CN106432584B - A kind of synthesis of imidazoles latency Epoxy curing accelerators with toughening effect and its application on epoxy-modified - Google Patents
A kind of synthesis of imidazoles latency Epoxy curing accelerators with toughening effect and its application on epoxy-modified Download PDFInfo
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- CN106432584B CN106432584B CN201610828392.XA CN201610828392A CN106432584B CN 106432584 B CN106432584 B CN 106432584B CN 201610828392 A CN201610828392 A CN 201610828392A CN 106432584 B CN106432584 B CN 106432584B
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- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 24
- 239000004593 Epoxy Substances 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 230000000694 effects Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- -1 alkene acyl chlorides Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- HZEOUPCNUWSUFL-UHFFFAOYSA-N 4,5,5-trimethyl-4-pentan-3-yl-1H-imidazole Chemical class C(C)C(C1(N=CNC1(C)C)C)CC HZEOUPCNUWSUFL-UHFFFAOYSA-N 0.000 claims 1
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical group 0.000 claims 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims 1
- 238000007086 side reaction Methods 0.000 claims 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 13
- 230000008023 solidification Effects 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 150000002118 epoxides Chemical class 0.000 abstract description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000003335 steric effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000011938 amidation process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
Abstract
The invention discloses a kind of acrylate copolymers by simple free-radical polymerized synthesis imidazole ring-containing side group, and it is epoxy resin toughened simultaneously to be applied to latency Epoxy curing accelerators.Firstly, imidazoles to be connect to the catalytic activity that can reduce imidazole ring by steric effect on macromolecular chain, to achieve the purpose that latency；Secondly, acrylate molecule chain can participate in the formation of curable epoxide network, microphase-separated is formed in epoxy matrix improves the mechanical performance of epoxy resin.With the imidazoles latent curing accelerator of toughening effect prepared by the present invention, the solidification temperature that imidazoles are catalyzed DGEBA/MHHPA curing system can be improved to 180 DEG C or so, and there is good storage stability at room temperature.
Description
Technical field
The present invention relates to the imidazoles latent curing accelerator fields of epoxy resin, and in particular to passes through macromolecular steric hindrance
Effect reduces imidazoles curing activity and achievees the purpose that there is latency under room temperature.
Background technique
Resin matrix of the epoxy resin as adhesive, coating and composite material etc. is widely used in building, mechanical, electricity
The fields such as sub electrical, aerospace.In order to optimize the machining property of resin, people are to one of resin Composition --- curing agent
It has carried out many.Research On The Latent Accelerator For Epoxy Resin is the heat of recent domestic epoxy curing agent research
Point.So-called latent curing accelerator, refer to has certain storage at room temperature after being blended with epoxy resin and high-temperature curing agent
The promotor deposited stability, and curing reaction can be promoted to carry out under the conditions ofs heating, illumination, moisture, pressurization etc..Contain latency
The epoxy blend system of promotor, which has, simplifies production operation technique, prevents the pollution of the environment, improves product quality, adapts to existing
The advantages that for large-scale industrial production.Imidazole and its derivants are a kind of common epoxy hardeners, by it by physics and
The means of chemistry are improved, and the curing accelerator with latency can be prepared.
The method of preparation imidazoles latent curing accelerator generally comprises into the methods of imidazole salts, reactivity passivation.
And reactivity passivation is generally realized by the active hydrogen reaction of small molecule and imidazole ring, does not have macromolecular imidazoles latent yet at present
The research of volt property curing accelerator.Compared with small molecule imidazoles latent curing accelerator, macromolecular has higher steric hindrance
Effect, active passivation effect become apparent from, while flexible macromolecular long-chain being added in resin, can obviously improve resin after solidification
The crisp disadvantage of matter.
The present invention passes through simple amidation process first, and double bond is connected on imidazoles, synthesis one with imidazole ring from
It is copolymerized by base polymerized monomer, then with the monomer and other acrylic ester monomers, one kind being synthesized using simple free radical polymerization
Flexible macromolecular containing imidazoles side group can also improve epoxy resin toughness while being used as latent curing accelerator.Institute
The macromolecular subsidence feed of synthesis, with epoxy matrix have excellent compatibility, at normal temperature with epoxy resin and solidification
After agent methyl hexahydrophthalic anhydride is blended, stable storage, the viscosity of mixed system it can will not occur obviously to become under room temperature and low temperature
Change；And the solidification temperature range of the system is in 170~220 DEG C, hence it is evident that lower than epoxy/methyl hexahydrophthalic anhydride co-mixing system
Initial cure temperature (250 DEG C of >).Epoxy sample after solidification tests impact property, and toughness increases.
Summary of the invention
By simple amidation process, synthesis one has the free yl polymerizating monomer of imidazole ring, and reacts away imidazoles
Active hydrogen reduces the curing activity of imidazoles, then is copolymerized with the monomer and other acrylic ester monomers, and imidazole ring is connected to big point
In subchain side group, by the strong steric hindrance of macromolecular chain, it is further passivated imidazoles, to achieve the purpose that latency.It is soft simultaneously
Property macromolecular chain addition, can be formed and mutually be separated after hardening, when epoxy resin is by external world, can absorbed more
Stress improves epoxy resin toughness.And since the macromolecular curing accelerator participates in solidifying the formation of cross-linked network, thus will not
It forms large scale mutually to separate, loses the modulus and glass transition temperature of epoxy resin.
The present invention is to realize above-mentioned purpose by following technical solution.
Step 1: weigh appropriate acryloyl chloride (or derivatives thereof) be dissolved in 50mL tetrahydrofuran (THF), and in 0~10 DEG C
It is lower it is added drop-wise to dropwise imidazoles (or derivatives thereof) and the 100mL THF solution of triethylamine in, stirring, the above process exists
It is carried out in 250mL three-necked flask.Continue 24~48h of stirring after being added dropwise at normal temperature, reaction terminates.System is passed through into suction filtration
The ammonium salt generated in reaction process is removed, revolving removes the free redical comonomer that solvent has imidazole ring to get product.
Contain the monomer and other propylene of imidazole ring and double bond while step 2: weighing synthesized by the appropriate first step
Esters of gallic acid monomer (one of such as HEA, EHA, LA, GMA, DMA or a variety of), adds it in 100mL round-bottomed flask, and adds
Enter appropriate solvent ethyl acetate, reacts 10~30h at 70~85 DEG C.After product is added dropwise to precipitating reagent (water, first dropwise
Alcohol, ethyl alcohol, one or more of petroleum ether etc.) precipitating, white solid is obtained, is dried in vacuum overnight to get synthesized side
Base band has the acrylate random copolymers of imidazole ring.
Step 3: taking appropriate copolymer, it is dissolved in 10mL acetone, appropriate epoxy monomer is added, is stirred overnight, and is heated to 50
DEG C, it is sufficiently mixed and removes solvent, vacuum takes off residual solvent, and the curing agent with quality such as epoxy monomers is added, appropriate to defoam
Agent, deaerated under vacuum steeps after mixing, then pours into preheated mold, 60~80 DEG C of 1~2h of solidification, it is warming up to 100~
140 DEG C of 6~8h of solidification.
Specific flow chart is as shown in Figure of description 2.
The present invention has the advantages that compared with prior art:
(1) prepared by the common small molecule-modified imidazoles compared with latent curing accelerator, the designed synthesis of the present invention
Macromolecular latent curing accelerator structural stability it is good, macromolecular asepsis environment-protecting.
(2) prepared by the common small molecule-modified imidazoles compared with latent curing accelerator, macromolecular chain flexible can
It is mutually separated with forming small size during participating in curable epoxide, and there is excellent compatibility between epoxy matrix.By
When extraneous stress acts on, mutually separation can effectively improve the activity of cross linking of epoxy resin network and absorb the ability of energy, from
And improve toughness.
(3) compared with plain polypropylene acid esters liquid rubber is epoxy resin toughened, polymer and resin designed by the present invention
Compatibility it is good, additional amount is low, will not lose the glass transition temperature and other machinery performance of resin.And synthesis step
Simply, it can be achieved that mass production and industrial applications.
Detailed description of the invention
Attached drawing 1 is the synthesis of latent curing accelerator and its schematic diagram of epoxy resin cured product.
Attached drawing 2 is the preparation flow figure of epoxy resin cured product.
Specific embodiment:
Below with reference to specific example, the present invention is further explained.These examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.
Embodiment 1
Step 1: weighing methacrylic chloride 5.227g, it is dissolved in 50mL tetrahydrofuran (THF), and by it at 0~10 DEG C
It is added drop-wise in the 100mLTHF solution of 2-methylimidazole (4.105g) and triethylamine (6.07g), stirs dropwise, the above process exists
It is carried out in 250mL three-necked flask.Continue 24~48h of stirring after being added dropwise at normal temperature, reaction terminates.System is passed through into suction filtration
The ammonium salt generated in reaction process is removed, revolving removes the free redical comonomer that solvent has imidazole ring to get product.
Step 2: contain the monomer 3.380g of imidazole ring and double bond while weighing synthesized by the first step, and
HEA2.907g, EHA7.370g, LA2.422g are added it in 100mL round-bottomed flask, and 50mL ethyl acetate is added,
It is reacted for 24 hours at 85 DEG C.After product be added dropwise in precipitating reagent dropwise precipitate, obtain white solid, be dried in vacuum overnight, i.e.,
Obtain the acrylate random copolymers that synthesized side group has imidazole ring.
Step 3: taking 5g copolymer, it is dissolved in 10mL acetone, 50g epoxy monomer is added, is stirred overnight, and be heated to 50 DEG C,
It is sufficiently mixed and removes solvent, vacuum takes off residual solvent, it is added the curing agent with quality such as epoxy monomers, proper quantity of defoaming agent,
Deaerated under vacuum steeps after mixing, then pours into preheated mold, and 80 DEG C of solidification 1h are warming up to 100~140 DEG C of solidifications 6
~8h.
Embodiment 2
Step 1: being dissolved in 50mL tetrahydrofuran (THF), and in 0~10 step 1: weigh methacrylic chloride 6.320g
It is added drop-wise to dropwise at DEG C in the 100mL THF solution of 2-methylimidazole (4.105g) and triethylamine (6.07g), stirring, on
Process is stated to carry out in 250mL three-necked flask.Continue 24~48h of stirring after being added dropwise at normal temperature, reaction terminates.By system
The ammonium salt generated in reaction process is removed by filtering, it is total that revolving removes free redical of the solvent to get product with imidazole ring
Polycondensation monomer.
Step 2: containing the monomer 3.380g and HEA of imidazole ring and double bond while weighing synthesized by the first step
2.907g, EHA 7.370g, LA 2.422g, add it in 100mL round-bottomed flask, and 50mL ethyl acetate is added, 85
It is reacted for 24 hours at DEG C.After product be added dropwise in precipitating reagent dropwise precipitate, obtain white solid, be dried in vacuum overnight to get
Synthesized side group has the acrylate random copolymers of imidazole ring.
Step 3: taking 5g copolymer, it is dissolved in 10mL acetone, 50g epoxy monomer is added, is stirred overnight, and be heated to 50 DEG C,
It is sufficiently mixed and removes solvent, vacuum takes off residual solvent, it is added the curing agent with quality such as epoxy monomers, proper quantity of defoaming agent,
Deaerated under vacuum steeps after mixing, then pours into preheated mold, and 80 DEG C of solidification 1h are warming up to 100~140 DEG C of solidifications 6
~8h.
Step 1: weighing 2-methylimidazole (4.105g) and triethylamine (6.07g), it is dissolved in 100mL tetrahydrofuran (THF),
And it is added dropwise dropwise at 0~10 DEG C in the 50mL THF solution of methacrylic chloride (5.227g), it stirs, the above process exists
It is carried out in 250mL three-necked flask.Continue 24~48h of stirring after being added dropwise at normal temperature, reaction terminates.System is passed through into suction filtration
The ammonium salt generated in reaction process is removed, revolving removes the free redical comonomer that solvent has imidazole ring to get product.
Step 2: containing the monomer 3.380g and HEA of imidazole ring and double bond while weighing synthesized by the first step
2.907g, EHA 7.370g, LA 2.422g, add it in 100mL round-bottomed flask, and 50mL ethyl acetate is added, 85
It is reacted for 24 hours at DEG C.After product be added dropwise in precipitating reagent dropwise precipitate, obtain white solid, be dried in vacuum overnight to get
Synthesized side group has the acrylate random copolymers of imidazole ring.
Step 3: taking 5g copolymer, it is dissolved in 10mL acetone, 50g epoxy monomer is added, is stirred overnight, and be heated to 50 DEG C,
It is sufficiently mixed and removes solvent, vacuum takes off residual solvent, it is added the curing agent with quality such as epoxy monomers, proper quantity of defoaming agent,
Deaerated under vacuum steeps after mixing, then pours into preheated mold, and 80 DEG C of solidification 1h are warming up to 100~140 DEG C of solidifications 6
~8h.
Claims (3)
1. a kind of imidazoles latency Epoxy curing accelerators with toughening effect, which is characterized in that its synthesis step is as follows:
Step 1: appropriate acryloyl chloride or derivatives thereof and triethylamine is taken to be added in round-bottomed flask first, and tetrahydro furan is added
It mutters and is dissolved；Then, appropriate imdazole derivatives are weighed and are dissolved in THF, and at 6~8 DEG C in 1h by the THF of imdazole derivatives
Solution is added drop-wise in round-bottomed flask dropwise, is stirred simultaneously；Continue to stir 48h at normal temperature after being added dropwise, reaction terminates；Product
Filter and remove the ammonium salt generated in reaction process, then revolving removes solvent to get product；
Contain the monomer and other acrylate of imidazole ring and double bond while step 2: weighing synthesized by the appropriate first step
Class monomer, adds it in round-bottomed flask, and appropriate solvent ethyl acetate is added, and 10~30h is reacted at 70~85 DEG C；Terminate
Product is added dropwise to precipitating reagent precipitating dropwise afterwards, obtains white solid, is dried in vacuum overnight to get synthesized side group with miaow
The acrylate random copolymers of azoles ring；The precipitating reagent is one or more of water, methanol, ethyl alcohol, petroleum ether.
2. a kind of imidazoles latency Epoxy curing accelerators with toughening effect according to claim 1, feature
It is, the actual conditions in the synthesis step are as follows:
(1) it when double bond containing imidazoles monomer synthesizes, needs to control imidazoles and acryloyl chloride group molar ratio example is greater than 1:1, to subtract
The generation of few side reaction；Reaction uses one of 2-methylimidazole, diethyl tetramethyl imidazoles, diphenyl-imidazole, Yi Jibing
One of alkene acyl chlorides, methacrylic chloride；
(2) used acrylic ester monomer includes methyl methacrylate, hydroxy-ethyl acrylate, propylene when copolymer synthesizes
One of the different monooctyl ester of acid, tert-butyl acrylate, dodecyl acrylate, methacrylic N, N-dimethylamino ethyl ester monomer or
It is several.
3. a kind of imidazoles latency Epoxy curing accelerators with toughening effect according to claim 1, feature
Be, the application method on epoxy-modified are as follows: epoxy resin, MHHPA, curing accelerator weight be 50:50:
3~8.
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| CN201610828392.XA CN106432584B (en) | 2016-09-18 | 2016-09-18 | A kind of synthesis of imidazoles latency Epoxy curing accelerators with toughening effect and its application on epoxy-modified |
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| CN105802219B (en) * | 2016-06-02 | 2018-10-12 | 黑龙江省科学院石油化学研究院 | A kind of extremely-low density, low-loss cyanic acid ester group composite foam material and preparation method thereof |
| CN106916283B (en) * | 2017-03-16 | 2019-04-12 | 宁波工程学院 | A kind of preparation method of branched structure anhydride curing accelerator |
| CN108383979B (en) * | 2018-03-13 | 2020-01-31 | 烟台大学 | Use of curing agent for fractured-self-healing organic glass with reduced molecular weight |
| CN109824500A (en) * | 2018-08-09 | 2019-05-31 | 阜阳市诗雅涤新材料科技有限公司 | A kind of preparation method and application of 2- benzylimidazoline and Pyromellitic Acid anhydride adduct |
| CN109988287B (en) * | 2019-04-16 | 2021-10-22 | 广东固研电子材料有限公司 | Epoxy resin latent curing agent with high bonding strength and toughness and preparation method thereof |
| CN110790903A (en) * | 2019-12-05 | 2020-02-14 | 江南大学 | Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof |
| DE102020201334A1 (en) | 2020-02-04 | 2021-08-05 | Tesa Se | High Tg acrylate copolymers with nitrogen-containing aromatic heterocyclic group |
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| JP2014118397A (en) * | 2012-12-19 | 2014-06-30 | Shikoku Chem Corp | Imidazole(meth)acrylate compound |
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| EP1193558A2 (en) * | 2000-09-18 | 2002-04-03 | JSR Corporation | Radiation-sensitive resin composition |
| JP2014118397A (en) * | 2012-12-19 | 2014-06-30 | Shikoku Chem Corp | Imidazole(meth)acrylate compound |
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