CN105111737A - High-heat-resistant flame-retardant resin matrix and preparation method thereof - Google Patents
High-heat-resistant flame-retardant resin matrix and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-heat-resistant flame-retardant resin matrix and a preparation method thereof and solves the technical problems that existing adamantine biphenyl phthalonitrile resin has a high processing temperature and a narrow processing window. The high-heat-resistant flame-retardant resin matrix is made from adamantine biphenyl phthalonitrile and cyanate ester, using 4, 4-diamino diphenyl sulfone as a solidifying agent. The invention also discloses the preparation method of the matrix. The matrix is widely applicable to the fields such as aviation and defense military industry.
Description
Technical field
The invention belongs to fibre composite preparation field, particularly a kind of high-temp resistant fire-retarding resin matrix composite material and preparation method thereof.
Background technology
Diamantane a kind ofly possesses the ester ring type carbohydrate that the carbonatoms constructing same structure with diamond is 10, and the structure unit due to it is all the hexanaphthene of chair-type shape, therefore it to have structure neat, the feature that the transparency and stability etc. are excellent.It is made to show wide application prospect at functional materials neighborhood, as adamantane framework introduced main chain or the side chain of the polymkeric substance such as polyester, urethane, polymeric amide, polyimide, polyethers, polysulfones, polyethylene, the light transmission of polymkeric substance, wet-hot aging performance, dielectric properties, weather resistance, light fastness, thermostability performance, antioxidant property, chemical-resistant resistance and organic solvent corrosive nature etc. obviously can be improved.
Cyanate ester resin has excellent mechanical property, process industrial art performance, heat-resisting/wet-hot aging performance, extremely low dielectric loss and low and stable specific inductivity, and the change of dielectric properties to temperature and wave frequency all demonstrates broadband.And be a class high-performance thermosetting resin containing the resin of bi-phthalonitrile structure, the thermostability of its excellence, thermo-oxidative stability, chemical stability, flame retardant resistance, moistureproofness and good processibility.
The essential reason of diamantane bi-phthalonitrile resin thermal characteristics excellence is that a large amount of cyano group can be polymerized the fragrant heterocycle structure forming excellent heat resistance under certain temperature condition or catalytic condition owing to containing cyano group in monomer whose structure.Because monomer whose melt viscosity is very low, general between 0.1 ~ 0.2Pas, its solidification process is polyaddition reaction, therefore generate without small molecule by-product in its polymerization process, the goods of final molding are fine and close, zero defect, and its polymerization velocity controls by regulating its curing additive consumption and processing temperature.But because phthalonitrile monomer melt temperature is up to 190 DEG C; Initial cure temperature is at 235 DEG C, and processing temperature window only has about 40 DEG C; Slow and the temperature required height of curing reaction of curing reaction speed, after fixing required time is long, makes its course of processing of dimethoxy nitrile resin more difficult.Although can curing speed be regulated by the add-on of amine substance, but add-on very little, be not enough to the curing reaction speed improving diamantane bi-phthalonitrile, add-on is too much because amine substance decomposition temperature is lower than the initial cure temperature of diamantane bi-phthalonitrile, amine will certainly be caused first to decompose and then cause material porosity to increase, subsurface defect increases, and finally affect the physical strength of goods, the promoter action that therefore this regulative mode plays is limited.
Summary of the invention
The present invention, with regard in order to solve the technical problem that diamantane bi-phthalonitrile resin processing temperature is high, process window is narrow, provides a kind of high-temp resistant fire-retarding resin matrix and preparation method thereof.
For this reason, the invention provides a kind of high-temp resistant fire-retarding resin matrix, it is obtained by diamantane bi-phthalonitrile and cyanate, and solidifying agent is 4,4-diaminodiphenylsulfone(DDS).
Preferably, cyanate is bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanate, bisphenol S type cyanate, bis-phenol M type cyanate.
The present invention provides a kind of preparation method of high-temp resistant fire-retarding resin matrix simultaneously, and it comprises the steps: (1) by diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin according to mass ratio (30 ~ 70): (70 ~ 30) are heating and melting respectively; By the time diamantane bi-phthalonitrile resin melts and after color becomes blackish green generations B b stage resin b by brownish black, joins in the cyanate ester resin melting magnetic agitation afterwards; (2) resin mixed is taken out a part, 4, the 4-diaminodiphenylsulfone(DDS)s adding weight resin 1%wt ~ 2%wt continue magnetic agitation and build batten, according to temperature programming solidification, test mechanical property after cooling; (3) adding solvent N-methyl pyrilidone while hot by remaining the resin mixed in step (1), being made into the pre-polymer solution that solid content is 40wt%, fully stir and prepolymer is dissolved completely; Under room temperature by above-mentioned solution brushing on the glasscloth of anticipating, hang under room temperature, make solvent evaporates, the prepreg prepared is stand-by; (4) glasscloth scribbling prepolymer dried is put into baking oven pre-treatment, gained prepreg, through cutting, laying, is placed in compression moulding under certain technique under press.
Preferably, in step (1), the melt temperature of diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin is respectively 200 DEG C and 110 DEG C.
Preferably, in step (2), the program of elevated cure is 150 DEG C/2h+180 DEG C/2h+210 DEG C/3h+240 DEG C/2h.
Preferably, in step (4), pressing process is as follows: add 3MPa pressure after placing several minutes at 150 DEG C, then discharge, three times to get rid of the air in prepreg interlayer repeatedly, then applies pressure 10MPa, according to the solidification of 150 DEG C/2h+180 DEG C/2h+220 DEG C/2h technique, take out after naturally cooling, cutting machine is cut into the batten of desired size, and carry out aftertreatment according to the program of 220 DEG C/2h+250 DEG C/4h+280 DEG C/4h in high temperature oven.
Preferably, in step (4), pretreatment temperature is 150 DEG C.
Effect of the present invention is: 1) by adding cyanate ester resin in diamantane bi-phthalonitrile resin, greatly reduce the processing temperature of diamantane bi-phthalonitrile resin; 2) cyanate radical and cyano group easily react, and by regulating the proportioning between cyanate ester resin, solidifying agent, provide the novel composite resin system that a kind of temperature of reaction reduces, high thermal resistance is good, comprehensive mechanical property is excellent, working life is long; 3) after solidification, resin and matrix material have excellent thermomechanical property, flame retardant properties, wet and heat ageing resistant, dielectric properties etc.
Accompanying drawing explanation
Fig. 1 is that the flexural strength of the embodiment of the present invention and comparative example contrasts schematic diagram;
Fig. 2 is that the modulus in flexure of the embodiment of the present invention and comparative example contrasts schematic diagram.
Embodiment
By following examples, the present invention is described in detail, but the invention is not restricted to following specific embodiment.
Embodiment 1
Step I: by purified diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin after certain mass synthesis according to mass ratio 70:30 respectively 200 DEG C and 110 DEG C of heating and melting.By the time diamantane bi-phthalonitrile resin melts and after color becomes blackish green generations B b stage resin b by brownish black, joins in the cyanate ester resin melting magnetic agitation afterwards.
Step II: the resin mixed is taken out a part, add 4 of 1%wt ~ 2%wt, 4-diaminodiphenylsulfone(DDS) continues magnetic agitation and builds batten in 5 minutes, according to program 150 DEG C/2h+180 DEG C/2h+210 DEG C/3h+240 DEG C/2h elevated cure, tests mechanical property after cooling.
Step II I: adding appropriate solvent N-methyl pyrilidone while hot by remaining the resin mixed in step I, being made into the pre-polymer solution that solid content is about 40wt%, fully stirs and prepolymer is dissolved completely.Under room temperature by above-mentioned solution brushing on the 20 layers of glasscloth (20cm × 20cm) anticipated, hang 24h under room temperature and make solvent evaporates, the prepreg prepared is stand-by.
Step IV: the glasscloth scribbling prepolymer dried is put into baking oven pre-treatment several minutes at 150 DEG C, gained prepreg, through cutting, laying, is placed in compression moulding under certain technique under press.Pressing process is as follows: add 3MPa pressure after placing several minutes at 150 DEG C, then discharge, three times to get rid of the air in prepreg interlayer repeatedly, then pressure 10MPa is applied, according to the solidification of 150 DEG C/2h+180 DEG C/2h+220 DEG C/2h technique, take out after naturally cooling, cutting machine is cut into the batten of desired size, and carry out aftertreatment according to the program of 220 DEG C/2h+250 DEG C/4h+280 DEG C/4h in high temperature oven.
Embodiment 2
Step I: by purified diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin after certain mass synthesis according to mass ratio 50:50 respectively 200 DEG C and 110 DEG C of heating and melting.By the time diamantane bi-phthalonitrile resin melts and after color becomes blackish green generations B b stage resin b by brownish black, joins in the cyanate ester resin melting magnetic agitation afterwards.
Step II: the resin mixed is taken out a part, add 4 of 1%wt ~ 2%wt, 4-diaminodiphenylsulfone(DDS) continues magnetic agitation and builds batten in 5 minutes, according to program 150 DEG C/2h+180 DEG C/2h+210 DEG C/3h+240 DEG C/2h elevated cure, tests mechanical property after cooling.
Step II I: adding appropriate solvent N-methyl pyrilidone while hot by remaining the resin mixed in step I, being made into the pre-polymer solution that solid content is about 40wt%, fully stirs and prepolymer is dissolved completely.Under room temperature by above-mentioned solution brushing on the 20 layers of glasscloth (20cm × 20cm) anticipated, hang 24h under room temperature and make solvent evaporates, the prepreg prepared is stand-by.
Step IV: the glasscloth scribbling prepolymer dried is put into baking oven pre-treatment several minutes at 150 DEG C, gained prepreg, through cutting, laying, is placed in compression moulding under certain technique under press.Pressing process is as follows: add 3MPa pressure after placing several minutes at 150 DEG C, then discharge, three times to get rid of the air in prepreg interlayer repeatedly, then pressure 10MPa is applied, according to the solidification of 150 DEG C/2h+180 DEG C/2h+220 DEG C/2h technique, take out after naturally cooling, cutting machine is cut into the batten of desired size, and carry out aftertreatment according to the program of 220 DEG C/2h+250 DEG C/4h+280 DEG C/4h in high temperature oven.
Embodiment 3
Step I: by purified diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin after certain mass synthesis according to mass ratio 30:70 respectively 200 DEG C and 110 DEG C of heating and melting.By the time diamantane bi-phthalonitrile resin melts and after color becomes blackish green generations B b stage resin b by brownish black, joins in the cyanate ester resin melting magnetic agitation afterwards.
Step II: the resin that mixes is taken out a part, 4, the 4-diaminodiphenylsulfone(DDS)s adding 1%wt ~ 2%wt continue magnetic agitation and build batten in 5 minutes, according to program 150 DEG C/2h+180 DEG C/2h+210 DEG C/5h elevated cure, test mechanical property after cooling.
Step II I: adding appropriate solvent N-methyl pyrilidone while hot by remaining the resin mixed in step I, being made into the pre-polymer solution that solid content is about 40wt%, fully stirs and prepolymer is dissolved completely.Under room temperature by above-mentioned solution brushing on the 20 layers of glasscloth (20cm × 20cm) anticipated, hang 24h under room temperature and make solvent evaporates, the prepreg prepared is stand-by.
Step IV: the glasscloth scribbling prepolymer dried is put into baking oven pre-treatment several minutes at 120 DEG C, gained prepreg, through cutting, laying, is placed in compression moulding under certain technique under press.Pressing process is as follows: add 3MPa pressure after placing several minutes at 120 DEG C, then discharge, three times to get rid of the air in prepreg interlayer repeatedly, then pressure 10MPa is applied, according to 120 DEG C/2h+150 DEG C/2h+180 DEG C/2h+220 DEG C/2h technique solidification, take out after naturally cooling, cutting machine is cut into the batten of desired size, and carry out aftertreatment according to the program of 220 DEG C/2h+250 DEG C/6h in high temperature oven.
Comparative example
By diamantane bi-phthalonitrile resin purified after certain mass synthesis 200 DEG C of heating and melting.By the time diamantane bi-phthalonitrile resin melt and color by brownish black become take out after blackish green generations B b stage resin b a part of, add 4 of 1%wt ~ 2%wt, 4-diaminodiphenylsulfone(DDS) continues magnetic agitation and builds batten in 5 minutes, according to program 150 DEG C/2h+180 DEG C/2h+210 DEG C/5h elevated cure, after cooling, test mechanical property.Survey pour mass bending property and see Fig. 1 and Fig. 2.
Claims (7)
1. a high-temp resistant fire-retarding resin matrix, it is characterized in that being obtained by diamantane bi-phthalonitrile and cyanate, solidifying agent is 4,4-diaminodiphenylsulfone(DDS).
2. high-temp resistant fire-retarding resin matrix according to claim 1, is characterized in that described cyanate is bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanate, bisphenol S type cyanate, bis-phenol M type cyanate.
3. the preparation method of high-temp resistant fire-retarding resin matrix as claimed in claim 1, is characterized in that comprising the steps:
(1) by diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin according to mass ratio (30 ~ 70): (70 ~ 30) are heating and melting respectively; By the time diamantane bi-phthalonitrile resin melts and after color becomes blackish green generations B b stage resin b by brownish black, joins in the cyanate ester resin melting magnetic agitation afterwards;
(2) resin mixed is taken out a part, 4, the 4-diaminodiphenylsulfone(DDS)s adding weight resin 1%wt ~ 2%wt continue magnetic agitation and build batten, according to temperature programming solidification, test mechanical property after cooling;
(3) adding solvent N-methyl pyrilidone while hot by remaining the resin mixed in step (1), being made into the pre-polymer solution that solid content is 40wt%, fully stir and prepolymer is dissolved completely; Under room temperature by above-mentioned solution brushing on the glasscloth of anticipating, hang under room temperature, make solvent evaporates, the prepreg prepared is stand-by;
(4) glasscloth scribbling prepolymer dried is put into baking oven pre-treatment, gained prepreg, through cutting, laying, is placed in compression moulding under certain technique under press.
4. the preparation method of high-temp resistant fire-retarding resin matrix according to claim 3, is characterized in that in step (1), and the melt temperature of diamantane bi-phthalonitrile resin and bisphenol A cyanate ester resin is respectively 200 DEG C and 110 DEG C.
5. the preparation method of high-temp resistant fire-retarding resin matrix according to claim 3, is characterized in that in step (2), the program of elevated cure is 150 DEG C/and 2h+180 DEG C/2h+210 DEG C/3h+240 DEG C/2h.
6. the preparation method of high-temp resistant fire-retarding resin matrix according to claim 3, it is characterized in that in step (4), pressing process is as follows: add 3MPa pressure after placing several minutes at 150 DEG C, then discharge, three times to get rid of the air in prepreg interlayer repeatedly, then pressure 10MPa is applied, according to the solidification of 150 DEG C/2h+180 DEG C/2h+220 DEG C/2h technique, take out after naturally cooling, cutting machine is cut into the batten of desired size, and carries out aftertreatment according to the program of 220 DEG C/2h+250 DEG C/4h+280 DEG C/4h in high temperature oven.
7. the preparation method of high-temp resistant fire-retarding resin matrix according to claim 3, is characterized in that, in step (4), pretreatment temperature is 150 DEG C.
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| CN115466389A (en) * | 2022-09-13 | 2022-12-13 | 中国人民解放军国防科技大学 | Low-temperature fast-curing cyanate ester resin containing hydroxyl structure and preparation method thereof |
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Cited By (4)
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| CN115466389A (en) * | 2022-09-13 | 2022-12-13 | 中国人民解放军国防科技大学 | Low-temperature fast-curing cyanate ester resin containing hydroxyl structure and preparation method thereof |
| CN115466389B (en) * | 2022-09-13 | 2023-07-25 | 中国人民解放军国防科技大学 | Low-temperature rapid-curing hydroxyl-structure-containing cyanate resin and preparation method thereof |
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