CN111848926A - Fluorine modified curing agent and preparation method thereof - Google Patents
Fluorine modified curing agent and preparation method thereof Download PDFInfo
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- CN111848926A CN111848926A CN202010632134.0A CN202010632134A CN111848926A CN 111848926 A CN111848926 A CN 111848926A CN 202010632134 A CN202010632134 A CN 202010632134A CN 111848926 A CN111848926 A CN 111848926A
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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
- C08G59/40—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 characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention relates to the technical field of curing agents, in particular to a fluorine modified curing agent and a preparation method thereof. The raw materials of the fluorine modified curing agent comprise a compound with a general formula (I), an amine compound and a fluorine-containing monomer; the molar ratio of the compound of the general formula (I) to the amine compound is 1: (1-10); the compound of the general formula (I) is:
wherein, R is1Represents a hydrogen atom, a C1-C5 alkyl group; the R is2Alkyl of C2-C20, - (R)e‑O‑Rf‑O‑Rg) -; wherein, R ise、Rf、RgEach independently represents an alkyl group having 3-6 carbon atoms or an alkenyl group having 3-6 carbon atoms. The fluorine modified curing agent prepared by the invention has obviously improved mechanical property, corrosion resistance and weather resistance.
Description
Technical Field
The invention relates to the technical field of curing agents, in particular to a fluorine modified curing agent and a preparation method thereof.
Background
The epoxy resin not only has epoxy groups and hydroxyl groups with higher activity, but also contains more stable benzene rings and ether bond structures, and after curing and crosslinking by a curing agent, the epoxy resin has very excellent adhesive force, mechanical properties and corrosion resistance, thereby being widely applied. However, the development of the product is limited because the carbon-carbon bond energy is small, so that the surface energy is high, and the product is hard and brittle and has poor weather resistance.
At present, a great deal of modification is carried out on epoxy resin, such as: hydrogenated epoxy resins have been developed, but their use has been limited due to their high price. At present, fluorine modifiers are introduced by two methods, namely a physical method and a chemical method, wherein the physical method has low requirement on simple operation, but the problem of uneven dispersion is easy to exist, and the stability of the product is influenced. The chemical method can obtain products with uniform structures, at present, the method is more researched, but most of the methods are directly added with a fluorine modifier instead of a fluorine-containing monomer, the performance of the epoxy resin is difficult to improve from the molecular structure, and most of the methods produce the fluorine modified epoxy resin at present, have long production period after research and development, and have great influence on the curing process parameters of the epoxy resin.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fluorine modified curing agent in a first aspect, wherein the raw materials of the fluorine modified curing agent comprise a compound of a general formula (I), an amine compound and a fluorine-containing monomer; the molar ratio of the compound of the general formula (I) to the amine compound is 1: (1-10); the compound of the general formula (I) is:
wherein, R is1Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is2Represents C2-C20 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R is e、Rf、RgEach independently represents a C3-C6 alkyl group or a C3-C6 alkenyl group.
As a preferred technical scheme, the R is2Represents C2-C10 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C5 alkyl group.
As a preferred technical scheme, the R ise、Rf、RgEach independently represents a C3-C4 branched alkyl group or a C3-C4 linear alkyl group.
As a preferred technical scheme, the fluorine-containing monomer is fluorine-substituted acrylic acid and/or a compound of a general formula (II); the compound of the general formula (II) is:
wherein, R is3Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is4Represents any one of a fluorine-substituted C1-C20 alkyl group, a fluorine-substituted C2-C20 alkenyl group, a fluorine-substituted C2-C20 alkynyl group, a fluorine-substituted C1-C20 alkoxy group, a fluorine-substituted C1-C10 acyl group and a fluorine-substituted aryl group.
As a preferred technical scheme, the R is4Represents a fluorine-substituted C1-C10 alkyl group.
As a preferable technical scheme, the fluorine substituted C1-C10 alkyl is selected from one or more of trifluoro substituted C1-C10 alkyl, tetrafluoro substituted C1-C10 alkyl, pentafluoro substituted C1-C10 alkyl, hexafluoro substituted C1-C10 alkyl, heptafluoro substituted C1-C10 alkyl, octafluoro substituted C1-C10 alkyl, nonafluoro substituted C1-C10 alkyl and dodecafluoro substituted C1-C10 alkyl.
As a preferable technical scheme, the mass of the fluorine-containing monomer is 1-10 wt% of the total mass of the compound of the general formula (I) and the amine compound.
As a preferred technical scheme, the amine compound is selected from R5NH2、
Wherein R is5、R6、R7、R8Each independently represents any one of an alkyl group having 2-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, and an aryl group having 6-20 carbon atoms.
As a preferred technical scheme, the R is7、R8Each independently represents a C2-C5 linear alkyl group.
The second aspect of the present invention provides a method for preparing the fluorine modified curing agent, comprising the following steps:
under the protection of water bath nitrogen, dropwise adding the compound of the general formula (I) into an amine compound, and reacting for 2-48 h; then, dropwise adding fluorine-containing monomer, reacting for 1-24h, and determining the reaction end point through chromatography and amine value titration.
The third aspect of the invention provides an application of the fluorine modified curing agent in the fields of automobiles, electronic material adhesives and the like.
Has the advantages that: according to the fluorine modified curing agent provided by the invention, the fluorine-containing monomer is introduced, so that the fluorine modified curing agent not only has excellent hardness and adhesive force of epoxy resin, but also enhances the weather resistance and water resistance of the resin; the preparation method of the fluorine modified curing agent has shorter production period from research and development than that of fluorine modified epoxy resin, has small influence on curing process parameters of the epoxy resin, and has simple process, easy operation and low requirement on equipment.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the technical problems, the invention provides a fluorine modified curing agent in a first aspect, wherein the raw materials of the fluorine modified curing agent comprise a compound of a general formula (I), an amine compound and a fluorine-containing monomer; the molar ratio of the compound of the general formula (I) to the amine compound is 1: (1-10); the compound of the general formula (I) is:
wherein, R is1Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is2Represents C2-C20 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C6 alkyl group or a C3-C6 alkenyl group.
In one embodiment, the molar ratio of the compound of formula (I) to the amine compound is 1: (2-5).General formula (VII) (I) Of (a) a compound
In one embodiment, the compound of formula (i) is:
wherein, R is1Represents a hydrogen atom or an alkyl group having from C1 to C3; the R is2Represents C2-C10 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C6 alkyl group.
In a preferred embodiment, R is1Represents any of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
More preferably, R is1Represents a hydrogen atom or a methyl group.
In a preferred embodiment, R is2Represents C2-C10 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C5 alkyl group.
In a preferred embodiment, R is2Represents C2-C6 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C5 alkyl group.
In a preferred embodiment, the C2-C6 alkyl group is selected from-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH(CH3)CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH(CH3)CH2-、-CH2C(CH3)2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH(CH3)CH2-、-CH2CH2CH(CH3)CH2CH2-one or more of (a) and (b).
More preferably, the C2-C6 alkyl is selected from-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-one or more of (a) and (b).
In a preferred embodiment, R ise、Rf、RgEach independently represents a C3-C4 branched alkyl group or a C3-C4 linear alkyl group.
In a preferred embodiment, R ise、Rf、RgEach independently represents a branched alkyl group of C3-C4.
In a preferred embodiment, the C3-C4 branched alkyl group is-CH2CH(CH3)CH2-or-CH2CH(CH3)-。
More preferably, the branched alkyl group of C3-C4 is-CH2CH(CH3)-。
In a more preferred embodiment, the method comprisesR2represents-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-(Re-O-Rf-O-Rg) -any of; wherein, R ise、Rf、RgEach independently represents-CH2CH(CH3)-。
In a most preferred embodiment, the compound of formula (I) is A1，A1Is represented by the structural formula:
wherein R is11Represents a hydrogen atom, R21Is represented by (R)e-O-Rf-O-Rg) -and said Re、Rf、RgEach independently represents-CH2CH(CH3) -; or a compound of the formula (I) is A2，A2Is represented by the structural formula:
wherein R is12Represents a hydrogen atom, R22represents-CH2CH2CH2CH2-; or a compound of the formula (I) is A3，A3Is represented by the structural formula:
wherein R is13Represents a hydrogen atom, R23represents-CH2CH2CH2CH2CH2CH2-; or a compound of the formula (I) is A4，A4Is represented by the structural formula:
wherein R is14Represents a methyl group, R24represents-CH2CH2-。
Amine compound
In one embodiment, the amine compound is selected from R5-NH2、
Wherein R is5、R6、R7、R8Each independently represents any one of an alkyl group having 2-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, and an aryl group having 6-20 carbon atoms.
In a preferred embodiment, R is 5An alkyl group having a cyclohexyl group and representing C6-C10.
In a preferred embodiment, the C6-C10 cyclohexyl-containing alkyl group is selected from one or more of 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-n-propylcyclohexyl, 2-isopropylcyclohexyl, 2-n-butylcyclohexyl, 3, 5-trimethylcyclohexyl.
More preferably, the C6-C10 alkyl containing cyclohexyl is selected from one or more of 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, and 3,3, 5-trimethylcyclohexyl.
In a more preferred embodiment, R is5-NH2Wherein R is5Represents any of 2-methylcyclohexyl group, 3-methylcyclohexyl group, and 4-methylcyclohexyl group.
In a most preferred embodiment, R is5-NH2Is B11，B11Is represented by the structural formula (II)51-NH2Wherein R is51Represents a 2-methylcyclohexyl group.
In a preferred embodiment, R is6Straight-chain alkyl radicals representing C2-C10 or
In a preferred embodiment, the C2-C10 linear alkyl groups are selected from-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-one or more of (a) and (b).
More preferably, the C2-C10 linear alkyl is-CH2CH2-and/or-CH2CH2CH2CH2CH2CH2-。
In a more preferred embodiment, R is 6represents-CH2CH2-、-CH2CH2CH2CH2CH2CH2-, or
Any of the above.
In a most preferred embodiment, the method comprises
Is B21，B21The structural formula of (A) is:
wherein R is61represents-CH2CH2CH2CH2CH2CH2-; or
Is B22，B22The structural formula of (A) is:
wherein R is62represents-CH2CH2-; or
Is B23，B23The structural formula of (A) is:
wherein R is63To represent
In a preferred embodiment, R is7、R8Each independently represents a C2-C5 linear alkyl group.
In a preferred embodiment, the C2-C5 linear alkyl groups are selected from-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-one or more of (a) and (b).
More preferably, the C2-C5 linear alkyl is-CH2CH2-。
In a more preferred embodiment, R is7、R8All represent-CH2CH2-。
In a most preferred embodiment, the method comprises
Is B31，B31The structural formula of (A) is:
wherein R is71represents-CH2CH2-。
In a most preferred embodiment, the method comprises
Is B41，B41The structural formula of (A) is:
wherein R is81represents-CH2CH2-。
In one embodiment, the mass of the fluorine-containing monomer is 1 to 10 wt% of the total mass of the compound of the general formula (I) and the amine compound.
Preferably, the mass of the fluorine-containing monomer is 3-10 wt% of the total mass of the compound of the general formula (I) and the amine compound.
More preferably, the amount of the fluorine-containing monomer is 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, or 10 wt% of the total amount of the compound of the general formula (I) and the amine compound.
Fluorine-containing monomer
In one embodiment, the fluoromonomer is a fluorine substituted acrylic acid and/or a compound of formula (II); the compound of the general formula (II) is:
wherein, R is3Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is4Represents any one of a fluorine-substituted C1-C20 alkyl group, a fluorine-substituted C2-C20 alkenyl group, a fluorine-substituted C2-C20 alkynyl group, a fluorine-substituted C1-C20 alkoxy group, a fluorine-substituted C1-C10 acyl group and a fluorine-substituted aryl group.
In a preferred embodiment, the fluoromonomer is a compound of formula (II); the compound of the general formula (II) is:
wherein, R is3Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is4Represents any one of a fluorine-substituted C1-C20 alkyl group, a fluorine-substituted C2-C20 alkenyl group, a fluorine-substituted C2-C20 alkynyl group, a fluorine-substituted C1-C20 alkoxy group, a fluorine-substituted C1-C10 acyl group and a fluorine-substituted aryl group.
In a preferred embodimentIn the embodiment (1), the R is3Represents any of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, a 2-pentyl group and a 3-pentyl group.
More preferably, R is3Represents a hydrogen atom or a methyl group.
In a preferred embodiment, R is 4Represents a fluorine-substituted C1-C10 alkyl group.
In a preferred embodiment, the fluorine substituted C1-C10 alkyl group is selected from one or more of trifluoro substituted C1-C10 alkyl group, tetrafluoro substituted C1-C10 alkyl group, pentafluoro substituted C1-C10 alkyl group, hexafluoro substituted C1-C10 alkyl group, heptafluoro substituted C1-C10 alkyl group, octafluoro substituted C1-C10 alkyl group, nonafluoro substituted C1-C10 alkyl group, and dodecafluoro substituted C1-C10 alkyl group.
More preferably, the fluorine-substituted C1-C10 alkyl is selected from one or more of trifluoro-substituted C1-C10 alkyl, hexafluoro-substituted C1-C10 alkyl, nonafluoro-substituted C1-C10 alkyl and dodecafluoro-substituted C1-C10 alkyl.
In a most preferred embodiment, R is4represents-CF3、-CF2CHFCF3、-CF2CF2CF2CF2CF2CHF2Any one of the above.
In a most preferred embodiment, the fluoromonomer is C1Said C is1Is represented by the structural formula:
wherein, R is31Represents a methyl group, said R41represents-CF3(ii) a Or the fluorine-containing monomer is C2Said C is2Is represented by the structural formula:
wherein, R is32Represents a hydrogen atom, said R42represents-CF2CHFCF3(ii) a Or the fluorine-containing monomer is C3Said C is3Is represented by the structural formula:
wherein, R is33Represents a methyl group, said R 43represents-CF2CHFCF3(ii) a Or the fluorine-containing monomer is C4Said C is4Is represented by the structural formula:
wherein, R is34Represents a methyl group, said R44represents-CF2CF2CF2CF2CF2CHF2。
The second aspect of the present invention provides a method for preparing the fluorine modified curing agent, comprising the following steps:
under the protection of water bath nitrogen, dropwise adding the compound of the general formula (I) into an amine compound, and reacting for 2-48 h; then, dropwise adding fluorine-containing monomer, reacting for 1-24h, and determining the reaction end point through chromatography and amine value titration.
In one embodiment, the method for preparing the fluorine-modified curing agent comprises the following steps:
feeding the compound of the general formula (I) and the amine compound in proportion in a flask which is protected by nitrogen gas in a room-temperature water bath, slowly dropwise adding the compound of the general formula (I) into the amine compound, controlling the dropwise adding speed to finish the dropwise adding within 0.5-8 hours, and reacting for 2-48 hours; slowly dripping the fluorine-containing monomer into the reaction liquid for 1-24h, and determining the reaction end point by chromatography and amine value titration.
The applicant has unexpectedly found in the course of their research that when employed
And a fluorine-containing monomer
(said R is4Alkyl of C1-C10 representing fluorine substitution) and amine, introduces fluorine-containing groups, utilizes the characteristic of high fluorocarbon bond energy, and effectively solves the problem of low cost The problems of hardness, brittleness, poor weather resistance and the like of products caused by small carbon-hydrogen bond energy are obviously improved in mechanical property, corrosion resistance and weather resistance, the preparation period of the fluorine modified curing agent from research and development to production is shorter than that of fluorine modified epoxy resin, the influence on curing process parameters of the epoxy resin is small, the process is simple and easy to operate, and the requirement on equipment is low. More importantly, compared with fluorosilane, the molecular structure of the fluorine modified curing agent prepared by the invention is controlled singly, and the reason considered by the inventor is probably due to the fluorine-containing monomer
(said R is4Alkyl of C1-C10 representing fluorine substitution) can react at normal temperature or low temperature below 60 ℃ by using the Michael addition of the carbon-carbon double bond and amine, so that the reaction molecular structure can be better controlled, and the problems of uneven molecular weight distribution and the like of a curing agent prepared by fluorosilane modification after polycondensation due to high-temperature polycondensation under reaction conditions can be avoided. During further research, the inventor unexpectedly found that the amine compound is added first and then
The fluorine-containing monomer is added into the amine compound in a dropwise manner, and the amine compound is aliphatic amine or alicyclic amine, so that the heat resistance, the mechanical strength and the corrosion resistance are excellent, and the toxicity and the irritation of the aliphatic amine are reduced; furthermore, the amine compound is added first and then 
The fluorine modified curing agent is dripped into an amine compound, and finally, the fluorine-containing monomer is added, so that the reaction is not gelled, and the obtained fluorine modified curing agent has different molecular structures.
The third aspect of the invention provides an application of the fluorine modified curing agent in the fields of automobiles, electronic material adhesives and the like.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Example 1 provides a fluorine-modified curing agent, the raw material of which comprises a compound A of the general formula (I)1Amine compounds B21、B23And a fluorine-containing monomer C2；
A is described1Is represented by the structural formula:
wherein R is11Represents a hydrogen atom, R21Is represented by (R)e-O-Rf-O-Rg) -and said Re、Rf、RgEach independently represents-CH2CH(CH3)-；
B is21The structural formula of (A) is:
wherein R is61represents-CH2CH2CH2CH2CH2CH2-; b is23The structural formula of (A) is:
wherein R is63To represent 
Said C is2Is represented by the structural formula:
wherein, R is32Represents a hydrogen atom, said R42represents-CF2CHFCF3。
The preparation method of the fluorine modified curing agent comprises the following steps:
110.6g of amine compound B was put into a 500mL flask equipped with a nitrogen blanket in a room temperature water bath21And 55.5g of an amine compound B23Starting stirring to fully and uniformly stir, and slowly dropwise adding 143.7g of the compound A of the general formula (I)1Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 15.5g of fluoromonomer C2Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 2
Embodiment 2 provides a fluorine-modified curing agent, the raw material of which comprises a compound A of the general formula (I)2Amine compounds B21、B23And a fluorine-containing monomer C2；
A is described2Is represented by the structural formula:
wherein R is12Represents a hydrogen atom, R22represents-CH2CH2CH2CH2-；
B is21The structural formula of (A) is:
wherein R is61represents-CH2CH2CH2CH2CH2CH2-; b is23The structural formula of (A) is:
wherein R is63To represent
Said C is2Is represented by the structural formula:
wherein, R is32Represents a hydrogen atom, said R42represents-CF2CHFCF3。
The preparation method of the fluorine modified curing agent comprises the following steps:
115.5g of amine compound B was put into a 500mL flask equipped with a nitrogen blanket in a room temperature water bath 23And 58g of amine compound B21Starting stirring to stir the mixture sufficiently and uniformly, and slowly dropwise adding 154g of the compound A of the general formula (I)2Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 32.7g of fluoromonomer C2Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 3
Embodiment 3 provides a fluorine-modified curing agent, the raw material of which comprises a compound A of the general formula (I)3Amine compounds B11、B41And a fluorine-containing monomer C1；
A is described3Is represented by the structural formula:
wherein R is13Represents a hydrogen atom, R23represents-CH2CH2CH2CH2CH2CH2-；
B is11Is represented by the structural formula (II)51NH2Wherein R is51Represents 2-methylcyclohexyl; b is41The structural formula of (A) is:
wherein R is81represents-CH2CH2-；
Said C is1Is represented by the structural formula:
wherein, R is31Represents a methyl groupSaid R is41represents-CF3；
Said C is4Is represented by the structural formula:
wherein, R is34Represents a methyl group, said R44represents-CF2CF2CF2CF2CF2CHF2。
The preparation method of the fluorine modified curing agent comprises the following steps:
84.5g of the amine compound B was put into a 500mL flask equipped with a nitrogen blanket in a room temperature water bath11And 87.6g of amine compound B41Starting stirring to stir the mixture sufficiently and uniformly, and slowly adding 126g of the compound A of the general formula (I) dropwise 3Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 8.9g of fluoromonomer C1Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 4
Embodiment 4 provides a fluorine-modified curing agent, the raw material of which comprises a compound A of the general formula (I)1Amine compounds B23And a fluorine-containing monomer C4；
A is described1Is represented by the structural formula:
wherein R is11Represents a hydrogen atom, R21Is represented by (R)e-O-Rf-O-Rg) -and said Re、Rf、RgEach independently represents-CH2CH(CH3)-；
B is23The structural formula of (A) is:
wherein R is63To represent
Said C is4Is represented by the structural formula:
wherein, R is34Represents a methyl group, said R44represents-CF2CF2CF2CF2CF2CHF2。
The preparation method of the fluorine modified curing agent comprises the following steps:
194g of amine compound B was put into a 500mL flask equipped with nitrogen gas protection in a room temperature water bath23With stirring, 126g of the compound A of the formula (I)1Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 25.6g of fluoromonomer C4Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 5
Example 5 provides a fluorine-modified curing agent, the raw material of which comprises a compound A of the general formula (I) 3Amine compounds B21And a fluorine-containing monomer C4；
A is described3Is represented by the structural formula:
wherein R is13Represents a hydrogen atom, R23represents-CH2CH2CH2CH2CH2CH2-；
B is21The structural formula of (A) is:
wherein R is61represents-CH2CH2CH2CH2CH2CH2-；
Said C is4Is represented by the structural formula:
wherein, theR34Represents a methyl group, said R44represents-CF2CF2CF2CF2CF2CHF2。
The preparation method of the fluorine modified curing agent comprises the following steps:
150.8 g of amine compound B was placed in a 500mL flask equipped with nitrogen gas protection in a room temperature water bath21With stirring, 146.9g of the compound A of the formula (I)3Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 17.9g of fluoromonomer C4Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 6
Example 6 provides a fluorine-modified curing agent whose raw materials include Compound A of the general formula (I)1Amine compounds B23、B41And a fluorine-containing monomer C2；
A is described1Is represented by the structural formula:
wherein R is11Represents a hydrogen atom, R21Is represented by (R)e-O-Rf-O-Rg) -and said Re、Rf、RgEach independently represents-CH2CH(CH3)-；
B is23The structural formula of (A) is:
wherein R is63To represent
B is41The structural formula of (A) is:
wherein R is81represents-CH2CH2-；
Said C is2Is represented by the structural formula: 
Wherein, R is32Represents a hydrogen atom, said R42represents-CF2CHFCF3。
The preparation method of the fluorine modified curing agent comprises the following steps:
106.2g of the amine compound B was put into a 500mL flask equipped with a nitrogen blanket in a room temperature water bath23And 67.1g of amine compound B41Starting stirring to stir the mixture sufficiently and uniformly, and slowly dropwise adding 138g of the compound A of the general formula (I)1Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 12.4g of fluoromonomer C2Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Example 7
Example 7 provides a fluorine-modified curing agent whose raw material includes a compound A of the general formula (I)2Amine compounds B11、B21And a fluorine-containing monomer C1；
A is described2Is represented by the structural formula:
wherein R is12Represents a hydrogen atom, R22represents-CH2CH2CH2CH2-；
B is11Is represented by the structural formula (II)51-NH2Wherein R is51Represents 2-methylcyclohexyl; b is21The structural formula of (A) is:
wherein R is61represents-CH2CH2CH2CH2CH2CH2-；
Said C is1Is represented by the structural formula:
wherein, R is31Represents a methyl group, said R41represents-CF3。
The preparation method of the fluorine modified curing agent comprises the following steps:
166.3g of the amine compound B was placed in 500mL flasks equipped with a nitrogen blanket at room temperature in a water bath 11And 62.6g of amine compound B21Starting stirring to stir the mixture sufficiently and uniformly, and slowly dropwise adding 166.3g of the compound A of the general formula (I)2Controlling the dropping speed to be 2 hours, and continuing to perform heat preservation reaction for 6 hours after the dropping is finished; 15.2 fluoromonomer C1Slowly dropping into the reaction solution for 6h, and determining the reaction end point by chromatography and amine value titration.
Performance testing
The fluorine-modified epoxy curing agents described in examples 1 to 7 and hexamethylenediamine were cured with bisphenol A type epoxy resin 168, respectively, and paint films were prepared according to the standard of GB1727-79 and were tested according to the following standard, and the test results are shown in Table 1.
The paint film test method used the following criteria:
1. water resistance: GB/T1733-2003;
2. chemical resistance: GB 1763-79;
the chemical resistance agent includes acid resistance (H)2SO4(30 wt%)/800 h, HCl (10 wt%)/800 h), alkali resistance (NaOH (10 wt%)/1000 h), and salt water resistance (NaCl (3.5 wt%)/1000 h));
3. hardness: GB/T6739-2006;
4. salt spray resistance: GB/T1771-2007;
5. adhesion force: GB/9286-1998;
6. impact strength: GB/T2567-2008;
7. tensile strength: GB/T8813-2008;
8. bending strength: GB/T2567-2008;
9. weather resistance ((artificially accelerated aging (QUV-A): GB/T1865-2009).
Table 1 results of performance testing
From the test results in table 1, the mechanical properties, corrosion resistance and weather resistance of the fluorine modified curing agent prepared by the invention are remarkably improved.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The fluorine modified curing agent is characterized in that raw materials of the fluorine modified curing agent comprise a compound with a general formula (I), an amine compound and a fluorine-containing monomer; the molar ratio of the compound of the general formula (I) to the amine compound is 1: (1-10); the compound of the general formula (I) is:
wherein, R is1Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is2Represents C2-C20 alkyl or- (R) e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C6 alkyl group or a C3-C6 alkenyl group.
2. The fluorine-modified curing agent according to claim 1, wherein R is2Represents C2-C10 alkyl or- (R)e-O-Rf-O-Rg) -; wherein, R ise、Rf、RgEach independently represents a C3-C5 alkyl group.
3. According toThe fluorine-modified curing agent according to claim 2, wherein R ise、Rf、RgEach independently represents a C3-C4 branched alkyl group or a C3-C4 linear alkyl group.
4. The fluorine modified curing agent according to any one of claims 1 to 3, wherein the fluorine-containing monomer is a fluorine-substituted acrylic acid and/or a compound of the general formula (II); the compound of the general formula (II) is:
wherein, R is3Represents a hydrogen atom or an alkyl group having from C1 to C5; the R is4Represents any one of a fluorine-substituted C1-C20 alkyl group, a fluorine-substituted C2-C20 alkenyl group, a fluorine-substituted C2-C20 alkynyl group, a fluorine-substituted C1-C20 alkoxy group, a fluorine-substituted C1-C10 acyl group and a fluorine-substituted aryl group.
5. The fluorine-modified curing agent according to claim 4, wherein R is4Represents a fluorine-substituted C1-C10 alkyl group.
6. The fluorine modified curing agent according to claim 5, wherein the fluorine substituted alkyl group of C1-C10 is selected from one or more of trifluoro substituted alkyl group of C1-C10, tetrafluoro substituted alkyl group of C1-C10, pentafluoro substituted alkyl group of C1-C10, hexafluoro substituted alkyl group of C1-C10, heptafluoro substituted alkyl group of C1-C10, octafluoro substituted alkyl group of C1-C10, nonafluoro substituted alkyl group of C1-C10, and dodecafluoro substituted alkyl group of C1-C10.
7. The fluorine-modified curing agent according to claim 4, wherein the mass of the fluorine-containing monomer is 1 to 10 wt% of the total mass of the compound of the general formula (I) and the amine compound.
8. The fluorine-modified curing agent according to any one of claims 1 to 3, wherein the amine compound is selected from R5-NH2、
Wherein R is5、R6、R7、R8Each independently represents any one of an alkyl group having 2-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, and an aryl group having 6-20 carbon atoms.
9. The fluorine-modified curing agent according to claim 8, wherein R is7、R8Each independently represents a C2-C5 linear alkyl group.
10. A method for preparing a fluorine-modified curing agent according to any one of claims 1 to 9, comprising the steps of:
under the protection of water bath nitrogen, dropwise adding the compound of the general formula (I) into an amine compound, and reacting for 2-48 h; then, dropwise adding fluorine-containing monomer, reacting for 1-24h, and determining the reaction end point through chromatography and amine value titration.
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| US20100222520A1 (en) * | 2005-12-28 | 2010-09-02 | Kaneka Corporation | Curable composition for both thermal radical curing and latent thermal curing with epoxy |
| TW201326216A (en) * | 2011-10-19 | 2013-07-01 | Daikin Ind Ltd | Fluorine-containing composition and use thereof |
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| US20100222520A1 (en) * | 2005-12-28 | 2010-09-02 | Kaneka Corporation | Curable composition for both thermal radical curing and latent thermal curing with epoxy |
| TW201326216A (en) * | 2011-10-19 | 2013-07-01 | Daikin Ind Ltd | Fluorine-containing composition and use thereof |
| CN104870509A (en) * | 2013-01-08 | 2015-08-26 | Sika技术股份公司 | Hardeners for low-emission epoxy resin products |
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