CN1156732A - Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process - Google Patents
Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process Download PDFInfo
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- CN1156732A CN1156732A CN 96117848 CN96117848A CN1156732A CN 1156732 A CN1156732 A CN 1156732A CN 96117848 CN96117848 CN 96117848 CN 96117848 A CN96117848 A CN 96117848A CN 1156732 A CN1156732 A CN 1156732A
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- liquid crystal
- diphenyl methane
- epoxy resin
- methane dimaleimide
- resin copolymer
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Abstract
A process for preparing diphenyl methane dimaleimide/epoxy resin copolymer with liquid crystal characteristics features that under the existance of catalyst and solvent the reflux reaction between epoxy resin, diphenyl methane dimaleimide and aromatic diamine takes place at 80-140 deg.C for 2-8 hr to obtain the solution of dipheny/methane dimaleimide/epoxy resin copolymer. A laminated composite material with higher strength and thermal stability is made up through immersing glass cloth or rubber cloth in said solution, baking at 60-120 deg.C for 0.5-1 hr, and pressing at 150-200 deg.C and 100-200 MPa for 2-6 hr.
Description
The present invention relates to a kind of novel liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and preparation method, belong to the synthetic field of macromolecular material.
U.S.P 4,440, and 945 have reported the preparation of polyether ester type epoxy resin by using liquid crystal, adopt comparatively complicated two key oxidation routes to realize that U.S.P 4,764,581 disclosed 4,4 '-dihydroxyl 2 methyl stilbenes are the synthesizing of epoxy resin by using liquid crystal of raw material.In public publication, Journal of Polymer Science, PartA; Polymer Chemistry, 31,2249 (1993) have studied polyester ether type epoxy resin by using liquid crystal, Macromolecules, 25,133 (1992) have reported from the liquid crystal liquid crystal property diamine and have set about successfully having prepared side chain type liquid crystal Resins, epoxy, Polymer Materials Scicnce andEngineering, 63,356,387 (1990), studied the curing action of epoxy resin by using liquid crystal under magnetic field by G.G.Barclay etc.Preparation method's complexity of above-mentioned these epoxy resin by using liquid crystal, raw material monomer are difficult for obtaining, and the resin solidification system only limits to aromatic diamine, is difficult in the high temperature resistant composite and uses.
The objective of the invention is provides a kind of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and manufacture method at the deficiencies in the prior art, be characterized in main chain liquid crystal Resins, epoxy and bismaleimides, the aromatic diamine copolyreaction obtains liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, it and the compound manufacturing laminar composite of woven fiber glass.In very large range can adjust the structure and the performance of resin product, thereby obtain the laminar composite that different needs is asked.The heat resisting temperature index is greater than 200 ℃, flexural strength 600～900MPa, and surface resistivity is greater than 10
12Ω, volume resistance is 10
13More than the Ω m.
The objective of the invention is to adopt following technical measures to realize:
The starting raw material recipe ingredient (by weight) of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer is:
10～200 parts of diphenyl methane dimaleimides
100～200 parts of main chain liquid crystal Resins, epoxy
2～50 parts of aromatic diamines (available sulfobenzide diamines, diphenylmethane diamine, phenyl ether diamines, Ursol D and mphenylenediamine)
1～5 part of catalyzer (available triethylamine, normal-butyl bromination ammonium and normal-butyl ammonium hydroxide)
300～500 parts of solvents (available dimethyl formamide, N,N-DIMETHYLACETAMIDE, acetone and toluene)
The preparation method of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer:
1. the preparation of main chain liquid crystal Resins, epoxy
With 100～300 parts of '-biphenyl diphenols, 100～500 parts of dimethyl formamides, add and have agitator, thermometer is in the reactor of water trap and reflux exchanger, add 50～350 parts of epoxy chloropropane, start agitator, add 60～120 parts in sodium hydroxide again, 2～5 parts of normal-butyl bromination ammoniums, and drip 2～10 parts in water, be warming up to 80～120 ℃ of reflux temperatures, reacted 10～20 hours, steam excessive epoxy chloropropane, precipitate in the impouring water, with deionized water wash four times, recrystallizing methanol was in 80 ℃ of vacuum tightness 10-30mmHg of temperature vacuum-drying 24 hours, obtain main chain liquid crystal Resins, epoxy, its structure is:
2. the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With the diphenyl methane dimaleimide in the above-mentioned recipe ingredient, main chain liquid crystal Resins, epoxy, aromatic diamine, the weighing respectively of catalyzer and solvent, add and have agitator, in the reactor of thermometer and reflux exchanger, start agitator, be warming up to 80～140 ℃ of back flow reaction 2～8 hours, be cooled to room temperature, obtain liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, solid content 25～65%, polymerization velocity in the time of 160 ℃ 3～60 minutes, 115～220 ℃ of liquid crystal phase transition temperature.
3. the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer laminar composite
Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution impregnation woven fiber glass with above-mentioned acquisition, woven fiber glass behind the gluing was 60～120 ℃ of bakings 0.5～2 hour, and thickness is repeatedly put neatly on demand, sends in the thermocompressor, 150～200 ℃ of temperature, pressure 100～200MPa, heat-insulation pressure keeping 2～6 hours is cooled to 100 ℃ naturally and takes out down, obtain laminar composite, the heat resisting temperature index is greater than 200 ℃, flexural strength 600-900MPa, and surface resistivity is greater than 10
12Ω, volume specific resistance is greater than 10
13Ω m can be used as special engineering plastics.
The present invention has following advantage:
1. introduce main chain liquid crystal Resins, epoxy in double-dimaleic type polyimide system, improve the mechanical property and the adhesiveproperties of double-dimaleic type polyimide resin, widened use range.
2. form and the variation of formula rate the structure of may command product and performance by raw material.
3. improve cementability with woven fiber glass.
4. raw material sources are abundant, and manufacturing process is simple, and broad range of applicability has higher performance, is easy to apply, and remarkable economic efficiency and social benefit are arranged.
Embodiment:
1. one of preparation of main chain liquid crystal Resins, epoxy
With '-biphenyl diphenol 100 grams, dimethyl formamide 100 grams add and have agitator, thermometer, in the reactor of water trap and reflux exchanger, add epoxy chloropropane 150 grams, start agitator, add 60 grams in the hydroxide, normal-butyl bromination ammonium 2 grams drip water 2 grams, are warming up to 80～85 ℃ of reactions 20 hours, steam excessive epoxy chloropropane, precipitate in the product impouring water, use deionized water wash four times, recrystallizing methanol, in 80 ℃ of following vacuum tightness 10-20mmHg vacuum-dryings of temperature 24 hours, obtain yellow product, productive rate is 78%, 164～170 ℃ of fusing points, molecular weight 2108,108～180 ℃ of liquid crystal phase transition temperature.
2. two of the preparation of main chain liquid crystal Resins, epoxy
With '-biphenyl diphenol 186 grams, dimethyl formamide 300 grams add and have agitator, thermometer in the reactor of water trap and reflux exchanger, adds epoxy chloropropane 180 grams, start agitator, add sodium hydroxide 120 grams, normal-butyl bromination ammonium 5 grams, and drip water 10 grams, and be warming up to 120 ℃, reacted 15 hours, operation obtains white product with embodiment 1 below, and productive rate is 82%, 154～158 ℃ of fusing points, molecular weight 1230,123～174 ℃ of liquid crystal phase transition temperature.
3. three of the preparation of main chain liquid crystal Resins, epoxy
With '-biphenyl diphenol 300 grams, dimethyl formamide 500 grams add and have agitator, thermometer, in the reactor of water trap and reflux exchanger, add epoxy chloropropane 350 grams, start agitator, add sodium hydroxide 100 grams, normal-butyl bromination ammonium 3 grams drip water 5 grams, be warming up to 80 ℃ of reactions 10 hours, operation obtains white product with embodiment 1 below, productive rate 86%, 138 ℃ of fusing points, molecular weight 272,115～152 ℃ of liquid crystal phase transition temperature.
4. one of preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With diphenyl methane dimaleimide 10 grams, main chain liquid crystal Resins, epoxy 100 grams that embodiment 1 makes, sulfobenzide diamines 26 grams, triethylamine 1 gram, N,N-DIMETHYLACETAMIDE 300 grams, add and have in the reactor of agitator, thermometer and reflux exchanger, start agitator, be warming up to 140 ℃, back flow reaction 2 hours is cooled to room temperature, obtain liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, polymerization velocity during 35%, 160 ℃ of solid content 16.2 minutes, 120～170 ℃ of liquid crystal phase transition temperature.
5. two of the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With diphenyl methane dimaleimide 100 grams, main chain liquid crystal Resins, epoxy 200 grams that embodiment 1 makes, phenyl ether diamines 50 grams, normal-butyl bromination ammonium 3 grams, dimethyl formamide 500 gram adds in the identical equipment of embodiment 4, is warming up to 100 ℃, reacted 4 hours, be cooled to room temperature, obtain liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, solid content 41%, polymerization velocity in the time of 160 ℃ 23 minutes, 120～180 ℃ of liquid crystal phase transition temperature.
6. three of the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With diphenyl methane dimaleimide 200 grams, embodiment 2 makes main chain liquid crystal Resins, epoxy 200 grams, Ursol D 10 grams.Normal-butyl bromination ammonium 5 grams, dimethyl formamide 500 grams, add in the identical equipment of embodiment 4, be warming up to 180 ℃, reacted 8 hours, be cooled to room temperature, obtain liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, polymerization velocity during about 44%, 160 ℃ of solid content 38.21 minutes, 120～200 ℃ of liquid crystal phase transition temperature.
7. four of the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With diphenyl methane dimaleimide 200 grams, embodiment 3 makes main chain liquid crystal Resins, epoxy 100 grams, mphenylenediamine 10 grams, acetone 100 grams, N,N-DIMETHYLACETAMIDE 200 gram, triethylamine 10 grams add in the identical equipment of embodiment 4, be warming up to 80 ℃, reacted 6 hours, cooling obtains liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, solid content 50%, polymerization velocity in the time of 160 ℃ 48 minutes, 120～210 ℃ of liquid crystal phase transition temperature.
8. five of the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With diphenyl methane dimaleimide 100 grams, embodiment 3 makes main chain liquid crystal Resins, epoxy 200 grams, sulfobenzide diamines 50 grams, triethylamine 10 grams, dimethyl formamide 200 gram, toluene 100 grams add in the identical equipment of embodiment 4, be warming up to 80 ℃, reacted cooling, acquisition liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, solid content 54% 6 hours, polymerization velocity in the time of 160 ℃ 40.64 minutes, 118～180 ℃ of liquid crystal phase transition temperature.
Embodiment 1～8 raw materials used industrial goods and the chemically pure reagent that is the market purchase.
9. the preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer laminar composite
The liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution that above-mentioned 4～8 embodiment make is distinguished impregnated glass-fiber cloth, adhesive plaster dried by the fire 1 hour in 60 ℃ of baking ovens, 120 ℃ of bakings of temperature 30 minutes, thickness is repeatedly put neatly on demand, send in the thermocompressor, 160 ℃ of temperature, 150MPa exerts pressure, heat-insulation pressure keeping 3 hours is warming up to 200 ℃, and 200MPa exerts pressure, heat-insulation pressure keeping 3 hours, naturally be cooled to 100 ℃ and take out down, obtain the liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer laminar composite, its performance is as shown in table 1.And using the performance of diphenyl methane dimaleimide/bisphenol A type epoxy resin multipolymer woven fiber glass pressing plate as shown in table 2, the result shows that the performance of laminar composite of liquid crystal diphenyl methane dimaleimide/epoxy resin is good.
Table 1 liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer glass laminates performance of composites embodiment make flexural strength surface resistivity volume specific resistance heat resisting temperature index resin numbering (MPa) (Ω) (Ω m) (℃) 4 937 1.62 * 10
131.94 * 10
142,315 823 2.93 * 10
133.90 * 10
152,266 721 9.04 * 10
128.61 * 10
142,187 608 6.33 * 10
131.27 * 10
152,208 790 5.98 * 10
132.23 * 10
15220
The performance of table 2 diphenyl methane dimaleimide/bisphenol A type epoxy resin glass cloth laminated board
Flexural strength surface resistivity volume specific resistance heat resisting temperature index sample
(MPa) (Ω) (Ωm) (℃)1 619 4.1×10
13 3.9×10
12 1802 499 1.8×10
13 1.0×10
13 1973 584 6.3×10
13 9.8×10
12 190
Claims (6)
1. a liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer is characterized in that the starting raw material recipe ingredient (by weight) of this multipolymer is
10～200 parts of diphenyl methane dimaleimides
100～200 parts of main chain liquid crystal Resins, epoxy
2～50 parts of aromatic diamines
1～5 part of catalyzer
300～500 parts of solvents
2. according to the described liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer of claim 1, it is characterized in that this aromatic diamine of getting thing altogether is the sulfobenzide diamines, diphenylmethane diamine, phenyl ether diamines, Ursol D and mphenylenediamine.
3. according to the described liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer of claim 1, the catalyzer that it is characterized in that this multipolymer is a triethylamine, normal-butyl bromination ammonium and normal-butyl ammonium hydroxide.
4. according to the described liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer of claim 1, the solvent that it is characterized in that this multipolymer is dimethyl formamide, N,N-DIMETHYLACETAMIDE, acetone and toluene.
5. according to the manufacture method of the described liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer of claim 1, it is characterized in that:
(1) preparation of main chain liquid crystal Resins, epoxy
With 100～300 parts of '-biphenyl diphenols, 100～500 parts of dimethyl formamides, add and have agitator, thermometer is in the reactor of water trap and reflux exchanger, add 150～350 parts of epoxy chloropropane, start agitator, add 60～120 parts in sodium hydroxide again, 2～5 parts of normal-butyl bromination ammoniums, and drip 2～10 parts in water, be warming up to 80～120 ℃ of reflux temperatures, reacted 10～20 hours, steam excessive epoxy chloropropane, precipitate in the impouring water, with deionized water wash four times, recrystallizing methanol was in 80 ℃ of vacuum tightness 10-30mmHg of temperature vacuum-drying 24 hours, obtain main chain liquid crystal Resins, epoxy, its structure is:
(2) preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer
With the diphenyl methane dimaleimide in the above-mentioned recipe ingredient, main chain liquid crystal Resins, epoxy, aromatic diamine, the weighing respectively of catalyzer and solvent, add and have agitator, in the reactor of thermometer and reflux exchanger, start stirring, be warming up to 80～140 ℃ of back flow reaction 2～8 hours, be cooled to room temperature, obtain liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution, solid content is 25～60%, polymerization velocity in the time of 160 ℃ is 3～60 minutes, 115～220 ℃ of liquid crystal phase transition temperature.
(3) preparation of liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer laminar composite
With liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer solution impregnation woven fiber glass, woven fiber glass behind the gluing was 60 ℃～120 ℃ bakings 0.5～2 hour, thickness is repeatedly put neatly on demand, sends in the thermocompressor 150～200 ℃ of temperature, pressure 100～200MPa, heat-insulation pressure keeping 2-6 hour, be cooled to 100 ℃ naturally and take out down, obtain laminar composite, flexural strength is at 600～900MPa, and surface resistivity reaches 10
12More than the Ω, volume specific resistance reaches 10
13More than the Ω m, the heat resisting temperature index is more than 200 ℃.
6. according to the purposes of the described liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer of claim, it is characterized in that this copolymer solution and woven fiber glass composite laminate can be used as the special engineering plastics material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96117848 CN1156732A (en) | 1996-12-23 | 1996-12-23 | Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96117848 CN1156732A (en) | 1996-12-23 | 1996-12-23 | Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process |
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| CN1156732A true CN1156732A (en) | 1997-08-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153728A (en) * | 2011-02-28 | 2011-08-17 | 桂林理工大学 | Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group |
| CN102363646A (en) * | 2011-06-28 | 2012-02-29 | 衡阳恒缘电工材料有限公司 | Modified bismaleimide resin and preparation method thereof |
| CN113831461A (en) * | 2021-09-28 | 2021-12-24 | 泉州师范学院 | Bismaleimide/acrylic acid liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
-
1996
- 1996-12-23 CN CN 96117848 patent/CN1156732A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153728A (en) * | 2011-02-28 | 2011-08-17 | 桂林理工大学 | Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group |
| CN102153728B (en) * | 2011-02-28 | 2012-10-31 | 桂林理工大学 | Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group |
| CN102363646A (en) * | 2011-06-28 | 2012-02-29 | 衡阳恒缘电工材料有限公司 | Modified bismaleimide resin and preparation method thereof |
| CN113831461A (en) * | 2021-09-28 | 2021-12-24 | 泉州师范学院 | Bismaleimide/acrylic acid liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
| CN113831461B (en) * | 2021-09-28 | 2023-11-21 | 泉州师范学院 | Bismaleimide/acrylic acid liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
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