CN114685743A - Low-temperature epoxy resin curing agent and preparation method thereof - Google Patents

Low-temperature epoxy resin curing agent and preparation method thereof Download PDF

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CN114685743A
CN114685743A CN202210386289.XA CN202210386289A CN114685743A CN 114685743 A CN114685743 A CN 114685743A CN 202210386289 A CN202210386289 A CN 202210386289A CN 114685743 A CN114685743 A CN 114685743A
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adamantane
diisocyanate
curing agent
diamine
epoxy resin
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CN114685743B (en
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陈长敬
刘涛
曹阳
李帅
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Weiertong Technology Co ltd
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Weldtone Xiamen Technology Co Ltd
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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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides an epoxy resin low-temperature curing agent and a preparation method thereof, and relates to the technical field of epoxy resin curing agents. The preparation method of the epoxy resin low-temperature curing agent comprises the following steps: mixing cardanol or ginkgo diphenol and adamantane modified diamine, adding formaldehyde or paraformaldehyde for condensation reaction, and dehydrating to obtain a low-temperature curing agent; the adamantane-modified diamine is prepared by the following method: uniformly mixing adamantane diamine, diisocyanate and amino-terminated polyether, reacting at-5-10 ℃ for 0.5-3 hours, adding alkyl polyamine, and continuing to react for 0.5-2 hours to obtain the adamantane modified diamine. The curing agent can realize the curing of epoxy resin from low temperature to medium temperature by adjusting the distribution density of the adamantane structure on the molecular structure, and has better toughening effect on the epoxy resin.

Description

Epoxy resin low-temperature curing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of epoxy resin curing agents, and relates to an epoxy resin low-temperature curing agent and a preparation method thereof.
Background
The phenolic aldehyde amine curing agent obtained by Mannich reaction of phenol and derivatives thereof with organic amine compounds (usually primary amine) and formaldehyde (or paraformaldehyde) is an excellent low-temperature curing agent for epoxy resin, and can realize curing of epoxy resin at normal temperature or lower.
However, the curing temperature applicable range of the curing agent obtained by the current method for preparing the phenolic aldehyde amine curing agent is small, the phenolic aldehyde amine curing agent applicable to the temperature range from low temperature (0-10 ℃) to medium temperature (50-80 ℃) is difficult to obtain by one method, and even if the formula or process adjustment is carried out, the obtained phenolic aldehyde amine curing agent is generally the curing agent in the medium temperature range, and the operation time at low temperature is not high.
Disclosure of Invention
One of the objectives of the present invention is to overcome the above drawbacks in the prior art, and to provide a method for preparing an epoxy resin low-temperature curing agent, which employs a side chain structure with a large steric hindrance to reduce the activity of a phenolic aldehyde amine curing agent, and can change the curing activity of the phenolic aldehyde amine curing agent according to the density distribution of the introduced side chain structure with a large steric hindrance.
The second purpose of the invention is to provide the epoxy resin low-temperature curing agent prepared by the method.
The technical scheme of the invention is as follows:
a preparation method of an epoxy resin low-temperature curing agent comprises the steps of mixing cardanol or ginkgo diphenol and adamantane modified diamine, adding formaldehyde or paraformaldehyde for condensation reaction, and dehydrating to obtain the epoxy resin low-temperature curing agent;
the adamantane-modified diamine is prepared by the following method: uniformly mixing adamantane diamine, diisocyanate and amino-terminated polyether, reacting at-5-10 ℃ for 0.5-3 hours, adding alkyl polyamine, and continuously reacting for 0.5-2 hours to obtain adamantane modified diamine;
the molar ratio of the adamantane diamine to the diisocyanate to the amino-terminated polyether is 0.05-0.3:1: 0.1-0.6;
the ratio of the mole number of the diisocyanate to the sum of the mole numbers of the adamantane diamine, the amino-terminated polyether and the alkyl polyamine is 1: 1.3-2.
Preferably, the weight ratio of the cardanol or the ginkgol, the adamantane modified diamine and the formaldehyde or the paraformaldehyde is 100:30-60: 15-40.
Preferably, the general structural formula of the adamantane diamine is NH2(CH2)nR1(CH2)nNH2Wherein R is1Represents an adamantane structure, and n is 0, 1, 2 or 3.
Preferably, the adamantanediamine is 1, 3-bis (4-aminophenyl) adamantane.
Preferably, the diisocyanate is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and toluene diisocyanate trimer.
Preferably, the amino-terminated polyether has a number average molecular weight of not more than 1500.
Preferably, the general structural formula of the alkyl polyamine is NH2R2NH2Wherein R is2Is C2-C6 alkylene or substituted alkylene.
Preferably, the alkyl polyamine is one or a combination of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
Preferably, the specific conditions of the condensation reaction are as follows: the reaction is carried out for 0.2-1 hour at 70-90 ℃ and then for 1-5 hours at 100-130 ℃.
An epoxy resin low-temperature curing agent prepared by the preparation method of any one of the embodiments.
The phenolic aldehyde amine curing agent is a common low-temperature curing agent for epoxy resin, and has the characteristics of extremely high curing speed and low-temperature curing (even lower than 0 ℃). However, for some applications, it is required that the epoxy resin can be cured at low temperature and have a good operation time, and the curing rate is fast after the curing is started, or a curing agent can be provided, so that the epoxy resin can be cured at medium temperature (50-80 ℃) fast, but the epoxy resin is cured at low temperature (0-10 ℃) slowly and has a long operation time. Therefore, the inventor designs a phenolic aldehyde amine curing agent with a special structure, adamantane diamine with a large three-dimensional structure is used as one of raw materials for preparing the phenolic aldehyde amine curing agent, an adamantane structure with a large steric hindrance function is introduced into a side chain of a molecular structure of the phenolic aldehyde amine curing agent, the adamantane structure with the large steric hindrance function can hinder the curing activity of the phenolic aldehyde amine to a certain extent, the higher the distribution density of the adamantane structure is, the larger the hindrance effect is, the slower the curing speed is, but when the temperature is increased, the molecular chain movement is accelerated, the hindrance effect of the adamantane structure is rapidly reduced, and the curing speed is accelerated. Therefore, the curing activity of the phenolic aldehyde amine curing agent can be adjusted by adjusting the distribution density of the adamantane side chain structure in the phenolic aldehyde amine structure, and the following purposes are achieved: (1) the curing agent has certain operation time at low temperature, and the curing rate is high due to the temperature rise of the exothermic reaction after the curing is started; (2) curing is fast at medium temperatures but slow at low temperatures, allowing longer operating times at low temperatures.
The invention has the beneficial effects that:
(1) according to the invention, adamantane diamine and other diamino compounds are reacted with diisocyanate to obtain amino-terminated polyurethane prepolymer with an adamantane structure on a side chain, and the amino-terminated polyurethane prepolymer is subjected to Mannich reaction with cardanol or ginkgol and formaldehyde or paraformaldehyde to generate the phenolic aldehyde amine curing agent.
(2) The phenolic aldehyde amine curing agent molecule of the invention has the following characteristics: 1) the side chain is grafted with the adamantane structure with a large three-dimensional structure, so that a certain shielding effect can be generated on the activity of amino groups, the shielding effect is larger when the distribution density of the adamantane structure is higher, and the curing activity of the phenolic aldehyde amine curing agent can be adjusted by adjusting the distribution density of the adamantane, so that the adamantane structure can be used as a low-temperature curing agent and a medium-temperature curing agent; 2) the benzene ring of the cardanol or the ginkgol contains a longer carbon chain structure, so that the cardanol or the ginkgol can play a toughening role in epoxy resin; 3) the polyurethane chain segment and the adamantane structure can also play a toughening and reinforcing role on the epoxy resin. Therefore, the low-temperature curing agent of the invention also has better toughening and reinforcing effects on the epoxy resin, and simultaneously plays roles of the epoxy resin curing agent and the toughening and reinforcing agent.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The invention provides a preparation method of an epoxy resin low-temperature curing agent, which comprises the steps of mixing cardanol or ginkgo diphenol and adamantane modified diamine, adding formaldehyde or paraformaldehyde for condensation reaction, and dehydrating to obtain the epoxy resin low-temperature curing agent;
the adamantane-modified diamine is prepared by the following method: uniformly mixing adamantane diamine, diisocyanate and amine-terminated polyether, reacting for 0.5-3 hours at the temperature of-5-10 ℃, adding alkyl polyamine, and continuing to react for 0.5-2 hours to obtain adamantane modified diamine;
the molar ratio of the adamantane diamine to the diisocyanate to the amino-terminated polyether is 0.05-0.3:1: 0.1-0.6;
the ratio of the number of moles of diisocyanate to the sum of the number of moles of adamantanediamine, amine-terminated polyether and alkylpolyamine is 1: 1.3-2.
According to the invention, the adamantane diamine and the amino-terminated polyether are adopted to react with the diisocyanate, the amino-terminated polyether can not only provide a flexible chain segment, but also play a role in spacing to prevent the continuous reaction of the adamantane diamine and an isocyanate group from deteriorating due to steric hindrance and shielding effects of a large stereo structure of the adamantane, and simultaneously the adamantane diamine and the amino-terminated polyether are simultaneously added to react with the diisocyanate, so that the side chains of the adamantane on a polyurethane main chain are uniformly distributed, uniform steric hindrance can be generated, and the activity of the curing agent can be better controlled. When the amino-containing chain segment on the adamantane structure of the adamantanediamine is long enough, such as containing 3 carbon atoms, the steric hindrance and shielding effect of the adamantane becomes small, and the amino-terminated polyether can be added little; when the adamantane structure of the adamantane diamine contains a short amino-containing chain segment, such as containing 0 or 1 carbon atom, the steric hindrance and shielding effect of the adamantane is large, and a large amount of amino-terminated polyether needs to be added; if the main chain of the diisocyanate contains more carbon atoms, such as more than 6 carbon atoms, the steric hindrance and shielding effect of the adamantane are smaller, and the amino-terminated polyether can be less added; if the diisocyanate has fewer carbon atoms in its backbone, e.g., 0, 1, 2 or 3 carbon atoms, the adamantane is more sterically hindered and shielding, and a relatively large amount of the amine-terminated polyether may be added. However, the amounts of the adamantane diamine, the amino-terminated polyether and the diisocyanate are all added in the invention in order to adjust the distribution density of the adamantane, and the proportion of the raw materials can be adjusted according to the needs.
The continuous addition of the alkyl polyamine can convert the end group from isocyanate to primary amino, i.e. the adamantane-modified diamine of the present invention is obtained, and the subsequent Mannich reaction can be continued.
In the invention, the distribution density of the adamantane in the product curing agent can be controlled by the adding amount of the added adamantane diamine, so that the curing agent is suitable for different curing temperatures. For example, to make the curing agent suitable for use at 0-5 ℃, the molar ratio of adamantanediamine, diisocyanate, and amino-terminated polyether may be 0.05-0.1:1: 0.1-0.6; to make the curing agent suitable for use at 20-40 ℃, the molar ratio of adamantanediamine, diisocyanate, and amino-terminated polyether can be 0.15-0.2:1: 0.1-0.6; to make the curing agent suitable for use at 60-80 ℃, the molar ratio of adamantanediamine, diisocyanate, and amino-terminated polyether may be 0.25-0.3:1: 0.1-0.6. However, the curing speed of the epoxy resin depends on the kind of the epoxy resin, the curing accelerator, the filler, and other factors in addition to the temperature. Therefore, the suitable curing temperature of the curing agent is only a rough range and is not intended to limit the present invention.
In a preferred embodiment of the invention, the molar ratio of the adamantanediamine, the diisocyanate and the amino-terminated polyether is from 0.05 to 0.25:1:0.15 to 0.5 and the ratio of the number of moles of diisocyanate to the sum of the number of moles of the adamantanediamine, the amino-terminated polyether and the alkyl polyamine is from 1:1.5 to 1.8. The amount of diisocyanate relative to the adamantane diamine, the amine-terminated polyether and the alkyl polyamine is insufficient, the end group of the obtained product, namely the adamantane modified diamine, is an amino group, and the molar ratio of the isocyanate to the amino group is controlled, so that the molecular weight of the adamantane modified diamine is not large, and the end amino group still has high activity.
In a preferred embodiment of the invention, the weight ratio of cardanol or ginkgo diphenol, adamantane modified diamine and formaldehyde or paraformaldehyde is 100:30-60: 15-40. Paraformaldehyde, also known as polyoxymethylene, polyformaldehyde, can replace aqueous formaldehyde solutions and can reduce subsequent water treatment. More preferably, the paraformaldehyde of the present invention may be a low polymerization degree paraformaldehyde, such as a paraformaldehyde having a polymerization degree of 2 to 8.
In a preferred embodiment of the present invention, the general structural formula of the adamantanediamine is NH2(CH2)nR1(CH2)nNH2Wherein R is1Represents an adamantane structure, and n is 0, 1, 2 or 3. More preferably, n is 0 or 1.
In a preferred embodiment of the invention, the adamantanediamine is 1, 3-bis (4-aminophenyl) adamantane.
In a preferred embodiment of the present invention, the diisocyanate is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and toluene diisocyanate trimer.
In a preferred embodiment of the invention, the amino-terminated polyether has a number average molecular weight of not more than 1500. More preferably, the amino-terminated polyether has a number average molecular weight of not more than 1000. Further preferably, the amino-terminated polyether has a number average molecular weight of not more than 800. Still more preferably, the amino-terminated polyether has a number average molecular weight of not less than 200. Specifically, the number average molecular weight may be 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, or 800.
In a preferred embodiment of the present invention, the alkyl polyamine has the general structural formula NH2R2NH2Wherein R is2Is C2-C6 alkylene or substituted alkylene. More preferably, the alkylene group is selected from ethylene, propylene and butylene, the substituted alkylene group is amino substituted alkylene group, and the structural general formula is- (CH)2)mNH(CH2)m-, where m is 1, 2 or 3.
In a preferred embodiment of the present invention, the alkyl polyamine is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
In a preferred embodiment of the present invention, the specific conditions of the condensation reaction are: the reaction is carried out for 0.2-1 hour at 70-90 ℃ and then for 1-5 hours at 100-130 ℃.
The invention also provides an epoxy resin low-temperature curing agent prepared by the preparation method of any one of the embodiments.
The technical solution of the present invention will be further described and illustrated below with reference to various embodiments. Unless otherwise specified, the parts described in the following examples and comparative examples are parts by weight.
Preparation example 1
Adding 0.06mol of 1, 3-adamantane diamine, 1mol of hexamethylene diisocyanate and 0.4mol of amino-terminated polyethylene glycol-350 (350 represents the number average molecular weight, and the like) into a container, reacting for 2 hours at 0 ℃, then adding 1.1mol of ethylenediamine, and continuing to react for 1.5 hours to obtain the adamantane modified diamine.
Preparation example 2
Adding 0.12mol of adamantane-1, 3-dimethylamine, 1mol of isophorone diisocyanate and 0.3mol of double-end amino polyethylene glycol-350 into a container, reacting for 2.5 hours at 0 ℃, adding 1.3mol of diethylenetriamine, and continuing to react for 1.5 hours to obtain the adamantane modified diamine.
Preparation example 3
Adding 0.2mol of adamantane-1, 3-dimethylamine, 1mol of isophorone diisocyanate and 0.4mol of amino-terminated polyethylene glycol-700 into a container, reacting for 3 hours at 3 ℃, then adding 1.2mol of diethylenetriamine, and continuing to react for 2 hours to obtain the diamondoid modified by the adamantane.
Preparation example 4
Adding 0.25mol of 1, 3-bis (4-amino benzene ring) adamantane, 1mol of toluene diisocyanate and 0.45mol of amino-terminated polyethylene glycol-700 into a container, reacting for 2 hours at 3 ℃, adding 1mol of diethylenetriamine, and continuing to react for 2 hours to obtain the adamantane modified diamine.
Example 1
100 parts of cardanol and 32 parts of adamantane-modified diamine described in preparation example 1 were mixed, 16 parts of paraformaldehyde having an average degree of polymerization of 4.2 was added, and the mixture was reacted at 75 ℃ for 0.6 hour, and further at 105 ℃ for 4 hours, followed by vacuum dehydration to obtain a phenalkamine low-temperature curing agent.
Example 2
100 parts of cardanol and 40 parts of adamantane-modified diamine in preparation example 2 were mixed, 25 parts of paraformaldehyde with an average degree of polymerization of 4.2 was added, and the mixture was reacted at 80 ℃ for 0.5 hour and then at 110 ℃ for 3 hours, followed by vacuum dehydration to obtain a phenalkamine low-temperature curing agent.
Example 3
100 parts of cardanol and 50 parts of adamantane-modified diamine in preparation example 3 were mixed, 32 parts of paraformaldehyde having an average degree of polymerization of 4.2 was added, and the mixture was reacted at 80 ℃ for 0.6 hour and then at 110 ℃ for 3.5 hours, followed by vacuum dehydration to obtain a phenalkamine low-temperature curing agent.
Example 4
100 parts of cardanol and 60 parts of adamantane-modified diamine described in preparation example 4 were mixed, 40 parts of paraformaldehyde having an average degree of polymerization of 4.2 was added, and the mixture was reacted at 75 ℃ for 0.8 hour, and further at 105 ℃ for 4 hours, followed by vacuum dehydration to obtain a phenalkamine low-temperature curing agent.
Example 5
100 parts of ginkgo diphenol and 35 parts of adamantane modified diamine in preparation example 1 are mixed, 20 parts of paraformaldehyde with the average polymerization degree of 3.7 are added, the mixture is reacted for 0.7 hour at 82 ℃, and then the mixture is reacted for 4 hours at 110 ℃, and the mixture is subjected to vacuum dehydration to obtain the phenolic aldehyde amine low-temperature curing agent.
Example 6
100 parts of ginkgo diphenol and 45 parts of adamantane modified diamine in preparation example 2 are mixed, 27 parts of paraformaldehyde with the average polymerization degree of 3.7 is added, the mixture is reacted at 82 ℃ for 0.7 hour, and then the reaction is carried out at 100 ℃ for 4.5 hours, and the mixture is dehydrated in vacuum, so that the phenalkamine low-temperature curing agent is obtained.
Example 7
100 parts of ginkgo diphenol and 50 parts of adamantane diamine obtained in preparation example 3 were mixed, 35 parts of paraformaldehyde with an average degree of polymerization of 3.7 was added, and the mixture was reacted at 82 ℃ for 0.7 hour and at 105 ℃ for 4 hours, followed by vacuum dehydration to obtain a phenalkamine low-temperature curing agent.
Example 8
100 parts of ginkgo diphenol and 55 parts of adamantane modified diamine in preparation example 4 are mixed, 32 parts of paraformaldehyde with the average polymerization degree of 3.7 is added, the mixture is reacted for 0.7 hour at 82 ℃, and then the mixture is reacted for 4 hours at 105 ℃, and the mixture is subjected to vacuum dehydration to obtain the phenolic aldehyde amine low-temperature curing agent.
Comparative example 1
Mixing 100 parts of cardanol and 32 parts of diethylenetriamine, adding 25 parts of paraformaldehyde with the average polymerization degree of 4.2, reacting for 0.6 hour at 75 ℃, reacting for 3.5 hours at 110 ℃, and performing vacuum dehydration to obtain the phenolic aldehyde amine low-temperature curing agent.
Comparative example 2
Adding 1mol of isophorone diisocyanate and 0.4mol of amino-terminated polyethylene glycol-350 into a container, reacting for 2.5 hours at 0 ℃, adding 1.3mol of diethylenetriamine, and continuing to react for 1.5 hours to obtain modified diamine.
100 parts of cardanol and 32 parts of the modified diamine are mixed, 22 parts of paraformaldehyde with the average polymerization degree of 4.2 is added into a container, the mixture reacts for 0.6 hour at 75 ℃, then the mixture reacts for 3.5 hours at 110 ℃, and the mixture is dehydrated in vacuum, so that the phenolic aldehyde amine low-temperature curing agent is obtained.
Comparative example 3
Adding 100 parts of cardanol, 32 parts of double-end amino polyethylene glycol-350 and 20 parts of paraformaldehyde with the average polymerization degree of 4.2 into a container, reacting at 75 ℃ for 0.6 hour, reacting at 105 ℃ for 4 hours, and performing vacuum dehydration to obtain the phenolic aldehyde amine low-temperature curing agent.
Comparative example 4
Adding 0.2mol of adamantane-1, 3-dimethylamine and 1mol of isophorone diisocyanate into a container, reacting for 2 hours at 3 ℃, adding 0.4mol of double-end amino polyethylene glycol-200, continuing to react for 2 hours, then adding 1.2mol of diethylenetriamine, and continuing to react for 2 hours to obtain the adamantane modified diamine.
Adding 100 parts of cardanol, 32 parts of adamantane modified diamine and 16 parts of paraformaldehyde with the average polymerization degree of 4.2 into a container, reacting at 75 ℃ for 0.6 hour, reacting at 105 ℃ for 4 hours, and dehydrating in vacuum to obtain the phenolic aldehyde amine low-temperature curing agent.
Comparative example 5
100 parts of ginkgo diphenol, 50 parts of adamantane modified diamine in comparative example 4 and 35 parts of paraformaldehyde with the average polymerization degree of 3.7 are added into a container, reacted at 82 ℃ for 0.7 hour, then reacted at 105 ℃ for 4 hours, and vacuum-dehydrated to obtain the phenolic aldehyde amine low-temperature curing agent.
Test example
The phenolic aldehyde amine low-temperature curing agent in the examples 1-8 and the comparative examples 1-5 is prepared according to the following formula: 100 parts of bisphenol A epoxy resin, 100 parts of phenol aldehyde amine low-temperature curing agent and 2 parts of triethylamine curing accelerator, and uniformly mixing the three raw materials at-5 ℃. The tack-free time and the tack-free time at different temperatures were measured separately.
The tensile shear strength is cast into a standard mechanical property test sample bar with the thickness of 4mm according to the requirement of GB/T7124-2008, the sample bar is cured for 72 hours at 25 ℃, then cured for 20 hours at 80 ℃, and then placed for 12 hours at 25 ℃ and then tested by a universal tensile machine.
The results are shown in Table 1.
TABLE 1
Figure BDA0003593854870000081
Figure BDA0003593854870000091
As can be seen from the data results in table 1, the low-temperature epoxy resin curing agent of the present invention has different curing activities by controlling the distribution density of the adamantane structure in the molecular structure of the curing agent, wherein the higher the distribution density of adamantane, the lower the curing activity, the higher the required curing temperature or the longer the curing time at the same temperature, the lower the distribution density of adamantane, the higher the curing activity, the lower the required curing temperature or the shorter the curing time at the same temperature, and the curing agent of the present invention has a better toughening effect on epoxy resin, and the higher the distribution density of adamantane, the higher the shear strength.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A preparation method of an epoxy resin low-temperature curing agent is characterized in that cardanol or ginkgol is mixed with adamantane modified diamine, formaldehyde or paraformaldehyde is added for condensation reaction, and dehydration is carried out to obtain the epoxy resin low-temperature curing agent;
the adamantane modified diamine is prepared by the following method: uniformly mixing adamantane diamine, diisocyanate and amino-terminated polyether, reacting at-5-10 ℃ for 0.5-3 hours, adding alkyl polyamine, and continuously reacting for 0.5-2 hours to obtain adamantane modified diamine;
the molar ratio of the adamantane diamine to the diisocyanate to the amino-terminated polyether is 0.05-0.3:1: 0.1-0.6;
the ratio of the mole number of the diisocyanate to the sum of the mole numbers of the adamantane diamine, the amino-terminated polyether and the alkyl polyamine is 1: 1.3-2.
2. The method of claim 1, wherein the weight ratio of cardanol or ginkgo biloba diol, adamantane-modified diamine, and formaldehyde or paraformaldehyde is 100:30-60: 15-40.
3. The method according to claim 1, wherein the adamantanediamine has a general structural formula of NH2(CH2)nR1(CH2)nNH2Wherein R is1Represents an adamantane structure, and n is 0, 1, 2 or 3.
4. The method according to claim 1, wherein the diamantane is 1, 3-bis (4-aminophenyl) adamantane.
5. The method according to claim 1, wherein the diisocyanate is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and toluene diisocyanate trimer.
6. The method of claim 1, wherein the amino terminated polyether has a number average molecular weight of not more than 1500.
7. The method of claim 1, wherein the alkyl polyamine has the general structural formula NH2R2NH2Wherein R is2Is C2-C6 alkylene or substituted alkylene.
8. The method according to claim 1, wherein the alkyl polyamine is one or more selected from diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
9. The preparation method according to claim 1, wherein the specific conditions of the condensation reaction are: the reaction is carried out for 0.2-1 hour at 70-90 ℃ and then for 1-5 hours at 100-130 ℃.
10. A low-temperature epoxy resin curing agent, which is prepared by the preparation method of any one of claims 1 to 9.
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