CN1031877C - Manufacturing method of tung oil acid anhydride phenyl maleimide - Google Patents
Manufacturing method of tung oil acid anhydride phenyl maleimide Download PDFInfo
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- CN1031877C CN1031877C CN 89105938 CN89105938A CN1031877C CN 1031877 C CN1031877 C CN 1031877C CN 89105938 CN89105938 CN 89105938 CN 89105938 A CN89105938 A CN 89105938A CN 1031877 C CN1031877 C CN 1031877C
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- tung oil
- acid anhydride
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- oil acid
- phenyl maleimide
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Abstract
The present invention relates to a method for preparing an epoxy resin curing agent, namely tung oil acid anhydride phenylmaleimide. With tung oil, maleic anhydride and phenylamine as raw materials, the present invention directly synthesizes the tung oil acid anhydride phenylmaleimide in one step. The present invention has the characteristics of simple production process and low production cost, and the prepared product has storing stabilization, favorable fire resistance and strong bonding strength of solidified materials, etc. B01J23/74, B01J27/14.
Description
The present invention relates to a kind of epoxy curing agent---the preparation method of tung oil acid anhydride phenyl maleimide.
The tung oil acid anhydride of making feedstock production with tung oil, MALEIC ANHYDRIDE is a kind of epoxy curing agent commonly used, because its cured article resistance toheat is poor, the cured article cohesive strength is low, its application more and more is restricted.China Machinery Industry Ministry Guilin Electric Science Institute compiles " insulating material communication " and closed " heat-resisting epoxy resin toughened solidifying agent-maleimide tung oil acid anhydride " literary composition that the 32-35 page of phase reported people such as Hubei Prov. Chemical Research Inst Wang Luo gift in 1980 5-6, disclose with tung oil, MALEIC ANHYDRIDE, bismaleimides is the epoxy curing agent of feedstock production---the maleimide tung oil acid anhydride, its preparation process is: generate bismaleimides by diamines and MALEIC ANHYDRIDE earlier, the reaction of bismaleimides and tung oil and MALEIC ANHYDRIDE generates the maleimide tung oil acid anhydride; Its complex manufacturing, production cost height, the resultant package stability is poor.
Purpose of the present invention is intended to overcome above-mentioned weak point of the prior art, proposes that a kind of production cost is low, the resistance toheat of the cured article of Resins, epoxy is good, cohesive strength is high, the preparation method of a step direct synthetic epoxy curing agent-tung oil acid anhydride phenyl maleimide.
The present invention adopts tung oil, MALEIC ANHYDRIDE, aniline to make feedstock production tung oil acid anhydride phenyl maleimide, and structural formula is:
, in the formula: R
1Expression contains the alkyl of acid anhydride base, R
2Expression contains the alkyl of phenyl maleimide, and reaction mechanism is as follows:
1. the generation of tung oil acid anhydride: Di Ersi-Aunar reaction takes place and generates tung oil acid anhydride (I) in the two keys in conjugated double bond in the tung oil and the MALEIC ANHYDRIDE.
2. the generation of tung oil acid anhydride phenyl maleimide: acid anhydride base in the tung oil acid anhydride (I) and the reaction of the amido in the aniline generate tung oil acid anhydride phenyl maleimide (II).
Content of the present invention is:
1. with 100 parts of weight tung oil, 20-40 parts of MALEIC ANHYDRIDE mixings,, obtain resultant (I) 90-180 ℃ of reactions 0.5-4 hours.
2. with 5-20 parts of (weight) aniline in adding (I) below 100 ℃, add 20-250 parts of organic solvents simultaneously, 100-200 ℃ of reactions 0.5-5 hours, obtain resultant (II), vacuumize then and (be preferably in 5.3 * 10
4-9.3 * 10
5Vacuumize under the Pa) flow out to aneroid, remove organic solvent in (II) etc.
Organic solvent in the content of the present invention can be benzene, toluene or dimethylbenzene.
The usage ratio of tung oil, MALEIC ANHYDRIDE, aniline is (weight) in the content of the present invention: 100: 25-32: 8-13.
Amine described in the content of the present invention is aniline, also can be other primary aromatic amine.
The tung oil acid anhydride phenyl maleimide of the present invention's preparation has following characteristics compared to existing technology:
1, compare with tung oil acid anhydride, the resistance toheat of cured article is improved, and the heatproof index is increased to more than 155 ℃ by 140 ℃, and cohesive strength is improved.
2, compare with the bismaleimides tung oil acid anhydride, it is that a step is directly synthetic that the present invention prepares the tung oil acid anhydride phenyl maleimide, and production cost reduces by 64%, and package stability obtains bigger raising.
Below the present invention is further described in detail:
Embodiment 1: with 100 parts of (weight) tung oil, 20 parts of MALEIC ANHYDRIDE, 90 ℃ of reactions 4 hours, adding 5 parts of aniline below 80 ℃ then, 250 parts of benzene 100 ℃ of reactions 5 hours, are evacuated to 9.3 * 10
5Pa to the aneroid outflow, obtains product (II), and performance sees Table 1.
Get 1 part of (weight) Resins, epoxy, 2.7 parts (II), 1.2 parts of vinylbenzene, 0.02 part of superoxide mixes, and cures 10 hours preparation cured article samples by 130-140 ℃, and performance sees Table 2.
Embodiment 2: with 100 parts of (weight) tung oil, 30 parts of MALEIC ANHYDRIDE, 150 ℃ of reactions 2 hours, adding 12 parts of aniline below 100 ℃ then, 135 parts of toluene 160 ℃ of reactions 2 hours, are evacuated to 9.3 * 10
5Pa to the aneroid outflow, obtains product (II), and performance sees Table 1.
Get 1 part of (weight) Resins, epoxy, 2.4 parts (II), 1.1 parts of vinylbenzene, 0.02 part of superoxide, mix, prepare the cured article sample by embodiment 1 condition, performance sees Table 2.
Embodiment 3: with 100 parts of (weight) tung oil, 40 parts of MALEIC ANHYDRIDE, 180 ℃ of reactions 0.5 hour, adding 20 parts of aniline below 80 ℃ then, 35 parts of toluene 200 ℃ of reactions 0.5 hour, are evacuated to 9.3 * 10
5Pa to the aneroid outflow, obtains product (II), and performance sees Table 1.
Get 1 part of (weight) Resins, epoxy, 2.6 parts (II), 1.2 parts of vinylbenzene, 0.02 part of superoxide, mix, prepare the cured article sample by embodiment 1 condition, performance sees Table 2.
Comparative Examples 1: with 100 parts of (weight) tung oil, 27 parts of MALEIC ANHYDRIDE, 160 ℃ of reactions 1 hour, obtain tung oil acid anhydride, performance sees Table 1.
Get 1.0 parts of (weight) Resins, epoxy, 1.9 parts of tung oil acid anhydrides, 1.0 parts of vinylbenzene, 0.02 part of superoxide, mix, prepare the cured article sample by embodiment 1 condition, performance sees Table 2.
Comparative Examples 2: with 100 parts of tung oil, 24 parts of maleic acid anhydrides, 160 ℃ of reactions 1 hour, add 31 parts of N then, N '-diphenyl methane dimaleimide (by 4.4 '-diaminodiphenylmethane and MALEIC ANHYDRIDE make), 130 ℃ of reactions 2 hours, obtain the maleimide tung oil acid anhydride.
Get 1.0 parts of (weight) maleimide tung oil acid anhydrides, 0.03 part of Resorcinol, 0.3 part of vinylbenzene, mixing is combined, and carries out shelf test, the results are shown in Table 3.
Get 1.0 parts of tung oil acid anhydride phenyl maleimides, 0.3 part of vinylbenzene, 0.03 part of Resorcinol, mix, carry out shelf test, the results are shown in Table 3.
The performance of table 1 tung oil acid anhydride phenyl maleimide
The performance of table 2 cured article
Table 3 storage stability test result
Claims (3)
1, a kind of preparation method of tung oil acid anhydride phenyl maleimide has structural formula:
In the formula: R
1Expression contains the alkyl of acid anhydride base,
R
2Expression contains the alkyl of phenyl maleimide, comprises final reacting product oil vacuum to aneroid is flowed out, and it is characterized in that:
1. 100 parts of (weight) tung oil, 20～40 parts of MALEIC ANHYDRIDE were reacted 0.5-4 hours at 90-180 ℃;
2. with 5-20 parts of aniline adding below 100 ℃, add 20-250 parts of organic solvents simultaneously, 100-200 ℃ of reactions 0.5-5 hours.
2, by the preparation method of the described tung oil acid anhydride phenyl maleimide of claim 1, it is characterized in that the usage ratio (weight) of tung oil, MALEIC ANHYDRIDE, aniline is 100: 25-32: 8-13.
3, by the preparation method of claim 1 or 2 described tung oil acid anhydride phenyl maleimides, it is characterized in that organic solvent is benzene, toluene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105938 CN1031877C (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of tung oil acid anhydride phenyl maleimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105938 CN1031877C (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of tung oil acid anhydride phenyl maleimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040786A CN1040786A (en) | 1990-03-28 |
| CN1031877C true CN1031877C (en) | 1996-05-29 |
Family
ID=4856571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89105938 Expired - Fee Related CN1031877C (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of tung oil acid anhydride phenyl maleimide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031877C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795988A (en) * | 2012-09-13 | 2012-11-28 | 重庆油桐产业研究中心 | Method for preparing nonane diacid and biomass diesel from tung oil |
| CN109575201B (en) * | 2018-12-06 | 2021-07-20 | 成都杰晟蜀邦新材料科技有限公司 | Tung oil phenyl maleimide modified aqueous acrylic acid dispersion and synthesis process thereof |
| CN111303435A (en) * | 2020-04-09 | 2020-06-19 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based nonionic self-emulsifying waterborne epoxy curing agent and preparation method thereof |
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1989
- 1989-07-27 CN CN 89105938 patent/CN1031877C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1040786A (en) | 1990-03-28 |
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