CN103483552B - A kind of carbon-fibre composite matrix resin and preparation method thereof - Google Patents
A kind of carbon-fibre composite matrix resin and preparation method thereof Download PDFInfo
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- CN103483552B CN103483552B CN201310460066.4A CN201310460066A CN103483552B CN 103483552 B CN103483552 B CN 103483552B CN 201310460066 A CN201310460066 A CN 201310460066A CN 103483552 B CN103483552 B CN 103483552B
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Abstract
The present invention relates to a kind of carbon-fibre composite matrix resin and preparation method thereof, described matrix resin is the N of 100:50-100:10-50:5-20:50-100:300-600 by mass ratio, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide epoxy resin, ES216 epoxy resin, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane, 3 of 2-, 3 '-dimethyl-4,4 '-bis-(4-carboxyl phthalimide group) ditane, solidifying agent and organic solvent form.Manufacturing process of the present invention is simple, raw material sources are convenient, gained matrix resin excellent combination property, high performance carbon-fibre composite can be obtained, can be applicable to the structured material in the fields such as sports equipment, aerospace, automobile, electronics microelectronics, be suitable for suitability for industrialized production, there is very high Commercial Prospect.
Description
Technical field
The invention belongs to macromolecular material and preparation field thereof, particularly a kind of carbon-fibre composite matrix resin and preparation method thereof.
Background technology
Along with aerospace, electronics, microelectronics, motor, electrically, the fast development of the high-tech sector such as automobile, motor-car high ferro, naval vessel submarine, the demand of advanced composite material is grown with each passing day, also more and more high to its performance requriements.Therefore, exploitation high-performance advanced composite material has become one of Main way of current field of new development, is subject to the great attention of countries in the world.
Matrix material forms primarily of two parts, i.e. matrix and strongthener.Different according to body material, matrix material can be divided into three major types: polymer matrix composites, metal-base composites and inorganic non-metallic based composites.In three kinds of matrix materials, be maximum with polymer matrix composites consumption, account for more than 90% of all matrix material consumptions.
Compared with traditional material, polymer matrix composites have three obvious features on design and manufaction: the free designability of material performance index; The consistence of material and structure; The freedom of product type body design.
Polymer matrix composites have outstanding advantage, are mainly manifested in:
(1) high-strength light, i.e. specific tenacity, specific modulus is high.Intensity, modulus, respectively divided by the value of density, are one of indexs weighing material supporting capacity.The specific tenacity of glass reinforced plastic can reach 4 times of steel; The specific tenacity of carbon-fibre reinforced epoxy resin composite material can reach 4.9 times of titanium, and specific modulus can reach more than 5.7 times of aluminium.This is quite large to the product meaning required from heavy and light.As the empennage of A340 airbus type aircraft, landing gear, hatch door, wing and cabin transition section outer rim, cab window frame etc. are polymer matrix composites, account for 15% of whole airplane structural part weight.
(2) fatigue resistance is good;
(3) damping property is good;
(4) fail-safety is good;
(5) chemical resistance is good;
(6) good electrical property;
(7) thermal conductivity is low, linear expansivity is little, and the thermal stresses produced when there being the temperature difference is more much lower than metal;
(8) product of transparent and various color can be obtained;
(9) moulded manufacturability is superior.
Therefore, current developed country and the developing country shown one's talent and area, all attach great importance to polymer matrix composites industrial expansion, also more and more large on national economy impact, advanced military equipment, aeronautics and space technology, energy project, biotechnology, oceanographic engineering and even multiple field such as industry and covil construction, communications and transportation, Leisure Sport are invariably closely bound up with polymer matrix composites.
As everyone knows, epoxy resin has many excellent performances: the adhesiveproperties that (1) is good: bonding strength is high, bonding wide, the bonding strength of it and many metals (as iron, steel, copper, aluminium, metal alloy etc.) or non-metallic material (as glass, pottery, timber, plastics etc.) is very high, what have even exceedes by the intensity of sticky material itself, therefore can be used in many stress members, is one of main component of structural adhesive; (2) good processing characteristics: the diversity of the handiness of Formulaion of epoxy resin, complete processing and product properties is the most outstanding in macromolecular material; (3) satisfactory stability performance: the solidification of epoxy resin mainly relies on the ring opening polyaddition of epoxy group(ing), therefore low-molecular material is not produced in solidification process, its cure shrinkage is one of kind minimum in thermosetting resin, be generally 1%-2%, if select suitable filler that shrinking percentage can be made to be down to about 0.2%; Epoxy main chains after solidification is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has excellent resistance to acids and bases.
Therefore, epoxy resin is widely used in the every field of national economy: no matter no matter is high-technology field or field of general technology, be defence and military or civilian industry, and even all can see its trace in daily life.
About high-temperature resistant epoxy oxygen system is reported to some extent: Chinese patent CN101148656A discloses a kind of preparation method of heat-resistant solvent-free epoxy adhesive, be primarily characterized in that: TGDDM epoxy resin, toughner, Hydrogenated Bisphenol A, solidifying agent, promotor mix, obtained heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has larger limitation, fail to meet the practical application under many hot environments.
Chinese patent CN101397486A discloses a kind of preparation method of two-pack solvent-free epoxy resin tackiness agent, be primarily characterized in that: it comprises component A and B component, wherein component A contains novolac epoxy, alicyclic type epoxy resin and nbr carboxyl terminal; B component is Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener.The addition of alicyclic type epoxy resin and nbr carboxyl terminal is respectively 20-35% and the 12%(mass percent of novolac epoxy).The addition of Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener is the 15-20%(mass percent of novolac epoxy), gained adhesive system good manufacturability.But its resistance toheat is desirable not enough.
Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy matrix resin used for advanced composite material and preparation method thereof, be primarily characterized in that: adopt 1,4-two (2,4-dimaleimide phenoxyl) four maleimide resins of benzene and polyfunctional epoxy resin, nbr carboxyl terminal CTBN be obtained by reacting the novel fire resistant resin of high tenacity, add organic solvent, stirring and dissolving is even, obtains the viscous liquid of homogeneous phase transparent, i.e. component A; Solidifying agent mixes with organic solvent, and stirring and dissolving is even, obtains B component; A, B component are mixed, stirs, obtain heat resist modification multi-functional epoxy substrate resin solution used for advanced composite material.
The people such as Yu Xinhai [development [J] of high-temperature resistant single-component epoxy tackiness agent. bonding, 2008, 29 (12): 16-19] a kind of preparation method of high-temperature resistant single-component epoxy tackiness agent is disclosed, be primarily characterized in that: with maleic anhydride (MA) for end-capping reagent, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) for main raw material synthesis obtain phenolic hydroxy group polyetherimide resin (HPEI), it is resistant, toughened dose with the synthesized HPEI obtained, with N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent etc., preparation obtains the high-temperature resistant single-component epoxy tackiness agent of excellent combination property.
Present method, although by the polyetherimide resin (HPEI) of synthesis containing active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to epoxy resin, and achieved good technique effect.But, also there are some shortcomings:
(1) reactable group is limited, and particularly the content of unsaturated double-bond is on the low side.Because maleic anhydride uses as end-capping reagent, the consumption of maleic anhydride is little.
The monomers such as (2) 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) are expensive, cause the cost of polyetherimide resin (HPEI) and tackiness agent very high, are unfavorable for large-scale promotion application, can only be confined to some special dimension.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of carbon-fibre composite matrix resin and preparation method thereof, this matrix resin thermotolerance, moulded manufacturability and excellent in mechanical performance; This matrix resin not only may be used for carbon fibre reinforced composite, and the manufacture of the advanced composite material that glass fiber reinforcement, organic fibre enhancing, silica fiber enhancing, basalt fibre enhancing and other inorganic fibre strengthen can be widely used in, in fields such as electronics microelectronics, vehicle, rigid copper coated foil plate (PCB), automobile, High power Traction motor, high power generation unit, aerospace, naval vessel, submarine, launch vehicle, sports equipments, have broad application prospects.
A kind of carbon-fibre composite matrix resin of the present invention, described matrix resin is the N of 100:50-100:10-50:5-20:50-100:300-600 by mass ratio, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide (TGDADPE) epoxy resin, ES216 epoxy resin, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane, 3 of 2-, 3 '-dimethyl-4,4 '-bis-(4-carboxyl phthalimide group) ditane, solidifying agent and organic solvent form; Wherein, solidifying agent is mass ratio is the aromatic anhydride of 10:0.5-2 and the mixture of 1,8-diazabicyclo (5.4.0) 11-7-alkene.
Described aromatic anhydride is selected from phthalic anhydride, 4-chloride anhydride, 3-chloride anhydride, 4-nitro phthalic anhydride, 4-bromobenzene acid anhydride, 4-phenylacetylene base phthalic anhydride, pyromellitic acid anhydride, trimellitic acid 1,2-anhydride, 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, two (3, the 4-di carboxyl phenyloxy) hexafluoropropane dianhydride of 2,2-, two (3, the 4-di carboxyl phenyloxy) propane dianhydride of 2,2-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) benzophenone dianhydride, one or more in 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfide dianhydride.
Described organic solvent is selected from acetone, methylethylketone, benzene, toluene, methylene dichloride, dimethylbenzene, ethylene dichloride, trichloromethane, trichloroethane, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, tetrahydrofuran (THF), methyltetrahydrofuran, dimethyl sulfoxide (DMSO).
The preparation method of a kind of carbon-fibre composite matrix resin of the present invention, comprises the steps:
(1) by N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl oxide epoxy resin and 3,3 '-dimethyl-4, reactor put into by 4 '-bis-(4-carboxyl phthalimide group) ditane, in 80 DEG C of-100 DEG C of stirring reactions after 0.5 hour-1 hour, add ES216 epoxy resin and two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2,2-, continue stirring reaction 0.5 hour-1 hour, add organic solvent, stir, obtain component A;
(2) by solidifying agent and organic solvent mixing, stirring and dissolving is homogeneous phase, obtains B component;
(3), when using, component A, B component are mixed.
beneficial effect
(1) preparation technology of the present invention is simple, cost is low, easy to operate, reaction raw materials convenient sources, can complete preparation process in general-purpose equipment, is conducive to realizing suitability for industrialized production;
(2) the present invention has good over-all properties;
(3) the present invention not only may be used for carbon fibre reinforced composite, and the manufacture of the advanced composite material that glass fiber reinforcement, organic fibre enhancing, silica fiber enhancing, basalt fibre enhancing and other inorganic fibre strengthen can be widely used in, in fields such as electronics microelectronics, automobile, rigid copper coated foil plate (PCB), High power Traction motor, high power generation unit, vehicle, aerospace, naval vessel, submarine, launch vehicle, sports equipments, have broad application prospects.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 1000 grams of N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl oxide (TGDADPE) epoxy resin and 50 gram 3,3 '-dimethyl-4, reactor put into by 4 '-bis-(4-carboxyl phthalimide group) ditane, in 80 DEG C of stirring reactions after 0.5 hour, adds 500 grams of ES216 epoxy resin and 500 gram 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2-, continue stirring reaction 0.5 hour, add 500 grams of toluene and 300 grams of acetone, stir, obtain 2850 grams of component A, be denoted as A1.
By 300 grams of phthalic anhydrides, 200 gram 2,2-two (3,4-di carboxyl phenyloxy) hexafluoropropane dianhydride and 25 gram 1,8-diazabicyclo (5.4.0) 11-7-alkene, 2000 grams of METHYLPYRROLIDONEs and 200 grams of tetrahydrofuran (THF) mixing, stirring and dissolving is homogeneous phase, obtain 2725 grams of B component, be denoted as B1.
During use, 2850 grams of A1 components, 2725 grams of B1 components are mixed, namely obtains 5575 grams of carbon-fibre composite matrix resins, be denoted as A1B1.
Embodiment 2
By 1000 grams of N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl oxide (TGDADPE) epoxy resin and 200 gram 3,3 '-dimethyl-4, reactor put into by 4 '-bis-(4-carboxyl phthalimide group) ditane, in 100 DEG C of stirring reactions after 1 hour, adds 1000 grams of ES216 epoxy resin and 100 gram 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2-, continue stirring reaction 1 hour, add 600 grams of dimethylbenzene and 400 grams of acetone, stir, obtain 3300 grams of component A, be denoted as A2.
By 100 gram 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 400 gram 2,2-two (3,4-di carboxyl phenyloxy) propane dianhydride, 200 gram of 2,2-two (3,4-di carboxyl phenyloxy) hexafluoropropane dianhydride and 140 gram 1,8-diazabicyclo (5.4.0) 11-7-alkene, 4000 grams of METHYLPYRROLIDONEs and 1000 grams of methyltetrahydrofuran mixing, stirring and dissolving is homogeneous phase, obtains 5840 grams of B component, is denoted as B2.
During use, 3300 grams of A2 components, 5840 grams of B2 components are mixed, namely obtains 9140 grams of carbon-fibre composite matrix resins, be denoted as A2B2.
Embodiment 3
Get the carbon-fibre composite matrix resin of A1B1, A2B2 of appropriate above-described embodiment 1, embodiment 2, and even application is in the test piece of standard stainless steel respectively, superimposed after hanging 1 hour under room temperature, clamping, put into convection oven to be cured: be heated to 60 DEG C from room temperature, be incubated 1 hour, continue to be warming up to 110 DEG C, be incubated 3 hours, continue to be warming up to 140 DEG C, be incubated 3 hours, continue to be warming up to 180 DEG C, be incubated 2 hours, naturally cool to room temperature.The tensile shear strength recorded is as shown in table 1.
Get the carbon-fibre composite matrix resin of A1B1, A2B2 of appropriate above-described embodiment 1, embodiment 2, pouring diameter into is in the stainless steel disk of 10cm (disk applies releasing agent in advance), thermofixation: be heated to 60 DEG C from room temperature, is incubated 1 hour, continues to be warming up to 110 DEG C, be incubated 3 hours, continue to be warming up to 140 DEG C, be incubated 3 hours, continue to be warming up to 180 DEG C, be incubated 2 hours, naturally cool to room temperature.Obtain the circular specimen that thickness is about 1mm, diameter 10cm, with distilled water immersion after 72 hours, survey its water-intake rate, result is as shown in table 1.
With the carbon-fibre composite matrix resin of A1B1, A2B2 of above-described embodiment 1, embodiment 2, impregnation of carbon fibers cloth strongthener respectively, preliminary drying is carried out to remove organic solvent in the temperature range of 80 DEG C-120 DEG C, obtain prepreg, laminated heat solidifies, and its pressure range is: 0.2MPa-2.5MPa; Its solidification value timing relationship is: be heated to 60 DEG C from room temperature, is incubated 1 hour, continues to be warming up to 110 DEG C, is incubated 3 hours, continue to be warming up to 140 DEG C, be incubated 3 hours, continue to be warming up to 180 DEG C, be incubated 2 hours, naturally cool to room temperature, the release demoulding, obtain high performance advanced composite material.Its salient features is as shown in table 2.
The tensile shear strength of table 1 carbon-fibre composite matrix resin and water-intake rate
The performance of table 2 carbon-fibre composite
Claims (2)
1. a carbon-fibre composite matrix resin, it is characterized in that: described matrix resin is the N of 100:50-100:10-50:5-20:50-100:300-600 by mass ratio, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide epoxy resin, ES216 epoxy resin, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane, 3 of 2-, 3 '-dimethyl-4,4 '-bis-(4-carboxyl phthalimide group) ditane, solidifying agent and organic solvent form, wherein, solidifying agent is mass ratio is the aromatic anhydride of 10:0.5-2 and the mixture of 1,8-diazabicyclo (5.4.0) 11-7-alkene, aromatic anhydride is selected from phthalic anhydride, 4-chloride anhydride, 3-chloride anhydride, 4-nitro phthalic anhydride, 4-bromobenzene acid anhydride, 4-phenylacetylene base phthalic anhydride, pyromellitic acid anhydride, trimellitic acid 1,2-anhydride, 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, two (3, the 4-di carboxyl phenyloxy) hexafluoropropane dianhydride of 2,2-, two (3, the 4-di carboxyl phenyloxy) propane dianhydride of 2,2-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) benzophenone dianhydride, one or more in 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, organic solvent is selected from acetone, methylethylketone, benzene, toluene, methylene dichloride, dimethylbenzene, ethylene dichloride, trichloromethane, trichloroethane, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, tetrahydrofuran (THF), methyltetrahydrofuran, dimethyl sulfoxide (DMSO).
2. a preparation method for carbon-fibre composite matrix resin as claimed in claim 1, comprises the steps:
(1) by N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl oxide epoxy resin and 3,3 '-dimethyl-4, reactor put into by 4 '-bis-(4-carboxyl phthalimide group) ditane, in 80 DEG C of-100 DEG C of stirring reactions after 0.5 hour-1 hour, add ES216 epoxy resin and two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2,2-, continue stirring reaction 0.5 hour-1 hour, add organic solvent, stir, obtain component A;
(2) by solidifying agent and organic solvent mixing, stirring and dissolving is homogeneous phase, obtains B component;
(3), when using, component A, B component are mixed.
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| CN104479299B (en) * | 2014-12-26 | 2016-11-30 | 东华大学 | A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof |
| CN106751498B (en) * | 2016-12-05 | 2018-10-23 | 东华大学 | A kind of preparation method of crystal waste slag/DAHTM type epoxy matrix resin composite materials |
| CN107964217B (en) * | 2017-12-14 | 2020-11-17 | 郑州四维特种材料有限责任公司 | Carbon fiber reinforced composite resin matrix, carbon fiber reinforced composite and preparation method thereof, and table tennis bat bottom plate |
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