CN108727562B - Epoxy resin curing agent, epoxy resin curing method and epoxy resin cured product obtained by epoxy resin curing method - Google Patents

Epoxy resin curing agent, epoxy resin curing method and epoxy resin cured product obtained by epoxy resin curing method Download PDF

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CN108727562B
CN108727562B CN201710270690.6A CN201710270690A CN108727562B CN 108727562 B CN108727562 B CN 108727562B CN 201710270690 A CN201710270690 A CN 201710270690A CN 108727562 B CN108727562 B CN 108727562B
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epoxy resin
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hydrogen
radical
independently selected
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CN108727562A (en
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成欣
苏朔
徐冰
段庆华
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/26—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having one or more free hydroxyl radicals

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Abstract

The invention provides an epoxy resin curing agent, an epoxy resin curing method and an obtained epoxy resin cured product. The epoxy resin curing agent is an amino compound, and has the following structure:

Description

Epoxy resin curing agent, epoxy resin curing method and epoxy resin cured product obtained by epoxy resin curing method
Technical Field
The invention relates to a curing agent, in particular to an epoxy resin curing agent and an epoxy resin cured product prepared by the same.
Background
The epoxy resin is a thermosetting polymer synthetic material with good bonding, corrosion resistance, electric insulation, high strength and other properties, and the uncured epoxy resin is viscous liquid or brittle solid and has corresponding use value only after generating a three-dimensional cross-linked network structure with a curing agent. After the epoxy group of the epoxy resin is subjected to ring opening by the curing agent and reacts to form a three-dimensional crosslinked network, the product has corresponding mechanical strength and other thermal and electrical properties, and has practical value.
In epoxy resin curing agents, amine curing agents are various in types, large in dosage and wide in application, but general amine curing agents (such as ethylenediamine, diethylenetriamine and the like) are high in volatility at normal temperature, high in toxicity, relatively quick in curing, strict in proportioning requirement, and even absorb carbon dioxide to reduce the curing effect.
The amide epoxy resin curing agent provided by the patent US 5576416 is a better epoxy resin curing agent, can be applied to an aqueous medium without a surfactant, and is multipurpose for manufacturing an aqueous coating.
The aromatic amine curing agent prepared in the patent US 3714121 has a relatively high curing temperature, and is easy to generate internal stress in the curing process, so that the shrinkage rate is increased.
The aliphatic polybasic primary amine curing agent has low toxicity, low exothermic peak value during curing, long working life and capability of resisting water vapor and CO in air2Low sensitivity, and is suitable for curing occasions at room temperature and medium temperature.
Disclosure of Invention
The invention provides an epoxy resin curing agent, an epoxy resin curing method and an obtained epoxy resin cured product.
The epoxy resin curing agent is an amino compound, and has the following structure:
Figure BDA0001277298300000011
wherein the group M has a structure obtained by removing p hydroxyl groups from a hydroxyl compound having p' hydroxyl groups; the group Link represents a connecting group selected from a single bond or C1-10Alkylene (preferably C)1-6Straight or branched alkylene, further preferably C1-4Linear or branched alkylene); radical R1And R2Are the same or different from each other and are each independently selected from hydrogen or C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); a radicals R3Or a radicals R4Are the same or different from each other and are each independently selected from hydrogen or C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); a radicals R6Or a radicals R7Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C1-10Hydrocarbyl (preferably optionally substituted C)1-6Straight or branched alkyl, further preferably optionally substituted C1-4Straight or branched alkyl) and
Figure BDA0001277298300000021
(whereinQ radicals R8Are the same or different from each other and are each independently selected from C1-40Alkylene, preferably C1-40Straight or branched alkylene, more preferably C1-20Straight or branched alkylene, further preferably C2-6A linear or branched alkylene group; q radicals R9Are the same or different from each other and are each independently selected from hydrogen or C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); radical R10Selected from hydrogen or C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); q is an integer between 1 and 50, preferably an integer between 1 and 10, more preferably 1,2, 3 or 4); a is an integer between 1 and 10, preferably an integer between 1 and 4, more preferably 1,2 or 3; a groups R' are the same or different and are each independently selected from a single bond or C1-10Alkylene (preferably C)1-6Straight or branched alkylene, further preferably C1-4Linear or branched alkylene, more preferably methylene or ethylene); radical R5Selected from hydrogen or C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl).
According to the invention, in formula (I), the group Link represents a linking group chosen from a single bond or C1-10Alkylene groups. Here, as the C1-10Alkylene group, for example, C1-10Straight or branched alkylene, C2-10Straight or branched alkenylene and C2-10Straight-chain or branched alkynylene, preferably C1-6Straight or branched alkylene, further preferably C1-4Straight or branched chain alkylene.
According to the invention, in the formula (I), the radical R1And R2Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight chain orA branched alkyl group.
According to the invention, in the formula (I) a number a of radicals R are present3And a radicals R4. Here, the a radicals R3Or the a radicals R4Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in the formula (I) a number a of radicals R are present6And a radicals R7. Here, the a radicals R6Or the a radicals R7Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C1-10A hydrocarbon group and
Figure BDA0001277298300000022
here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to a preferred embodiment of the invention, in the formula (I), in the radical R6Or a radical R7By "optionally substituted" in the definition of (a), it is preferably meant substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) hydroxyl groups.
According to the invention, in
Figure BDA0001277298300000031
In which q radicals R are present8. Here, the q radicals R8Are the same or different from each other and are each independently selected from C1-40Alkylene groups. As said C1-40Alkylene group, for example, C1-40Straight or branched alkylene, C2-40Straight-chain or branched alkenylene andC2-40straight-chain or branched alkynylene, preferably C1-40Straight or branched alkylene, more preferably C1-20Straight or branched alkylene, further preferably C2-6Straight or branched chain alkylene.
According to the invention, in
Figure BDA0001277298300000032
In which q radicals R are present9. Here, the q radicals R9Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in
Figure BDA0001277298300000033
In (1), the group R10Selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in
Figure BDA0001277298300000034
Q is an integer between 1 and 50, preferably an integer between 1 and 10, more preferably 1,2, 3 or 4.
According to the invention, in formula (I), a is an integer between 1 and 10, preferably an integer between 1 and 4, more preferably 1,2 or 3.
According to the invention, in formula (I), a radicals R' are present. Here, the a radicals R', which are identical or different from one another, are each independently selected from the group consisting of a single bond or C1-10Alkylene groups. Here, as the C1-10Alkylene radicals, e.g. ofMay include C1-10Straight or branched alkylene, C2-10Straight or branched alkenylene and C2-10Straight-chain or branched alkynylene, preferably C1-6Straight or branched alkylene, further preferably C1-4Straight or branched alkylene, more preferably methylene or ethylene.
According to the invention, in the formula (I), the radical R5Selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in formula (I), p is an integer between 1 and 10, preferably between 1 and 3, more preferably 1.
According to the invention, the group M has a structure obtained by removing p hydroxyl groups from a hydroxyl compound having p' hydroxyl groups. Here, p' is an integer between 1 and 10, preferably an integer between 1 and 3, more preferably 1. p is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1, and 1. ltoreq. p.ltoreq.p'. Accordingly, the group M has a structure obtained by removing p hydroxyl groups (p remaining unbound bonds) from a hydroxyl compound having p' hydroxyl groups.
According to the invention, p radicals
Figure BDA0001277298300000041
Are present independently of one another, and the definitions of the individual substituents and values in the p radicals may be identical to or different from one another between different radicals, each independently as described for formula (I).
According to the invention, the hydroxyl compounds having p' hydroxyl groups include polyols having a corresponding number of free hydroxyl groups, polyesters having a corresponding number of free hydroxyl groups, polyethers having a corresponding number of free hydroxyl groups and aromatic amines having a corresponding number of free hydroxyl groups.
According to the present invention, examples of the polyester having a corresponding number of free hydroxyl groups include a polyester having a hydroxyl group at one or both ends of a polymer chain, and a polyester having a larger number of hydroxyl groups obtained by using a comonomer such as a polyol. The structure of said polyesters with a corresponding number of free hydroxyl groups and the process for their manufacture are known in the art and will not be described in detail here.
According to the present invention, examples of the polyether having a corresponding number of free hydroxyl groups include a polyether having a hydroxyl group at one or both ends of a polymer chain, and a polyether having a larger number of hydroxyl groups obtained by using a comonomer such as a polyol.
According to the invention, mention may be made, as aromatic amines having a corresponding number of free hydroxyl groups, of, for example, anilines having one or more hydroxyl groups attached to the aniline in the ortho, para and meta positions.
According to one embodiment of the present invention, the polyether having the corresponding number of free hydroxyl groups includes, in particular, alkylene glycol polymers. Examples of the alkylene glycol polymer include polymers obtained by homopolymerizing or copolymerizing alkylene oxide, alkylene glycol, or oxacycloalkane. In the homopolymerization or copolymerization process, a comonomer may be further introduced as needed. The alkylene oxide includes, for example, alkylene oxides represented by the following formulae (a to IV), more specifically, ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and hexylene oxide, and preferably, ethylene oxide and propylene oxide. Examples of the alkylene glycol include compounds represented by the following formula (a-IV'), more specifically, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol, and preferably, ethylene glycol and propylene glycol. Examples of the oxacycloalkane include cyclic ethers represented by the following formula (A-IV "), and more specifically include oxetane and oxacyclohexane. Specific examples of the comonomer include polyhydric alcohols other than diols such as glycerol and pentaerythritol, and glycerol is preferred.
Figure BDA0001277298300000051
According to this embodiment of the invention, in formula (A-IV), the group Ru' is chosen from a single bond or C1-22Straight or branched chain alkyl. Here, as the C1-22Straight or branched alkyl, such as C1-20Straight or branched alkyl, C1-10Straight or branched alkyl or C1-4Straight or branched chain alkyl, preferably methyl.
HO-Ru”-OH (A-IV')
According to this embodiment of the invention, in formula (A-IV '), the group Ru' is chosen from C2-22Straight or branched chain alkyl. Here, as the C2-22Straight or branched alkyl, such as C2-20Straight or branched alkyl, C2-10Straight or branched alkyl or C2-6Straight or branched chain alkyl, preferably ethyl or propyl.
Figure BDA0001277298300000052
According to this embodiment of the invention, in formula (A-IV "), the group Ru'" is chosen from C3-22Straight or branched chain alkyl. Here, as the C3-22Straight or branched alkyl, such as C3-20Straight or branched alkyl, C3-10Straight or branched alkyl or C3-6Straight or branched chain alkyl, preferably propyl.
According to this embodiment of the present invention, the alkylene glycol polymer is more specifically a polyether represented by the following formula (III).
Figure BDA0001277298300000053
According to this embodiment of the invention, in formula (III), the radical R0Selected from hydrogen atoms and optionally substituted C1-50A hydrocarbyl group. Here, as the C1-50Examples of the hydrocarbon group include C1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C2-50Straight chainOr branched alkynyl, C6-50Monocyclic or polycyclic aryl and C3-50Monocyclic or polycyclic cycloalkyl, more specifically for example C1-20Straight or branched alkyl, C6-10Monocyclic or polycyclic aryl and C3-20Monocyclic or polycyclic cycloalkyl (or C)5-7Monocyclic or polycyclic cycloalkyl), especially C5-15Straight or branched chain alkyl, phenyl and cyclohexyl.
According to a preferred embodiment of the invention, in the formula (III), in the radical R0By "optionally substituted" in the definition of (a), it is preferably meant substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) C1-20Straight-chain or branched alkyl, preferably substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) C5-15Linear or branched alkyl. Here, as said group R0Specific examples thereof include a dodecylphenyl group and a nonylphenyl group.
According to one embodiment of the invention, in formula (III), there are y groups Ru. Here, the y radicals Ru, which are identical or different from one another, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, more preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3) -, more preferably-CH2-CH(CH3)-。
According to this embodiment of the invention, in formula (III), y is selected from any value between 1 and 200, preferably from 1 to 100, more preferably from 1 to 50, more preferably from 1 to 30. Here, y represents the average degree of polymerization of the polyether segment-O-Ru-, and thus may be a non-integer.
According to a preferred embodiment of the present invention, the amine-based compound has a structure represented by the following formula (II-A) or a structure represented by the following formula (II-B). In this case, the amine-based compound is generally referred to as a polyetheramine.
Figure BDA0001277298300000061
Wherein R attached to D11-is C1-20Hydrocarbyl, preferably C1-10Alkyl, D is a single bond or O, D' is H,
Figure BDA0001277298300000062
and at least one D' is
Figure BDA0001277298300000063
Wherein the definitions of the groups and letters are as described in the previous section.
According to this embodiment of the invention, in the formulae (II-A) and (II-B), the radicals and values are each as defined above in the description of the application.
According to this embodiment of the invention, the molecular weight Mn of the polyetheramine is generally from 500 to 10000, preferably from 500 to 4000.
According to an embodiment of the present invention, as the amine-based compound, a polyether amine represented by the following formula (II-C) is preferable. The molecular weight Mn of the polyetheramines is generally from 600 to 2000, preferably from 1000 to 1500.
Figure BDA0001277298300000071
According to one embodiment of the present invention, any of the above-mentioned amine-based compounds can be produced by the following production method. Specifically, the manufacturing method may include, for example, the following steps 1) to 3).
According to the present invention, in step 1), an alkenyl polymer represented by the following formula (A-I) is produced.
Figure BDA0001277298300000072
Of course, if the alkenyl polymer represented by the formula (A-I) is commercially available, the step 1) becomes an optional step rather than an essential step.
According to the invention, in formula (a-I), p is an integer between 1 and 10, preferably between 1 and 3, more preferably 1.
According to the invention, in the formula (A-I), it is emphasized that p radicals
Figure BDA0001277298300000073
Are present independently of one another, and the definitions of the individual substituents and of the numerical values in these radicals may be identical to or different from one another between different radicals, each independently as defined above.
According to the present invention, as the parent polymer of the alkenyl polymer, the hydroxyl compound may be those listed above for the parent polymer of the amine-based compound, preferably alkylene glycol polymer, polyol, more preferably the polyether represented by the formula (III).
Figure BDA0001277298300000074
3 according 3 to 3 a 3 preferred 3 embodiment 3 of 3 the 3 present 3 invention 3, 3 the 3 alkenyl 3 polymer 3 has 3 a 3 structure 3 represented 3 by 3 the 3 following 3 formula 3 ( 3 a 3- 3 a 3) 3 or 3 a 3 structure 3 represented 3 by 3 the 3 following 3 formula 3 ( 3 a 3- 3 b 3) 3. 3
Figure BDA0001277298300000081
3 according 3 to 3 this 3 embodiment 3 of 3 the 3 invention 3, 3 in 3 the 3 formulae 3 ( 3 A 3- 3 A 3) 3 and 3 ( 3 A 3- 3 B 3) 3, 3 the 3 radicals 3 and 3 the 3 values 3 are 3 each 3 as 3 defined 3 above 3 in 3 the 3 description 3 of 3 the 3 application 3. 3
According to the present invention, in step 1), as a method for producing the alkenyl polymer represented by the formula (a-I), for example, the following embodiment a) or embodiment B) can be given.
According to the present invention, an alkenyl polymer represented by the formula (a-I) is produced by reacting a hydroxyl compound represented by the following formula (a-II) with an alkenyl compound represented by the following formula (a-III) according to the formula a).
According to the mode a), the reaction may be carried out by introducing the alkenyl compound represented by the formula (a-III) into the polymerization reaction system of the hydroxyl compound during or after completion of the production of the hydroxyl compound represented by the formula (a-II).
Figure BDA0001277298300000083
According to the invention, in the formulae (A-II), the radicals M and the values p are each as defined correspondingly before in the description of the application.
According to the invention, according to the mode A), the hydroxyl compound may be, for example, those listed above for the parent polymer of the amine-based compound, preferably an alkylene glycol polymer, more preferably a polyether of the formula (III).
Figure BDA0001277298300000082
According to the invention, in formula (a-III), the group G represents a functional group, preferably a halogen or a hydroxyl group, capable of reacting with an-OH, such as at least one-OH, preferably all p-OH groups, on the hydroxyl compound represented by said formula (a-II) to remove the compound GH. Here, as the halogen, chlorine is more preferable.
According to the invention, in formula (A-III), the group Link represents a linking group chosen from a single bond or C1-10Alkylene groups. Here, as the C1-10Alkylene group, for example, C1-10Straight or branched alkylene, C2-10Straight or branched alkenylene and C2-10Straight-chain or branched alkynylene, preferably C1-6Straight or branched alkylene, further preferably C1-4Straight or branched chain alkylene.
According to the invention, in the formula (A-III), the radical R1And R2Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched chainAlkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in the formula (A-III), a radicals R are present3And a radicals R4. Here, the a radicals R3Or the a radicals R4Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in formula (a-III), a is an integer between 1 and 10, preferably an integer between 1 and 4, more preferably 1,2 or 3.
According to the invention, in the formula (A-III), a radicals R' are present. Here, the a radicals R', which are identical or different from one another, are each independently selected from the group consisting of a single bond or C1-10Alkylene groups. Here, as the C1-10Alkylene group, for example, C1-10Straight or branched alkylene, C2-10Straight or branched alkenylene and C2-10Straight-chain or branched alkynylene, preferably C1-6Straight or branched alkylene, further preferably C1-4Straight or branched alkylene, more preferably methylene or ethylene.
According to the invention, in the formula (A-III), the radical R5Selected from hydrogen or C1-10A hydrocarbyl group. Here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to the invention, in the mode A), more specific examples of the alkenyl compound represented by the formula (A-III) include allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 4-penten-2-ol, 4-penten-3-ol, 3-methyl-4-penten-1-ol, 2-methyl-4-penten-1-ol, 3-ethyl-4-penten-1-ol, 2-ethyl-4-penten-1-ol, 3-isobutyl-4-penten-1-ol, 2-isobutyl-4-penten-1-ol, allyl alcohol, 3-buten-1-ol, 3-methyl-2-penten-1-ol, 3-, 2, 3-dimethyl-4-pentene-1-ol, 2-dimethyl-4-pentene-1-ol, 3-dimethyl-4-pentene-1-ol, 5-hexen-1-ol, 4-methyl-5-hexenol, 3-methyl-5-hexenol, 2-methyl-5-hexenol, 3-ethyl-5-hexenol, 5-hexen-2-ol, 5-hexen-3-ol, 5-hexen-4-ol, 6-hepten-1-ol, 2-methyl-6-hepten-1-ol, 3-methyl-6-hepten-1-ol, 4-methyl-6-hepten-1-ol, 5-methyl-6-hepten-1-ol, 2-ethyl-6-hepten-1-ol, 3-ethyl-6-hepten-1-ol, 4-ethyl-6-hepten-1-ol, 5-ethyl-6-hepten-1-ol, 2-methyl-7-octen-1-ol, 3-methyl-7-octen-1-ol, 4-methyl-7-octen-1-ol, 5-methyl-7-octen-1-ol, 6-methyl-7-octen-1-ol, 3-ethyl-7-octen-1-ol, 9-decen-1-ol, 2-ethyl-6-hepten-1-ol, 2-methyl-7-octen-1-ol, 3-ethyl-7-octen-1-ol, 10-undecen-1-ol, 11-dodecen-1-ol, allyl halide, 3-buten-1-halide, 3-buten-2-halide, 3-methyl-3-buten-1-halide, 4-penten-2-halide, 4-penten-3-halide, 3-methyl-4-penten-1-halide, 2-methyl-4-penten-1-halide, 3-ethyl-4-penten-1-halide, 2-ethyl-4-penten-1-halide, 3-isobutyl-4-penten-1-halide, 2, 3-dimethyl-4-penten-1-halide, 2-isobutyl-4-penten-1-halide, allyl halide, 2, 2-dimethyl-4-pentene-1-halogen, 3-dimethyl-4-pentene-1-halogen, 5-hexene-1-halogen, 4-methyl-5-hexene-halogen, 3-methyl-5-hexene-halogen, 2-methyl-5-hexene-halogen, 3-ethyl-5-hexene-halogen, 5-hexene-2-halogen, 5-hexene-3-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 2-methyl-6-heptene-1-halogen, 3-methyl-6-heptene-1-halogen, 4-methyl-6-heptene-1-halogen, 2-methyl-5-heptene-1-halogen, 5-methyl-5-hexene-2-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 5-methyl-6-heptene-1-halide, 2-ethyl-6-heptene-1-halide, 3-ethyl-6-heptene-1-halide, 4-ethyl-6-heptene-1-halide, 5-ethyl-6-heptene-1-halide, 2-methyl-7-octene-1-halide, 3-methyl-7-octene-1-halide, 4-methyl-7-octene-1-halide, 5-methyl-7-octene-1-halide, 6-methyl-7-octene-1-halide, 3-ethyl-7-octene-1-halide, 9-decene-1-halide, 2-ethyl-6-heptene-1-halide, 3-ethyl-7-octene-1-halide, 4-methyl-7-octene-1-halide, 5-methyl-7-octene-, 10-undecene-1-halo, 11-dodecene-1-halo, 5-chloro-1, 3-pentadiene, 6-chloro-1, 3-hexadiene, 5-chloro-1, 3-hexadiene, 6-chloro-2, 4-hexadiene and 5-chloro-2, 4-hexadiene. These alkenyl compounds may be used alone or in combination of two or more.
According to the invention, according to the mode A), the molar ratio of the hydroxyl compound represented by the formula (A-II) to the alkenyl compound represented by the formula (A-III) is generally 1:1 to 1.5, preferably 1:1 to 1.2.
According to the invention, the reaction temperature is generally from 50 to 150 ℃ in accordance with variant A).
According to the invention, the reaction pressure is generally atmospheric according to variant A).
According to the invention, the reaction time is generally from 2 to 10h in accordance with variant A).
According to the invention, according to the mode A), a catalyst can be used as required. Examples of the catalyst include those generally used by those skilled in the art for this purpose, and specific examples thereof include basic catalysts, more specifically, alkali metals, alkali metal alkoxides and alkali metal hydroxides, and particularly potassium hydroxide and sodium methoxide. These catalysts may be used alone or in combination of two or more. When used, the molar ratio of the catalyst to the alkenyl compound of formula (A-III) is generally from 1 to 2:1, preferably from 1 to 1.5:1, most preferably from 1 to 1.1: 1.
According to the invention, according to mode A), a solvent may or may not be used. When used, the solvent includes, for example, C1-6The monohydric alcohol is more specifically exemplified by methanol, ethanol, isopropanol, and n-butanol. These solvents may be used alone or in combination of two or more.
According to the present invention, according to the mode B), in the production of the hydroxy compound represented by the formula (A-II), the alkenyl compound represented by the formula (A-III) is used as a starting agent. Here, "as an initiator" means that the hydroxyl compound is grown on the basis of the group G on the alkenyl compound represented by the formula (a-III) as a polymerization reaction initiation point by a subsequent chain extension reaction, thereby obtaining a hydroxyl compound terminated with the initiator (except the group G).
According to the present invention, as the mode B), a specific example is a method including the following step B-1) and step B-2).
According to the present invention, in step B-1), the alkenyl compound represented by the formula (A-III) is reacted with an alkylene oxide to obtain an alkenyl polyether represented by the following formula (A-V).
According to the present invention, in the step B-1), the alkylene oxide is represented by the following formula (A-IV). More specific examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and hexylene oxide, and ethylene oxide and propylene oxide are preferable. These alkylene oxides may be used alone or in combination of two or more.
Figure BDA0001277298300000111
According to the invention, in formula (A-IV), the group Ru' is chosen from a single bond or C1-22Straight or branched chain alkyl. Here, as the C1-22Straight or branched alkyl, such as C1-20Straight or branched alkyl, C1-10Straight or branched alkyl or C1-4Straight or branched chain alkyl, preferably methyl.
Figure BDA0001277298300000112
According to the invention, in the formula (A-V), there are y groups Ru. Here, the y radicals Ru, which are identical or different from one another, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, more preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3) -, more preferably-CH2-CH(CH3)-。
According to the invention, in formula (a-V), y is chosen from any value between 1 and 200, preferably between 1 and 100, more preferably between 1 and 50, more preferably between 1 and 30. Here, y represents the average degree of polymerization of the polyether segment-O-Ru-, and thus may be a non-integer.
According to the present invention, in step B-2), optionally, during or after completion of said step B-1), at least one end-capping agent selected from the group consisting of the compounds represented by the following formulae (a-VI) and the alkenyl compounds represented by said formulae (a-III) is introduced into the reaction system, and reacted with said alkenyl polyether represented by said formulae (a-V) which has been produced in the reaction system to convert at least a part of said alkenyl polyether into an alkenyl polyether represented by the following formulae (a-VII) or an alkenyl polyether represented by the following formulae (a-VIII). Here, both the compound represented by the formula (a-VI) and the alkenyl compound represented by the formula (a-III) function as a capping agent, and are collectively referred to as a capping agent.
G'-R'0 (A-VI)
According to the invention, in the formula (A-VI), the group G 'represents a functional group, preferably a halogen or a hydroxyl group, capable of reacting with-OH, such as the-OH group on the alkenyl polyether of the formula (A-V), to remove the compound G' H. Here, as the halogen, chlorine is more preferable.
According to the invention, in formula (A-VI), the radical R'0Selected from optionally substituted C1-50A hydrocarbyl group. Here, as the C1-50Examples of the hydrocarbon group include C1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C2-50Straight-chain or branched alkynyl, C6-50Monocyclic or polycyclic aryl and C3-50Monocyclic or polycyclic cycloalkyl, more specifically for example C1-20Straight or branched alkyl, C6-10Monocyclic or polycyclic aryl and C3-20Monocyclic or polycyclic cycloalkyl (or C)5-7Monocyclic or polycyclic cycloalkyl), especially C5-15Straight or branched chain alkyl, phenyl and cyclohexyl.
According to a preferred embodiment of the present invention, in formula (A-VI), in the radical R'0By "optionally substituted" in the definition of (a), it is preferably meant substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) C1-20Straight-chain or branched alkyl, preferably substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) C5-15Straight or branched alkyl radicalsAnd (4) generation. Here, as the group R'0Specific examples thereof include a dodecylphenyl group and a nonylphenyl group.
Figure BDA0001277298300000121
According to the invention, in the formulae (A-VII) and (A-VIII), the radicals and values are each as defined above in the description of the application.
According to the present invention, in step B-1), the molar ratio of the alkenyl compound represented by the formula (A-III) to the alkylene oxide is generally 1:1 to 100, preferably 1:10 to 40. In the step B-2), the molar ratio of the alkenyl polyether represented by the formula (A-V) to the end-capping agent is generally 1:1 to 1.5, preferably 1:1 to 1.2.
According to the invention, in step B-1) and step B-2), the reaction temperature is generally between 100 and 200 ℃, preferably between 100 and 150 ℃ and most preferably between 100 and 120 ℃.
According to the invention, the reaction pressure in step B-1) and step B-2) is generally from 1 to 5 kg, preferably from 1 to 3 kg, most preferably from 1 to 2 kg.
According to the invention, in step B-1), the reaction time is generally from 3 to 20h, preferably from 3 to 11 h. In step B-2), the reaction time is generally from 2 to 10h, preferably from 6 to 8 h.
According to the present invention, in step B-1), a catalyst may be used as required. Examples of the catalyst include those generally used by those skilled in the art for this purpose, and specific examples thereof include basic catalysts, more specifically, alkali metals, alkali metal alkoxides and alkali metal hydroxides, and particularly potassium hydroxide and sodium methoxide. These catalysts may be used alone or in combination of two or more. When used, the molar ratio of the catalyst to the alkenyl compound of formula (A-III) is generally from 1 to 2:1, preferably from 1 to 1.5:1, most preferably from 1 to 1.1: 1. According to the invention, in step B-1), a solvent may or may not be used. When used, the solvent includes, for example, C1-6The monohydric alcohol includes, more specifically, methanol, ethanol,Isopropanol and n-butanol. These solvents may be used alone or in combination of two or more.
According to the invention, in step 2), the alkenyl polymer of formula (A-I) is subjected to an oxidation reaction with an oxidizing agent, at least one (preferably a plurality of) groups comprised by the alkenyl polymer being oxidized
Figure BDA0001277298300000131
Oxidized to a radical
Figure BDA0001277298300000132
To obtain an oxidation product.
According to a preferred embodiment of the invention, in step 2), all p × a radicals are substituted
Figure BDA0001277298300000133
Oxidized to a radical
Figure BDA0001277298300000134
According to the invention, in step 2), the oxidation reaction can be carried out in any manner conventionally known to the person skilled in the art, provided that the at least one (preferably all p × a) groups can be reacted
Figure BDA0001277298300000135
Oxidized to a radical
Figure BDA0001277298300000136
And (4) finishing.
According to the present invention, in step 2), the oxidizing agent includes those generally used by those skilled in the art for the epoxidation of olefins, and specifically includes oxygen, ozone, hydrogen peroxide, metal oxide, metal peroxide, dichromic acid or a salt thereof, permanganic acid or a salt thereof, peracid or a salt thereof, hypohalous acid or a salt thereof, organic hydroperoxide and organic peroxide, and more specifically includes hydrogen peroxide, organic hydroperoxide and organic peroxide, and particularly hydrogen peroxide, sodium hypochlorite, etc,Ammonium peroxydisulfate, benzoyl peroxide, morpholine N-methyl oxide, methyl rhenium trioxide, osmium tetroxide, hypochlorous acid, KMnO4、K2Cr2O7、KNO3、Na2O2、MnO2Ozone and oxygen. More specifically, the organic hydroperoxide may be tert-butyl hydroperoxide. More specific example of the peroxygenated organic acid is C3-12Peroxyorganic acids, preferably peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxybutyric acid, peroxybenzoic acid or m-chloroperoxybenzoic acid. As the oxidizing agent, m-chloroperoxybenzoic acid and peracetic acid are particularly preferable, and m-chloroperoxybenzoic acid is most preferable. These oxidizing agents may be used alone or in combination of two or more.
According to the invention, in step 2), the oxidizing agent is reacted with the alkenyl polymer (in groups) of formula (A-I)
Figure BDA0001277298300000141
By) is generally 10-1:1, preferably 5-1:1, most preferably 3-1: 1.
According to the invention, in step 2), the reaction temperature of the oxidation reaction is generally from 20 to 80 ℃, preferably from 20 to 60 ℃ and most preferably from 30 to 50 ℃.
According to the invention, in step 2), the oxidation is generally carried out at a pressure of from 1 to 5 kg, preferably from 1 to 3 kg, most preferably from 1 to 2 kg.
According to the invention, in step 2), the reaction time of the oxidation reaction is generally between 1h and 8h, preferably between 2h and 6h, most preferably between 2h and 4 h.
According to the invention, in step 2), a catalyst may or may not be used. Examples of the catalyst include those generally used by those skilled in the art for the epoxidation of olefins, and specific examples thereof include hydrotalcite-based catalysts, molecular sieve-based catalysts, organic acids, and inorganic acids. Examples of the hydrotalcite-like catalyst include an intercalated hydrotalcite and a hydrotalcite-like compound. Examples of the molecular sieve-based catalyst include titanium silicalite moleculesAnd (4) screening. The organic acid includes, for example, C1-5Carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and valeric acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. These catalysts may be used alone or in combination of two or more. When used, the catalyst is reacted with the alkenyl polymer(s) of formula (A-I)
Figure BDA0001277298300000142
By) is generally from 0.1 to 5:1, preferably from 0.5 to 5.0:1, most preferably from 0.5 to 3.0: 1.
According to the invention, in step 2), a solvent may or may not be added. Specific examples of the solvent include C1-C8More specific examples of the alcohol include n-propanol, n-butanol and n-hexanol.
According to the invention, in step 3), the oxidation product obtained in step 2) is subjected to an amination reaction with an aminating agent, said group being obtained
Figure BDA0001277298300000143
Total amination to a radical
Figure BDA0001277298300000144
According to the present invention, in step 3), the aminating agent may be, for example, an aminating agent represented by the following formula (B-I), and specifically, ammonia or C1-C30Primary amine, C3-C30Secondary amines, alcohol amines and polyene polyamines, preferably ammonia and C1-C30Examples of the primary amine include ammonia, ethylamine, propylamine, ethylenediamine, ethanolamine and triethylenetetramine. These aminating agents may be used alone or in combination of two or more.
Figure BDA0001277298300000151
According to the invention, in the formula (B-I), the radical R6And R7Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C1-10A hydrocarbon group and
Figure BDA0001277298300000152
here, as the C1-10Examples of the hydrocarbon group include C1-10Straight or branched alkyl, C2-10Straight or branched alkenyl and C2-10Straight-chain or branched alkynyl, preferably C1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl.
According to a preferred embodiment of the invention, in the formula (B-I), in the radical R6Or a radical R7By "optionally substituted" in the definition of (a), it is preferably meant substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) hydroxyl groups.
According to the invention, in step 3), the aminating agent is reacted with the oxidation product (as a radical)
Figure BDA0001277298300000153
By) is generally 1-4:1, preferably 1-2:1, most preferably 1-1.5: 1. According to the invention, in step 3), the reaction temperature is generally from 100 to 180 ℃, preferably from 100 to 150 ℃ and most preferably from 120 to 150 ℃.
According to the invention, in step 3), the reaction pressure is generally from 1 to 5 kg, preferably from 1 to 3 kg, most preferably from 1 to 2 kg.
According to the invention, in step 3), the reaction time is generally from 1h to 8h, preferably from 2h to 6h, most preferably from 2h to 5 h.
According to the invention, in step 3), a solvent may or may not be added. Specific examples of the solvent include C1-C8More specific examples of the alcohol include n-propanol, n-butanol and n-hexanol.
According to the invention, in step 3), a catalyst may or may not be added. Examples of the catalyst include tertiary amines and phenols, and tertiary amines are preferred. Examples of the tertiary amine include trihydrocarbyl tertiary amines having a molecular weight of 10 to 500 and amino derivatives thereof, more specifically include trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, N-dimethyl-1, 3-propanediamine, N-dimethylpentylamine, N-dimethylhexylamine, N-dimethylheptylamine, N-dimethyloctylamine, N-dimethylnonylamine, N-dimethyldecylamine, triphenylamine and N, n-2 methylbenzylamine, preferably trimethylamine, triethylamine and N, N' -2 methylbenzylamine, most preferably trimethylamine and/or triethylamine. These tertiary amines may be used alone or in combination of two or more. Examples of the phenolic compound include monohydric, dihydric, polyhydric phenols and sodium phenolate having a molecular weight of 20 to 500, and electron donating groups such as alkoxy, phenyl and alkyl groups may be attached to the benzene ring. More specific examples of the phenol substance include phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, m-cresol, p-cresol, 2, 4-dimethylphenol, 2,4, 6-trimethylphenol, ethylphenol, sodium ethylphenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, sodium phenyl phenol, preferably phenol and/or sodium phenolate, and most preferably sodium phenolate. These phenolic compounds may be used alone or in combination of two or more.
According to the invention, in step 3), the catalyst is used with the oxidation product (as a group)
Figure BDA0001277298300000161
Calculated as above) is 0.1 to 1:1, preferably 0.1 to 0.5:1, most preferably 0.3 to 0.5: 1.
According to the present invention, after the process for producing the amine-based compound is completed, the amine-based compound is obtained by removing the catalyst and the solvent, if any, from the finally obtained reaction mixture by any conventionally known means.
The amine-based compounds of the present invention are particularly useful as curing agents for epoxy resins. Here, the epoxy resin curing agent includes any of the aforementioned amine-based compounds of the present invention or amine-based compounds manufactured according to the aforementioned manufacturing method of the present invention.
The epoxy resin curing method is to perform curing crosslinking reaction on the epoxy resin curing agent and the epoxy resin, and the mass ratio of the epoxy resin curing agent to the epoxy resin is preferably 1-10: 1. The time of the curing and crosslinking reaction is preferably 1-10 h. After the curing and crosslinking reaction is finished, preferably curing for 1-240 hours, and the obtained epoxy resin has good mechanical property and acid and alkali resistance.
According to the invention, the epoxy resin comprises: o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl epoxy resin, naphthol epoxy resin, alkylated phenyl epoxy resin, trifunctional epoxy resin, and tetrafunctional epoxy resin.
According to the invention, the amount of the epoxy resin curing agent is calculated according to the ratio of epoxy equivalent to amino equivalent of the epoxy resin of 0.9-1.2, preferably 0.95-1.1, and more preferably 0.98-1.05.
According to the invention, a flame retardant can be added into the epoxy resin, and the flame retardant is preferably a brominated flame retardant or a halogen-free flame retardant; the brominated flame retardant is a non-reactive or reactive brominated flame retardant, the reactive brominated flame retardant is brominated epoxy resin and is selected from one or more of brominated bisphenol A epoxy resin, brominated phenolic epoxy resin and brominated isocyanate modified epoxy resin, and the non-reactive brominated flame retardant is selected from one or more of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, ethylene bistetrabromophthalimide and brominated polycarbonate. The bromine content of the brominated epoxy resin is preferably 15-55%. The weight ratio of the using amount of the flame retardant to the epoxy resin curing agent is preferably 10-50: 100, more preferably 10 to 20:100, and still more preferably 10 to 15: 100.
According to the invention, a defoaming agent can be added into the epoxy resin, preferably a silicone oil defoaming agent is added, and the weight ratio of the defoaming agent to the epoxy resin curing agent is preferably 0.1-10: 100, more preferably 0.1-5: 100, and further preferably 1-5: 100.
The epoxy resin of the present invention is preferably an epoxy resin having a melt viscosity of not more than 0.5Pa.s at 150 ℃. The epoxy resin curing agent is suitable for curing various epoxy resins, and can ensure that the cured epoxy resin has high glass transition temperature, lower expansion coefficient, good chemical resistance and adhesion, lower toxicity, lower manufacturing cost and better flame retardant property.
The invention also provides an epoxy resin cured product prepared by the curing method. The epoxy resin cured product has the advantages of higher glass transition temperature, lower expansion coefficient, good chemical resistance and adhesiveness, lower toxicity, lower manufacturing cost and better flame retardant property.
Detailed Description
Example 1
1) And (3) preparing polyether. Adding a mixture of 58g of allyl alcohol and 0.75g of potassium hydroxide into a reaction kettle, replacing air in the reactor with nitrogen, sealing the reactor, heating to 110 ℃, reducing the pressure to 2000 Pa, evaporating water, introducing nitrogen into the reactor to restore normal pressure, raising the temperature to about 140 ℃, and continuously pressing 290g of propylene oxide into the reaction kettle for reaction until the pressure is not changed any more. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (4) evaporating water and volatile matters under reduced pressure to obtain the alkenyl polyether product.
The chemical formula of the obtained polyether is as follows:
Figure BDA0001277298300000171
the average degree of polymerization n of the resulting alkenyl polyether was 4.
2) Epoxidation of alkenyl polyethers. Adding 348g of alkenyl polyether and 35g of formic acid into a four-neck flask under the protection of nitrogen, heating to 60 ℃, mixing 255g of hydrogen peroxide, dropwise adding into the four-neck flask within two hours, reacting for 2-8 hours, washing a product with NaOH water until the pH value is about 7.0, washing with clean water for three times, drying, and performing rotary evaporation to obtain the epoxy polyether. The formula of the obtained epoxy polyether is as follows:
Figure BDA0001277298300000172
the average degree of polymerization n of the resulting epoxy polyether was 4.
3) And (3) pumping the treated materials into an amination reaction kettle, adding 30g of ethylenediamine and 4.5g of n-butanol, and reacting at the temperature of 150 ℃ for 2-6 hours to obtain a polyetheramine crude product. And washing and rotary steaming the product to obtain a polyetheramine product, wherein the nitrogen content of the product is 2.49 percent, and the total conversion rate is 70.14 percent. The obtained polyetheramine has the chemical formula:
Figure BDA0001277298300000181
the average degree of polymerization n of the resulting polyetheramine was 4.
Example 2
1) And (3) preparing polyether. A mixture of 109.13g of p-aminophenol and 0.79g of potassium hydroxide was charged into a reaction vessel, the temperature in the reaction vessel was raised to around 140 ℃ with nitrogen, about 290g of propylene oxide was continuously pressed into the reaction vessel to react until the pressure did not change, and the mixture was allowed to continue to react at 140 ℃ until the pressure did not change. 120.98g of allyl bromide and 56.1g of potassium hydroxide were charged, nitrogen gas was introduced, the mixture was heated to about 60 ℃ with stirring, and the mixture was refluxed for 6 hours, and after completion of the reaction, the reaction product was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (4) evaporating under reduced pressure to remove water and volatile matters to obtain the polyether product.
Figure BDA0001277298300000182
2) Adding the alkenyl polyether obtained in the step 2) and 29g of formic acid into a four-neck flask under the protection of nitrogen, heating to 60 ℃, mixing 255g of hydrogen peroxide, dropwise adding into the four-neck flask within two hours, reacting for 2-8 hours, washing a product with NaOH water until the pH value is about 7.0, washing with clear water for three times, drying, and performing rotary evaporation to obtain the epoxy polyether. The formula of the obtained epoxy polyether is as follows:
Figure BDA0001277298300000183
3) and (3) pumping the treated materials into an amination reaction kettle, introducing 68g of ammonia gas and 2.3g of n-butyl alcohol, reacting at the temperature of 150 ℃ for 2-6 hours to obtain a polyetheramine crude product. Washing and rotary steaming the product to obtain the polyether amine product, wherein the nitrogen content of the product is 5.45 percent, and the total conversion rate is 84.10 percent. The structural formula is as follows:
Figure BDA0001277298300000184
example 3
1) 106.12g of diethylene glycol, 185.04g of epichlorohydrin and 112.20g of potassium hydroxide are added into an autoclave, nitrogen is introduced, the mixture is heated to about 60 ℃ under stirring and refluxed for 6 hours, and after the reaction is finished, the reaction product is cooled to room temperature, neutralized by acetic acid, and washed by water to remove the catalyst. And (3) distilling under reduced pressure to remove water and volatile matters to obtain 669g of ethylene glycol diglycidyl ether, wherein the structural formula is as follows:
Figure BDA0001277298300000191
2) 669g of ethylene glycol diglycidyl ether is put into an amination reaction kettle, 120g of ethylenediamine and 4.5g of n-butanol are added, the reaction temperature is 150 ℃, and the reaction is carried out for 2 to 6 hours, thus obtaining the amino compound crude product. Washing and rotary steaming the product to obtain the amino compound product, wherein the nitrogen content of the product is 6.23 percent, and the total conversion rate is 87.75 percent. The obtained amino compound has the chemical formula:
Figure BDA0001277298300000192
comparative curing agent 1: DETA curing agent (diethylenetriamine, molecular weight 103.17, Dow chemical products)
Comparative curing agent 2: 593 curing agent (Diethylenetriamine butyl glycidyl ether, molecular weight 217.13, manufactured by Guangzhou Industrial chemicals Co., Ltd.)
Examples 4, 5, 6 preparation of epoxy resins
Under the condition of room temperature and according to the mixture ratio in the table 1, the epoxy curing agents prepared in the embodiments 1,2 and 3 are respectively taken, epoxy resin E-51, defoaming agent and fire retardant are added, under the condition of high-speed stirring, a milky water-based epoxy resin coating is prepared, and according to the national standard GB/T1728-1979, the milky water-based epoxy resin coating is coated on a plastic sheet to prepare a transparent epoxy resin coating which has good mechanical property and acid and alkali resistance. And the curing properties of comparative curing agents 1 and 2 were evaluated in the same manner. The evaluation results are shown in Table 1.
By comparison, the general amine (diethylenetriamine) curing agent has the advantages of high volatility, high toxicity, quick curing and low product hardness at normal temperature. The addition curing agent of glycidyl ether and amine (diethylenetriaminebutyl glycidyl ether) has an excessively long curing time and low shear strength. In the embodiment, the product obtained by the polyether amine curing agent has high hardness, moderate curing time, good flexibility and high adhesive force.
TABLE 1
Figure BDA0001277298300000201

Claims (18)

1. An epoxy resin curing agent, which has the structure:
Figure FDA0002691363660000011
wherein the group M has a structure obtained by removing p hydroxyl groups from a hydroxyl compound having p' hydroxyl groups; p' is an integer between 1 and 2; the group Link represents a connecting group selected from a single bond or C1-10A hydrocarbylene group; radical R1And R2Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group; a radicals R3Or a radicals R4Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group; a radicals R6Or a radicals R7Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C1-10A hydrocarbon group and
Figure FDA0002691363660000012
wherein q radicals R8Are the same or different from each other and are each independently selected from C1-40A hydrocarbylene group; q radicals R9Are the same or different from each other and are each independently selected from hydrogen or C1-10A hydrocarbyl group; radical R10Selected from hydrogen or C1-10A hydrocarbyl group; q is an integer between 1 and 50; a is an integer between 1 and 10; a groups R' are the same or different and are each independently selected from a single bond or C1-10A hydrocarbylene group; radical R5Selected from hydrogen or C1-10A hydrocarbyl group; p is an integer between 1 and 2;
the epoxy resin curing agent has a structure represented by the following formula (II-A), (II-B) or (II-C):
Figure FDA0002691363660000013
wherein R attached to D11-is C1-20A hydrocarbon radical, D is a single bond or O, D' is H or
Figure FDA0002691363660000021
And at least one D' is
Figure FDA0002691363660000022
Wherein the radical R0Selected from hydrogen atoms and optionally substituted C1-50A hydrocarbyl group; the y groups Ru being identical or different from one anotherEach independently selected from C2-24A linear or branched alkylene group; y is selected from any number between 1 and 200.
2. The curing agent for epoxy resins according to claim 1, wherein the group Link is selected from the group consisting of a single bond and C1-6A linear or branched alkylene group; radical R1And R2Each independently selected from hydrogen or C1-6A linear or branched alkyl group; radical R3Or a radical R4Each independently selected from hydrogen and C1-6A linear or branched alkyl group; radical R6Or a radical R7Each independently selected from hydrogen, optionally substituted C1-6Straight or branched alkyl and
Figure FDA0002691363660000023
wherein the radical R8Are the same or different from each other and are each independently selected from C1-40A linear or branched alkylene group; radical R9Each independently selected from hydrogen and C1-6A linear or branched alkyl group; radical R10Selected from hydrogen and C1-6A linear or branched alkyl group; q is an integer between 1 and 10; a is an integer between 1 and 4; the radicals R' are each independently selected from the group consisting of a single bond and C1-6A linear or branched alkylene group; radical R5Selected from hydrogen and C1-6A linear or branched alkyl group; p is an integer between 1 and 2; p' is an integer between 1 and 2.
3. The curing agent for epoxy resins according to claim 1, wherein a is 1,2 or 3.
4. Curing agent for epoxy resins according to claim 1, characterized in that the hydroxyl compound with p' hydroxyl groups is selected from the group consisting of polyols with a corresponding number of free hydroxyl groups, polyesters with a corresponding number of free hydroxyl groups, polyethers with a corresponding number of free hydroxyl groups and aromatic amines with a corresponding number of free hydroxyl groups.
5. The curing agent for epoxy resins according to claim 4, characterized in that the polyether having a corresponding number of free hydroxyl groups is an alkylene glycol polymer which is a polymer obtained by homopolymerizing or copolymerizing an alkylene oxide, an alkylene glycol or an oxacycloalkane.
6. The method for producing the epoxy resin curing agent according to claim 1, comprising the steps of:
1) optionally, a step of producing an alkenyl polymer represented by the following formula (A-I),
Figure FDA0002691363660000031
wherein the radicals M and p-O-bonds, taken together, represent the polymer main chain; p is an integer between 1 and 2; the group Link represents a linking group selected from a single bond and C1-10A hydrocarbylene group; radical R1And R2Are identical or different from each other and are each independently selected from hydrogen and C1-10A hydrocarbyl group; a radicals R3Or a radicals R4Are identical or different from each other and are each independently selected from hydrogen and C1-10A hydrocarbyl group; a is an integer between 1 and 10; a radicals R' identical or different from one another, each independently selected from the group consisting of a single bond and C1-10A hydrocarbylene group; radical R5Selected from hydrogen and C1-10A hydrocarbon group,
2) subjecting the alkenyl polymer to an oxidation reaction with an oxidizing agent to convert at least one group contained in the alkenyl polymer into a group
Figure FDA0002691363660000032
Oxidized to a radical
Figure FDA0002691363660000033
And a step of obtaining an oxidation product,
3) subjecting the oxidation product obtained in step 2) to amination reaction with an aminating agent represented by the following formula (B-I) to subject the group to amination reaction
Figure FDA0002691363660000034
AminationIs a group
Figure FDA0002691363660000035
In the step (2) of (a),
Figure FDA0002691363660000036
wherein the radical R6And R7Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C1-10A hydrocarbon group and
Figure FDA0002691363660000037
wherein q radicals R8Are the same or different from each other and are each independently selected from C1-40A hydrocarbylene group; q radicals R9Are identical or different from each other and are each independently selected from hydrogen and C1-10A hydrocarbyl group; radical R10Selected from hydrogen and C1-10A hydrocarbyl group; q is an integer between 1 and 50.
7. The process according to claim 6, wherein the oxidizing agent is one or more selected from the group consisting of oxygen, ozone, hydrogen peroxide, a metal oxide, a metal peroxide, dichromic acid or a salt thereof, permanganic acid or a salt thereof, a peracid or a salt thereof, a hypohalous acid or a salt thereof, an organic hydroperoxide, and an organic peroxide; the amination agent is selected from one or more of ammonia, ethylamine, propylamine, ethylenediamine, ethanolamine and triethylene tetramine.
8. The process according to claim 6, wherein the oxidizing agent is one or more selected from the group consisting of hydrogen peroxide, organic hydroperoxides and organic acids peroxide.
9. A method for curing an epoxy resin, comprising the step of subjecting the epoxy resin curing agent according to any one of claims 1 to 5 to a curing crosslinking reaction with an epoxy resin.
10. The curing method according to claim 9, wherein the mass ratio of the epoxy resin curing agent to the epoxy resin is 1 to 10: 1.
11. The curing process of claim 9, wherein the curing and crosslinking reaction time is 1 to 10 hours.
12. The curing method according to claim 9, wherein the curing and crosslinking reaction is performed for 1 to 240 hours after completion of the curing and crosslinking reaction.
13. The curing method according to claim 9, wherein the epoxy resin is one or more selected from the group consisting of o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl epoxy resin, naphthol epoxy resin, alkylated benzene epoxy resin, trifunctional epoxy resin, and tetrafunctional epoxy resin.
14. The curing method according to claim 9, wherein the ratio of the epoxy equivalent of the epoxy resin to the amine equivalent of the epoxy resin curing agent is 0.9 to 1.2.
15. The curing process of claim 9 wherein a flame retardant is added to the epoxy resin.
16. The curing process of claim 9 wherein an anti-foaming agent is added to the epoxy resin.
17. The curing process of claim 9 wherein said epoxy resin is an epoxy resin having a melt viscosity of no greater than 0.5pa.s at 150 ℃.
18. An epoxy resin cured product obtained by the curing method according to any one of claims 9 to 17.
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CN104387578A (en) * 2014-12-08 2015-03-04 广州腾威科技有限公司 Polyether amine composition and preparation method and application thereof
WO2016102329A1 (en) * 2014-12-22 2016-06-30 Henkel Ag & Co. Kgaa Epoxy resin composition
CN106432708A (en) * 2015-08-10 2017-02-22 中石化石油工程技术服务有限公司 Multi-branched polyether amine, preparation method and applications thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2304305C (en) * 1997-10-22 2009-04-07 The Dow Chemical Company Thermally stable polyetheramines
CN104387578A (en) * 2014-12-08 2015-03-04 广州腾威科技有限公司 Polyether amine composition and preparation method and application thereof
CN104387578B (en) * 2014-12-08 2016-07-13 广州腾威科技有限公司 Polyetheramine compositions, preparation method and its usage
WO2016102329A1 (en) * 2014-12-22 2016-06-30 Henkel Ag & Co. Kgaa Epoxy resin composition
CN106432708A (en) * 2015-08-10 2017-02-22 中石化石油工程技术服务有限公司 Multi-branched polyether amine, preparation method and applications thereof

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