CN110628181B - Toughened epoxy resin based on dumbbell-type copolymer and preparation method thereof - Google Patents
Toughened epoxy resin based on dumbbell-type copolymer and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 151
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 151
- 229920001577 copolymer Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000012745 toughening agent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 45
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- -1 polysiloxane Polymers 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229920001195 polyisoprene Polymers 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 230000000630 rising effect Effects 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229960001124 trientine Drugs 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- OWJSXGJJSUAIIQ-UHFFFAOYSA-L C(CCC)NN(C([S-])=S)NCCCC.[Zn+2].C(CCC)NN(C([S-])=S)NCCCC Chemical compound C(CCC)NN(C([S-])=S)NCCCC.[Zn+2].C(CCC)NN(C([S-])=S)NCCCC OWJSXGJJSUAIIQ-UHFFFAOYSA-L 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
A toughened epoxy resin based on a dumbbell type copolymer and a preparation method thereof belong to the technical field of high polymer materials. The toughening epoxy resin introduces a dumbbell type copolymer as a toughening agent into an epoxy resin composition, and the toughening epoxy resin comprises the following components in percentage by mass: 100 parts by mass of an epoxy resin; 10-100 parts by mass of a dumbbell-type copolymer; 10-100 parts by mass of a curing agent; 0 to 3 parts by mass of an accelerator. The dumbbell type copolymer consists of a middle chain segment and dumbbell type structures at two ends, and the side chain structure of the dumbbell type copolymer improves the compatibility between the macromolecular toughening agent and the epoxy resin and provides enough acting force for the macromolecular toughening agent to form a deformed second microphase structure in the epoxy resin. The invention has the advantages that the dumbbell copolymer forms a larger-size non-spherical second microphase structure in the epoxy resin, can effectively improve the toughness of the epoxy resin, simultaneously eliminates the plasticizing effect and inhibits the reduction of other properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a dumbbell copolymer-based toughened epoxy resin and a preparation method thereof.
Background
The epoxy resin has the characteristics of good water resistance, chemical resistance, adhesiveness, corrosion resistance, mechanical strength, dielectric property, molding processability, heat resistance, low shrinkage rate and the like, and is low in production cost, so that the epoxy resin has wide application fields. However, epoxy resin materials have disadvantages of high brittleness, poor fracture toughness, and the like, which limits their application in wider fields, and for this reason, people are always searching for an effective method for toughening epoxy resins.
The prior art has employed various amphiphilic linear block copolymers as epoxy tougheners, such tougheners having blocks that are incompatible with epoxy resins and blocks that are compatible with epoxy resins. Microphase separators in which the blocks incompatible with the epoxy resin are self-assembled or reaction-inducedThe second micro-phase structure is constructed in the epoxy resin, so that the effect of toughening the epoxy resin is achieved, the block compatible with the epoxy resin has the effect of interfacial compatibilization, and the formation of the second micro-phase structure is ensured. The structure-performance relationship indicates that the toughening effect is greatly dependent on the shape and size of the second microphase and the effect between the second microphase and the epoxy group. The second micro-phase structure mainly comprises a block incompatible with epoxy, and can be in a spherical shape, a vesicle shape and a worm shape in the epoxy resin, wherein the worm-shaped structure is more beneficial to improving the toughening effect of the epoxy resin. Because the toughening effect of the epoxy resin is increased along with the increase of the size of the second microphase, the good toughening effect theoretically requires that the block incompatible with the epoxy resin has higher molecular weight; at the same time, the molecular weight of the epoxy-compatible block should be increased accordingly to improve the interfacial compatibility and ensure the formation of the second microphase structure. In this case, the epoxy-compatible block forms a relatively thick hard transition layer, exhibits a pronounced plasticizing effect and greatly reduces the glass transition temperature (T) of the composite materialg) And other properties. Therefore, to balance the plasticizing and toughening effects, most epoxy thermoset resins are toughened with low molecular weight templating copolymers. Although styrenic thermoplastic elastomers with higher molecular weights can be successfully used for toughening of thermosets by epoxidation and sulfonation, the system does not eliminate the performance degradation caused by the plasticizing effect.
Therefore, as the performance requirements of the applied epoxy resin products increase, how to improve the toughness of the epoxy resin and eliminate the performance degradation caused by the plasticizing effect becomes a key problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a dumbbell copolymer-based toughened epoxy resin and a preparation method thereof, which can improve the toughness of the epoxy resin and eliminate performance reduction caused by a plasticizing effect.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
a dumbbell copolymer-based toughened epoxy resin is prepared by introducing the dumbbell copolymer into an epoxy resin composition as a toughening agent, wherein the toughened epoxy resin comprises the following components:
100 parts by mass of an epoxy resin;
10-100 parts by mass of a dumbbell-type copolymer;
10-100 parts by mass of a curing agent;
0 to 3 parts by mass of an accelerator.
The dumbbell-shaped copolymer consists of a middle chain segment and dumbbell-shaped structures at two ends. The middle chain segment is polysiloxane incompatible with epoxy resin, polyethylene propylene rubber, polyisoprene, polybutadiene, polycyclopentadiene, other polymer molecular chains with the glass transition temperature lower than room temperature or the use temperature of the epoxy resin, copolymer molecular chains or derivative molecular chains of the polymer molecular chains, and the number average molecular weight of the middle chain segment is 1.0 multiplied by 104～1.0×105(ii) a The dumbbell structure consists of main chain and side chain, and the main chain has number average molecular weight of 1.0X 102～1.0×104The side chain is polymethyl methacrylate, polylactide, polyethanol, polypropanol, polycaprolactone, polyethylene oxide, polypropylene oxide, epoxidized polybutadiene, epoxidized polyisoprene, other molecular chains compatible with epoxy resin, combinations of the above, copolymerized molecular chains of the above polymer molecular chains or derivative molecular chains, and the number average molecular weight of the side chain is 1.0 x 101～1.0×103The weight percentage of the side chain in the dumbbell type copolymer is 5 wt% -50 wt%.
The epoxy resin mainly comprises: bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, halogenated bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, novolac epoxy resins, alicyclic epoxy resins, polyfunctional glycidyl ether resins, heterocyclic epoxy resins, or combinations thereof.
The curing agent mainly comprises: m-phenylenediamine, N-aminoethylpiperazine, A2500, diaminodiphenylmethane, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, dicyandiamide, triethylenetetramine, or combinations of the foregoing.
The promoter mainly comprises: zinc N, N-dibutylaminodithiocarbamate, benzyltriethylammonium chloride, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, methylimidazole, 2, 4, 6-tris (dimethylaminomethyl) phenol, or combinations of the foregoing.
A preparation method of toughened epoxy resin based on dumbbell type copolymer comprises the following steps:
(1) dissolving 10-100 parts by mass of dumbbell type copolymer in an organic solvent to completely dissolve the polymer; adding 100 parts by mass of an epoxy resin precursor, and after fully mixing, slowly and fully volatilizing a solvent; and adding 10-100 parts by mass of a curing agent and 0-3 parts by mass of an accelerator to fully dissolve and uniformly disperse the curing agent in the epoxy resin composition.
(2) And after bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of inflation and air exhaust, preparing the toughened epoxy resin material according to a temperature rise program, naturally and slowly cooling after the curing process is finished, and testing the performance of the toughened epoxy resin material.
The organic solvent mainly comprises: toluene, xylene, tetrahydrofuran, pentane, cyclohexane, N-hexane, heptane, octane, N-dimethylformamide, or combinations of the foregoing.
The invention has the advantages that: the dumbbell copolymer forms a larger-size non-spherical second microphase structure in the epoxy resin, can effectively improve the toughness of the epoxy resin, can eliminate the plasticizing effect and inhibit the reduction of other properties.
Detailed Description
In order to further illustrate the present invention, the following examples are given by way of illustration only and are not to be construed in any way as limiting the scope of the present invention.
Comparative example 1
Uniformly mixing 100 parts by mass of bisphenol A epoxy resin precursor and 100 parts by mass of m-phenylenediamine curing agent; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 1
Polysiloxane, polystyrene and polymethyl methacrylate are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weights of the polysiloxane, the polystyrene and the polymethyl methacrylate are 10000, 100 and 1000 respectively, and the side chain accounts for 10 wt% of the dumbbell-shaped copolymer. Dissolving 10 parts by mass of the dumbbell-shaped copolymer in an organic solvent toluene to completely dissolve the polymer; adding 100 parts by mass of bisphenol A epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; 100 parts by mass of m-phenylenediamine curing agent is added to fully dissolve and uniformly disperse the curing agent in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 2
Uniformly mixing 100 parts by mass of a hydrogenated bisphenol A epoxy resin precursor, 90 parts by mass of an N-aminoethyl piperazine curing agent and 0.5 part by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 2
The polyethylene propylene rubber, the polyethylene and the polylactide are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weights of the middle chain segment, the main chain and the side chain are 10000, 100 and 10 respectively, and the weight percentage of the side chain in the dumbbell-shaped copolymer is 5 wt%. Dissolving 20 parts by mass of the dumbbell-shaped copolymer in an organic solvent xylene to completely dissolve the polymer; adding 100 parts by mass of hydrogenated bisphenol A epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; adding 90 parts by mass of N-aminoethyl piperazine curing agent and 0.5 part by mass of benzyltriethylammonium chloride accelerator, and fully dissolving and uniformly dispersing the curing agent and the accelerator in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 3
Uniformly mixing 100 parts by mass of halogenated bisphenol A epoxy resin precursor, 80 parts by mass of A2500 curing agent and 1.0 part by mass of 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 3
The polyisoprene, the polyethylene and the polyethanol are respectively a middle chain segment of the dumbbell type copolymer, a main chain and a side chain of the dumbbell type structure, the number average molecular weights of the polyisoprene, the polyethylene and the polyethanol are 10000, 100 and 100 respectively, and the side chain accounts for 15 wt% of the dumbbell type copolymer. Dissolving 30 parts by mass of the dumbbell-shaped copolymer in tetrahydrofuran which is an organic solvent to completely dissolve the polymer; adding 100 parts by mass of halogenated bisphenol A epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; 80 parts by mass of A2500 curing agent and 1.0 part by mass of 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea accelerator were added to dissolve the curing agent and accelerator sufficiently and disperse them uniformly in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 4
Uniformly mixing 100 parts by mass of bisphenol F epoxy resin precursor, 70 parts by mass of diaminodiphenylmethane curing agent and 1.5 parts by mass of methylimidazole accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 4
Polybutadiene, polystyrene and polypropylene alcohol are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weights of the polybutadiene, the polystyrene and the polypropylene alcohol are 10000, 1000 and 10 respectively, and the side chain accounts for 20 wt% of the dumbbell-shaped copolymer. Dissolving 40 parts by mass of the dumbbell-shaped copolymer in organic solvent pentane to completely dissolve the polymer; adding 100 parts by mass of bisphenol F epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; and adding 70 parts by mass of diaminodiphenylmethane curing agent and 1.5 parts by mass of methylimidazole accelerator to fully dissolve and uniformly disperse the curing agent and the accelerator in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 5
Uniformly mixing 100 parts by mass of a bisphenol S epoxy resin precursor, 70 parts by mass of a methyltetrahydrophthalic anhydride curing agent and 1.5 parts by mass of a2, 4, 6-tris (dimethylaminomethyl) phenol accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 5
The polycyclopentadiene, the polyethylene and the polycaprolactone are respectively a middle chain segment of the dumbbell type copolymer, a main chain and a side chain of the dumbbell type structure, the number average molecular weights of the polycyclopentadiene, the polyethylene and the polycaprolactone are 10000, 1000 and 100 respectively, and the weight percentage of the side chain in the dumbbell type copolymer is 25 wt%. Dissolving 50 parts by mass of the dumbbell-shaped copolymer in an organic solvent cyclohexane to completely dissolve the polymer; adding 100 parts by mass of bisphenol S epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; 70 parts by mass of a methyltetrahydrophthalic anhydride curing agent and 1.5 parts by mass of a2, 4, 6-tris (dimethylaminomethyl) phenol accelerator were added to dissolve the curing agent and the accelerator sufficiently and uniformly disperse in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 6
Uniformly mixing 100 parts by mass of a novolac epoxy resin precursor, 60 parts by mass of a methyl hexahydrophthalic anhydride curing agent, 1.0 part by mass of a methylimidazole accelerator and 1.0 part by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 6
The polyisoprene-butadiene copolymer chain, the polystyrene and the polyethylene oxide are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weights of the polyisoprene-butadiene copolymer chain, the polystyrene and the polyethylene oxide are 10000, 1000 and 1000 respectively, and the side chain accounts for 30 wt% of the dumbbell-shaped copolymer. Dissolving 60 parts by mass of the dumbbell-type copolymer in an organic solvent n-hexane to completely dissolve the polymer; adding 100 parts by mass of novolac epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; 60 parts by mass of methyl hexahydrophthalic anhydride curing agent, 1.0 part by mass of methylimidazole accelerator and 1.0 part by mass of benzyltriethylammonium chloride accelerator are added, so that the curing agent and the accelerator are fully dissolved and uniformly dispersed in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 7
Uniformly mixing 100 parts by mass of an alicyclic epoxy resin precursor, 50 parts by mass of a succinic anhydride curing agent and 2.5 parts by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 7
Hydrogenated polycyclopentadiene, polypropylene and polypropylene oxide are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weights of the hydrogenated polycyclopentadiene, the polypropylene and the polypropylene oxide are 10000, 10000 and 10 respectively, and the side chain accounts for 35 wt% of the dumbbell-shaped copolymer. Dissolving 70 parts by mass of the dumbbell-shaped copolymer in an organic solvent heptane to completely dissolve the polymer; adding 100 parts by mass of alicyclic epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; 50 parts by mass of succinic anhydride curing agent and 2.5 parts by mass of benzyltriethylammonium chloride accelerator are added to fully dissolve and uniformly disperse the curing agent and the accelerator in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 8
Uniformly mixing 100 parts by mass of a multifunctional glycidyl ether resin precursor, 30 parts by mass of a dicyandiamide curing agent and 3.0 parts by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 8
The polyisoprene, the polypropylene and the epoxidized polybutadiene are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of a dumbbell-shaped structure, the number average molecular weights of the polyisoprene, the polypropylene and the epoxidized polybutadiene are respectively 50000, 5000 and 100, and the side chain accounts for 40 wt% of the dumbbell-shaped copolymer. 80 parts by mass of the dumbbell-shaped copolymer is dissolved in organic solvent octane to completely dissolve the polymer; adding 100 parts by mass of a multifunctional glycidyl ether resin precursor, and after fully mixing, slowly and fully volatilizing the solvent; adding 30 parts by mass of dicyandiamide curing agent and 3.0 parts by mass of benzyltriethylammonium chloride accelerator, and fully dissolving and uniformly dispersing the curing agent and the accelerator in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 9
Uniformly mixing 100 parts by mass of a heterocyclic epoxy resin precursor, 20 parts by mass of a triethylene tetramine curing agent and 1.0 part by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 9
The hydrogenated polyisoprene-butadiene copolymer chain, the polystyrene and the epoxidized polyisoprene are respectively a middle chain segment of the dumbbell-shaped copolymer, a main chain and a side chain of the dumbbell-shaped structure, the number average molecular weight of the hydrogenated polyisoprene-butadiene copolymer chain, the polystyrene and the epoxidized polyisoprene is respectively 50000, 5000 and 1000, and the side chain accounts for 45 wt% of the dumbbell-shaped copolymer. Dissolving 90 parts by mass of the dumbbell-shaped copolymer in an organic solvent N, N-dimethylformamide to completely dissolve the polymer; adding 100 parts by mass of heterocyclic epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; and adding 20 parts by mass of triethylene tetramine curing agent and 1.0 part by mass of benzyltriethylammonium chloride accelerator to fully dissolve and uniformly disperse the curing agent and the accelerator in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Comparative example 10
Uniformly mixing 50 parts by mass of a bisphenol A epoxy resin precursor, 50 parts by mass of an alicyclic epoxy resin precursor, 5 parts by mass of a triethylene tetramine curing agent, 5 parts by mass of a m-phenylenediamine curing agent and 1.0 part by mass of a benzyltriethylammonium chloride accelerator; after the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operation of air inflation and air exhaust, and preparing the toughened epoxy resin material according to the following temperature rise procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Example 10
The polyisoprene is a middle chain segment of the dumbbell-shaped copolymer, the polystyrene is a main chain of the dumbbell-shaped structure, the number average molecular weights of the polyisoprene and the polystyrene are 100000 and 10000 respectively, the side chain of the dumbbell-shaped structure comprises polyvinyl alcohol and polypropylene alcohol, the number average molecular weight of the side chain is 500, and the weight percentage of the side chain in the dumbbell-shaped copolymer is 45 wt%. Dissolving 100 parts by mass of the dumbbell-shaped copolymer in a mixed solvent of toluene and xylene in a ratio of 1:1 to completely dissolve the polymer; adding 50 parts by mass of bisphenol A epoxy resin precursor and 50 parts by mass of alicyclic epoxy resin precursor, fully mixing, and slowly and fully volatilizing the solvent; and adding 5 parts by mass of triethylene tetramine curing agent, 5 parts by mass of m-phenylenediamine curing agent and 1.0 part by mass of benzyltriethylammonium chloride accelerator, so that the curing agent and the accelerator are fully dissolved and uniformly dispersed in the epoxy resin composition. After the air bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of air inflation and air suction, and preparing the toughened epoxy resin material according to the following temperature rising procedure: curing at 65 ℃ for 1 hour, curing at 120 ℃ for 2 hours, curing at 180 ℃ for 2 hours, naturally and slowly cooling after the curing process is finished, and testing the performance of the material, as shown in table 1.
Table 1 results of performance testing
As can be seen from Table 1, the dumbbell copolymer is effective in improving the toughness of the epoxy resin and suppressing the deterioration of other properties, as compared with the results of the corresponding comparative experiment.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (6)
1. The toughened epoxy resin based on the dumbbell-shaped copolymer is characterized in that the dumbbell-shaped copolymer is introduced into an epoxy resin composition as a toughening agent, wherein the dumbbell-shaped copolymer consists of a middle chain segment and dumbbell-shaped structures at two ends, and the toughened epoxy resin comprises the following components in parts by weight:
100 parts by mass of an epoxy resin;
10-100 parts by mass of a dumbbell-type copolymer;
10-100 parts by mass of a curing agent;
0 to 3 parts by mass of an accelerator;
the middle chain segment of the dumbbell-type copolymer is polysiloxane, polyethylene propylene rubber, polyisoprene, polybutadiene, polycyclopentadiene, other polymer molecular chains with the glass transition temperature lower than room temperature or the use temperature of epoxy resin, or the middle chain segment of the dumbbell-type copolymer is polysiloxane, polyethylene propylene rubber, polyisoprene, polybutadiene, polycyclopentadiene, other polymer molecular chains with the glass transition temperature lower than the use temperature of the epoxy resin, or the middle chain segment of the polymer molecular chainsThe number average molecular weight of the intermediate block of the copolymer chain is 1.0X 104～1.0×105；
The dumbbell-shaped structure of the dumbbell-shaped copolymer consists of a main chain and side chains, wherein the main chain has the number average molecular weight of 1.0 multiplied by 102～1.0×104The side chain is polymethyl methacrylate, polylactide, polycaprolactone, polyethylene oxide, polypropylene oxide, epoxidized polybutadiene, epoxidized polyisoprene, other molecular chains compatible with epoxy resin, the combination of the above, or a copolymerized molecular chain of the above polymer molecular chains, and the number average molecular weight of the side chain is 1.0 × 101～1.0×103The weight percentage of the side chain in the dumbbell type copolymer is 5 wt% -50 wt%.
2. The toughened epoxy resin based on a dumbbell copolymer according to claim 1, wherein the epoxy resin comprises: bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, halogenated bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, novolac epoxy resins, alicyclic epoxy resins, polyfunctional glycidyl ether resins, heterocyclic epoxy resins, or combinations thereof.
3. The toughened epoxy resin based on the dumbbell copolymer as claimed in claim 1, wherein the curing agent comprises: m-phenylenediamine, N-aminoethylpiperazine, diaminodiphenylmethane, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, dicyandiamide, triethylenetetramine, or combinations of the foregoing.
4. The toughened epoxy resin based on the dumbbell copolymer as claimed in claim 1, wherein the accelerator comprises: benzyltriethylammonium chloride, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, methylimidazole, 2, 4, 6-tris (dimethylaminomethyl) phenol, or a combination of the foregoing.
5. The method for preparing the toughened epoxy resin based on the dumbbell copolymer in any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) dissolving 10-100 parts by mass of dumbbell type copolymer in an organic solvent to completely dissolve the polymer; adding 100 parts by mass of an epoxy resin precursor, and after fully mixing, slowly and fully volatilizing a solvent; adding 10-100 parts by mass of a curing agent and 0-3 parts by mass of an accelerator to fully dissolve and uniformly disperse the curing agent in the epoxy resin composition;
(2) and after bubbles in the epoxy resin composition are fully discharged, pouring the epoxy resin composition into a mould, putting the mould into a vacuum oven for repeated operations of inflation and air exhaust, preparing the toughened epoxy resin material according to a temperature rise program, naturally and slowly cooling after the curing process is finished, and testing the performance of the toughened epoxy resin material.
6. The method for preparing the toughened epoxy resin based on the dumbbell copolymer according to claim 5, wherein the organic solvent comprises: toluene, xylene, tetrahydrofuran, pentane, cyclohexane, N-hexane, heptane, octane, N-dimethylformamide, or combinations of the foregoing.
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| US5140069A (en) * | 1989-02-24 | 1992-08-18 | Ciba-Geigy Corporation | Tough epoxy casting resins based on polybutadiene-polyoxyalkleneglycol copolymers |
| US20080214773A1 (en) * | 2000-02-16 | 2008-09-04 | John Ta-Yuan Lai | S-(Alpha, Alpha'-Disubstituted-Alpha"-Acetic Acid) - Substituted Dithiocarbonate Derivatives For Controlled Radical Polymerizations, Process and Polymers Made Therefrom |
| CN109721947A (en) * | 2017-10-27 | 2019-05-07 | 财团法人工业技术研究院 | Composition epoxy resin |
| CN109836778A (en) * | 2019-02-26 | 2019-06-04 | 金安国纪科技（杭州）有限公司 | A kind of composition epoxy resin, preparation method and application |
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| US5140069A (en) * | 1989-02-24 | 1992-08-18 | Ciba-Geigy Corporation | Tough epoxy casting resins based on polybutadiene-polyoxyalkleneglycol copolymers |
| US20080214773A1 (en) * | 2000-02-16 | 2008-09-04 | John Ta-Yuan Lai | S-(Alpha, Alpha'-Disubstituted-Alpha"-Acetic Acid) - Substituted Dithiocarbonate Derivatives For Controlled Radical Polymerizations, Process and Polymers Made Therefrom |
| CN109721947A (en) * | 2017-10-27 | 2019-05-07 | 财团法人工业技术研究院 | Composition epoxy resin |
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