CN101157623B - Method for preparing 1,4-di(4-amino-benzene oxygen) benzene - Google Patents
Method for preparing 1,4-di(4-amino-benzene oxygen) benzene Download PDFInfo
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- CN101157623B CN101157623B CN2007100414100A CN200710041410A CN101157623B CN 101157623 B CN101157623 B CN 101157623B CN 2007100414100 A CN2007100414100 A CN 2007100414100A CN 200710041410 A CN200710041410 A CN 200710041410A CN 101157623 B CN101157623 B CN 101157623B
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Abstract
The invention relates to a preparation method for 1, 4-double (4-amido phenoxyl) benzene. The method comprises the steps as follows: (1) hydrochinone and 4-halogenated nitrobenzene with a mole rate of 1.00: 1.80 to 2.80 are heated to carry a back flow water dividing reaction for 2 to 18 hours inside halogen agent, strong polarity non-proton or organic solvent system; the reaction is condensed andthe reaction article system is cooled; water is filled in; a Kelly solid product is separated out and then is filtered and dried; (2) 1, 4-double (4-nitryl phenoxyl) benzene reacts for 2 to 20 hours by the common effect of ferric chloride/20 to 95 percent hydrazine hydrate reduction system, alcohol alike solvent and active carbon under a temperature ranging from 50 DEG C to 90 DEG C, and then the1, 4-double(4-nitryl phenoxyl) benzene is deoxidized to the 1, 4-double (4-amido phenoxyl) benzene crystal product. The invention has the advantages of easy operation, environment protection, being suitable to be used for industrial production, high product yield and more than 99 percent of purity. Besides, the solvent can be recycled and applied again and again.
Description
Technical field
The invention belongs to the preparation field of aromatic dicarboxylic primary amine, particularly relate to a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-.
Background technology
Aromatic polyimide has outstanding thermostability, anti-nuclear radiation, excellent mechanical property, electric property and organic solvent resistance, has obtained widespread use in space flight and aviation, electronics microelectronics, field such as electric.
Along with the information electronic product towards high performance, lightweight, slimming, the development that becomes more meticulous, the insulating material of flexible copper-clad plate (FCCL) is had higher requirement, low-dielectric loss heat-resisting, high strength etc. as the needs height.Therefore, polyimide material enjoys blue or green hiding in the FCCL field, and particularly the thermoplastic polyimide material of using in two stratotype FCCL is of greatest concern.
The aromatic dicarboxylic primary amine is one of important source material of synthesis of polyimides material, and the aromatic dicarboxylic primary amine of ether-containing key is the important source material of synthetic thermoplastic polyimide in the molecular structure.
Chinese patent CN1485315A, disclose a kind of 3,4 '-preparation method of diaminodiphenyl oxide;
Chinese patent CN1425644A, disclose a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Japanese Patent JP63-126848, disclose a kind of 4,4 '-two (3-amino-benzene oxygens)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
Japanese Patent JP62-248635, disclose a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) biphenyl;
U.S. Pat 4377525, disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-;
U.S. Pat 4064107, disclose a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) phenyl ether;
People such as Yu Xinhai (the insulating material communication, 1999,32 (5): 1-4) disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-, simultaneously, the also synthetic series of heat plastic polyimide that obtained.
People such as Yu Xinhai (insulating material, 2001,34 (4): 13-16) disclose a kind of 3,3 '-preparation method of diaminodiphenyl oxide;
People such as Yu Xinhai (insulating material, 2001,34 (6): 3-6) disclose a kind of 2, the preparation method of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-;
People such as Yu Xinhai (insulating material, 2002,35 (4): 3-7) disclose a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Yu Xinhai (New Chemical Materials, 2003,31 (10): 24-27) disclose a kind of 2, two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That people such as Yu Xinhai (insulating material, 2006,39 (5): 1-3,6) disclose is a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) benzophenone;
It is a kind of 1 that people such as Yu Xinhai (insulating material, 2006,39 (3): 1-4,8) disclose, the preparation method of two (4-amino-benzene oxygen) benzene of 3-.
People (Journal of Polymer Research such as Chin-Ping Yang, 1995,2 (3): 179-186) disclose a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, be primarily characterized in that, the first step: the mixture of Resorcinol, 4-chloronitrobenzene, Anhydrous potassium carbonate and DMF is in 160 ℃ of back flow reaction after 8 hours, cooling, pour into subsequently in the mixed solution of first alcohol and water (volume is 1: 1) and separate out solid product, filter, use the Glacial acetic acid recrystallization, obtain 1, two (4-nitrophenoxy) benzene of 4-, yield 67%; Second step: 1, two (4-nitrophenoxy) benzene of 4-close at the 10%Pd/C-alcohol-water and carry out reduction reaction in the hydrazine system, after reaction finishes, filter, remove Pd/C, cooling, separate out 1 of white, two (4-amino-benzene oxygen) the benzene solid products of 4-filter, and use methanol wash, dry, obtain 1, two (4-amino-benzene oxygen) benzene of 4-, yield 65%.
This preparation method's shortcoming is: (1) operating procedure complexity, and kind with an organic solvent is more, has increased buying and carrying cost virtually; (2) synthetic 1, in the process of two (4-nitrophenoxy) benzene of 4-, reaction mixture is directly poured in the mixed solution of first alcohol and water and is separated out product, causes waste water serious, and the processing costs height is unfavorable for environment protection; (3) organic solvent reclaims difficulty; (4) synthetic obtain 1, two (4 nitro-phenoxy) benzene of 4-also need pass through the Glacial acetic acid recrystallization, this has not only increased cost, but also has additionally produced the three wastes; (5) use 10%Pd/C in the reduction reaction, cause product cost to raise, be unfavorable for commercially producing; (6) 1 of the reduction reaction acquisition, two (4-amino-benzene oxygen) benzene of 4-also need be used methanol wash, and this has not only increased cost, has produced the three wastes, and has increased the burden of solvent recuperation again; (7) the first step and the yield in second step are on the low side, cause total recovery lower, have only 67%*65%=43.55%.
Summary of the invention
Chemical equation of the present invention is as follows:
Wherein, X is a halogen atom, i.e. fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
The invention provides a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, this method technology is simple, cost is low, environmental friendliness, purity and yield height.
Of the present invention a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-comprises the steps:
(1) mol ratio is 1.00: 1.80～2.80 Resorcinol and 4-halogenated nitrobenzene, and in salt forming agent, strong aprotic, polar and water-insoluble organic solvent system, reflux is divided water, 80 ℃-190 ℃, react after 2～18 hours concentration of reaction solution, reclaim solvent with recycle, the cooling reactant system adds water, separates out the yellow-green colour solid product, filter, drying obtains 1, two (4-nitrophenoxy) benzene of 4-;
Two (4-nitrophenoxy) benzene of (2) 1,4-are under the acting in conjunction of the reduction system of iron trichloride/20%～95% hydrazine hydrate, alcoholic solvent, gac, 50 ℃-90 ℃, reacted 2～20 hours, reduction obtains 1 of white, two (4-amino-benzene oxygen) the benzene crystalline products of 4-.
Described 4-halogenated nitrobenzene is selected from one or more mixtures in 4-fluoro oil of mirbane, 4-chloronitrobenzene, 4-bromo nitryl benzene, the 4-iodo oil of mirbane.
Described salt forming agent is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
Described salt forming agent is 0.10～8.00: 1.00 with the ratio of the mole number of Resorcinol.
The envelope-bulk to weight ratio of described organic solvent and Resorcinol is 5 milliliters～80 milliliters: 1 gram.
Described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
Described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
Described water-insoluble organic solvent is 1: 0.05～10 with the volume ratio of strong polar non-proton organic solvent.
Described 1, two (4-nitrophenoxy) benzene of 4-are 1: 5～30 with the ratio of the mole number of hydrazine hydrate.
Described iron trichloride and 1, the ratio of the weight of two (4-nitrophenoxy) benzene of 4-is 1: 2～50.
Described alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
Described alcoholic solvent and 1, the envelope-bulk to weight ratio of two (4-nitrophenoxy) benzene of 4-is 1 milliliter～100 milliliters: 1 gram.
Described gac and 1, the ratio of the weight of two (4 nitro-phenoxy) benzene of 4-is 1: 0.5～50.
Beneficial effect
(1) the present invention is preparation 1, the commercial run of two (4-amino-benzene oxygen) benzene of 4-;
(2) environmentally friendly, the three wastes are few;
(3) simple to operate, reaction process is carried out under normal pressure, does not relate to also not producing corrosives, equipment is not had particular requirement, less investment;
(4) kind of used organic solvent is few;
(5) organic solvent reclaims conveniently, and Recycling repeatedly;
(6) product yield and purity are all very high;
(7) raw materials used convenient sources, cost is lower, does not relate to the use noble metal catalyst;
(6) production cost of products is cheap, helps it and further applies.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 11.0 gram (0.10 mole) Resorcinol, 44.1 gram (0.28 mole) 4-chloronitrobenzene, 110.4 gram (0.80 mole) salt of wormwood, 700 milliliters of N, dinethylformamide and 180 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 18 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system, add water, separate out the yellow-green colour solid product, drying, obtain 35.1 grams 1, two (4-nitrophenoxy) benzene of 4-, fusing point is 239.6 ℃, purity is 99.9%, obtain 1 according to reality, amount of two (4-nitrophenoxy) benzene of 4-and theoretical amount (35.2 gram) calculate 1, and the yield of two (4-nitrophenoxy) benzene of 4-is 99.7%.
Embodiment 2
With 11.0 gram (0.10 mole) Resorcinol, 44.5 gram (0.22 mole) 4-bromo nitryl benzene, 55.2 gram (0.40 mole) salt of wormwood, 150 milliliters of N, N-N,N-DIMETHYLACETAMIDE and 15 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 2 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system, add water, separate out the yellow-green colour solid product, drying, obtain 33.6 grams 1, two (4 nitro-phenoxy) benzene of 4-, fusing point is 239.1 ℃, purity is 99.9%, obtain 1 according to reality, amount of two (4-nitrophenoxy) benzene of 4-and theoretical amount (35.2 gram) calculate 1, and the yield of two (4-nitrophenoxy) benzene of 4-is 95.5%.
Embodiment 3
With 11.0 gram (0.10 mole) Resorcinol, 28.4 gram (0.18 mole) 4-chloronitrobenzene, 10.6 gram (0.10 mole) yellow soda ash, 40 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 15 milliliters of dichlorobenzenes are put into reactor, stir, after reflux divides water to react 10 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system, add water, separate out the yellow-green colour solid product, drying obtains 31.1 grams 1, two (4-nitrophenoxy) benzene of 4-, fusing point is 238.2 ℃, purity is 99.5%, obtains 1 according to reality, amount of two (4-nitrophenoxy) benzene of 4-and theoretical amount (31.7 gram), calculate 1, the yield of two (4-nitrophenoxy) benzene of 4-is 98.1%.
Embodiment 4
With 11.0 gram (0.10 mole) Resorcinol, 39.5 gram (0.28 mole) 4-fluoro oil of mirbane, 11.8 gram (0.21 mole) potassium hydroxide, 20 milliliters of N, dinethylformamide and 400 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 15 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system, add water, separate out the yellow-green colour solid product, drying, obtain 33.1 grams 1, two (4-nitrophenoxy) benzene of 4-, fusing point is 238.1 ℃, purity is 99.5%, obtain 1 according to reality, amount of two (4 nitro-phenoxy) benzene of 4-and theoretical amount (35.2 gram) calculate 1, and the yield of two (4-nitrophenoxy) benzene of 4-is 94%.
Embodiment 5
With 11.0 gram (0.10 mole) Resorcinol, 44.1 gram (0.28 mole) 4-chloronitrobenzene, 80.0 gram (0.80 mole) saleratus, 300 milliliters of dimethyl sulfoxide (DMSO) and 100 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 18 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system, add water, separate out the yellow-green colour solid product, drying obtains 34.9 grams 1, two (4-nitrophenoxy) benzene of 4-, fusing point is 238.8 ℃, purity is 99.7%, obtains 1 according to reality, amount of two (4-nitrophenoxy) benzene of 4-and theoretical amount (35.2 gram), calculate 1, the yield of two (4-nitrophenoxy) benzene of 4-is 99.1%.
Embodiment 6
With 35.2 gram (0.10 moles) 1, two (4-nitrophenoxy) benzene of 4-, 17.6 the gram iron trichloride, 3520 milliliters of ethanol and 70.4 gram gacs are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 20% hydrazine hydrate, totally 750.0 grams (3.00 moles), last 3 hours, after hydrazine hydrate was added dropwise to complete, heat temperature raising to 77 was kept reaction after 17 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter, drying obtains 1 of 25.1 gram whites, two (4-amino-benzene oxygen) the benzene crystal of 4-, fusing point is 172.8 ℃-173.4 ℃, and purity is 99.6%, obtains 1 according to reality, amount of two (4-amino-benzene oxygen) benzene of 4-and theoretical amount (29.2 gram), calculating yield is 86%.
Embodiment 7
With 35.2 gram (0.10 moles) 1, two (4-nitrophenoxy) benzene of 4-, 0.7 gram iron trichloride, 40 milliliters of ethylene glycol and 0.7 gram gac are put into reactor together, stir heat temperature raising to 50 ℃, begin to drip concentration and be 90% hydrazine hydrate, totally 28.0 grams (0.50 mole) last 1 hour, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 75 ℃, keep reaction after 19 hours, cooling reaction solution, heat filtering, remove gac, the cooling mother liquor is separated out white solid product, filters, dry, obtain 13.1 grams 1, two (4-amino-benzene oxygen) the benzene crystal of 4-obtain 1 according to reality, amount of two (4-amino-benzene oxygen) benzene of 4-and theoretical amount (29.2 gram), calculating yield is 45%.
Embodiment 8
With 35.2 gram (0.10 moles) 1, two (4-nitrophenoxy) benzene of 4-, 8.2 gram iron trichloride, 300 milliliters of 2-methyl cellosolves and 50.0 gram gacs are put into reactor together, stir heat temperature raising to 50 ℃, begin to drip concentration and be 80% hydrazine hydrate, totally 125.0 grams (2.00 moles) last 1 hour, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 70 ℃, keep reaction after 20 hours, cooling reaction solution, heat filtering, remove gac, the cooling mother liquor is separated out white solid product, filters, dry, obtain 25.7 grams 1, two (4-amino-benzene oxygen) the benzene crystal of 4-obtain 1 according to reality, amount of two (4-amino-benzene oxygen) benzene of 4-and theoretical amount (29.2 gram), calculating yield is 88%.
Embodiment 9
With 35.2 gram (0.10 moles) 1, two (4-nitrophenoxy) benzene of 4-, 10.0 the gram iron trichloride, 400 milliliter 1, ammediol and 30.0 gram gacs are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 95% hydrazine hydrate, totally 157.9 grams (3.00 moles), last 0.5 hour, after hydrazine hydrate was added dropwise to complete, heat temperature raising to 82 ℃ was kept reaction after 2 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter, drying obtains 24.2 grams 1, two (4-amino-benzene oxygen) the benzene crystal of 4-, obtain 1 according to reality, amount of two (4-amino-benzene oxygen) benzene of 4-and theoretical amount (29.2 gram), calculating yield is 83%.
Embodiment 10
With 35.2 gram (0.10 moles) 1, two (4-nitrophenoxy) benzene of 4-, 5.4 gram iron trichloride, 600 milliliters of ethanol and 26.8 gram gacs are put into reactor together, stir heat temperature raising to 50 ℃, begin to drip concentration and be 85% hydrazine hydrate, totally 58.8 grams (1.00 moles) last 1.5 hours, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 90 ℃, keep reaction after 15 hours, cooling reaction solution, heat filtering, remove gac, the cooling mother liquor is separated out white solid product, filters, dry, obtain 22.8 grams 1, two (4-amino-benzene oxygen) the benzene crystal of 4-obtain 1 according to reality, amount of two (4-amino-benzene oxygen) benzene of 4-and theoretical amount (29.2 gram), calculating yield is 78%.
Claims (13)
1.
1,4The preparation method of-two (4-amino-benzene oxygen) benzene comprises step:
(1) mol ratio is 1.00: 1.80～2.80 Resorcinol and 4-halogenated nitrobenzene, and in salt forming agent, strong aprotic, polar and water-insoluble organic solvent system, reflux is divided water, 80 ℃-190 ℃, reacted concentration of reaction solution, cooling reactant system 2～18 hours, add water, separate out the yellow-green colour solid product, filter drying, obtain 1, two (4-nitrophenoxy) benzene of 4-;
Two (4-nitrophenoxy) benzene of (2) 1,4-are under the acting in conjunction of the reduction system of iron trichloride/20%～95% hydrazine hydrate, alcoholic solvent, gac, 50 ℃-90 ℃, reacted 2～20 hours, reduction obtains 1 of white, two (4-amino-benzene oxygen) the benzene crystalline products of 4-.
2. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, it is characterized in that the 4-halogenated nitrobenzene described in the step (1) is selected from one or more mixtures in 4-fluoro oil of mirbane, 4-chloronitrobenzene, 4-bromo nitryl benzene, the 4-iodo oil of mirbane.
3. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, it is characterized in that the salt forming agent described in the step (1) is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
4. according to claim 1 or 3 described a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that the salt forming agent described in the step (1) is 0.10～8.00: 1.00 with the ratio of the mole number of Resorcinol.
5. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that the envelope-bulk to weight ratio of the organic solvent described in the step (1) and Resorcinol is 5 milliliters～80 milliliters: 1 restrains.
6. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, it is characterized in that, strong polar non-proton organic solvent described in the step (1) is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
7. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, it is characterized in that the water-insoluble organic solvent described in the step (1) is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
8. according to claim 1 or 6 or 7 each is described a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that, the water-insoluble organic solvent described in the step (1) is 1: 0.05～10 with the volume ratio of strong polar non-proton organic solvent.
9. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that, 1 described in the step (2), and two (4-nitrophenoxy) benzene of 4-are 1: 5～30 with the ratio of the mole number of hydrazine hydrate.
10. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that, the iron trichloride and 1 described in the step (2), and the ratio of the weight of 4-pair of (4-nitrophenoxy) benzene is 1: 2～50.
11. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that, the gac and 1 described in the step (2), and the ratio of the weight of 4-pair of (4-nitrophenoxy) benzene is 1: 0.5～50.
12. according to claim 1 a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-, it is characterized in that, alcoholic solvent described in the step (2) is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
13. according to claim 1 or 12 described a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-is characterized in that, the alcoholic solvent and 1 described in the step (2), and the envelope-bulk to weight ratio of two (4-nitrophenoxy) benzene of 4-is 1 milliliter～100 milliliters: 1 restrains.
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| US5886134A (en) * | 1997-10-06 | 1999-03-23 | National Science Council Of Republic Of China | Bismaleimide-triazine resin and production method thereof |
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| US5886134A (en) * | 1997-10-06 | 1999-03-23 | National Science Council Of Republic Of China | Bismaleimide-triazine resin and production method thereof |
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