WO2018010604A1 - 多官能度氧杂环丁烷类化合物及其制备方法 - Google Patents
多官能度氧杂环丁烷类化合物及其制备方法 Download PDFInfo
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- WO2018010604A1 WO2018010604A1 PCT/CN2017/092227 CN2017092227W WO2018010604A1 WO 2018010604 A1 WO2018010604 A1 WO 2018010604A1 CN 2017092227 W CN2017092227 W CN 2017092227W WO 2018010604 A1 WO2018010604 A1 WO 2018010604A1
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- GQYZURCXLMNNRM-UHFFFAOYSA-N CCC(C)(CC(C)(C)N=C=O)N=C=O Chemical compound CCC(C)(CC(C)(C)N=C=O)N=C=O GQYZURCXLMNNRM-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C)C1OC1COC(COC(C)(C)*)N(C1CC1)OCC1(COC1)C1(C2)C2C1 Chemical compound CCC(C)C1OC1COC(COC(C)(C)*)N(C1CC1)OCC1(COC1)C1(C2)C2C1 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Cc(ccc(N=C=O)c1)c1N=C=O Chemical compound Cc(ccc(N=C=O)c1)c1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N O=C=NCc1ccc(CN=C=O)cc1 Chemical compound O=C=NCc1ccc(CN=C=O)cc1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N O=C=Nc1ccc(Cc(cc2)ccc2N=C=O)cc1 Chemical compound O=C=Nc1ccc(Cc(cc2)ccc2N=C=O)cc1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- 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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
-
- 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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
Definitions
- the invention belongs to the field of organic chemistry, and particularly relates to a polyfunctional oxetane compound and a preparation method thereof.
- the cationic photocuring system has the advantages of being unaffected by oxygen inhibition and having a small volume shrinkage.
- the reactive diluent monomers used are mainly vinyl ether compounds, epoxy compounds and oxetane. Class of compounds.
- the epoxy-based monomer can give a cured product having good heat resistance, adhesion, and chemical resistance, but the monomer has low reactivity.
- the vinyl ether monomer has high polymerization activity, but its hardness, abrasion resistance, chemical resistance and the like are inferior, and it cannot be used as a protective film for a hard coating agent and various substrates.
- oxetane monomers have high reactivity and are excellent in physical properties after curing, and thus are increasingly used in cured compositions.
- the use of oxetane monomers in combination with epoxy monomers has become a common form of cationic photocuring systems.
- Cipheral Patent No. CN103497691A discloses a photocurable adhesive composition for the manufacture of a polarizing plate, which is a bifunctional oxetane compound.
- Compound a is used in combination with an epoxy compound to provide a significant improvement in the balance of adhesion and durability;
- a bifunctional oxetane compound is disclosed in Japanese Patent No. 4003264B2 (Compound b) can significantly increase the curing speed of the cationic curing system.
- the polyfunctionalization of oxetane monomers has attracted attention in many fields of application, such as adhesives, sealants, encapsulants, and the like, particularly those used in components and assemblies of LED devices. This is also an inevitable trend in the development of oxetane-based cationically polymerizable monomers.
- the polyfunctional oxetane monomers reported in the existing literature still have shortcomings. The outstanding point is that the hardness, flexibility and adhesion properties of the post-cured products are difficult to be well balanced. The overall performance still needs to be further improved.
- polyfunctional oxetane compounds having higher reactivity and superior application properties and a process for the preparation thereof.
- These polyfunctional oxetane-based cationically polymerizable monomers are used in combination with an epoxy compound to have a high curing speed, and the cured product is excellent in hardness, flexibility, adhesion, and heat resistance.
- the present invention first provides a polyfunctional oxetane compound having the structure represented by the general formula (I):
- R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 20 m-valent alkenyl group, or a C 6 -C 40 m-valent aryl group, wherein -CH 2 - Optionally optionally oxygen atoms, -NH- or Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;
- R 2 represents a C 1 -C 20 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked, and optionally , one or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;
- R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C An alkylcycloalkyl group of 20 , a C 2 -C 10 alkenyl group or a C 6 -C 20 aryl group, optionally, one or more of the hydrogen atoms of these groups may be independently selected from the group consisting of an alkane Substituted by a group of a halogen, a nitro group;
- n an integer from 1-8.
- the compound of the above formula (I) contains two or more oxetane groups.
- R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 10 linear or branched m-valent alkenyl group, or a C 6 -C 30 a m-valent aryl group, wherein -CH 2 - may be optionally taken up by an oxygen atom, -NH- or Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group.
- R 1 may be selected from the following structures: a linear or branched 1-4 valent alkyl group of C 1 -C 12 , a linear or branched 1-4 valent alkenyl group of C 2 -C 6 , CH 3 -O-CH 2 CH 2 *, *CH 2 CH 2 -NH-CH 2 CH 2 *,
- R 2 represents a C 1 -C 10 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that the two -O- are not directly bonded. Further preferably, R 2 represents a C 1 -C 6 straight or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked .
- R 3 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 Alkylcycloalkyl, C 2 -C 8 alkenyl, phenyl. Further preferably, R 3 represents a C 1 -C 4 linear or branched alkyl group, or a C 4 -C 8 cycloalkylalkyl group.
- m is preferably an integer of from 1 to 6, more preferably an integer of from 1 to 4.
- C 1 -C 10 includes C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , "integer of 1-4" includes 1, 2, 3, 4.
- the present invention also relates to a process for producing a polyfunctional oxetane compound represented by the above formula (I), which comprises a hydroxyl group-containing compound represented by the formula (II) and an oxygen group represented by the formula (III).
- the heterocyclic butane alkyl epoxy compound is used as a raw material, and the product is obtained by reacting in the presence of a catalyst, and the reaction formula is as follows:
- the catalyst used may be: an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like; an alkali metal salt of an alcohol such as sodium methoxide, potassium ethoxide, sodium t-butoxide or the like; alkali metal carbonate a salt such as sodium carbonate, potassium carbonate or the like; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; an alkyl metal lithium compound such as butyl lithium, phenyl lithium or the like; an amine lithium compound such as two different Lithium propylamino, lithium hexamethyldisilazide, and the like.
- the amount of the catalyst used can be easily determined by those skilled in the art, and preferably, the amount of the catalyst is from 0.1 to 20%, more preferably from 1 to 20%, based on the mole of the compound of the formula (II).
- the reaction system may optionally contain an organic solvent depending on the kind of the raw material.
- the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N,N.
- An amide solvent such as dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; or an aromatic solvent such as benzene, toluene or xylene.
- These solvents may be used singly or in combination of two or more. The total amount may be appropriately adjusted depending on the homogeneity and stirring property of the reaction system, which is easily determined by those skilled in the art.
- the reaction temperature varies depending on the kind of the raw material, and is usually 25 to 200 ° C, preferably 50 to 150 ° C.
- the present invention provides a cationically polymerizable monomer produced by reacting a polyfunctional oxetane compound represented by the above formula (I) with epichlorohydrin, which has a structure represented by the formula (IV) :
- R 1 , R 2 , R 3 and m have the same definitions as described in the general formula (I).
- the method for preparing a cationically polymerizable monomer represented by the formula (IV) comprises: reacting a polyfunctional oxetane compound represented by the formula (I) with epichlorohydrin under alkaline conditions;
- a basic compound such as an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like; an alkali metal carbonate such as sodium carbonate, potassium carbonate or the like; an alkali metal hydrogencarbonate may be added to the reaction system. Salts such as sodium hydrogencarbonate, potassium hydrogencarbonate, and the like.
- the basic compound can facilitate the progress of the reaction, and the amount thereof can be easily determined by those skilled in the art.
- the basic compound is used in an amount of 1 to 20 times, more preferably m-, the molar amount of the compound of the formula (I). 10 times.
- an organic solvent may be selectively used as a carrier medium in the reaction system depending on the kind of the raw material.
- the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, acetonitrile or propylene.
- Nitrile solvent such as nitrile or benzonitrile
- amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone
- ether such as tetrahydrofuran or dioxane Solvent
- aromatic solvent such as benzene, toluene or xylene.
- the present invention provides a cationically polymerizable monomer obtained by reacting a compound represented by the above formula (I) with an ester compound represented by the formula (V).
- R 4 represents an n-valent linking group
- R 5 represents a C 1 -C 10 linear or branched alkyl group
- n represents an integer of 1-8;
- the condition is that the cationically polymerizable monomer has at least two oxetane groups.
- R 4 represents a C 1 - C 20 linear or branched n-valent alkyl group, a C 2 - C 20 n-valent alkenyl group, and C 3 20 monovalent -C n cycloalkyl, n-valent C 4 -C 20 cycloalkylalkyl group, an n-valent C 4 -C 20 alkylcycloalkyl, or n-valent aryl group of C 6 -C 40;
- -CH 2 - in these groups may be substituted by an oxygen atom or a 1,4-phenylene group, provided that two -O- are not directly bonded; optionally, one of these groups or
- a plurality of hydrogen atoms may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group.
- R 4 represents a C 1 -C 10 linear or branched n-valent alkyl group, a C 2 -C 10 n-valent alkenyl group, a C 3 -C 10 n-valent cycloalkyl group, C 4 -C n value of 10 cycloalkylalkyl, C n valence 4 -C 10 alkylcycloalkyl, C 6 -C n or a divalent aromatic group 20; optionally, these groups are -CH 2 - may be substituted by an oxygen atom or a 1,4-phenylene group, provided that the two -O- are not directly bonded.
- R 4 represents a C 1 -C 8 linear or branched n-valent alkyl group, a C 7 -C 12 n-valent aryl group, or an n-valent phenyl group.
- R 5 is selected from a linear or branched alkyl group of C 1 - C 4 , particularly a methyl group and an ethyl group.
- n is an integer from 1 to 4.
- ester compound represented by the formula (V) is selected from the following compounds, but is not limited to these compounds:
- the method for producing the above cationically polymerizable monomer comprises a transesterification reaction of a polyfunctional oxetane compound represented by the formula (I) and an ester compound represented by the formula (V) in the presence of a catalyst.
- the catalyst used in the reaction is preferably a titanate compound, more preferably 2-ethylhexyl titanate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate.
- a titanate compound more preferably 2-ethylhexyl titanate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate.
- the amount of the catalyst used can be readily determined by those skilled in the art.
- the amount of the catalyst is from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the compound of the formula (I).
- the reaction system contains an organic solvent as a carrier medium, and the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, such as benzene, toluene, xylene, and the like.
- the amount of the solvent to be used can be appropriately adjusted depending on the uniformity and agitation of the reaction system, which is easily determined by those skilled in the art.
- the reaction temperature varies depending on the kind of the raw material, and is usually from 0 to 200 ° C, preferably from 50 to 150 ° C.
- the product is obtained by washing with water, filtration, and distillation under reduced pressure.
- the present invention provides a cationically polymerizable monomer obtained by reacting a compound represented by the above formula (I) with an isocyanate compound represented by the formula (VI).
- R 6 represents a p-valent linking group, and p represents an integer of 1 to 8; provided that the cationically polymerizable monomer has at least two oxetane groups.
- R 6 represents a C 1 - C 20 linear or branched p-valent alkyl group, a C 2 - C 20 p-valent alkenyl group, or C.
- -CH 2 - in these groups may be substituted by an oxygen atom or 1,4-phenylene, provided that two -O- are not directly attached; optionally, one of these groups Or a plurality of hydrogen atoms may be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group.
- R 6 represents a C 1 -C 10 linear or branched p-valent alkyl group, a C 2 -C 10 p-valent alkenyl group, a C 3 -C 10 p-valent cycloalkyl group, a C 4 a p-valent cycloalkylalkyl group of -C 10 , a p-valent alkylcycloalkyl group of C 4 -C 10 , a p-valent aryl group of C 6 -C 20 ; optionally, -CH 2 - in these groups It may be substituted by an oxygen atom or a 1,4-phenylene group, provided that two -O- are not directly bonded; optionally, one or more of the hydrogen atoms of these groups may be independently substituted by an alkyl group.
- R 6 represents a C 1 -C 8 linear or branched p-valent alkyl group, a C 6 -C 12 p-valent aryl group; optionally, -CH 2 - in these groups may be an oxygen atom or a substituted 1,4-phenylene, provided that the two are not directly linked -O-; optionally, one of these groups or more hydrogen atoms may be independently a C 1 -C 4 alkyl Substituted by the base.
- p is an integer from 1 to 4.
- the isocyanate compound represented by the formula (VI) is selected from the following compounds, but is not limited to these compounds:
- the method for producing the above cationically polymerizable monomer comprises reacting a polyfunctional oxetane compound represented by the formula (I) with an isocyanate compound represented by the formula (VI) in the presence of a catalyst.
- the catalyst is dibutyltin laurate in an amount of from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the compound of formula (I).
- an organic solvent may be selectively used as a carrier medium in the reaction system depending on the kind of the raw material.
- the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without affecting the reaction, and may be, for example, acetonitrile or propylene.
- Nitrile solvent such as nitrile or benzonitrile
- amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone
- ether such as tetrahydrofuran or dioxane Solvent
- aromatic solvent such as benzene, toluene or xylene.
- the reaction temperature varies depending on the kind of the raw material, and is usually from 0 to 100 ° C, preferably from 20 to 80 ° C.
- the polyfunctional oxetane compound represented by the formula (I) is reacted with epichlorohydrin, an ester compound represented by the formula (V) or an isocyanate compound represented by the formula (VI).
- the oxetane compound can exhibit similar or superior properties to the compound of the formula (I). By introducing a new functional group in the general formula (I), a better performance adjustability can be obtained to meet different system application requirements.
- Compound 5 was prepared by the procedure of Example 1, and its structure was confirmed by GC-MS and 1 H-NMR.
- the product 7-13 having the structure shown in Table 1 was synthesized from the corresponding reagent.
- the application properties of the polyfunctional oxetane monomers of the present invention are evaluated by formulating exemplary photocurable compositions, including curing speed, hardness, flexibility, adhesion, heat resistance and the like.
- TTA21 and E-51 are represented by epoxy monomers
- PAG-202 is used as a cationic photoinitiator
- compounds a and/or b described in the background are used as comparative polyfunctional oxetane.
- Alkane monomer Alkane monomer.
- the raw materials were placed in the mass parts shown in Table 2, and after mixing uniformly in the dark room, about 1 mg of the sample was weighed and spread on aluminum crucible.
- the samples were scanned and cured using a Perkin Elmer Differential Scanning Calorimeter (DSC 8000) equipped with a mercury arc lamp UV source (OmniCure-S2000).
- the polyfunctional oxetane monomer of the present invention is used in combination with an epoxy monomer in a cationic photocuring system, and has a fast curing speed, which is superior to the existing structural compound of the same type. b.
- the polyfunctional oxetane monomer or compounds a and b of the present invention are mixed with the epoxy monomer TTA21 in a 1:1 mass ratio, and then the 2% initiator PAG-202 is added, and stirred and mixed in a dark room. After homogenization, the formulation was applied to a sandpaper-polished tinplate substrate with a 25# wire rod to obtain a coating having a thickness of about 25 ⁇ m, and then fully exposed in a crawler exposure machine (RW-UV.70201). The single exposure was 80 mj/cm2 and then tested after 24 hours.
- the cured film was tested at a temperature of 23 ° C and a relative humidity of 50%.
- the pencil hardness evaluation method specified in GB/T 6739-2006 was used as a standard, and the pencil was inserted into the test instrument and fixed with a clip to maintain the level. Place the tip of the pencil on the surface of the paint film and push it at a distance of 1 mm/s away from itself by at least 7 mm. If no scratches occur, repeat the test in the untested area and replace the pencil with a higher hardness until at least 3 mm long.
- the hardness of the coating is indicated by the hardness of the hardest pencil which does not scratch the coating.
- the cured film was tested at a temperature of 23 ° C and a relative humidity of 70%.
- the outer side of the tinplate coated with the cured coating was sequentially wound in the longitudinal direction based on the GB/T1731-93 paint film flexibility test method.
- the cured film was tested at a temperature of 23 ° C and a relative humidity of 50%.
- the coating film is cut into a hundred grid, the cutting edge is to be cut with the substrate, and the cutting edge is sharp, and the cutting edge and the coating film are formed. 45-degree angle.
- Use a soft brush to remove the paint scraps stick the 3M transparent tape on the lined 100 grids, and apply force to make the tape firmly adhere to the film surface and the cross-section.
- Within 2 min hold one end of the 3M tape at a 60 degree angle and smoothly peel off the tape within 1 second and evaluate according to the following criteria.
- Level 0 The cutting edge is completely smooth and has no shedding
- Level 1 There is a little coating peeling off at the intersection of the incisions, but the cross-cut area is not affected by significantly more than 5%;
- Level 2 There is a coating peeling off at the intersection of the incision and/or along the edge of the incision, which is significantly affected by more than 5%, but not significantly greater than 15%;
- Level 3 The coating peels off partially or completely along the cutting edge with large fragments, and/or partially or completely peels off at different parts of the lattice.
- the affected cross-cut area is significantly greater than 15%, but not significantly greater than 35%;
- Level 4 The coating peels off along the cutting edge, and/or some of the squares are partially or completely detached, and the affected cross-cut area is significantly greater than 35%, but not significantly greater than 65%;
- Level 5 The degree of peeling exceeds level 4.
- the cured film was tested by differential scanning calorimeter (PE DSC 8000) under the nitrogen atmosphere at a rate of 10 ° C/min from -20 ° C to 200 ° C, at 200 ° C for 1 min, then at 10 ° C / The rate of min was cooled from 200 ° C to -20 ° C, held at -20 ° C for 1 min, and then heated from -20 ° C to 200 ° C at a rate of 10 ° C / min, thereby measuring the glass transition temperature Tg (° C.).
- PE DSC 8000 differential scanning calorimeter
- thermogravimetric analyzer PE STA6000
- T thermal decomposition temperature
- the thermal decomposition temperature T (°C) above 300 is indicated as: ⁇ ;
- the thermal decomposition temperature T (°C) is above 250-300 and is recorded as: ⁇ ;
- the thermal decomposition temperature T (°C) is expressed as 250 or less: ⁇ .
- the polyfunctional oxetane compound of the present invention has a significant advantage in hardness, flexibility, adhesion, and heat resistance after being applied to a cationic photocuring system as compared with the compound a; Compared with the compound b which is closer in structure, the present invention exhibits better performance in terms of flexibility, adhesion, and heat resistance, and the overall performance is more excellent.
- the polyfunctional oxetane compound of the invention has excellent application performance in a cationic photocuring system, has good structure and performance adjustability, and can meet different system application requirements.
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Abstract
Description
Claims (26)
- 一种多官能度氧杂环丁烷类化合物,其特征在于,所述化合物具有通式(I)所示结构:其中,R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基或C6-C40的m价芳基,其中的-CH2-可任选地被氧原子、-NH-或者所取代,条件是两个-O-不直接相连;并且任选地,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;R2表示C1-C20的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连,并且任选地,基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;R3表示氢、卤素、硝基、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C2-C10的链烯基或C6-C20的芳基,任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;m表示1-8的整数。
- 根据权利要求1所述的多官能度氧杂环丁烷类化合物,其特征在于,m取2以上的数值;或者当m=1时,R1中含有至少1个氧杂环丁烷基团。
- 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物,其特征在于,R2表示C1-C10的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连;优选地,R2表示C1-C6的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连。
- 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物,其特征在于,R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基或苯基;优选地,R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
- 根据权利要求1或2所述的多官能度氧杂环丁烷类化合物,其特征在于,m为1-6的整数,优选1-4的整数。
- 根据权利要求10所述的阳离子聚合性单体,其特征在于,通式(V)所示酯化合物中,R4表示C1-C20的直链或支链的n价烷基、C2-C20的n价链烯基、C3-C20的n价环烷基、C4-C20的n价环烷基烷基、C4-C20的n价烷基环烷基、C6-C40的n价芳基;任选地,这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代,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。
- 根据权利要求10或11所述的阳离子聚合性单体,其特征在于,R4表示C1-C10的直链或支链的n价烷基、C2-C10的n价链烯基、C3-C10的n价环烷基、C4-C10的n价环烷基烷基、C4-C10的n价烷基环烷基、C6-C20的n价芳基;任选地,这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代,条件是两个-O-不直接相连。
- 根据权利要求10或11所述的阳离子聚合性单体,其特征在于,R4表示C1-C8的直链或支链的n价烷基、C7-C12的n价芳基、n价苯基。
- 根据权利要求10所述的阳离子聚合性单体,其特征在于,R5选自C1-C4的直链或支链烷基,优选R5选自甲基或乙基。
- 根据权利要求10所述的阳离子聚合性单体,其特征在于,n为1-4的整数。
- 权利要求10至15中任一项所述的阳离子聚合性单体的制备方法,包括:通式(I)所示多官能度氧杂环丁烷类化合物与通式(V)所示酯化合物在催化剂存在条件下进行酯交换反应。
- 根据权利要求16所述的制备方法,其特征在于,所述酯交换反应中使用的催化剂是钛酸酯类化合物,优选地,所述催化剂为钛酸-2-乙基己酯、钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯中的一种或两种以上的组合。
- 根据权利要求18所述的阳离子聚合性单体,其特征在于,R6表示C1-C20的直链或支链的p价烷基、C2-C20的p价链烯基、C3-C20的p价环烷基、C4-C20的p价环烷基烷基、C4-C20的p价烷基环烷基、C6-C40的p价芳基;任选地,这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代,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。
- 根据权利要求18或19所述的阳离子聚合性单体,其特征在于,R6表示C1-C10的直链或支链的p价烷基、C2-C10的p价链烯基、C3-C10的p价环烷基、C4-C10的p价环烷基烷基、C4-C10的p价烷基环烷基、C6-C20的p价芳基;任选地,这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代,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烷基所取代。
- 根据权利要求18或19所述的阳离子聚合性单体,其特征在于,R6表示C1-C8的直链或支链的p价烷基、C6-C12的p价芳基;任选地,这些基团中的-CH2-可被氧原子或者1,4-亚苯基所取代,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C1-C4的烷基所取代。
- 根据权利要求18所述的阳离子聚合性单体,其特征在于,p为1-4的整数。
- 权利要求18至22中任一项所述的阳离子聚合性单体的制备方法,其特征在于,所述制备方法包括:通式(I)所示多官能度氧杂环丁烷类化合物与通式(VI)所示异氰酸酯化合物在催化剂存在条件下反应,得到所述阳离子聚合性单体。
- 根据权利要求23所述的制备方法,其特征在于,所述催化剂为月桂酸二丁基锡。
- 权利要求1至6中任一项所述的多官能度氧杂环丁烷类化合物、或者权利要求8、10至15和18至22中任一项所述的阳离子聚合性单体在阳离子光固化组合物中的应用。
- 根据权利要求25所述的应用,其特征在于,所述光固化组合物中含有环氧类单体。
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Publication number | Publication date |
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JP6773815B2 (ja) | 2020-10-21 |
US11555022B2 (en) | 2023-01-17 |
CN107619399A (zh) | 2018-01-23 |
JP2019521118A (ja) | 2019-07-25 |
CN107619399B (zh) | 2021-04-27 |
US20190144405A1 (en) | 2019-05-16 |
EP3486238A1 (en) | 2019-05-22 |
KR20190028689A (ko) | 2019-03-19 |
US20210053929A1 (en) | 2021-02-25 |
EP3486238A4 (en) | 2020-01-22 |
EP3486238B1 (en) | 2021-06-16 |
US10906882B2 (en) | 2021-02-02 |
KR102183004B1 (ko) | 2020-11-27 |
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