CN108192082A - The epoxy resin toughened method of reversible crosslink is prepared using ontology click chemistry reaction - Google Patents
The epoxy resin toughened method of reversible crosslink is prepared using ontology click chemistry reaction Download PDFInfo
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- CN108192082A CN108192082A CN201810092901.6A CN201810092901A CN108192082A CN 108192082 A CN108192082 A CN 108192082A CN 201810092901 A CN201810092901 A CN 201810092901A CN 108192082 A CN108192082 A CN 108192082A
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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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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Abstract
The present invention relates to a kind of preparation method of the thermoplastic toughening epoxy resin with thermal reversion chemical crosslinking characteristic, this method includes the following steps：1) after, being mixed using difunctional epoxy resin with polyfunctional epoxy resin, the intermediate that end group is furans functional group is obtained with furfurylmercaptan click-reaction；Difunctional epoxy resin be containing there are two the epoxy monomer of epoxy group, polyfunctional epoxy resin be containing there are three and three or more epoxy groups epoxy monomer；2), the intermediate is reacted with the crosslinking agent generation Diels Alder containing maleimide base group, forms the epoxy resin toughened of reversible crosslink.The present invention overcomes determining for conventional curing epoxy resin indissoluble infusibility；The thermoplasticity reversible crosslink is epoxy resin toughened to realize the recycling of cross-linked epoxy resin using Diels Alder covalent bonds, and still is able to keep the performance of conventional epoxies, and method is easy, has prospects for commercial application.
Description
Technical field
The present invention relates to a kind of thermoplastic toughening epoxy resin and preparation method thereof with thermal reversion chemical crosslinking characteristic,
That is, under tertiary amine catalyst effect, after being mixed in a certain ratio using difunctional epoxy resin and polyfunctional epoxy resin,
The intermediate that end group is furans functional group is obtained with furfurylmercaptan click-reaction, is occurred with the crosslinking agent containing maleimide base group
Diels-Alder reacts, and forms the epoxy resin toughened of reversible crosslink, and solution crosslinking can occur at high temperature, so as to fulfill increasing
The repetition recycling of tough epoxy resin and secondary operation.
Background technology
Epoxy resin is a kind of important thermosetting polymer, with its chemical stability is strong, shrinkage is low, high dielectric property
It is widely used in the fields such as adhesive, structural material, printed circuit board, Electronic Packaging.Traditional covalent cross-linking epoxy resin
Since crosslink density is higher, there is larger brittleness, limit its application.And the epoxy resin of curing molding is anti-due to being crosslinked
The irreversibility answered, it is difficult to which the methods of being such as heat-treated by some is reprocessed, and is limited it and is repeated to recycle, causes
The larger waste of resource.
Toughening modifying based on epoxy resin has more research, and Chinese patent CN106674902A discloses a kind of toughening
Epoxy resin and preparation method thereof, using addition plasticizer, low molecular weight toughener, thermoplastic resin and heat-resistant powder filler etc.
Toughening methods promote the toughness of epoxy resin and maintain preferable mechanical property, but the product after epoxy curing agent cures
Can not secondary operation utilize, service efficiency substantially reduces.There are also researchs at this stage to be dedicated to reversible crosslink epoxy resin
It prepares.Chinese patent CN103483605A discloses a kind of THERMALLY REVERSIBLE COVALENT epoxy resin and preparation method thereof, and method is
The linear epoxy resin that synthesis side chain carries crosslink sites is reacted with epoxy monomer using divinyl macromer monoamine, is dissolved
After rear and dienophile crosslinking agent is sufficiently mixed into solvent, solvent is removed in vacuum drying oven, is then carried out at 20-90 DEG C
The epoxy resin of THERMALLY REVERSIBLE COVALENT is made in cross-linking reaction.However the method is more traditional, amine and epoxy group reaction rate compared with
Slowly cross-linking reaction can be just carried out and after solvent need to be removed, operation is complex, it is difficult on a large scale for practical application.Chinese patent
CN101348560A discloses a kind of epoxy resin containing furan group and preparation method thereof, the epoxy resin and polyfunctionality
Maleimide carries out curing achievable reversible crosslink.However this method for preparing the epoxy resin containing furan group is needed to undergo and be taken off
Multiple steps such as water ring, organic extraction, vacuum distillation, it is relatively complicated.Chinese patent CN103249712A discloses one kind can
The preparation process of epoxy resin new compound is reused, using polyamine, polymercaptan or the curing agent solidification ring for thering is acid to be inclined to
Oxygen resin.The resin can decompose the recycling so as to fulfill epoxy resin under conditions of temperature gradually rises in acid.
However this way of recycling need to be implemented under the conditions of specific acidity, operating condition is more limited to.
Also there is the report much about reversible crosslinked polymer preparation and performance in document.Bai Jing et al., referring to
Macromolecules, Vol.48,3539-3546 (2015) are prepared for the butadiene modified rubber of reversible crosslink.It is molten in toluene
In agent, by the double bond click-reaction in furfurylmercaptan and butadiene rubber, furan group is introduced on side chain, is reacted using DA
To curing rubber.Modified butadiene rubber has certain mechanical property and repeats processing performance.
Turkenburg et al., referring to Polymer, Vol.79,187-194 (2015) are prepared for a kind of with self-repairability
The epoxy resin of energy and thermal reversion.Preparation method is：By chaff amine and epoxy resin in 125 DEG C of curing a period of times, generation
Side chain carries the performed polymer of furans crosslink sites.Performed polymer is squeezed with maleimide by double screw extruder bulk reaction
Go out, curing obtain can self-regeneration epoxy resin.Technological deficiency present in it is：Amine and epoxy reaction rate are slower, instead
Answer condition harsher, and reaction conversion rate cannot reach 100%, it is 94% to be mentioned in document.And do not stress to propose in text
The mechanical property of the epoxy resin of self-regeneration, especially toughness.
Kuang Xiao et al., referring to Polymer, Vol.84,1-9 (2016) are prepared for the ring with shape memory function
Oxygen resin.By the way that material composition ratio is controlled to obtain different glass transition temperatures, coordinate the thermal reversion key of DA, design is provided
There is the new material of shape memory function.But all substantially using amine cured epoxy resin in above-mentioned report, the reaction time is longer, Gu
It is generally not high to change efficiency；Obtained modified epoxy mechanical property is not generally good enough, and industrial application value has to be hoisted.
Invention content
The technical problem to be solved in the present invention is to provide a kind of reversible crosslink increasings prepared using the reaction of ontology click chemistry
The method of tough epoxy resin, the shortcomings that so as to overcome conventional curing epoxy resin indissoluble infusibility；The thermoplasticity reversible crosslink toughening
Epoxy resin realizes the recycling of cross-linked epoxy resin using Diels-Alder covalent bonds, and still is able to keep traditional ring
The performance of oxygen resin, and method is easy, has prospects for commercial application.
In order to solve the above technical problem, the present invention provides a kind of reversible crosslinks prepared using the reaction of ontology click chemistry
Epoxy resin toughened method, includes the following steps：
1) it after, being mixed using difunctional epoxy resin with polyfunctional epoxy resin, is obtained with furfurylmercaptan click-reaction
End group is the intermediate of furans functional group；
The difunctional epoxy resin is containing there are two the epoxy monomer of epoxy group, the polyfunctional epoxy resins
For contain there are three and three or more epoxy groups epoxy monomer；
2), the intermediate is reacted with the crosslinking agent generation Diels-Alder containing maleimide base group, is formed reversible
It is crosslinked epoxy resin toughened.
The method epoxy resin toughened as the reversible crosslink prepared using the reaction of ontology click chemistry of the present invention is changed
Into：
Step 1), the intermediate that end group is furans functional group：
Under inert gas (argon gas or nitrogen etc.) protection, under solvent-free conditions, in 20~100 DEG C by 50~140 parts
Difunctional epoxy resin and 20~100 parts of polyfunctional epoxy resins are uniformly mixed, and are added in 15~80 parts of furfurylmercaptans and are fully stirred
It mixes, then adds in 0.5~5 part of tertiary amine catalyst 0.1~3h of isothermal reaction, obtain the intermediate that end group is furans functional group；
Alternatively, under inert gas (argon gas or nitrogen etc.) protection, under solvent-free conditions, in 20~100 DEG C by 50~
The epoxy resin and 20~100 parts of polyfunctional epoxy resins generated after 140 parts of chain extensions is uniformly mixed, and adds in 15~80 parts of chaff sulphur
Alcohol is sufficiently stirred 0.1~3h of isothermal reaction, obtains the intermediate that end group is furans functional group；
Step 2) is that prepare reversible crosslink epoxy resin toughened for the intermediate of furans functional group with end group：
Under inert gas (argon gas or nitrogen) protection, under solvent-free conditions, 60~100 parts are contained in 100~160 DEG C
The crosslinking agent for having maleimide base group is added in the intermediate that the end group obtained by step 1) is furans functional group and is sufficiently stirred,
Prior to 100~160 DEG C 0.1~0.5h of reaction, then then at 20~90 DEG C of (preferably 60~90 DEG C) 0.1~48h of cross-linking reaction,
It is epoxy resin toughened to obtain reversible crosslink.
The epoxy resin toughened method of reversible crosslink prepared using the reaction of ontology click chemistry as the present invention into
One step is improved：
The epoxy resin generated after the chain extension is aromatics epoxy monomer, in non-aromatic based epoxy resin monomer
It is at least one to carry out the ring generated after click-reaction chain extension under tertiary amine catalyst effect by double mercapto functional group compounds
Oxygen resin；
Preparation method is：
Under inert gas (argon gas or nitrogen) protection, under solvent-free conditions, in 20~80 DEG C by 30~90 parts of virtue
At least one of fragrant based epoxy resin monomer, non-aromatic based epoxy resin monomer and 19~45 parts of difunctional sulfydryl chemical combination
Object (that is, double mercapto functional group compounds) is uniformly mixed, and is sufficiently stirred, and then adds in 0.5~5 part of tertiary amine catalyst in 20~80
DEG C reaction 0.1~5h, obtain end group be epoxy-functional chain-extened epoxy resin；
The difunctional sulfhydryl compound is containing there are two the sulfhydryl compound monomers of mercapto groups.
The epoxy resin toughened method of reversible crosslink prepared using the reaction of ontology click chemistry as the present invention into
One step is improved：
The difunctional sulfhydryl compound is glycol dimercaptosuccinate, 1,6- ethanthiols, meso -2,3- two
Dimercaptosuccinic acid, dithioerythritol, 1,2- dithioglycols, 1,3- dimercaptopropanes, 1,2- succinimide mercaptans, 4,4 '-thiobis benzene sulphur
Phenol, dimercaprol dimercaptopropanol, Toluene-3,4-dithiol, 4- dithiols.
The epoxy resin toughened method of reversible crosslink prepared using the reaction of ontology click chemistry as the present invention into
One step is improved：
The difunctional epoxy resin for aromatics epoxy monomer, in non-aromatic based epoxy resin monomer at least
It is a kind of；The aromatics epoxy monomer is bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol S two shrink
Glycerin ether, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester,；
The non-aromatic based epoxy resin monomer is ethylene glycol diglycidylether, propylene glycol diglycidylether, fourth two
Alcohol diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether and polypropylene oxide two are shunk sweet
Oily ether；
The polyfunctional epoxy resin is glycidyl amine epoxy resin monomer, glycidyl ether type epoxy resin list
Body；
The glycidyl amine epoxy resin monomer is 4,4'- diaminodiphenylmethane epoxy resin, three-glycidyl
Bis- (N, N- the 2-glycidyl ammonia of base para-aminophenol, triglycidyl meta-aminophenol, epoxidation m-xylene diamine, 1,3-
Methyl) hexamethylene；
It is sweet that the glycidyl ether type epoxy resin monomer is novolac epoxy resin, three (4- hydroxy phenyls) methane three shrink
Oleyl ether, 1,1,1- tri- (4- hydroxy phenyls) ethyl triglycidyl ether, 2,2 ', 2 ", 2 " '-[1,2- ethanetetrayls four (4,
1- phenylene methylenes oxygen)] tetraoxane, Dicycldpentadiene-phenol glycidyl ether resin.
The epoxy resin toughened method of reversible crosslink prepared using the reaction of ontology click chemistry as the present invention into
One step is improved：
The tertiary amine catalyst is 2,4,6- tri- (dimethylamino methyl) phenol, N, N- dimethyl benzylamines, N, N- dimethyl
Cyclohexylamine, bis- (2- dimethylaminoethyls) ethers, triethylamine, N, accelerine.
The epoxy resin toughened method of reversible crosslink prepared using the reaction of ontology click chemistry as the present invention into
One step is improved：
The crosslinking agent containing maleimide base group for N-N '-(4,4- methylenediphenyls) bismaleimide,
N-N- (4- methyl-1s, 3- phenylenes) bismaleimide, N-N '-penylene bismaleimide, the bis- (maleimides of 1,2-
Amine) ethane or 4-4 '-dimaleoyl imino diphenyl-methane.
The present invention reversible crosslink it is epoxy resin toughened, can occur at high temperature solution crosslinking, so as to fulfill flexibilizing epoxy
The repetition recycling of resin and secondary operation.
Thermoplasticity reversible crosslink provided by the invention was epoxy resin toughened both superior with thermosetting chemistry cross-linked material
Mechanical property is significantly increased compared with conventional epoxies toughness；Also there is thermoplastic material to repeat processing simultaneously (can repeatedly recycle and add
Work utilization) advantage, so as to fulfill the recycling of resource.
Thermoplasticity reversible crosslink provided by the invention it is epoxy resin toughened can by change crosslink sites quantity, crosslinking it is close
Degree and epoxy resin ingredient, material property is adjusted in wide range, meets various products demand, before having commercial Application
Scape.Specifically, the amount of the substance for the furfurylmercaptan for passing through addition, the quantity of controllable crosslink sites, have simple and convenient controllable
Technical advantage；Amount by the substance for changing the crosslinking agent added in, controllable crosslink density.
The epoxy resin toughened preparation process of thermoplasticity reversible crosslink provided by the invention greatly promotes biography without using solvent
Matter efficiency；Reaction step is efficiently quick；Furans crosslink sites are introduced using click-reaction, reaction condition is mildly convenient, reacts
Journey is precisely efficient.
The present invention is melted by high-temperature body, adding in the substance containing maleimide base group, is stirred in machinery
It mixes material mixing is uniform under the action of device, directly takes out and cure under certain condition, without removing solvent.
The epoxy resin toughened low production cost of thermoplasticity reversible crosslink provided by the invention, preparation method is easy, is easy to
Industrialized production.
In conclusion a kind of thermoplastic toughening epoxy resin with thermal reversion chemical crosslinking characteristic of present invention synthesis,
One step of furans functional group is rapidly and efficiently introduced into epoxy resin end using the click-reaction of sulfydryl-epoxy in ontology, is used
Dienophile crosslinking agent carries out crosslinking curing, and solution crosslinking can occur at high temperature, so as to fulfill epoxy resin toughened repetition
Recycling and secondary operation；Epoxy resin after curing has higher Young's modulus and elongation at break, and toughness significantly increases
By force.Ontology click-reaction is not required to add any solvent, and the time required to greatly reducing mass transfer, and click-reaction is rapidly and efficiently, method
Step is easy, has prospects for commercial application.
Specific embodiment
The present invention is specifically described below by embodiment, but protection scope of the present invention is not limited to these implementations
Example.
The epoxy resin toughened preparation method of embodiment 1, a kind of reversible crosslink, difunctional epoxy resin select propylene glycol
Diglycidyl ether, polyfunctional epoxy resin select novolac epoxy resin, and tertiary amine catalyst selects 2,4,6- tri- (dimethylaminos
Methyl) phenol, step is as follows：
1), under nitrogen protection, in 20 DEG C of thermostatical oil baths, by 50g propylene glycol diglycidylethers and 27.5g phenolic aldehyde
Epoxy resin is added in the three neck round bottom flask of 150ml, is uniformly mixed using mechanical agitation；Then 24.3g chaffs are sequentially added
2,4,6- tri- (dimethylamino methyl) phenol of mercaptan and 1.1g, isothermal reaction 3 hours obtain end group as in furans functional group
Mesosome, grafting rate reach 99.5%.
2), under nitrogen protection, intermediate obtained by the reaction and 62g N-N '-(4,4- methylenediphenyl) span are come
Acid imide stirs evenly in 160 DEG C of thermostatical oil baths, fully reaction 0.1 hour, pours into the polytetrafluoroethylene (PTFE) mould for being placed in baking oven
In tool, carry out cross-linking reaction 24 hours in 70 DEG C, obtain the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 2, a kind of reversible crosslink, difunctional epoxy resin select bisphenol-A
Diglycidyl ether, polyfunctional epoxy resin select triglycidyl group para-aminophenol, and tertiary amine catalyst selects N, N- bis-
Methylbenzylamine, step are as follows：
1), under nitrogen protection, in 100 DEG C of thermostatical oil baths, 72g bisphenol A diglycidyl ethers and 54g tri- are shunk
Glyceryl para-aminophenol is added in the three neck round bottom flask of 250ml, is uniformly mixed using mechanical agitation；Then it sequentially adds
45g furfurylmercaptans and 3.5g N, N- dimethyl benzylamines, isothermal reaction 0.1 hour obtain the intermediate that end group is furans functional group,
Grafting rate reaches 99.8%.
2), under nitrogen protection, by intermediate obtained by the reaction and 78g 1, bis- (maleimide) ethane of 2- are at 100 DEG C
Stirred evenly in thermostatical oil bath, fully reaction 0.5 hour, pour into and be placed in the Teflon mould of baking oven, in 90 DEG C into
Row cross-linking reaction 0.1 hour obtains the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 3, a kind of reversible crosslink, difunctional epoxy resin select Bisphenol F
The mixture of diglycidyl ether and butanediol diglycidyl ether selects 1,6- ethanthiols as chain extension substance, multifunctional
Group's epoxy resin selects three (4- hydroxy phenyls) methane triglycidyl group ethers, and tertiary amine catalyst selects n,N-Dimethylaniline,
Step is as follows：
1), under nitrogen protection, in 20 DEG C of thermostatical oil baths, by 20g Bisphenol Fs diglycidyl ether and 28g butanediols
Diglycidyl ether is added in the three neck round bottom flask of 100ml, is uniformly mixed using mechanical agitation；Then 22g is sequentially added
1,6- ethanthiol and 1.5g n,N-Dimethylaniline, isothermal reaction 5 hours obtain the difunctional asphalt mixtures modified by epoxy resin of sulfydryl chain extension
Fat.
2), under nitrogen protection, in 55 DEG C of thermostatical oil baths, by the difunctional epoxy resin of obtained sulfydryl chain extension
It is mixed with (4- hydroxy phenyls) the methane triglycidyl groups of 52g tri- ether, 48g furfurylmercaptans, isothermal reaction 1.5 hours obtains end group
For the intermediate of furans functional group, grafting rate reaches 99.9%.
3), under nitrogen protection, intermediate obtained by the reaction and 72g N-N- (4- methyl-1s, 3- phenylenes) span are come
Acid imide stirs evenly in 120 DEG C of thermostatical oil baths, fully reaction 0.4 hour, pours into the polytetrafluoroethylene (PTFE) mould for being placed in baking oven
In tool, carry out cross-linking reaction 24 hours in 80 DEG C, obtain the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 4, a kind of reversible crosslink, difunctional epoxy resin select bisphenol S
The mixture of diglycidyl ether and o-phthalic acid diglycidyl ester selects 4,4'- thiobis-benzenethiols as chain extension object
Matter, polyfunctional epoxy resin select 2,2 ', 2 ", 2 " '-[1,2- ethanetetrayl four (4,1- phenylene methylene oxygen)] four epoxies
Ethane, tertiary amine catalyst select triethylamine, and step is as follows：
1), under nitrogen protection, in 80 DEG C of thermostatical oil baths, by 27g bisphenol-S diglycidyl ethers and 48g neighbour's benzene two
Formic acid 2-glycidyl ester is added in the three neck round bottom flask of 150ml, is uniformly mixed using mechanical agitation；Then it sequentially adds
36g4,4'- thiobis-benzenethiol and 4g triethylamines, isothermal reaction 0.1 hour obtain the difunctional asphalt mixtures modified by epoxy resin of sulfydryl chain extension
Fat.
2), under nitrogen protection, in 40 DEG C of thermostatical oil baths, by the difunctional epoxy resin of obtained sulfydryl chain extension
With 56g2,2 ', 2 ", 2 " '-[1,2- ethanetetrayls four (4,1- phenylene methylenes oxygen)] tetraoxanes, 76g furfurylmercaptans mix
It closes, isothermal reaction 2.5 hours, obtains the intermediate that end group is furans functional group, grafting rate reaches 99.6%.
3), under nitrogen protection, by intermediate obtained by the reaction and 69g N-N '-penylene bismaleimide 140
It is stirred evenly in DEG C thermostatical oil bath, fully reaction 0.2 hour, pours into and be placed in the Teflon mould of baking oven, in 60 DEG C
It carries out cross-linking reaction 36 hours, obtains the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 5, a kind of reversible crosslink, difunctional epoxy resin select isophthalic two
The mixture of formic acid 2-glycidyl ester and terephthalic acid diglycidyl ester selects 1,2- dithioglycols as chain extension object
Matter, polyfunctional epoxy resin select 4, and 4 '-diaminodiphenylmethane epoxy resin, tertiary amine catalyst selects N, N- diformazan basic rings
Hexylamine, step are as follows：
1), under nitrogen protection, in 40 DEG C of thermostatical oil baths, by 22g Diglycidyl M-phthalates and 22g pairs
Phthalic acid 2-glycidyl ester is added in the three neck round bottom flask of 100ml, is uniformly mixed using mechanical agitation；Then successively
20g 1 is added in, 2- dithioglycols and 1.4gN, N- dimethyl cyclohexyl amine, isothermal reaction 2 hours obtain the difunctionality of sulfydryl chain extension
Group's epoxy resin.
2), under nitrogen protection, in 40 DEG C of thermostatical oil baths, by the difunctional epoxy resin of obtained sulfydryl chain extension
With 58g4,4 '-diaminodiphenylmethane epoxy resin, the mixing of 36g furfurylmercaptans, isothermal reaction 2.5 hours obtains end group as furans
The intermediate of functional group, grafting rate reach 99.6%.
3), under nitrogen protection, intermediate obtained by the reaction and 90g 4-4 '-dimaleoyl imino diphenyl-methane are existed
It is stirred evenly in 120 DEG C of thermostatical oil baths, fully reaction 0.4 hour, pours into and be placed in the Teflon mould of baking oven, in 80
DEG C cross-linking reaction 24 hours is carried out, obtain the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 6, a kind of reversible crosslink, difunctional epoxy resin select ethylene glycol
The mixture of diglycidyl ether and polypropylene glycol diglycidyl ether selects toluene-3,4-dithiol as chain extension substance, more
Functional group epoxy resin selects epoxidation m-xylene diamine, and tertiary amine catalyst selects bis- (2- dimethylaminoethyls) ethers, and step is such as
Under：
1), under nitrogen protection, in 80 DEG C of thermostatical oil baths, by 39g ethylene glycol diglycidylethers and 8g poly- the third two
Alcohol diglycidyl ether is added in the three neck round bottom flask of 100ml, is uniformly mixed using mechanical agitation.Then it sequentially adds
23g toluene-3,4-dithiols and bis- (2- dimethylaminoethyls) ethers of 1.8g, isothermal reaction 0.1 hour obtain the double of sulfydryl chain extension
Functional group epoxy resin.
2), under nitrogen protection, in 40 DEG C of thermostatical oil baths, by the difunctional epoxy resin of obtained sulfydryl chain extension
It is mixed with 24g epoxidations m-xylene diamine, 21g furfurylmercaptans, isothermal reaction 2.5 hours, obtains end group as in furans functional group
Mesosome, grafting rate reach 99.6%.
3), under nitrogen protection, intermediate obtained by the reaction and 62g 4-4 '-dimaleoyl imino diphenyl-methane are existed
It is stirred evenly in 140 DEG C of thermostatical oil baths, fully reaction 0.2 hour, pours into and be placed in the Teflon mould of baking oven, in 40
DEG C cross-linking reaction 42 hours is carried out, obtain the reversible epoxy resin toughened of yellow transparent.
The epoxy resin toughened preparation method of embodiment 7, a kind of reversible crosslink, difunctional epoxy resin select poly- second two
The mixture of alcohol diglycidyl ether, Bisphenol F diglycidyl ether and polypropylene oxide diglycidyl ether selects dimercapto second
Sour glycol ester selects 1,1,1- tri- (4- hydroxy phenyls) ethyl three-glycidyl as chain extension substance, polyfunctional epoxy resin
Ether, tertiary amine catalyst select triethylamine, and step is as follows：
1), under nitrogen protection, in 55 DEG C of thermostatical oil baths, by 25g polyethyleneglycol diglycidylethers, 10g bis-phenols
F diglycidyl ethers and 2g polypropylene oxide diglycidyl ethers are added in the three neck round bottom flask of 100ml, are stirred using machinery
It mixes uniformly mixed；Then 22g glycol dimercaptosuccinates and 2.1g triethylamines are sequentially added, isothermal reaction 0.7 hour obtains
The difunctional epoxy resin of sulfydryl chain extension.
2), under nitrogen protection, in 75 DEG C of thermostatical oil baths, by the difunctional epoxy resin of obtained sulfydryl chain extension
With 37g1,1,1- tri- (4- hydroxy phenyls) ethyl triglycidyl ether, the mixing of 21g furfurylmercaptans are placed in during nitrogen protective atmosphere encloses, instead
It answers 0.6 hour, obtains the intermediate that end group is furans functional group, grafting rate reaches 99.9%.
3), under nitrogen protection, intermediate obtained by the reaction and 88g N-N '-(4,4- methylenediphenyl) span are come
Acid imide stirs evenly in 140 DEG C of thermostatical oil baths, fully reaction 0.2 hour, pours into the polytetrafluoroethylene (PTFE) mould for being placed in baking oven
In tool, carry out cross-linking reaction 30 hours in 70 DEG C, obtain the reversible epoxy resin toughened of yellow transparent.
Comparative example 1-1, by " 39g ethylene glycol diglycidylethers and the 8g polypropylene glycol diglycidyl ethers in embodiment 6
It is added in the three neck round bottom flask of 100ml, is uniformly mixed using mechanical agitation.Then 23g Toluene-3,4-dithiols, bis- sulphur of 4- are sequentially added
Phenol and bis- (2- dimethylaminoethyls) ethers of 1.8g " make " 71.8g ethylene glycol diglycidylethers " into, remaining is equal to embodiment 6.
Comparative example 1-2, by " 39g ethylene glycol diglycidylethers and the 8g polypropylene glycol diglycidyl ethers in embodiment 6
It is added in the three neck round bottom flask of 100ml, is uniformly mixed using mechanical agitation.Then 23g Toluene-3,4-dithiols, bis- sulphur of 4- are sequentially added
Phenol and bis- (2- dimethylaminoethyls) ethers of 1.8g " make " 71.8g polypropylene glycol diglycidyl ethers " into, remaining is equal to embodiment
6。
Comparative example 1-3, the step 1) in embodiment 6 is removed, by " the sulfydryl that will be obtained in the step 2) in embodiment 6
The difunctional epoxy resin of chain extension and 24g epoxidations m-xylene diamine " makes " 95.8g epoxidations m-xylene diamine " into, remaining
It is equal to embodiment 6.
The epoxy resin toughened standard tensile batten of the obtained reversible crosslink of above-mentioned case is subjected to tension test test, is surveyed
Test result is shown in Table 1.
The epoxy resin toughened tensile property of 1 reversible crosslink of table summarizes
Data above, which shows that reversible crosslink produced by the present invention is epoxy resin toughened, has preferable elongation at break and drawing
Intensity is stretched, is obviously improved compared with conventional epoxy toughness.
The epoxy resin toughened stretch broken of reversible crosslink of 6 gained of embodiment is subjected to heating melting after 95 DEG C,
Enter to be placed in the Teflon mould of baking oven, cross-linking reaction is carried out 48 hours in 70 DEG C.To obtained standard tensile batten into
Its mechanical property repeatedly utilized is tested in row tension test.This test loop 5 times, test result is shown in Table 2.
The epoxy resin toughened tensile property of 2 reversible crosslink of table summarizes
| Number of repetition | Tensile strength/MPa | Stretch modulus/MPa | Elongation at break/% |
| 1 | 70.6±3.5 | 2584±177 | 134.8±7.5 |
| 2 | 68.7±4.1 | 2368±142 | 128.4±9.3 |
| 3 | 66.4±2.3 | 2494±136 | 126.2±5.4 |
| 4 | 69.9±3.1 | 2511±192 | 131.1±8.2 |
| 5 | 68.5±2.6 | 2460±148 | 129.2±7.7 |
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
Bright to be not limited to above example, acceptable there are many deform.Those of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (7)
1. utilize the epoxy resin toughened method of reversible crosslink prepared by the reaction of ontology click chemistry, it is characterised in that including following
Step：
1) after, being mixed using difunctional epoxy resin with polyfunctional epoxy resin, end group is obtained with furfurylmercaptan click-reaction
Intermediate for furans functional group；
The difunctional epoxy resin be containing there are two the epoxy monomer of epoxy group, the polyfunctional epoxy resin be containing
There are three and three or more epoxy groups epoxy monomer；
2), the intermediate is reacted with the crosslinking agent generation Diels-Alder containing maleimide base group, forms reversible crosslink
It is epoxy resin toughened.
2. the epoxy resin toughened side of the reversible crosslink according to claim 1 prepared using the reaction of ontology click chemistry
Method, it is characterised in that：
Step 1), the intermediate that end group is furans functional group：
Under inert gas shielding, under solvent-free conditions, in 20~100 DEG C by 50~140 parts of difunctional epoxy resin and
20~100 parts of polyfunctional epoxy resins are uniformly mixed, and are added in 15~80 parts of furfurylmercaptans and are sufficiently stirred, then add in 0.5~5 part
Tertiary amine catalyst 0.1~3h of isothermal reaction obtains the intermediate that end group is furans functional group；
Alternatively, under inert gas shielding, under solvent-free conditions, in 20~100 DEG C by 50~140 parts of chain extensions after the ring that generates
Oxygen resin and 20~100 parts of polyfunctional epoxy resins are uniformly mixed, and are added in 15~80 parts of furfurylmercaptans and are sufficiently stirred isothermal reaction
0.1~3h obtains the intermediate that end group is furans functional group；
Step 2) is that prepare reversible crosslink epoxy resin toughened for the intermediate of furans functional group with end group：
Under inert gas shielding, under solvent-free conditions, contain maleimide base group by 60~100 parts in 100~160 DEG C
Crosslinking agent be added in the intermediate that the end group obtained by step 1) is furans functional group and be sufficiently stirred, it is anti-prior to 100~160 DEG C
0.1~0.5h is answered, then then at 20~90 DEG C of 0.1~48h of cross-linking reaction, it is epoxy resin toughened to obtain reversible crosslink.
3. the epoxy resin toughened side of the reversible crosslink according to claim 2 prepared using the reaction of ontology click chemistry
Method, it is characterised in that：
The epoxy resin generated after the chain extension for aromatics epoxy monomer, in non-aromatic based epoxy resin monomer at least
It is a kind of to carry out the asphalt mixtures modified by epoxy resin generated after click-reaction chain extension under tertiary amine catalyst effect by double mercapto functional group compounds
Fat；
Preparation method is：
Under inert gas shielding, under solvent-free conditions, in 20~80 DEG C by 30~90 parts of aromatics epoxy monomer,
At least one of non-aromatic based epoxy resin monomer is uniformly mixed with 19~45 parts of difunctional sulfhydryl compound, is fully stirred
It mixes, then adds in 0.5~5 part of tertiary amine catalyst and react 0.1~5h in 20~80 DEG C, obtain the chain extension that end group is epoxy-functional
Epoxy resin；
The difunctional sulfhydryl compound is containing there are two the sulfhydryl compound monomers of mercapto groups.
4. the epoxy resin toughened side of the reversible crosslink according to claim 3 prepared using the reaction of ontology click chemistry
Method, it is characterised in that：
The difunctional sulfhydryl compound is glycol dimercaptosuccinate, 1,6- ethanthiols, meso -2,3- dimercaptos
Succinic acid, dithioerythritol, 1,2- dithioglycols, 1,3- dimercaptopropanes, 1,2- succinimide mercaptans, 4,4 '-thiobis-benzenethiol, two
Mercaprol, Toluene-3,4-dithiol, 4- dithiols.
5. according to any reversible crosslink flexibilizing epoxy tree prepared using the reaction of ontology click chemistry of claim 2~4
The method of fat, it is characterised in that：
The difunctional epoxy resin is at least one in aromatics epoxy monomer, non-aromatic based epoxy resin monomer
Kind；It is sweet that the aromatics epoxy monomer is bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol S two shrink
Oily ether, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester,；
The non-aromatic based epoxy resin monomer is ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol two
Glycidol ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether and polypropylene oxide diglycidyl ether；
The polyfunctional epoxy resin is glycidyl amine epoxy resin monomer, glycidyl ether type epoxy resin monomer；
The glycidyl amine epoxy resin monomer is 4,4 '-diaminodiphenylmethane epoxy resin, triglycidyl group pair
Amino-phenol, triglycidyl meta-aminophenol, epoxidation m-xylene diamine, 1,3- bis- (N, N- 2-glycidyl aminomethyls)
Hexamethylene；
The glycidyl ether type epoxy resin monomer is novolac epoxy resin, three (4- hydroxy phenyls) methane triglycidyl groups
Ether, 1,1,1- tri- (4- hydroxy phenyls) ethyl triglycidyl ether, 2,2 ', 2 ", 2 " '-[(the 4,1- Asias of 1,2- ethanetetrayls four
Phenyl methylidene oxygen)] tetraoxane, Dicycldpentadiene-phenol glycidyl ether resin.
6. the epoxy resin toughened side of the reversible crosslink according to claim 5 prepared using the reaction of ontology click chemistry
Method, it is characterised in that：
The tertiary amine catalyst is 2,4,6- tri- (dimethylamino methyl) phenol, N, N- dimethyl benzylamines, N, N- dimethyleyelohexanes
Amine, bis- (2- dimethylaminoethyls) ethers, triethylamine, N, accelerine.
7. the epoxy resin toughened side of the reversible crosslink according to claim 6 prepared using the reaction of ontology click chemistry
Method, it is characterised in that：The crosslinking agent containing maleimide base group carrys out acyl for N-N '-(4,4- methylenediphenyls) span
Imines, N-N- (4- methyl-1s, 3- phenylenes) bismaleimide, N-N '-penylene bismaleimide, the bis- (Malaysias of 1,2-
Acid imide) ethane or 4-4 '-dimaleoyl imino diphenyl-methane.
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