CN102504211A - Thermoset imide resin modified silazane and preparation method of composite material thereof - Google Patents
Thermoset imide resin modified silazane and preparation method of composite material thereof Download PDFInfo
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- CN102504211A CN102504211A CN2011103424331A CN201110342433A CN102504211A CN 102504211 A CN102504211 A CN 102504211A CN 2011103424331 A CN2011103424331 A CN 2011103424331A CN 201110342433 A CN201110342433 A CN 201110342433A CN 102504211 A CN102504211 A CN 102504211A
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- silazane
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- 0 *[Si](Nc1ccccc1)(Nc1ccccc1)Nc1ccccc1 Chemical compound *[Si](Nc1ccccc1)(Nc1ccccc1)Nc1ccccc1 0.000 description 1
- VOFAMSOGMPDBAX-UHFFFAOYSA-N c(cc1)ccc1N[Si](Nc1ccccc1)(Nc1ccccc1)Nc1ccccc1 Chemical compound c(cc1)ccc1N[Si](Nc1ccccc1)(Nc1ccccc1)Nc1ccccc1 VOFAMSOGMPDBAX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to thermoset imide resin modified silazane and a preparation method of a composite material thereof. On the premise of not influencing the heat resistance of silazane, the mechanical strength of a glass-fiber reinforced composite of the thermoset imide resin modified silazane is improved. The thermoset imide resin modified silazane and the preparation method of the composite material thereof are technically characterized in that the glass-fiber reinforced composite is prepared by dissolving 50 to 80 parts by weight of silazane resin and 20 to 50 parts by weight of thermoset imide resin into a solvent to be uniformly mixed, impregnating glass fibers in the solvent, removing the solvent and curing according to a certain curing process. The thermoset imide resin modified silazane and the preparation method of the composite material thereof have the advantages that the thermoset imide resin with good forming process is selected to modify the silazane and is beneficial for preparing the high-performance composite material; the low boiling point solvent is selected; the process is simple; the thermoset imide resin modified silazane system prepared by the method provided by the invention has excellent heat resistance, dielectrical property, water resistant performance and mechanical property; the composite material prepared by using the thermoset imide resin modified silazane as a composite resin matrix has excellent mechanical property and has a glass transition temperature of 330 to 365 DEG C at normal temperature and bending strength of 300 to 390 MPa at normal temperature.
Description
Technical field
The invention belongs to a kind of preparation method of novel resin-based composite material, particularly a kind of thermosetting imide resin is to the modification of silazane.
Background technology
It is the research of representative with chemist Fink that the research of silazane starts from the sixties in 20th century, has proposed to encircle two, the compound method of ring three, cyclotetrasilazane.Along with going deep into of silazane research, People more and more is recognized its exploitation value and application prospects, and silazane is huge in aspect prospects such as preparation ceramic forerunner, heat-stable material elder generation body, fiber elder generation bodies, has also obtained some important use.Current scientific worker has developed a variety of silazane on the basis of ring silazane; A kind of just silazane monomer resin of holding ethynyl that contains of silazane involved in the present invention; Synthesis technique is simple, has good thermostability, water tolerance and excellent dielectric properties after the curing.But because itself and the bad adhesion of spun glass, the mechanical property of the glass fibre reinforced composion that makes is lower, and the flexural strength deficiency 200MPa under the normal temperature has limited its application aspect structural composite material.
Contain imide group in the thermoset polyimide resin molecule, have good thermostability, dielectric properties and excellent processing characteristics after the curing.Thermosetting imide resin involved in the present invention is an ethynyl end-blocking imide; Have the advantages that no volatile matter is emitted in the low and cross-linking process of crosslinking temperature; Crosslinked back forms the tridimensional network of low porosity; Making it have excellent thermotolerance, is a kind of high-performance fire resistant resin of excellence.The thermosetting imide resin that the present invention uses is two (ethynyl phenyl phthalic imidine between N-) ethers, and its structure is suc as formula shown in (1):
It has good thermotolerance, and the polarity of molecule own is very strong, and good with the cohesiveness of spun glass, technology is simple, is a kind of good high performance composite resin matrix.
Four (ethynyl aniline)-silane, three (ethynyl aniline)-silane that the present invention adopted and two (the ethynyl aniline)-silane (Song Ning that announced; Ni Lizhong; Xu Fang. a kind of novel silazane-diacetylene aniline silane and preparation method thereof (P): CN 101709062A, it is simpler 2010-05-19.) to compare synthesis technique, can place air for a long time; Water tolerance is strong, can prepare high performance composite.
Through consulting a large amount of domestic and foreign literature data, the Application and Development of silazane has more and more obtained people's attention, but does not also see the report of relevant ethynyl end-blocking imide resin modification silazane so far.
Summary of the invention
The technical problem that solves
The present invention utilizes the thermosetting imide resin that silazane is carried out modification; The both contains the end ethynyl; Co-curing at a lower temperature, the cohesive force of modified system and spun glass is higher, with expectation on the basis of the reduction silazane excellent heat resistance of trying one's best few, excellent dielectric properties; Improve the mechanical strength of its glass fiber impregnated matrix material; Improve manufacturability, satisfy the moulding process of various advanced composite materials, thereby further widen the application of silazane at high-technology fields such as space flight, aviations.
Technical scheme
1. the silazane that the present invention adopted is four (ethynyl aniline)-silane and/or three (ethynyl aniline)-silane, and its structural formula structure is shown in (2)-(3):
Wherein, the structure of ethynyl aniline is ortho position, contraposition or a position; R, R
1, R
2Be H, CH
3, C
6H
5, carbonatoms is alkyl or the alkylene of 1-12.
2. technical characterictic of the present invention is that the prescription of modified resin system is formed and counts by quality: silazane 50-80 part, two (ethynyl phenyl phthalic imidine between N-) the ether 20-50 parts of thermosetting imide resin.
3. the prepared matrix material matrix material of the present invention, it is characterized in that: the composition of said matrix material is following: thermosetting imide resin modified silazane resin matrix is 30-40 part, and the spun glass drills is 60-70 part.
4. the preparation of thermosetting imide resin modified silazane and matrix material thereof is characterized in that comprising the steps:
(1) thermosetting imide resin and the silazane with the different mass proportioning is blended in the organic solvent
(2) treat fully dissolving after, with the spun glass drills of different relative contents even dipping in resin solution, removal of solvent under reduced pressure obtains material prepreg at normal temperatures
(3) above-mentioned dipping and the spun glass drills that eliminates solvent are folded; According to certain technology compression moulding; Pressing process is: the curing molding starting temperature is 160-190 ℃, final temperature 260-290 ℃, and pressure 2-4MPa; Time 13-15 hour, promptly obtain a kind of matrix material of thermosetting imide resin modified silazane
5. described organic solvent is one or more the mixed solvent in acetone, THF, ETHYLE ACETATE, ether, the ethanol
Beneficial effect
The thermosetting imide resin modified silazane that the present invention adopts is a kind of novel modified system; The mixed solvent of one or more in employing acetone, THF, ETHYLE ACETATE, ether, the ethanol; Can be at room temperature well solution heat solidity imide resin and silazane; Technical process is simple, helps the preparation of high performance composite.The second-order transition temperature 330-365 of its glass fibre reinforced composion ℃, the normal temperature flexural strength reaches 300-390Mpa, and performance is superior to two (ethynyl aniline)-silane performance of composites.
Embodiment
Embodiment 1. takes by weighing the good spun glass drills 45.6g of thermal treatment, phenyl-three (3-acetylene aniline) base silane 21.3g, two (ethynyl phenyl phthalic imidine between N-) ether 9.1g, in acetone (acetone quality 71.4g), mixes, after treating to dissolve fully; The spun glass drills is evenly flooded in solution; Vacuumized under the normal temperature 2 hours, and removed solvent, obtain material prepreg; It according to the certain process curing molding, is obtained matrix material.Moulding process is: pressure 2.4MPa, 190 ℃/3h-220 ℃/4h-250 ℃/4h-280 ℃/4h.
The gained performance of composites is following:
Normal temperature flexural strength: 328.1MPa, the flexural strength under 240 ℃: 297.2MPa, retention rate are 90.6%; In zero(ppm) water, soaking 96 hours water-intake rates under the normal temperature is 1.08%; The specific inductivity of the matrix material under the normal temperature is 4.02, and the dielectric loss tangent value is 5.82 * 10
-3The quality retention rate of 10 minutes matrix materials of 500 ℃ of held is 93.8%.
Embodiment 2. takes by weighing the good spun glass drills 44.2g, four of thermal treatment (3-acetylene aniline) base silane 14.3g, two (ethynyl phenyl phthalic imidine between N-) ether 9.5g; In THF (THF quality 36.2g), mix; After treating to dissolve fully, the spun glass drills is evenly flooded in solution, vacuumized under the normal temperature 2 hours; Remove solvent, obtain material prepreg.It according to the certain process curing molding, is obtained matrix material.Moulding process is: pressure 3.8MPa, 170 ℃/3h-200 ℃/3h-230 ℃/4h-260 ℃/4h.
The gained performance of composites is following:
Normal temperature flexural strength: 385.7MPa, the flexural strength under 240 ℃: 373.1MPa, retention rate are 96.7%; In zero(ppm) water, soaking 96 hours water-intake rates under the normal temperature is 1.06%; The specific inductivity of the matrix material under the normal temperature is 3.95, and the dielectric loss tangent value is 5.73 * 10
-3The quality retention rate of 10 minutes matrix materials of 500 ℃ of held is 97.5%.
Embodiment 3: take by weighing the good spun glass drills 47.1g of thermal treatment, methyl-three (3-acetylene aniline) base silane 7.6g, four (3-acetylene aniline) base silane 9.4g, two (ethynyl phenyl phthalic imidine between N-) ether 8.4g; In acetone (acetone quality 59.3g), mix; After treating to dissolve fully, the spun glass drills is evenly flooded in solution, vacuumized under the normal temperature 2 hours; Remove solvent; Obtain material prepreg, it according to the certain process curing molding, is obtained matrix material.Moulding process is: pressure 3.1MPa, 180 ℃/3h-210 ℃/3h-240 ℃/4h-270 ℃/3h
The gained performance of composites is following:
Normal temperature flexural strength: 310.4MPa, the flexural strength under 240 ℃: 278.2MPa, retention rate are 89.6%; In zero(ppm) water, soaking 96 hours water-intake rates under the normal temperature is 1.14%; The specific inductivity of the matrix material under the normal temperature is 3.86, and the dielectric loss tangent value is 5.70 * 10
-3The quality retention rate of 10 minutes matrix materials of 500 ℃ of held is 92.3%.
Embodiment 4. takes by weighing the good spun glass drills 41.9g, three of thermal treatment (3-acetylene aniline) base silane) 11.3g, two (ethynyl phenyl phthalic imidine between N-) ether 11.3g g, mix in ethanol (ethanol quality 52.7g), after treating to dissolve fully; The spun glass drills is evenly flooded in solution; Vacuumized under the normal temperature 2 hours, and removed solvent, obtain material prepreg; It according to the certain process curing molding, is obtained matrix material.Moulding process is: pressure 2.6MPa, 160 ℃/3h-190 ℃/3h-230 ℃/3h-250 ℃/3h-280 ℃/3h.
The gained performance of composites is following:
Normal temperature flexural strength: 320.6MPa, the flexural strength under 240 ℃: 281.2MPa, retention rate are 87.7%; In zero(ppm) water, soaking 96 hours water-intake rates under the normal temperature is 1.21%; The specific inductivity of the matrix material under the normal temperature is 3.82, and the dielectric loss tangent value is 4.74 * 10
-3The quality retention rate of 10 minutes matrix materials of 500 ℃ of held is 90.3%.
Embodiment 5. takes by weighing the good spun glass drills 43.5g, four of thermal treatment (4-acetylene aniline) base silane 17.1g, two (ethynyl phenyl phthalic imidine between N-) ether 11.4g g, in acetone (acetone quality 66.5g), mixes, after treating to dissolve fully; The spun glass drills is evenly flooded in solution; Vacuumized under the normal temperature 2 hours, and removed solvent, obtain material prepreg; It according to the certain process curing molding, is obtained matrix material.Moulding process is: pressure 3.0MPa, 180 ℃/3h-210 ℃/4h-240 ℃/4h-270 ℃/3h.
The gained performance of composites is following:
Normal temperature flexural strength: 353.9MPa, the flexural strength under 240 ℃: 327.7MPa, retention rate are 92.6%; In zero(ppm) water, soaking 96 hours water-intake rates under the normal temperature is 1.10%; The specific inductivity of the matrix material under the normal temperature is 3.94, and the dielectric loss tangent value is 5.27 * 10
-3The quality retention rate of 10 minutes matrix materials of 500 ℃ of held is 93.9%.
Claims (7)
1. the preparation of thermosetting imide resin modified silazane and matrix material thereof; It is characterized in that employed imide resin is two (ethynyl phenyl phthalic imidine between N-) ethers; The composition of raw materials of modified resin system is designated as by quality: silazane 50-80 part, imide resin 20-50 part.
2. thermosetting imide resin modified silazane system as claimed in claim 1 is characterized in that: described silazane is four (ethynyl aniline)-silane and/or three (ethynyl aniline)-silane.
3. thermosetting imide resin modified silazane system according to claim 2 is characterized in that: described four (ethynyl aniline)-silane have structure shown in the formula (1):
Wherein, the structure of ethynyl aniline is ortho position, contraposition or a position; R, R
1, R
2Be H, CH
3, C
6H
5, carbonatoms is alkyl or the alkylene of 1-12.
4. thermosetting imide resin modified silazane system according to claim 2 is characterized in that: described three (ethynyl aniline)-silane have structure shown in the formula (2):
Wherein, the structure of ethynyl aniline is ortho position, contraposition or a position; R, R
1, R
2Be H, CH
3, C
6H
5, carbonatoms is alkyl or the alkylene of 1-12.
5. a thermosetting imide resin modified silazane prepares matrix material, and it is characterized in that: the composition of said matrix material is following: thermosetting imide resin modified silazane resin matrix is 30-40 part, and the spun glass drills is 60-70 part.
6. the preparation of matrix material according to claim 5 is characterized in that comprising the steps:
(1) thermosetting imide resin and the silazane with different proportionings mixes in organic solvent
(2) treat fully dissolving after, with the spun glass drills of different relative contents even dipping in resin solution, removal of solvent under reduced pressure obtains material prepreg at normal temperatures
(3) above-mentioned dipping and the spun glass drills that eliminates solvent are folded; According to certain technology compression moulding; Pressing process is: the curing molding starting temperature is 160-190 ℃, final temperature 260-290 ℃, and pressure 2-4MPa; Time 13-15 hour, promptly obtain a kind of polymer matrix composites of thermosetting imide resin modified silazane.
7. be one or more the mixed solvent in acetone, THF, ETHYLE ACETATE, ether, the ethanol according to the described organic solvent of the preparation method of claim 6.
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| CN201110342433.1A CN102504211B (en) | 2011-11-03 | 2011-11-03 | preparation method of thermoset imide resin modified silazane and its composite material |
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| CN201110342433.1A CN102504211B (en) | 2011-11-03 | 2011-11-03 | preparation method of thermoset imide resin modified silazane and its composite material |
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| CN102504211A true CN102504211A (en) | 2012-06-20 |
| CN102504211B CN102504211B (en) | 2014-04-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107916085A (en) * | 2017-10-09 | 2018-04-17 | 珠海固瑞泰复合材料有限公司 | A kind of heat-proof epoxy thermal conductive insulation glue and preparation method thereof |
| CN114714642A (en) * | 2013-03-15 | 2022-07-08 | 汉高知识产权控股有限责任公司 | Prepreg curing process for preparing composites with excellent surface finish and high fiber consolidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190679A (en) * | 2011-03-21 | 2011-09-21 | 华东理工大学 | Novel silazane-tetra(acetylenylaniline)-silane and preparation method thereof |
| CN102212079A (en) * | 2011-03-21 | 2011-10-12 | 华东理工大学 | Novel silazane-tri(ethynylphenylamine)-silicane and method for preparing same |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190679A (en) * | 2011-03-21 | 2011-09-21 | 华东理工大学 | Novel silazane-tetra(acetylenylaniline)-silane and preparation method thereof |
| CN102212079A (en) * | 2011-03-21 | 2011-10-12 | 华东理工大学 | Novel silazane-tri(ethynylphenylamine)-silicane and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| ZHOU QUAN AND NI LIZHONG: "Bismaleimide-Modified Methyl-Di(phenylethynyl)silane Blends and Composites: Cure Characteristics, Thermal Stability, and Mechanical Property", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 高万星等: "双（N-间乙炔基苯基邻苯二甲酰亚胺）醚改性苯乙炔基硅氧硼烷", 《功能高分子学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114714642A (en) * | 2013-03-15 | 2022-07-08 | 汉高知识产权控股有限责任公司 | Prepreg curing process for preparing composites with excellent surface finish and high fiber consolidation |
| CN107916085A (en) * | 2017-10-09 | 2018-04-17 | 珠海固瑞泰复合材料有限公司 | A kind of heat-proof epoxy thermal conductive insulation glue and preparation method thereof |
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| Publication number | Publication date |
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| CN102504211B (en) | 2014-04-30 |
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