环烷基、C 4～C 10的环烷基烷基、C 4～C 10的烷基环烷基，C 4～C 20的杂烷基或杂环基、苯基、联苯基、萘基或杂芳基，或上述基团中的一个或多个氢原子被选自烷基、苯基、卤素、硝基、烷氧基、羰基的基团取代后形成的第二取代基；所述R 5选自C 1～C 10的亚烃基，或上述基团的主链中的一个或多个-CH 2-被氧原子取代形成的第三取代基，所述第三取代基中两个-O-不直接相连，或所述第三取代基中的一个或多个氢原子可以独立地被选自烷基、卤素、硝基的基团取代形成的第四取代基；所述m为1～5的整数。
- 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的制备方法，其特征在于，所述原料b选自
组成的组中的一种或多种。
- 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的制备方法，其特征在于，所述原料a、所述原料b和所述原料c的摩尔数之比为1：(1～4.0)：(1～2.0)。
- 根据权利要求4所述的氧杂环丁烷改性的异氰脲酸酯的制备方法，其特征在于，所述第一聚合反应和所述第二聚合反应在有机溶剂的存在下进行，优选地，在所述第二聚合反应之后，所述氧杂环丁烷改性的异氰脲酸酯的制备方法还包括：将所述第二聚合反应的产物体系依次进行分相、水洗、萃取剂旋蒸及重结晶处理后，得到所述氧杂环丁烷改性的异氰脲酸酯。
- 根据权利要求4所述的氧杂环丁烷改性的异氰脲酸酯的制备方法，其特征在于，所述第一聚合反应的温度为80～200℃，反应时间为1～5h；所述第二聚合反应的温度为-5～40℃，反应时间为6～20h。
- 一种氧杂环丁烷改性的异氰脲酸酯，其特征在于，采用权利要求1至6中任一项所述的制备方法制得。
- 根据权利要求7所述的氧杂环丁烷改性的异氰脲酸酯，其特征在于，所述氧杂环丁烷改性的异氰脲酸酯具有(I)、(Ⅱ)或(Ⅲ)所示的结构：
其中，各所述R 1、各所述R 2、各所述R 3与权利要求1具有相同的定义。 - 一种能量固化组合物，包括基体树脂、活性单体和引发剂，其特征在于，所述活性单体包括权利要求7或8所述的氧杂环丁烷改性的异氰脲酸酯。
- 一种权利要求7或8所述的氧杂环丁烷改性的异氰脲酸酯在固化领域的应用。
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| US20070231745A1 (en) * | 2006-03-31 | 2007-10-04 | Fujifilm Corporation | Method for preparation of lithographic printing plate and lithographic printing plate precursor |
| CN102775363A (zh) * | 2012-08-06 | 2012-11-14 | 恒昌涂料（惠阳）有限公司 | 一种聚氨酯丙烯酸酯光敏树脂低聚物及制备方法 |
| CN105503755A (zh) * | 2016-01-10 | 2016-04-20 | 江苏博砚电子科技有限公司 | 一种彩色光阻用赛克基丙烯酸酯树脂及其制备方法 |
| JP2017132751A (ja) * | 2016-01-21 | 2017-08-03 | 四国化成工業株式会社 | オキセタン環を有するイソシアヌレート化合物、その合成方法および該イソシアヌレート化合物の利用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070231745A1 (en) * | 2006-03-31 | 2007-10-04 | Fujifilm Corporation | Method for preparation of lithographic printing plate and lithographic printing plate precursor |
| CN102775363A (zh) * | 2012-08-06 | 2012-11-14 | 恒昌涂料（惠阳）有限公司 | 一种聚氨酯丙烯酸酯光敏树脂低聚物及制备方法 |
| CN105503755A (zh) * | 2016-01-10 | 2016-04-20 | 江苏博砚电子科技有限公司 | 一种彩色光阻用赛克基丙烯酸酯树脂及其制备方法 |
| JP2017132751A (ja) * | 2016-01-21 | 2017-08-03 | 四国化成工業株式会社 | オキセタン環を有するイソシアヌレート化合物、その合成方法および該イソシアヌレート化合物の利用 |
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