CN102153837B - High-performance high-temperature-resistant modified epoxy resin - Google Patents
High-performance high-temperature-resistant modified epoxy resin Download PDFInfo
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- CN102153837B CN102153837B CN201110139423A CN201110139423A CN102153837B CN 102153837 B CN102153837 B CN 102153837B CN 201110139423 A CN201110139423 A CN 201110139423A CN 201110139423 A CN201110139423 A CN 201110139423A CN 102153837 B CN102153837 B CN 102153837B
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- epoxy resin
- benzoxazine
- cyanoethyl
- methylimidazole
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Abstract
The invention provides a benzoxazine modified epoxy resin composition, which comprises the following components in parts by weight: 10-50 parts of benzoxazine resin, 10-100 parts of epoxy resin, 40-120 parts of anhydride curing agent and 2-4 parts of imidazole accelerator. The benzoxazine resin is taken as a modifier for modifying an epoxy resin crosslinked anhydride curing agent, so that the glass transition temperature and shock strength of a crosslinkging product of epoxy resin and the anhydride curing agent can be enhanced at the same time, and the technical problem that the glass transition temperature and shock strength cannot be enhanced at the same time is well solved. The obtained benzoxazine modified epoxy resin keeps high temperature resistance of benzoxazine and has high processability and mechanical property.
Description
Technical field
The present invention relates to a kind of modified epoxy and preparation method thereof, relate in particular to a kind of high-performance heat resist modification resin that utilizes the benzoxazine colophony modified epoxy and obtain.
Background technology
The thermosetting resin based composites is a kind of matrix material of studying at most at present, using the most extensively.It has that light weight, intensity are high, modulus is big, good corrosion resistance, electrical property is excellent, raw material sources are extensive; Characteristics such as machine-shaping is easy, production efficiency height; And have material designability and a some other property; Like vibration damping, noise reduction, pass through characteristics such as hertzian wave, stealthy, anti-ablation, having become can't substituted important materials in national economy, national defense construction and the development in science and technology.In the thermosetting resin based composites, use maximum resins to remain this three big thermosetting resin of resol, unsaturated polyester junket resin and epoxy resin.These three kinds of resin rank performances respectively have characteristics: the thermotolerance of resol is higher, acid resistance good, curing speed is fast, but more crisp, need high-pressure molding; Good manufacturability, the price of unsaturated polyester junket resin are minimum, but poor-performing; The cohesive strength of epoxy resin and cohesive strength are high, and erosion resistance and dielectric properties are excellent, and over-all properties is best, but price is more expensive.Therefore, epoxy resin composite material is used for the demanding occasion of use properties more in actual engineering, as being used as structured material, corrosion resistant material, electrically insulating material and electromagnetic wave transparent material etc.
Many industries have proposed urgent demand to high-temperature-resistant structure with composite product, and for example some electrical parts need stable performance under the high temperature, and some load spares still have enough strength and stiffness under the high temperature wet heat condition.These demands have proposed new problem for the matrix material manufacturing.
Use the epoxy resin of anhydride-cured to have excellent thermal property, hydrothermal aging performance and electrical insulation properties, but the fragility of cured resin has limited its use.At present the most frequently used method for toughening is the oligopolymer that in resin, adds flexible structure such as polyoxyethylene glycol, but this method usually can be influential to the thermal property of material, can reduce the second-order transition temperature of material to a certain extent.
Summary of the invention
The object of the present invention is to provide modified epoxy of a kind of excellent heat resistance and preparation method thereof, the above-mentioned shortcoming that exists with the cross-linking products that solves epoxy resin and anhydride curing agent.
For achieving the above object, the present invention adopts following technical scheme:
A kind of benzoxazine modified epoxy is characterized in that, comprises the component of following weight part:
Said benzoxazine resin is the mixture of one or both in the structure shown in the formula (I):
Wherein, R is-C (CH
3)
2-or-C (CF
3)
2-.
In the above-mentioned formula (I), when R is-C (CH
3)
2In-time, be called for short BENA; When R is-C (CF
3)
2In-time, be called for short BENF.
Above-mentioned benzoxazine resin can prepare through following method: in the there-necked flask of being furnished with whipping appts, nitrogen ingress pipe and prolong, add stoichiometric dihydroxyphenyl propane or Bisphenol F, Paraformaldehyde 96 and aniline; Be heated to 100 ℃ under stirring, reaction is dissolved in product in the chloroform after finishing, and with the sodium hydroxide solution washing, is washed till neutrality with deionized water then.Distillation at last removes to desolvate and promptly gets benzoxazine colophony.
Preferable, said epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F epoxy resin and 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl manthanoate.
The structure of said bisphenol A type epoxy resin is following:
Preferred model is DOW DER 331.
The structure of said bisphenol F epoxy resin is following:
Preferred model is DOW DER 354.
3,4-epoxycyclohexyl methyl-3, the structure of 4-epoxycyclohexyl manthanoate (2021P) is following:
Preferable, said anhydride curing agent is selected from liquid methyl tetrahydro phthalic anhydride (MTHPA), methyl hexahydrophthalic anhydride (MHHPA) and methyl carbic anhydride (MNA).
Preferable; Said imidazoles promotor is selected from glyoxal ethyline (2MZ), 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-undecyl imidazole (C11Z), 2-heptadecyl imidazoles (C17Z), 1 benzyl 2 methyl imidazole (1B2MZ), 1-dodecyl-2-methyl-3-benzylimidazolium chloride (SFZ), 1; 3-dibenzyl-glyoxal ethyline muriate (FFZ), glyoxal ethyline quinoline (2MZL), 2-phenyl-4-methylimidazole (2P4MZ), 1-1-cyanoethyl-2-methylimidazole (2MZ-CN), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), 1-cyanoethyl-2-undecyl imidazole (C11Z-CN), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 1-1-cyanoethyl-2-methylimidazole trimellitic acid salt (2MZ-CNS), 1-cyanoethyl-2-phenylimidazole trimellitic acid salt (2PZ-CNS), 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitic acid salt (2E4MZ-CNS), 1-cyanoethyl-2-undecyl imidazole trimellitic acid salt (C11Z-CNS) and 2,4-diamino--6 [2 '-Methylimidazole-(1 ')] ethyl-S-triazine (2MZ-A).
The present invention also further discloses the preparation method of above-mentioned benzoxazine modified epoxy; Comprise the steps: benzoxazine resin and epoxy resin to be stirred down up to homogeneous phase in 60-80 ℃ by proportioning; Cool to room temperature then; Add anhydride curing agent and imidazoles promotor by proportioning again, continue to stir up to homogeneous phase.
The present invention with the benzoxazine resin as properties-correcting agent; The cross linking of epoxy resin anhydride curing agent is carried out modification; Can improve the glass transition temp and the resistance to impact shock of the cross-linking products of epoxy resin and anhydride curing agent simultaneously, solve the technical problem that two kinds of performances of glass transition temp and resistance to impact shock can not raise simultaneously well.The benzoxazine modified epoxy that is obtained has not only kept the resistance to elevated temperatures of benzoxazine, and has good processing properties and mechanical property.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that these embodiment only are used to explain the present invention, and unrestricted scope of the present invention.
Employed various epoxy resin, anhydride curing agent and imidazole curing agent all can obtain through commercially available approach among the present invention.
The benzoxazine resin (BENA) that is adopted in the following example can prepare through following test:
In being furnished with the 100ml there-necked flask of whipping appts, nitrogen ingress pipe and prolong, add stoichiometric dihydroxyphenyl propane 11.4g (0.05mol), Paraformaldehyde 96 6.01g (0.2mol), aniline 9.4 (0.1mol).Be heated to 100 ℃ under stirring, reacted 20 minutes.After reaction finishes, product is dissolved in the chloroform, washs three times, be washed till neutrality with deionized water then with the sodium hydroxide solution of 3mol/L.Distillation at last removes to desolvate and promptly gets fragrant ethynyl benzo oxazine resin.Productive rate is 73.7%.
1H-NMR(CDCl
3，TMS)δ：1.60(C-CH
3)，4.56(Ar-CH
2-N)，5.30(O-CH
2-N)。
The benzoxazine resin (BENF) that is adopted in the following example can prepare through following test:
In being furnished with the 100ml there-necked flask of whipping appts, nitrogen ingress pipe and prolong, add stoichiometric Bisphenol F 111g (0.05mol), Paraformaldehyde 96 6.01g (0.2mol), aniline 9.4 (0.1mol).Be heated to 100 ℃ under stirring, reacted 20 minutes.After reaction finishes, product is dissolved in the chloroform, washs three times, be washed till neutrality with deionized water then with the sodium hydroxide solution of 3mol/L.Distillation at last removes to desolvate and promptly gets fragrant ethynyl benzo oxazine resin.Productive rate is 71.76%.The nuclear-magnetism appraising datum,
1H-NMR (CDCl
3, TMS) δ: 4.56 (Ar-CH
2-N), 5.30 (O-CH
2-N).
In the following example; The preparation method of benzoxazine modified epoxy is: benzoxazine resin and epoxy resin are added in the flask; Be heated to 60-100 ℃ of stirring up to homogeneous phase, cool to room temperature adds solidifying agent and curing catalyst more then, continues to stir up to homogeneous phase.
In the following example, glass transition temp uses the DSC method to measure 10 ℃/min of temperature rise rate; Shock strength is tested according to ASTM D256 standard.
Embodiment 1
Among this embodiment, epoxy resin selects for use DER 331 and benzoxazine resin to select BENA for use, and anhydride curing agent is selected MTHPA for use, and solidifying agent is selected 2E4MZ for use, and concrete performance and prescription (weight part) are as shown in table 1:
| Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 | |
| DER?331 | 100 | 90 | 70 | 50 |
| BENA | 0 | 10 | 30 | 50 |
| MTHPA | 85 | 78 | 65 | 42 |
| 2E4MZ | 2 | 2 | 2 | 2 |
| Second-order transition temperature (℃) | 130 | 136 | 148 | 159 |
| Shock strength (J.cm -2) | 0.5 | 0.72 | 1.36 | 1.54 |
Embodiment 2
Among this embodiment, epoxy resin is selected epoxy 2021P for use, and the benzoxazine resin is selected BENF for use, and anhydride curing agent is selected MTHPA for use, and solidifying agent is selected 2MZ for use, and concrete performance and prescription (weight part) are as shown in table 2:
Table 2
| Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 | |
| 2021P | 100 | 90 | 70 | 50 |
| BENF | 0 | 10 | 30 | 50 |
| MHHPA | 130 | 120 | 90 | 65 |
| 2MZ | 2 | 2 | 2 | 2 |
| Second-order transition temperature (℃) | 198 | 190 | 185 | 185 |
| Shock strength (J.cm -2) | 0.42 | 0.49 | 0.88 | 1.13 |
Embodiment 3
Among this embodiment, epoxy resin is selected DER 354 for use, and the benzoxazine resin is selected BENF for use, and anhydride curing agent is selected MTHPA for use, and solidifying agent is selected 2P4MZ for use, and concrete performance and prescription (weight part) are as shown in table 3:
Table 3
| Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 | |
| DER354 | 100 | 90 | 70 | 50 |
| BENF | 0 | 10 | 30 | 50 |
| MHHPA | 90 | 80 | 65 | 45 |
| 2P4MZ | 2 | 2 | 2 | 2 |
| Second-order transition temperature (℃) | 119 | 126 | 141 | 155 |
| Shock strength (J.cm -2) | 0.65 | 0.78 | 1.41 | 1.58 |
The foregoing description is that example describes with 2E4MZ, 2MZ and three kinds of imidazoles promotor of 2P4MZ, adopt other imidazoles promotor as: 2PZ, C11Z, C17Z, 1B2MZ, SFZ, FFZ, 2MZL, 2MZ-CN, 2PZ-CN, C11Z-CN, 2E4MZ-CN, 2MZ-CNS, 2PZ-CNS, 2E4MZ-CNS, C11Z-CNS and 2MZ-A etc. substitute above-mentioned three kinds of imidazoles promotor also can obtain same effect.
Claims (5)
1. a benzoxazine modified epoxy is characterized in that, comprises the component of following weight part:
Said benzoxazine resin is the mixture of one or both in the structure shown in the formula (I):
Wherein, R is-C (CH
3)
2-or-C (CF
3)
2-.
2. benzoxazine modified epoxy as claimed in claim 1 is characterized in that, said epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F epoxy resin and 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl manthanoate.
3. according to claim 1 or claim 2 benzoxazine modified epoxy; It is characterized in that; Said imidazoles promotor is selected from glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 1 benzyl 2 methyl imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1; 3-dibenzyl-glyoxal ethyline muriate, glyoxal ethyline quinoline, 2-phenyl-4-methylimidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-1-cyanoethyl-2-methylimidazole trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitic acid salt, 1-cyanoethyl-2-undecyl imidazole trimellitic acid salt and 2,4-diamino--6 [2 '-Methylimidazole-(1 ')] ethyl-S-triazine.
4. according to claim 1 or claim 2 benzoxazine modified epoxy is characterized in that said anhydride curing agent is selected from methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride and methyl carbic anhydride.
5. according to claim 1 or claim 2 the preparation method of benzoxazine modified epoxy; Comprise the steps: benzoxazine resin and epoxy resin to be stirred down up to homogeneous phase in 60-100 ℃ by proportioning; Cool to room temperature then; Add anhydride curing agent and imidazoles promotor by proportioning again, continue to stir up to homogeneous phase.
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| CN201110139423A CN102153837B (en) | 2011-05-26 | 2011-05-26 | High-performance high-temperature-resistant modified epoxy resin |
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| CN102153837B true CN102153837B (en) | 2012-09-05 |
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| EP2762528B1 (en) * | 2011-09-30 | 2020-03-11 | JX Nippon Oil & Energy Corporation | Benzoxazine resin composition, and fiber-reinforced composite material |
| EP2814802B1 (en) * | 2012-02-17 | 2020-12-16 | Huntsman Advanced Materials Americas LLC | Mixture of benzoxazine, epoxy and anhydride |
| CN104553229B (en) * | 2014-12-23 | 2017-01-04 | 上海南亚覆铜箔板有限公司 | A kind of preparation method of high Tg Halogen low dielectric type copper coated foil plate |
| CN105017508B (en) * | 2015-08-21 | 2017-07-18 | 广州聚合新材料科技股份有限公司 | Corrosion resistant epoxy-resin systems and its preparation method and application are worn in resistance |
| CN108997560A (en) * | 2017-06-07 | 2018-12-14 | 洛阳尖端技术研究院 | A kind of epoxy resin composite material and its preparation method and application |
| CN111151710B (en) * | 2020-01-16 | 2021-07-23 | 夏文松 | Environment-friendly precoated sand casting process |
| CN115232583A (en) * | 2022-09-23 | 2022-10-25 | 武汉市三选科技有限公司 | High-storage-property underfill adhesive, preparation method thereof and chip packaging structure |
| CN118005993B (en) * | 2024-02-02 | 2024-10-29 | 广东博汇新材料科技有限公司 | Composition of degradable anhydride cured epoxy resin and method for degrading regenerated anhydride cured epoxy resin |
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