CN100523087C - Thermostable benzoxazine resin compound and its preparation method and uses - Google Patents
Thermostable benzoxazine resin compound and its preparation method and uses Download PDFInfo
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- CN100523087C CN100523087C CNB200610020858XA CN200610020858A CN100523087C CN 100523087 C CN100523087 C CN 100523087C CN B200610020858X A CNB200610020858X A CN B200610020858XA CN 200610020858 A CN200610020858 A CN 200610020858A CN 100523087 C CN100523087 C CN 100523087C
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Abstract
The invention relates the heat-durability benzoxazine resin compound and preparing method, comprising the following steps: dissolving 50-95wt% benzoxazine resin intermediate, 0-50wt% aromatic compounds liquid resin with aldehyde group and 0-50wt% benzoxazine resin with aldehyde group into solvent between room temperature and 50Deg.C, getting heat-durability benzoxazine resin compound solvent, carrying out coating or dipping technology, getting prepreg, or mixing and getting solid resin compound, forming at 150Deg.C, carrying out heat treatment at 180Deg.C, and getting the product.
Description
Technical field
The present invention relates to a kind of thermostable benzoxazine resin compound and preparation method thereof, belong to thermosetting resin and high performance composite matrix resin and preparation field thereof.
Background technology
Benzoxazine is the benzo hexa-member heterocycle system that a class is made of Sauerstoffatom and nitrogen-atoms, characteristics with ring-opening polymerization, not having small molecules during polymerization discharges, form the reticulated structure of similar resol after the polymerization, the cure shrinkage of goods is little, and porosity is low, excellent mechanical property, electric property and flame retardant properties are arranged.The forties in 20th century, abroad the reaction of phenols intermediate, amine intermediate and formaldehyde has been carried out having synthesized the intermediate that contains the benzoxazine ring texture than systematic research:
Since the seventies, carried out preliminary study with regard to the ring-opening polymerization and the goods exploitation of benzoxazine abroad.After the nineties, both at home and abroad carried out extensive studies, applied for a patent tens of pieces at synthetic, the ring-opening polymerization and the aspects such as structure and property relationship of benzoxazine intermediate.The present inventor is from the research of beginning benzoxazine in 1993, and achievement in research has been applied for four patents of invention to Patent Office of the People's Republic of China, now all authorizes.The patent of ZL 94111852.5 is entitled as " ring-opening polymerization resol and fibre reinforced composites ", synthetic and the ring-opening polymerization of having summarized the benzoxazine intermediate in background technology prepares the domestic and international research situation of novel phenoplast, this resin and matrix material have good preparation and forming process, physical and mechanical properties is good, is suitable for high-temperature-resistant structure material and the electrically insulating material of making 150～180 ℃ of life-time service.ZL 95111413.1 patents are entitled as " the middle and preparation method of granular polybenzoxazine ", this method reacting balance, cyclisation rate height, product yield height, solvent-free, environmental pollution is little, be easy to realize serialization production, the granular solids intermediate can be directly used in makes various high performance phenoplast goods.The ZL99114603.4 patent is entitled as " plant oil modified benzoxazine intermediate and preparation method and purposes ", this method reacting balance, and forming process is good, and intrinsic toughening obviously improves condensate performance.ZL 03117779.4 patent is entitled as " can be used for modified benzoxazine resin of resin transfer moulding and preparation method thereof ", is to be mixed with the low viscosity compound resin that is used for resin transfer moulding with containing ethynyl, itrile group, allylic benzoxazine intermediate and other low-molecular-weight benzoxazine intermediates or Resins, epoxy or resol.
But related benzoxazine all is a benzoxazine of not being with polymerisable other reactive functional groups in above-mentioned these technology, the cross-linking density of the formed cross-linked network of this Jin You oxazine ring ring-opening polymerization is lower, thermotolerance is restricted, and is difficult to satisfy the requirement of some high heat resistance application scenarios.Therefore, the thermotolerance that further improves benzoxazine colophony becomes the topic of current focus.
ZL 03117779.4 patent is entitled as " can be used for modified benzoxazine resin of resin transfer moulding and preparation method thereof ", it is another patent that the present inventor is authorized, this method is with ethynyl, itrile group, allyl group isoreactivity functional group introduces in the benzoxazine intermediate, obtained the low viscous ethynyl that contains, itrile group, allylic benzoxazine intermediate, again with itself and other low-molecular-weight benzoxazine intermediate, or Resins, epoxy, or resol mixes, in the viscosity that reduces resin system simultaneously, by the crosslinking reaction of other reactive functionality in the benzoxazine solidification process, improved the cross-linking density and the thermotolerance of cured article.But this method or cost an arm and a leg or, use and still be restricted because of monomer because of thermotolerance promotes not obviously.
Summary of the invention
A kind of thermostable benzoxazine resin compound that provides at the deficiencies in the prior art and its production and use is provided, be characterized in to contain the lower molecular weight solidifying agent introducing resin system of aldehyde radical active function groups, make that aldehyde radical participates in reaction in benzoxazine open loop solidification process, further improve the cross-linking density of cured article, make the thermostability of cured article, the benzoxazine intermediate cured article of second-order transition temperature and the more corresponding single structure of thermal expansivity is significantly improved.
Purpose of the present invention is realized that by following technical measures wherein raw materials used umber is parts by weight except that specifying.
The recipe ingredient of thermostable benzoxazine resin compound is:
0～50 part of the phenolic compound that contains aldehyde radical
Contain 50～0 parts in aldehyde radical benzoxazine intermediate
50～95 parts in benzoxazine intermediate
Wherein, containing the phenolic compound of aldehyde radical and contain aldehyde radical benzoxazine intermediate can not be zero simultaneously, and the component that participates in reaction is not less than 5 parts;
(1) chemical structure that contains the phenolic compound of aldehyde radical is one of following listed compound structure
A. the aldehyde compound of single phenyl ring
B. naphthalene nucleus or conjugation are encircled aldehyde compound more
Or
C. heterocyclic aldehydes based compound
(2) contain in the structure of aldehyde radical benzoxazine intermediate, the structural formula that has not only contained the phenyl aldehyde base but also contained the benzoxazine cyclic cpds is:
D. the monocyclic aldehyde radical benzoxazine intermediate that contains
E. the diamines type contains aldehyde radical benzoxazine intermediate
F. Polyamine Type contains the aldehyde radical benzoxazine
(in the chemical structure of 3) benzoxazine intermediates, the structural formula that contains the benzoxazine ring is:
A. monocycle benzoxazine intermediate
B. diamines type bi-benzoxazine intermediate
C. bisphenol type bi-benzoxazine intermediate
The preparation method of thermostable benzoxazine resin compound:
(1) solution mixes, with 50～95 parts in benzoxazine intermediate with contain 0～50 part of the phenolic compound of aldehyde radical and/or contain 50～0 parts of liquid resins of aldehyde radical benzoxazine intermediate or solid powder, ℃ be dissolved in acetone, tetrahydrofuran (THF), toluene, dioxane, N-Methyl pyrrolidone or the DMF solvent in room temperature～50, obtain thermostable benzoxazine resin compound solution, adopt coating or impregnation technology to prepare the resin complexes prepreg of fiber or fabric this solution then; Or
(2) melting mixing, with 50～95 parts in benzoxazine intermediate with contain 0～50 part of the phenolic compound of aldehyde radical and/or contain 50～0 parts of liquid resins of aldehyde radical benzoxazine intermediate or semi-solid powder, in room temperature～100 ℃ melting mixing, obtain under the room temperature is the resin complexes of liquid or semi-solid, the viscosity of this mixture in ℃ temperature range of room temperature～100 can prepare the resin complexes prepreg or the composite product of resin complexes cured article or preparation fiber or fabric by casting, coating, dipping, injection or resin transfer molding (RTM) process less than 300cp; Or
(3) mechanically mixing, with the benzoxazine intermediate is fine powder with containing 0～50 part of the phenolic compound of aldehyde radical and/or containing 50～0 parts of solids pulverizing of aldehyde radical benzoxazine intermediate for 50～95 parts, mix by mechanical stirring or kneading technology under the room temperature, obtain the resin complexes of solid, powdery, this mixture can be at room temperature with chopped strand or fleut mechanically mixing after mold pressing, lamination or injection technique prepare composite product;
Above-mentioned resin compounded Tetramune or composite product must be in moulding more than 150 ℃ and carrying out hot aftertreatment more than 180 ℃, to obtain high thermotolerance.
The present invention has obtained following positively effect or advantage
After the present invention adopts the phenolic compound that contains aldehyde radical and contains aldehyde radical benzoxazine intermediate, in the benzoxazine open loop solidification process in resin complexes, aldehyde radical participates in crosslinking reaction simultaneously, further improves the cross-linking density of cured article, thereby improves the thermotolerance of cured article.By embodiments of the invention and Comparative Examples as can be seen, compare with the benzoxazine intermediate cured article of corresponding single structure, the glass transition temperature Tg that adopts the present invention to contain the thermostable benzoxazine resin compound gained cured article of aldehyde radical improves 20 ℃ (glass transition temperature Tg is that the peak value that adopts the dynamic viscoelasticity spectrum instrument to measure (DMA) out-of-phase modulus curve obtains) here; Adopt thermal gravimetric analyzer test (TGA) thermostability, the heat decomposition temperature in nitrogen atmosphere has improved 100 ℃, and 800 o'clock carbon yield improves 10%; 30～150 ℃ thermal expansivity decline (5～10) * 10 of adopting thermomechanical analyzer to measure
-6* k
-1The cured article of this thermostable benzoxazine resin compound and matrix material can be used as the high performance structures material, electrically insulating material or the electronic package material that use more than 155 ℃; As emery wheel, ablation resistant material or brake material.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1 preparation terephthalaldehyde (TPA)/diamines type benzoxazine (B-BOZ) mixture
Diamines type benzoxazine (B-BOZ) 90g and terephthalaldehyde (TPA) 10g are mixed for about 90 ℃ in temperature, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 2 hours at 140 ℃, following 3 hours at 150 ℃, 160 ℃ following 1 hour, 170 ℃ following 1 hour, following 1 hour at 180 ℃, following 1 hour at 190 ℃, 200 ℃ following 1 hour, 220 ℃ following 1 hour, obtain cured article, its second-order transition temperature is 240 ℃, tensile strength is 75MPa, and tensile modulus is 4.7Gpa, and tension set is 1.8%, flexural strength is 115MPa, and modulus in flexure is 4.7GPa.Mass ablative rate is 0.0201g/s.Its cured article is analyzed through TGA heat, and its test result sees Table 1
Embodiment 2 preparations contain aldehyde radical monocycle benzoxazine (AS-BOZ)/diamines type benzoxazine (B-BOZ) mixture
With diphenylmethane diamine type benzoxazine (B-BOZ) 77g and 3-phenyl-6-aldehyde radical-3, (23g of AS-BOZ) mixes under 90 ℃ of temperature 4-dihydro-2H-1,3-benzoxazine, vacuumizes 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 1 hour at 140 ℃, 150 ℃ following 2 hours, 160 ℃ following 1 hour, following 1 hour at 170 ℃, following 1 hour at 180 ℃, 190 ℃ following 1 hour, 200 ℃ following 1 hour, 220 ℃ solidified in following 1 hour after.Analyze through TGA heat, its test result sees Table 1
Embodiment 3 preparation furfural and diamines type benzoxazine (B-BOZ) mixtures
Diamines type benzoxazine (B-BOZ) 91g and furfural (Furfural) 9g are mixed for about 90 ℃ in temperature, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, stopped 3 hours down at 130 ℃ again, 140 ℃ the degree following 1 hour, 150 ℃ following 1 hour, 160 ℃ are following 1 hour, 170 ℃ following 1 hour, 180 ℃ following 2 hours, 200 ℃ following 1 hour, 220 ℃ solidified in following 1 hour after, analyze through TGA heat, its test result sees Table 1
Embodiment 4 preparation 2-naphthaldehyde and diamines type benzoxazine (B-BOZ) mixtures
Diamines type benzoxazine (B-BOZ) 80g and 2-naphthaldehyde 20g are mixed for about 100 ℃ in temperature, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, stopped 3 hours down at 130 ℃ again, spend following 1 hour for 140 ℃, 150 ℃ following 1 hour, 160 ℃ following 1 hour, 170 ℃ following 1 hour, 180 ℃ are down 2 little, following 1 hour at 200 ℃, after 220 ℃ of curing in following 2 hours, to analyze through TGA heat, its test result sees Table 1
Embodiment 5 preparations contain aldehyde radical dicyclo benzoxazine (AB-BOZ)/diamines type benzoxazine (B-BOZ) mixture
With diamines type benzoxazine (B-BOZ) 50g with contain aldehyde radical dicyclo type benzoxazine (AB-BOZ) 50g and under 90 ℃ of temperature, mix, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 1 hour at 140 ℃, 150 ℃ following 2 hours, 160 ℃ following 1 hour, following 1 hour at 170 ℃, following 1 hour at 180 ℃, 190 ℃ following 1 hour, 200 ℃ following 1 hour, 220 ℃ solidified in following 1 hour after.Analyze through TGA heat, its test result sees Table 1
Embodiment 6 preparations contain aldehyde radical and encircle benzoxazine (AM-BOZ)/diamines type benzoxazine (B-BOZ) mixture more
With diamines type benzoxazine (B-BOZ) 64g with contain the how ring-like benzoxazine of aldehyde radical (AM-BOZ) 36g and under 90 ℃ of temperature, mix, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 1 hour at 140 ℃, 150 ℃ following 2 hours, 160 ℃ following 1 hour, following 1 hour at 170 ℃, following 1 hour at 180 ℃, 190 ℃ following 1 hour, 200 ℃ following 1 hour, 220 ℃ solidified in following 1 hour after.Analyze through TGA heat, its test result sees Table 1
Embodiment 7 preparation terephthalaldehyde (TPA)/bisphenol A-type benzoxazine (BF-BOZ) mixtures
With bisphenol A-type benzoxazine (BF-BOZ) 70g and terephthalaldehyde (TPA) 30.Mix for about 90 ℃ in temperature, vacuumized 0.5 hour in 120 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, stopped 3 hours down at 130 ℃ again, spend following 1 hour for 140 ℃, 150 ℃ following 1 hour, 160 ℃ following 1 hour, 170 ℃ following 1 hour, 180 ℃ are down 2 little, following 1 hour at 200 ℃, after 220 ℃ of curing in following 2 hours, through the TGA test, its test result sees Table 2
Embodiment 8 preparation terephthalaldehydes (TPA) and benzoxazine (DS64) mixture
Single dicyclo mixed type benzoxazine (BS64-BOZ) 83g and terephthalaldehyde (TPA) 17g are mixed for about 90 ℃ in temperature, vacuumized 0.5 hour in 120 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 2 hours at 130 ℃, 150 ℃ following 3 hours, 160 ℃ following 1 hour, following 1 hour at 170 ℃, following 1 hour at 180 ℃, 190 ℃ following 1 hour, 200 ℃ following 1 hour, after to obtain its second-order transition temperature of cured article be 218 ℃.Its cured article is analyzed through TGA heat, and its test result sees Table 3
Embodiment 9 preparations contain the mixture of aldehyde radical monocycle benzoxazine (AS-BOZ) and single dicyclo mixed type benzoxazine (DS64)
Containing aldehyde radical monocycle benzoxazine (AS-BOZ) 30g and single dicyclo mixed type benzoxazine (DS64) 70g mixes under 70 ℃ of temperature, vacuumized 0.5 hour in 130 ℃ of temperature at vacuum tightness 0.05～0.095MPa then, following 2 hours at 130 ℃, 140 ℃ following 2 hours, solidified in following 5 hours at 150 ℃.The thermal expansivity of testing cured article then is 43.6910
-6* C
-1.
Embodiment 10 preparation terephthalaldehydes (TPA) and many ring benzoxazine (PBBOZ) mixtures
To encircle benzoxazine (PBBOZ) 95g and terephthalaldehyde (TPA) 5g at room temperature mixes more, the mould of inserting powdered mixture is placed in a conventional oven, following 2 hours of 60 ℃ of temperature, 70 ℃ following 2 hours, 80 ℃ are following 2 hours, 90 ℃ of Procuring in following 2 hours, to put in the press through the module after the Procuring then, slight pressurization is warmed up to 150 ℃, stopped 10 minutes, and be forced into 70Kgf/cm then
2, be warmed up to 190 ℃, pressurize 1 hour, cured article promptly.Survey TGA heat analysis in its cured article nitrogen, its test result sees Table 4
Embodiment 11 preparation terephthalaldehydes (TPA) and many ring benzoxazine (PBBOZ) mixtures
Identical with embodiment 10, different is many ring benzoxazine (PBBOZ) 90g, terephthalaldehyde (TPA) 10g, other is identical with embodiment 1, surveys TGA heat analysis in its cured article nitrogen, and its test result sees Table 4
Embodiment 12 adopts terephthalaldehyde (TPA) and many ring benzoxazine (PBBOZ) mixtures to prepare emery wheel.
To encircle benzoxazine (PBBOZ) 95g and terephthalaldehyde (TPA) 5g at room temperature mixes, the mixture 410g with quartz sand and additive mixes then, prepares emery wheel through 180 ℃ of compression moldings more.The wear resistance of this emery wheel rises to 25686 teeth from 20448 teeth of resol emery wheel.
Comparative Examples 1 preparation diamines type benzoxazine (B-BOZ) cured article
Identical with embodiment 1, different is only to contain diamines type benzoxazine (B-BOZ) condition of cure in the system with embodiment 1, and the second-order transition temperature of cured article is 194 ℃.Analyze through TGA heat, its test result sees Table 1
Comparative Examples 2 preparation bisphenol A-type benzoxazine (BF-BOZ) cured articles
Identical with enforcement 7, different is only to contain single dicyclo mixed type benzoxazine (BS64-BOZ) in the system, and condition of cure is with embodiment 7, and the second-order transition temperature of cured article only is 165 ℃.Analyze through TGA heat, its test result sees Table 2.
Comparative Examples 3 preparation single dicyclo mixed type benzoxazine (BS64) cured articles
Identical with enforcement 8, different is only to contain single dicyclo mixed type benzoxazine (BS64-BOZ) in the system, and condition of cure is with embodiment 8, and the second-order transition temperature of cured article only is 165 ℃.Analyze through TGA heat, its test result sees Table 3.
Comparative Examples 4 preparation how ring-like benzoxazine (PB-BOZ) moulding materials
Identical with embodiment 10, different is that system only contains how ring-like benzoxazine (PB-BOZ), and its condition of cure is identical with embodiment 10, surveys weightlessness in its cured article nitrogen, and its test result sees Table 4
Comparative Examples 5 preparation polyfunctional group mixed type benzoxazine (DS64) resin and Resins, epoxy (JEH-011) mixtures
With polyfunctional group mixed type benzoxazine (DS64) 91g, mix under low temperature with Resins, epoxy (JEH-011) 9g and C17Z0.2g, under 130 ℃, vacuumized 0.5 hour then, vacuum tightness 0.05～0.095MPa, 130 ℃ following 2 hours, 140 ℃ following 2 hours, solidified in following 5 hours at 150 ℃.Test the thermal expansivity and the second-order transition temperature of each cured article then, the results are shown in Table 5.
Comparative Examples 6 single dicyclo mixed type benzoxazine (DS64) resin of preparation and Resins, epoxy (E-51) mixtures
Identical with Comparative Examples 5, the Resins, epoxy that different is adopts is 9g E-51, and other and Comparative Examples 5 are identical, and test result sees Table 5.
The thermal characteristics of table 1 aldehyde radical linking agent modification diamines type benzoxazine relatively
| For example | The benzoxazine mixture | Weightless 5% temperature (℃) | Weightless 10% temperature (℃) | 800 ℃ of carbon yields (%) |
| Embodiment 1 | AS-BOZ and B-BOZ | 471 | 560 | 68.4 |
| Embodiment 2 | TPA and B-BOZ | 485 | 580 | 71.0 |
| Embodiment 3 | Furfural and B-BOZ | 408 | 498 | 68.6 |
| Embodiment 4 | 2-naphthaldehyde and B-BOZ | 490 | 597 | 74.3 |
| Embodiment 5 | AB-BOZ and B-BOZ | 482 | 567 | 68.7 |
| Embodiment 6 | AM-BOZ and B-BOZ | 491 | 596 | 70.3 |
| Comparative Examples 1 | B-BOZ | 404 | 435 | 44.9 |
The thermal characteristics of table 2 aldehyde radical linking agent modified bisphenol A type benzoxazine relatively
| For example | The benzoxazine mixture | Weightless 5% temperature (℃) | Weightless 10% temperature (℃) | 800 ℃ of carbon yields (%) |
| Embodiment 7 | TPA and BF-BOZ | 437 | 502 | 64.3 |
| Comparative Examples 2 | BF-BOZ | 340 | 400 | 40.2 |
The thermal characteristics of the single dicyclo mixed type of table 3 aldehyde radical linking agent modification benzoxazine relatively
| For example | The benzoxazine mixture | Weightless 5% temperature (℃) | Weightless 10 temperature (℃) | 800 ℃ of carbon yields (%) |
| Embodiment 8 | TPA and DS64-BOZ | 410 | 480 | 60.0 |
| Comparative Examples 3 | DS64-BOZ | 320 | 390 | 39.1 |
The thermal characteristics that table 4 aldehyde radical AS-BOZ modification encircles diamines type benzoxazine more compares
| For example | The benzoxazine mixture | Weightless 5% temperature (℃) | Weightless 10% temperature (℃) | 800 ℃ of carbon yields (%) |
| Embodiment 10 | TPA and PB-BOZ mass ratio 1/20 | 433 | 495 | 63.1 |
| Embodiment 11 | TPA and PB-BOZ mass ratio 1/10 | 451 | 530 | 70.0 |
| Comparative Examples 4 | PB-BOZ | 390 | 450 | 56.1 |
The thermal characteristics of each cured article of table 5
| For example | Resin formula | The glass transition temperature Tg of cured article (℃) | Thermal expansivity (10 -6×C -1) |
| Embodiment 9 | DS64 and AS-BOZ mass ratio 7/3 | 140 | 43.69 |
| Comparative Examples 5 | DS64 and JEH-011 and C175 mass ratio 100/10/0.2 | 131.10 | 48.77 |
| Comparative Examples 6 | DS64 and E-51 and C175 mass ratio 100/10/0.2 | 120.02 | 50.79 |
Claims (3)
1, thermostable benzoxazine resin compound is characterized in that the prescription composition of this benzoxazine resin compound is by weight:
0～50 part of the phenolic compound that contains aldehyde radical
Contain 50～0 parts in aldehyde radical benzoxazine intermediate
50～95 parts in benzoxazine intermediate
Wherein, containing the phenolic compound of aldehyde radical and contain aldehyde radical benzoxazine intermediate can not be zero simultaneously, and the component that participates in reaction is not less than 5 parts;
(1) chemical structure that contains the phenolic compound of aldehyde radical is one of following listed compound structure
A. the aldehyde compound of single phenyl ring
B. naphthalene nucleus or conjugation are encircled aldehyde compound more
C. heterocyclic aldehydes based compound
(2) contain in the structure of aldehyde radical benzoxazine intermediate, the structural formula that has not only contained the phenyl aldehyde base but also contained the benzoxazine cyclic cpds is:
D. the monocyclic aldehyde radical benzoxazine intermediate that contains
E. the diamines type contains aldehyde radical benzoxazine intermediate
F. Polyamine Type contains the aldehyde radical benzoxazine
(in the chemical structure of 3) benzoxazine intermediates, the structural formula that contains the benzoxazine ring is:
A. monocycle benzoxazine intermediate
B. diamines type bi-benzoxazine intermediate
C. bisphenol type bi-benzoxazine intermediate
In the benzoxazine open loop solidification process of this resin complexes, aldehyde radical participates in reaction simultaneously, further improve the cross-linking density of cured article, thereby improve the thermotolerance of cured article, compare with the benzoxazine intermediate cured article of corresponding single structure, this resin complexes glass transition temperature Tg improves 20 ℃, and the carbon yield in the nitrogen atmosphere 800 ℃ the time improves 10%, 30～150 ℃ thermal expansivity (5～10) * 10 that descend
-6* k
-1
2,, it is characterized in that this method may further comprise the steps according to the preparation method of the described thermostable benzoxazine resin compound of claim 1:
(1) solution mixes: with 50～95 parts in benzoxazine intermediate with contain 0～50 part of the phenolic compound of aldehyde radical and/or contain 50～0 parts of liquid resins of aldehyde radical benzoxazine intermediate or solid powder, ℃ be dissolved in acetone, tetrahydrofuran (THF), toluene, dioxane, N-Methyl pyrrolidone or the DMF solvent in room temperature～50, obtain thermostable benzoxazine resin compound solution, adopt coating or impregnation technology to prepare the resin complexes prepreg of fiber or fabric this solution then; Or
(2) melting mixing: with 50～95 parts in benzoxazine intermediate with contain 0～50 part of the phenolic compound of aldehyde radical and/or contain 50～0 parts of liquid resins of aldehyde radical benzoxazine intermediate or semi-solid powder, in room temperature～100 ℃ melting mixing, obtain under the room temperature is the resin complexes of liquid or semi-solid, the viscosity of this mixture in ℃ temperature range of room temperature～100 can prepare the resin complexes prepreg or the composite product of resin complexes cured article or preparation fiber or fabric by casting, coating, dipping, injection or resin transfer molding (RTM) process less than 300cp; Or
(3) mechanically mixing: with the benzoxazine intermediate is fine powder with containing 0～50 part of the phenolic compound of aldehyde radical and/or containing 50～0 parts of solids pulverizing of aldehyde radical benzoxazine intermediate for 50～95 parts, mix by mechanical stirring or kneading technology under the room temperature, obtain the resin complexes of solid, powdery, this mixture can be at room temperature with chopped strand or fleut mechanically mixing after mold pressing, lamination or injection technique prepare composite product;
Above-mentioned resin compounded Tetramune or composite product must be in moulding more than 150 ℃ and carrying out hot aftertreatment more than 180 ℃, to obtain high thermotolerance.
3,, it is characterized in that the cured article of this resin complexes and matrix material, as the high performance structures material, electrically insulating material or the electronic package material that use more than 155 ℃ according to the purposes of the described thermostable benzoxazine resin compound of claim 1; As emery wheel, ablation resistant material or brake material.
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| CN103030933A (en) * | 2012-11-23 | 2013-04-10 | 中国航空工业集团公司北京航空材料研究院 | Method for reducing cure shrinkage rate of resin matrix for liquid molding |
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| CN112239586A (en) * | 2020-06-23 | 2021-01-19 | 航天特种材料及工艺技术研究所 | Curable resin composition containing benzoxazine and preparation method thereof |
| CN111892728B (en) * | 2020-06-23 | 2022-09-23 | 航天特种材料及工艺技术研究所 | Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process |
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2006
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