CN1451679A - Modified benzoxazine resin capable of using for RTM and process for preparing same - Google Patents
Modified benzoxazine resin capable of using for RTM and process for preparing same Download PDFInfo
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- CN1451679A CN1451679A CN 03117779 CN03117779A CN1451679A CN 1451679 A CN1451679 A CN 1451679A CN 03117779 CN03117779 CN 03117779 CN 03117779 A CN03117779 A CN 03117779A CN 1451679 A CN1451679 A CN 1451679A
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Abstract
A modified benzoxazine resin able to be used for RTM is prepared through feeding low-voscosity benzoxazine intermediate and epoxy resin (or arylacetylene resin) proportionally into a reactor, mixing, reaction at 50-100 deg.C for 5-10 min, adding catalyst, and reaction for 5-10 min. It can also be prepared from low-viscosity benzoxazine intermediate and bimaleimide resin.
Description
One, technical field
The present invention relates to a kind ofly can be used for resin transfer moulding (Resin Transfer Molding, RTM) modified benzoxazine resin of moulding and preparation method thereof belongs to fiber-reinforced resin matrix compound material and manufacture field.
Two, background technology
RTM technology is the processing technology of a kind of polymer matrix composites of developing rapidly the nineties in 20th century, its primary process is: liquid low viscosity, not solvent-laden thermosetting resin are injected die cavity, the strongthener preform of dipping predetermined fixed in die cavity, and curing, demoulding post-treatment become goods at a certain temperature.RTM technology is easy to control the content and structure of of fortifying fibre; the product surface quality better; the dimensional precision height; mechanical property is outstanding, can produce high performance complex-shaped large-scale product, the production efficiency height; application prospect is extensive; especially under the situation of environmental protection requirement increasingly stringent, RTM more has its outstanding advantage as a kind of closed mould operations.One of key problem in technology of RTM technology is to satisfy resin dedicated that its technology and product properties require: 1. this resin dedicated under injection temperature viscosity low, general requirement viscosity is less than 1000cp, and viscosity is the most suitable at 200～500cp, the viscosity variation is little under the injection working temperature, working life is long, has good wetting property with strongthener for resin; 2. resin solidifies under solidification value comparatively fast, and no volatile matter discharges; 3. the cure shrinkage of resin is low, and goods have excellent mechanical property.At present, the matrix resin that RTM technology is used has unsaturated polyester, urethane, Vinylite, Resins, epoxy, benzocyclobutane olefine resin, bismaleimides etc., and back three classes belong to resistant to elevated temperatures performance resins.Yet these resins all have certain shortcoming, or cost is higher, or high-temperature behavior is relatively poor, or poor processability, and certain cure shrinkage is especially arranged, and influence the dimensional precision of goods.Secondly, in order to satisfy under the injecting condition requirement of resin low viscosity and long pot life, usually the RTM resin is the constituent formation of lower molecular weight, low reaction activity, cause that solidification value height, set time are long, the molecular weight of cured product is not high, cross-linking density is little, and the performance of goods is lower.Therefore, requirement to the RTM resin, be exactly how to seek new RTM resin combination system by molecular designing and material design, and contradiction etc. how to coordinate resin injection technology, cure process and goods high-performance three aspects, these problems all have crucial researching value.
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 three patents of invention to Patent Office of the People's Republic of China, wherein authorizes in 2000 for two.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.But this benzoxazine intermediate be in organic solvent through the solution method synthetic, resin solution that obtains or thickness arborescens product are restricted in industrial applications.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.But this class benzoxazine intermediate product cured article fragility is bigger.Application number 99114603.4 patents are 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.But existing benzoxazine intermediate all adopts resin solution or pressed powder form forming composite goods, is difficult to use in RTM technology.
Three, summary of the invention
The objective of the invention is provides modified benzoxazine resin of a kind of RTM of can be used for and preparation method thereof at the deficiencies in the prior art, be characterized under heating and/or catalyst action, between the low viscosity benzoxazine intermediate or with other modified copolymers and catalyzer blending reaction, obtain can be used for the modified benzoxazine resin of RTM.
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 that can be used for the modified benzoxazine resin of RTM is:
A. low viscosity benzoxazine intermediate: 50～100 parts
B. reactive copolymer component: 50～0 parts
C. catalyzer: 0.1～2 part
This RTM resin is in 50～110 ℃ temperature range, viscosity is less than 400cp, constant temperature is 2 hours in 50～110 ℃ temperature range, the increasing degree of viscosity is less than 50%, the pour mass of RTM resins and fibre composite can solidify moulding in 6～10 hours in 170～200 ℃ of scopes of temperature.
1. low viscosity benzoxazine intermediate is the technological line synthetic that provides according to Chinese patent ZL 94111852.5, formaldehyde, phenolic compound and aminated compounds, under the alkaline condition of PH=8～9, in toluene, dioxane or dimethylbenzene equal solvent, in 75～80 ℃ of reactions 4～5 hours, product removes solvent in the system through vacuum extraction, obtains following benzoxazine intermediate:
(1) single benzoxazine intermediate, its structural formula is as follows
Wherein phenolic compound is a phenol, C1～C4 alkyl substituted phenol, at least a in the 2-chavicol.Aminated compounds is an aniline, 3-ethynyl aniline, 4-alkynes propoxy-aniline, 4-amido cyanobenzene, at least a in the p-aminophenol.
(2) low viscosity diamines type bi-benzoxazine intermediate, its structural formula is as follows
Wherein phenolic compound is a phenol, C1～C4 alkyl substituted phenol, at least a in the 2-chavicol.Aminated compounds is the aromatic diamine that contains flexible bridge joint group, as mphenylenediamine, and 4,4 '-two amido ditanes, 3,3 '-two amido ditanes, 4, at least a in 4 '-diamines yl diphenyl ether.
(3) low viscosity bisphenol type bi-benzoxazine intermediate, its structural formula is as follows
Wherein phenolic compound is the aromatics dihydric phenol that contains flexible bridge joint group, and as 2,2-two (4,4 '-hydroxy phenyl) propane, 4,4 '-dihydroxy phenyl ether, 4,4 '-dihydroxy-benzene methylmethane, 2, two (2,2 '-allyl group-4, the 4 '-hydroxy phenyl) propane of 2-, 2,2 '-allyl group-4,4 '-dihydroxy phenyl ether, 2,2 '-allyl group-4, at least a in 4 '-dihydroxy-benzene methylmethane.Aminated compounds is an aniline, 3-ethynyl aniline, 4-alkynes propoxy-aniline, 4-amido cyanobenzene, at least a in the p-aminophenol.
2. modified copolymer is:
(1) Resins, epoxy, its structural formula is as follows
(2) aryl ethane resin, its structural formula is as follows
(3) bimaleimide resin, its structural formula is as follows
3. catalyzer has the characteristics of latent, and in the resin injection process, katalysis is not obvious, and when curing molding, promotes reaction to carry out fast.Catalyzer is a hexanodioic acid, oxalic acid, certain herbaceous plants with big flowers diacid, suberic acid, tertiary amine, boron trifluoride complex, at least a in dicumyl peroxide and/or the benzoyl peroxide.
The preparation method of modified benzoxazine resin:
With 50～100 parts in low viscosity benzoxazine intermediate, with 50～0 parts of Resins, epoxy or aryl ethane resins, add and have in the reactor of thermometer, agitator and reflux exchanger, mixed 5～10 minutes for 50～100 ℃ in temperature, add 0.1～2 part of catalyzer, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding.Perhaps with 50～100 parts in low viscosity benzoxazine intermediate, 50～0 parts of bimaleimide resins 120～130 ℃ of prepolymerization reactions of temperature 20～30 minutes, add 0.1～2 part of catalyzer, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding.
This RTM resin is in 50～110 ℃ temperature range, viscosity is less than 400cp, constant temperature is 2 hours in 50～110 ℃ temperature range, the increasing degree of viscosity is less than 50%, the pour mass of RTM resins and fibre composite can solidify moulding in 6～10 hours in 170～200 ℃ of scopes of temperature.
The matrix material that can be used for the modified benzoxazine resins of RTM has excellent physical and mechanical properties and thermotolerance, is suitable for the high-temperature-resistant structure material and the ablator of life-time service in 150～200 ℃ of scopes of temperature.
The present invention has the following advantages:
1. reactive or non-reacted side group is introduced in the structure of benzoxazine intermediate, the viscosity of benzoxazine intermediate is significantly reduced.
2. by introducing second kind of reactive functional group, or with hybrid reactions such as modified copolymer and catalyzer, both can reduce the viscosity of resin, prolong the working life of resin under the injecting condition; Can increase the crosslinking reaction point again, improve cross-linking density, obtain the matrix resin matrix material of excellent combination property.
3. the modified benzoxazine resin that can be used for RTM, the characteristics such as curing reaction is very fast under, working life low except that viscosity under injection temperature long, the mold temperature, no small molecules volatile matter is emitted, the cure shrinkage of resin is low, its goods also have advantages such as excellent mechanical property, resistance to elevated temperatures, low porosity, agent of low hygroscopicity, good flame retardant property, the goods of part special construction at high temperature can have high carbon yield, can be used for being produced on the high-temperature-resistant structure material and the ablation resistant material of life-time service in 150～200 ℃ of scopes of temperature.
Four, 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. with phenol 47.0g, aniline 46.5g, formalin (37%) 81.1g, sodium hydroxide solution (10%) 3ml, adding has in the reactor of thermometer, agitator and reflux exchanger, lowers the temperature after 5 hours in 80 ℃ of back flow reaction of temperature, standing demix, separate upper water liquid, lower floor's liquid removes solvent through vacuum extraction, gets faint yellow thickness benzoxazine intermediate.This liquid intermediate is 180cp in the viscosity of 50 ℃ of temperature, 50 ℃ of constant temperature after 2 hours viscosity do not change, 80 ℃ of constant temperature after 5 hours viscosity be 150cp.
2. with diphenylmethane diamine 49.5g, formalin (37%) 81.1g, phenol 47.0g, sodium hydroxide (10%) 3ml, ethanol 35ml, toluene 88ml adds in the identical equipment of embodiment 1, lowers the temperature after 5 hours in 80 ℃ of back flow reaction of temperature, standing demix, separate upper water liquid, vacuum extraction removes solvent, gets faint yellow benzoxazine intermediate solid.Its fusing point is 60 ℃, and the gelation time when 170 ℃ of temperature is 40 minutes, and the viscosity in the time of 110 ℃ is 250cp, 110 ℃ of constant temperature after 2 hours viscosity be 380cp.
3. with adjacent diallyl bisphenol 44.8g, aniline 37.2g, formalin (37%) 64.9g, toluene 30ml, add in the identical equipment of embodiment 1, after 5 hours, standing demix separates upper water liquid in 80 ℃ of back flow reaction of temperature, vacuum extraction removes solvent, obtain amber transparent thick benzoxazine intermediate, the viscosity when 100 ℃ of temperature is 220cp, and the viscosity of 110 ℃ of constant temperature after 2 hours is 150cp.This benzoxazine intermediate 46g, diphenylmethane diamine type bismaleimides 36g is with example 1 synthetic benzoxazine intermediate 21g, dicumyl peroxide 0.1g, 100 ℃ of hybrid reactions 5 minutes the reddish-brown clear solution, the viscosity when 100 ℃ of temperature is 250cp.The resin-cast body solidified 4 hours for 180 ℃ in temperature, and 190 ℃ solidified 4 hours, and second-order transition temperature is 165 ℃.
4. with example 2 benzoxazine intermediate 100g, hexanodioic acid 0.5g adds in the identical equipment of embodiment 1, hybrid reaction 5～10 minutes, gelation time when 170 ℃ of temperature shortens to 7 minutes, and the viscosity in the time of 110 ℃ is 200cp, 110 ℃ of constant temperature after 2 hours viscosity be 420cp.The resin-cast body solidifies moulding in 4 hours for 180 ℃ in temperature, and cured resin sample second-order transition temperature is 194 ℃, and tensile strength is 86MPa, and tensile modulus is 4.5Gpa, and tension set is 2.3%, and flexural strength is 172MPa, and modulus in flexure is 4.7GPa.Tensile strength by the glass cloth laminated board of this resins is 546MPa, and tensile modulus is 23GPa.
5. with the liquid benzoxazine intermediate of example 1 synthetic 80g, E-51 Resins, epoxy 20g, N, N-dimethyl benzylamine 1g adds in the identical equipment of embodiment 1, hybrid reaction makes the low viscosity liquid resin, gelation time when 160 ℃ of temperature is 8 minutes and 30 seconds, and the viscosity in the time of 80 ℃ is 200cp, and the viscosity of 80 ℃ of constant temperature after 2 hours is 350cp.The resin-cast body solidifies moulding in 4 hours for 180 ℃ in temperature, and tensile strength is 55MPa, and tensile modulus is 4.1GPa, and the temperature of TGA weightlessness 5% is 340 ℃, and second-order transition temperature is 160 ℃.The flexural strength that adopts the glass cloth laminated board of this resins is 560MPa (room temperature) and 300MPa (155 ℃).
6. with example 1 synthetic benzoxazine intermediate 40g, example 2 synthetic benzoxazine intermediate 60g, oxalic acid 0.3g, add in the identical equipment of embodiment 1, obtain the low viscosity liquid resin after the mixing, gelation time when 180 ℃ of temperature is 15 minutes and 32 seconds, and the viscosity in the time of 80 ℃ is 160cp, 80 ℃ of constant temperature after 4 hours viscosity be 250cp.The resin-cast body solidified 5 hours and 190 ℃ of curing moulding in 1 hour 180 ℃ of temperature respectively, and second-order transition temperature is 151 ℃, and tensile strength is 75MPa,, tensile modulus is 5.2GPa, tension set is 1.6%, flexural strength is 176MPa, and modulus in flexure is 4.8GPa.
7. with p-cresol 40.5g, phenol 35.3g, diphenylmethane diamine 37.1g, formalin (37%) 60.8g, ethanol 30ml, toluene 70ml, sodium hydroxide (10%) 5ml, add in the identical equipment of embodiment 1, lower the temperature after 5 hours in 80 ℃ of back flow reaction of temperature, standing demix separates upper water, the vacuum extraction desolventizing gets faint yellow benzoxazine intermediate solid.This solid product is in temperature softening fusion more than 60 ℃, and the viscosity in the time of 110 ℃ is 320cp, 110 ℃ of constant temperature after 2 hours viscosity be 450cp.The resin-cast body solidifies moulding in 4 hours for 180 ℃ in temperature, and second-order transition temperature is 184 ℃, and tensile strength is 82MPa, and tensile modulus is 5.2GPa, and tension set is 1.9%, and flexural strength is 177MPa, and modulus in flexure is 4.4GPa.
8. with m-aminophenyl acetylene 29.3g, phenol 23.5g, formalin (37%) 40.5g, toluene 25ml, add in the identical equipment of embodiment 1, in 80 ℃ of back flow reaction of temperature after 5 hours, standing demix, separate upper water liquid, the vacuum desolventizing obtains pale brown look liquid benzoxazine intermediate.The gelation time of this liquid product when 220 ℃ of temperature is 3 minutes and 11 seconds, and the viscosity in the time of 50 ℃ is 140cp, 50 ℃ of constant temperature after 2 hours viscosity do not change.The resin-cast body solidified 4 hours for 180 ℃ in temperature, and 250 ℃ solidified 2 hours, and second-order transition temperature is 311 ℃.Weightless 5% and 10% temperature is respectively 407 ℃ and 420 ℃ in the nitrogen, N when 800 ℃ of temperature
2Carbon yield is greater than 65% in the atmosphere.
9. will be to alkynes propoxy-aniline 29.4g, phenol 18.8g, formalin (37%) 32.4g, toluene 20ml, add in the identical equipment of embodiment 1, in 80 ℃ of back flow reaction of temperature after 5 hours, standing demix, remove upper water liquid, the vacuum desolventizing obtains pale brown look liquid benzoxazine intermediate.The gelation time of this liquid product when 220 ℃ of temperature is 3 minutes and 23 seconds, and the viscosity in the time of 50 ℃ is 160cp, 50 ℃ of constant temperature after 2 hours viscosity do not change.The resin-cast body solidified 4 hours 180 ℃ of temperature, and 250 ℃ solidified 2 hours, and second-order transition temperature is 270 ℃, and weightless 5% and 10% temperature is respectively 384 ℃ and 406 ℃ in the nitrogen, N when 800 ℃ of temperature
2Carbon yield is greater than 62% in the atmosphere.
10. with the benzoxazine intermediate 67.8g of example 7 preparation, with the benzoxazine intermediate 130g of example 2 preparations, add in the identical equipment of embodiment 1, after 80 ℃ of melting mixing of temperature, obtain the low viscosity liquid resin.The gelation time of this liquid resin when 220 ℃ of temperature is 2 minutes and 43 seconds, 100 ℃ of constant temperature after 3 hours viscosity be 190cp.The resin-cast body solidified 5 hours for 180 ℃ in temperature, and 200 ℃ solidified 2 hours, and second-order transition temperature is 182 ℃, tensile strength 70MPa, and tensile modulus is 5.0GPa, elongation at break 1.6%, flexural strength 161MPa, modulus in flexure 5.2GPa; Weightless 5% and 10% temperature is respectively 380 ℃ and 400 ℃ in nitrogen, N when 800 ℃ of temperature
2Carbon yield is greater than 60% in the atmosphere.
11. with adjacent allyl phenol 32.0g, aniline 22.1g, formalin (37%) 38.6g, toluene 40ml, ethanol 10ml adds in the identical equipment of embodiment 1,80 ℃ of back flow reaction after 5 hours, and standing demix, remove upper water liquid, the vacuum desolventizing obtains yellow liquid benzoxazine intermediate.Should liquid state benzoxazine intermediate 25.1g, diphenylmethane diamine type bismaleimide resin 17.9g, 120～130 ℃ of reactions of temperature 20～30 minutes, obtain the thick resin prepolymer of red-brown, again with the benzoxazine intermediate 21.7g of example 2 preparation, even in 100 ℃ of hybrid reactions of temperature, obtain the low viscosity liquid resin.The gelation time of this liquid resin when 180 ℃ of temperature is 11 minutes 11 seconds, and 220 ℃ gelation time is 1 minute and 58 seconds, and 80 ℃ of viscosity are 230cp, 80 ℃ of constant temperature after 4 hours its viscosity be no more than 300cp.The resin-cast body solidified 4 hours for 180 ℃ in temperature, and 200 ℃ solidified 4 hours, and second-order transition temperature is 155 ℃, tensile strength 69MPa, and tensile modulus is 5.3GPa, elongation at break 1.3%, flexural strength 154MPa, modulus in flexure 4.6GPa.
Claims (5)
1, the modified benzoxazine resin that can be used for RTM is characterized in that the recipe ingredient (by weight) of this resin is:
50～100 parts in low viscosity benzoxazine intermediate
50～0 parts of modified copolymers
0.1～2 part of catalyzer
This RTM resin is in 50～110 ℃ temperature range, viscosity is less than 400cp, constant temperature is 2 hours in 50～110 ℃ temperature range, the increasing degree of viscosity is less than 50%, the pour mass of RTM resins and fibre composite can solidify moulding in 6～10 hours in 170～200 ℃ of scopes of temperature.
2,, it is characterized in that low viscosity benzoxazine intermediate is according to the described modified benzoxazine resin that can be used for RTM of claim 1:
A. single benzoxazine intermediate, its structural formula is as follows
B. low viscosity diamines type bi-benzoxazine intermediate, its structural formula is as follows
C. low viscosity bisphenol type bi-benzoxazine intermediate, its structural formula is as follows
3, according to the described modified benzoxazine resin that can be used for RTM of claim 1, it is characterized in that modified copolymer is:
A. Resins, epoxy, its structural formula is as follows
B. bimaleimide resin, its structural formula is as follows
C. aryl ethane resin, its structural formula is as follows
4,, it is characterized in that catalyzer is a hexanodioic acid, oxalic acid, certain herbaceous plants with big flowers diacid, suberic acid, tertiary amine, boron trifluoride complex, at least a in benzoyl peroxide and/or the dicumyl peroxide according to the described modified benzoxazine resin that can be used for RTM of claim 1.
5, according to the described preparation method who can be used for the modified benzoxazine resin of RTM of claim 1～4, it is characterized in that 50～100 parts in low viscosity benzoxazine intermediate, with 50～0 parts of Resins, epoxy or aryl ethane resins, add and have in the reactor of thermometer, agitator and reflux exchanger, 50～100 ℃ of hybrid reactions of temperature 5～10 minutes, add 0.1～2 part of catalyzer, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding; Perhaps with 50～100 parts in low viscosity benzoxazine intermediate, 50～0 parts of bimaleimide resins 120～130 ℃ of prepolymerization reactions of temperature 20～30 minutes, add 0.1～2 part of catalyzer, blending reaction 5～10 minutes, acquisition can be used for the benzoxazine colophony of RTM moulding.
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Cited By (15)
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| CN100393717C (en) * | 2006-05-25 | 2008-06-11 | 四川大学 | Benzoxazine containing maleimide and allyl ether and its preparing method |
| CN102020846A (en) * | 2010-09-29 | 2011-04-20 | 北京化工大学 | Furfurylamine type benzoxazine resin/maleimide compound composition |
| US7973158B2 (en) | 2006-11-29 | 2011-07-05 | Henkel Corporation | Method of preparing benzoxazines |
| 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 |
| CN101605837B (en) * | 2007-02-08 | 2013-06-12 | 亨斯迈先进材料（瑞士）有限公司 | Thermosetting composition |
| US8716377B2 (en) | 2008-05-09 | 2014-05-06 | Henkel Ag & Co. Kgaa | Polymerizable composition |
| CN106103519A (en) * | 2014-02-26 | 2016-11-09 | 亨斯迈先进材料美国有限责任公司 | Reaction hydridization benzoxazine resins and application thereof |
| CN106800654A (en) * | 2016-12-20 | 2017-06-06 | 江苏大学 | A kind of method that polybenzoxazole is prepared based on backbone chain type benzoxazine |
| CN106995582A (en) * | 2017-05-16 | 2017-08-01 | 江苏恒神股份有限公司 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
| CN107201037A (en) * | 2017-07-11 | 2017-09-26 | 苏州生益科技有限公司 | Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it |
| CN109054288A (en) * | 2018-07-04 | 2018-12-21 | 山东非金属材料研究所 | A kind of Wet Winding Process benzoxazine resin system |
| CN110343223A (en) * | 2019-06-21 | 2019-10-18 | 沈阳航空航天大学 | Containing alkynyl and aryl oxide nitrile structure benzoxazine resin, composite material and its preparation method |
| CN110770314A (en) * | 2017-06-14 | 2020-02-07 | 米其林集团总公司 | Metal or metallized reinforcement having a surface coated with a cured polybenzoxazine |
| CN113736255A (en) * | 2020-05-27 | 2021-12-03 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| CN117964870A (en) * | 2024-03-29 | 2024-05-03 | 成都飞机工业（集团）有限责任公司 | Benzoxazine resin-based fiber sizing agent and preparation method and application thereof |
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| CN100393717C (en) * | 2006-05-25 | 2008-06-11 | 四川大学 | Benzoxazine containing maleimide and allyl ether and its preparing method |
| US7973158B2 (en) | 2006-11-29 | 2011-07-05 | Henkel Corporation | Method of preparing benzoxazines |
| CN101605837B (en) * | 2007-02-08 | 2013-06-12 | 亨斯迈先进材料（瑞士）有限公司 | Thermosetting composition |
| TWI419926B (en) * | 2007-02-08 | 2013-12-21 | Huntsman Adv Mat Switzerland | Thermosetting composition |
| US8852382B2 (en) | 2007-02-08 | 2014-10-07 | Huntsman International Llc | Thermosetting composition |
| US8716377B2 (en) | 2008-05-09 | 2014-05-06 | Henkel Ag & Co. Kgaa | Polymerizable composition |
| CN102020846A (en) * | 2010-09-29 | 2011-04-20 | 北京化工大学 | Furfurylamine type benzoxazine resin/maleimide compound composition |
| CN102020846B (en) * | 2010-09-29 | 2014-03-19 | 北京化工大学 | Furfurylamine type benzoxazine resin/maleimide compound composition |
| 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 |
| CN106103519A (en) * | 2014-02-26 | 2016-11-09 | 亨斯迈先进材料美国有限责任公司 | Reaction hydridization benzoxazine resins and application thereof |
| CN106800654A (en) * | 2016-12-20 | 2017-06-06 | 江苏大学 | A kind of method that polybenzoxazole is prepared based on backbone chain type benzoxazine |
| CN106800654B (en) * | 2016-12-20 | 2019-02-05 | 江苏大学 | A method of polybenzoxazoles is prepared based on backbone chain type benzoxazine |
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| CN110770314A (en) * | 2017-06-14 | 2020-02-07 | 米其林集团总公司 | Metal or metallized reinforcement having a surface coated with a cured polybenzoxazine |
| CN110770314B (en) * | 2017-06-14 | 2021-10-01 | 米其林集团总公司 | Metal or metallized reinforcement having a surface coated with a cured polybenzoxazine |
| CN107201037A (en) * | 2017-07-11 | 2017-09-26 | 苏州生益科技有限公司 | Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it |
| CN109054288A (en) * | 2018-07-04 | 2018-12-21 | 山东非金属材料研究所 | A kind of Wet Winding Process benzoxazine resin system |
| CN110343223A (en) * | 2019-06-21 | 2019-10-18 | 沈阳航空航天大学 | Containing alkynyl and aryl oxide nitrile structure benzoxazine resin, composite material and its preparation method |
| CN110343223B (en) * | 2019-06-21 | 2022-04-22 | 辽宁鲸苇科技有限公司 | Benzoxazine resin containing alkynyl and aryl ether nitrile structure, composite material and preparation method thereof |
| CN113736255A (en) * | 2020-05-27 | 2021-12-03 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| CN113736255B (en) * | 2020-05-27 | 2023-07-14 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| CN117964870A (en) * | 2024-03-29 | 2024-05-03 | 成都飞机工业（集团）有限责任公司 | Benzoxazine resin-based fiber sizing agent and preparation method and application thereof |
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