CN104974346B - A kind of preparation method for the bimaleimide resin that liquid crystal type allyl compound is modified - Google Patents
A kind of preparation method for the bimaleimide resin that liquid crystal type allyl compound is modified Download PDFInfo
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- CN104974346B CN104974346B CN201510418690.7A CN201510418690A CN104974346B CN 104974346 B CN104974346 B CN 104974346B CN 201510418690 A CN201510418690 A CN 201510418690A CN 104974346 B CN104974346 B CN 104974346B
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Abstract
Bimaleimide resin that a kind of liquid crystal type allyl compound is modified and preparation method thereof, including Isosorbide-5-Nitrae two (4 allyloxy benzoic acid) phenyl ester class liquid crystal type allyl compound, 2,2 ' diallyl bisphenols and bismaleimide monomer etc..During preparation, Isosorbide-5-Nitrae two (4 allyloxy benzoic acid) phenyl ester class liquid crystal type allyl compound is heated and melted；2,2 ' diallyl bisphenols are added to be uniformly mixed；130 160 DEG C of temperature is controlled, bismaleimide monomer pre-polymerization is added while stirring until system becomes the brown liquid of transparent and homogeneous；Room temperature is cooled to, a kind of rufous transparent solid resin is obtained.The modified bismaleimide resin of the present invention is dissolved in the conventional low boiling point solvent such as acetone, chloroform, cure process is good, its solidfied material has excellent heat resistance and toughness, is the matrix resin of the advanced polymer matrix composite needed for Aero-Space, electric field.
Description
Technical field
The invention belongs to organic high performance polymer material field, and in particular to a kind of liquid crystal type allyl compound is modified
Bimaleimide resin preparation method.
Background technology
Bimaleimide resin is a kind of 20th century new type resin for developing of mid-term, and it has polyimides simultaneously
The heat resistance of resin and the excellent processability of epoxy resin, are a kind of high-strength, high mold materials, can be used as advanced polymer matrix and answer
Condensation material, but the crosslink density of bismaleimide resin is big, and toughness of products is poor, its shock resistance and anti-stress cracking performance is also beaten greatly
Discount.To improve its shortcoming, domestic and international many researchers are directed to the toughness reinforcing work of bimaleimide resin.
At present, conventional bimaleimide resin method of modifying has allyl compound modification, aromatic diamine to change
Property, thermoplastic resin modified and liquid-crystal compounds be modified etc., but most of is all to sacrifice bimaleimide resin
Other excellent properties reach the purpose of bismaleimide resin toughness reinforcing.Therefore, bimaleimide resin excellent properties base is being kept
On plinth, the toughness and manufacturability for improving bimaleimide resin have become the important content of high performance resin research and development.In order to
The high speed development of modern science and technology and industry is met, possesses the bimaleimide resin of prominent toughness and superior heat resistance performance
Research and development are extremely urgent and arisen at the historic moment.
Document (the .4,4' such as Nie Wangyan, Li Yang, Xu Hongyao bis- (4- allyloxys benzoic acid) phenyl ester bifunctional group liquid crystal
The preparation of body and performance [J] functional materials, 2009,40 (2):It is 342-344.) open to report 1,4 '-two (4- allyloxy benzene
Formic acid) phenyl ester synthetic method, but the document is just for synthesizing a kind of bifunctional group liquid crystal monomer, not follow-up report
Isosorbide-5-Nitrae '-two (4- allyloxys benzoic acid) phenyl ester, is not also used among the study on the modification of bimaleimide resin by road.
The content of the invention
The present invention is in order to avoid realizing the deficiency of toughness reinforcing to sacrifice other excellent properties of bimaleimide resin, carry
For a kind of preparation method of liquid crystal type allyl compound modified bismaleimide resin, span is being kept to come to reach
The purpose that toughness is significantly improved while imide resin excellent heat resistance energy.
To achieve the above object, the technical solution adopted by the present invention is to use Isosorbide-5-Nitrae-two (4- allyloxys benzoic acid) phenyl ester
Class liquid crystal type allyl compound joint 2,2 '-diallyl bisphenol increases as modifying agent to bimaleimide resin
Tough modification.It is comprised the following steps that：
1,4- bis- (4- allyloxys benzoic acid) phenyl ester class liquid crystal type allyl compound is heated first and melted；But add
Enter a certain amount of 2,2 '-diallyl bisphenol to stir；Finally be added portionwise a certain amount of bismaleimide monomer in
130 DEG C~160 DEG C stirring 30~90min of pre-polymerization, until system turns into homogeneous rufous transparency liquid, obtain liquid crystal type pi-allyl
Compound modified bimaleimide resin.Obtained prepolymer deaeration processing, after solidification, obtains liquid crystal type allyl
The bimaleimide resin solidfied material that based compound is modified.
Described bismaleimide monomer is N, N ' -4.4 '-diphenyl methane dimaleimide, N, N '-penylene pair
Maleimide and both mixtures
The amount of the bismaleimide monomer material and 2,2 '-diallyl bisphenol and (the 4- allyloxy benzene of 1,4- bis-
Formic acid) the ratio between the amount of phenyl ester class liquid crystal type allyl compound total material is 1:0.8~1.
The 2,2 '-diallyl bisphenol and 1,4- bis- (4- allyloxys benzoic acid) phenyl ester class liquid crystal type allylation
Compound mol ratio is 1:0.1~0.6.
The present invention proposes a kind of preparation method of liquid crystal type allyl compound modified bismaleimide resin, passes through
Modified bismaleimide resin prepared by this method, impact strength maximum can reach 15.6MPa, and 2,2 '-two are added than simple
90.2% is added during pi-allyl bisphenol-A；Bending modulus and bending strength are maximum respectively up to 4.24Gpa and 156.2Mpa, with
Simple to add 2,2 '-diallyl bisphenol modified bismaleimide resin is compared, and 11.58% He is added respectively
19.24%；T5%Heat decomposition temperature can reach 438 DEG C.The bismaleimide that obtained liquid crystal type allyl compound is modified
Polyimide resin impact strength, bending strength and bending modulus and heat resistance increase.
Brief description of the drawings
Fig. 1 is the liquid crystal figure of 1,4 '-two (4- allyloxys benzoic acid) phenyl esters melting later under petrographic microscope.
Fig. 2 is the thermogravimetric curve (N for the New Modified Bismaleimide Resin that embodiment one is prepared2, heating speed
20 DEG C/min of rate).
Fig. 3 is the SEM figures for the New Modified Bismaleimide Resin section that embodiment 1 is prepared.
Embodiment
The present invention is described further in conjunction with embodiment.
Embodiment 1
2.06g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 165 DEG C of heating, addition 13.26g 2,2 '-
After diallyl bisphenol melting, 19.68g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 140 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction, obtains modified bismaleimide
Resin.Obtained resin is put into the vacuum drying chamber that temperature is 140 DEG C and carries out deaeration processing 50min, preheating is subsequently poured into
To 140 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.Gu
Change and the BMI solidified resin that the liquid crystal type allyl compound is modified is produced after terminating.
Control group
Component is N, N ' -1.4 '-diphenyl methane dimaleimide and 2,2 '-diallyl bisphenol；
By 14.98g 2,2 '-diallyl bisphenol adds 20.01g N, N ' -4.4 '-hexichol in after 70 DEG C of heating meltings
Methane bismaleimide monomer carries out melting copolymerization in 140 DEG C, until system turns into homogeneous phase rufous transparency liquid, then
Insulation reaction, obtains modified bismaleimide resin.Obtained resin is put into the vacuum drying chamber that temperature is 140 DEG C
Row deaeration handles 50min, is subsequently poured into be preheated to 140 DEG C and apply to wipe and is solidified in the mould of releasing agent, and curing process is
180℃/1h+210℃/2h+250℃/6h.Solidification produces the new modified BMI solidified resin after terminating.
Embodiment 2
4.05g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 165 DEG C of heating, addition 11.59g 2,2 '-
After diallyl bisphenol melting, 19.36g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 140 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction, obtains modified bismaleimide
Resin.Obtained prepolymer is put into the vacuum drying chamber that temperature is 140 DEG C and carries out deaeration processing 50min, is subsequently poured into pre-
Heat to 140 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.
Solidification produces the BMI solidified resin that the liquid crystal type allyl compound is modified after terminating.
Embodiment 3
5.97g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 165 DEG C of heating, addition 9.98g 2,2 '-
After diallyl bisphenol melting, 19.05g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 150 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction obtains modified bismaleimide
Resin.Obtained prepolymer is put into the vacuum drying chamber that temperature is 150 DEG C and carries out deaeration processing 50min, is subsequently poured into pre-
Heat to 150 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.
Solidification produces the BMI solidified resin that the liquid crystal type allyl compound is modified after terminating.
Embodiment 4
7.84g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 170 DEG C of heating, addition 8.42g 2,2 '-
After diallyl bisphenol melting, 18.75g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 150 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction, obtains modified bismaleimide
Resin.Obtained prepolymer is put into the vacuum drying chamber that temperature is 150 DEG C and carries out deaeration processing 50min, is subsequently poured into pre-
Heat to 150 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.
Solidification produces the BMI solidified resin that the liquid crystal type allyl compound is modified after terminating.
Embodiment 5
9.64g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 170 DEG C of heating, addition 6.91g 2,2 '-
After diallyl bisphenol melting, 18.45g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 150 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction, obtains modified bismaleimide
Resin.Obtained prepolymer is put into the vacuum drying chamber that temperature is 150 DEG C and carries out deaeration processing 50min, is subsequently poured into pre-
Heat to 150 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.
Solidification produces the BMI solidified resin that the liquid crystal type allyl compound is modified after terminating.
Embodiment 6
11.39g Isosorbide-5-Nitraes '-two (4- allyloxys benzoic acid) phenyl ester is melted in 170 DEG C of heating, addition 5.44g 2,2 '-
After diallyl bisphenol melting, 18.17g N are added, N ' -4.4 '-diphenyl methane dimaleimide monomer enters in 150 DEG C
Row melting copolymerization, until system turns into homogeneous phase rufous transparency liquid, then insulation reaction, obtains modified bismaleimide
Resin.Obtained prepolymer is put into the vacuum drying chamber that temperature is 150 DEG C and carries out deaeration processing 50min, is subsequently poured into pre-
Heat to 150 DEG C and apply wipe releasing agent mould in solidified, curing process be 180 DEG C/1h+210 DEG C/2h+250 DEG C/6h.
Solidification produces the BMI solidified resin that the liquid crystal type allyl compound is modified after terminating.
The mechanical property and heat resistance of various embodiments of the present invention are contrasted with control group, comparing result is respectively such as table
Shown in I and Table II：
Table I is modified the mechanical property parameters of span system solidfied material
According to above-mentioned Table I data display, in contrast to using 2 merely, 2 '-diallyl bisphenol is to bimaleimide resin
It is modified, the toughness and intensity of the bimaleimide resin that liquid crystal type allyl compound prepared by the present invention is modified are obtained
Significantly improve.
Table II modified quartz sand system solidfied material Thermal Decomposition Parameters
According to upper Table II data display, in contrast to using 2 merely, 2 '-diallyl bisphenol enters to bimaleimide resin
Row is modified, and the bimaleimide resin base that liquid crystal type allyl compound prepared by the present invention is modified originally maintains original excellent
Different heat resistance.
Claims (3)
1. a kind of preparation method for the bimaleimide resin that liquid crystal type allyl compound is modified, it is characterised in that this pair
Maleimide resin includes 1,4- bis- (4- allyloxys benzoic acid) phenyl ester class liquid crystal type allyl compound, 2,2 '-diene
Propyl group bisphenol-A and BMI；Specifically preparation method is：First by 1,4- bis- (4- allyloxys benzoic acid) phenyl ester class liquid
The heating melting of crystal formation allyl compound；But add 2,2 '-diallyl bisphenol and stir；Span is finally added portionwise
Carry out dant monomer and stir 30~90min of pre-polymerization in 130 DEG C~160 DEG C, until system turns into homogeneous rufous transparency liquid；It is cold
But to room temperature, the bimaleimide resin of liquid crystal type allyl compound modification is obtained；
The amount of the bismaleimide monomer material and 2,2 '-diallyl bisphenol and (the 4- allyloxy benzene first of 1,4- bis-
Acid) the ratio between the amount of phenyl ester class liquid crystal type allyl compound total material is 1:0.87；
Described 2,2 '-diallyl bisphenol and 1,4- bis- (4- allyloxys benzoic acid) phenyl ester class liquid crystal type pi-allyl chemical combination
Thing mol ratio is 1:0.1~0.6.
2. preparation method according to claim 1, it is characterised in that described Isosorbide-5-Nitrae-two (4- allyloxys benzoic acid) benzene
Ester liquid crystal type allyl compound is 1,4- bis- (4- allyloxys benzoic acid) phenyl ester, 2- methyl isophthalic acids, (the 4- allyloxys of 4- bis-
Benzoic acid) phenyl ester, 2- ethyls -1,4- two (4- allyloxys benzoic acid) phenyl ester, (the 4- allyloxy benzene of the 2- tert-butyl groups -1,4- two
Formic acid) phenyl ester, 2- nitros -1,4- two (4- allyloxys benzoic acid) phenyl ester, the chloro- 1,4- bis- of 2- (4- allyloxys benzoic acid) benzene
The bromo- 1,4- bis- of ester, 2- (4- allyloxys benzoic acid) phenyl ester, 2,5- dimethyl -1,4- two (4- allyloxys benzoic acid) phenyl ester,
2,6- dimethyl -1,4- two (4- allyloxys benzoic acid) phenyl ester, 2,6- di-t-butyls -1,4- two (4- allyloxys benzoic acid)
The chloro- 1,4- bis- of phenyl ester, 2,3,5,6- tetra- (4- allyloxys benzoic acid) phenyl ester, bromo- (the 4- allyloxys of 1,4- bis- of 2,3,5,6- tetra-
Benzoic acid) phenyl ester, the fluoro- 1,4- bis- of 2,3,5,6- tetra- (4- allyloxys benzoic acid) phenyl ester, the fluoro- (3- of 1,4- bis- of 2,3,5,6- tetra-
Methyl -4- allyloxys benzoic acid) one kind in phenyl ester or mixture.
3. preparation method according to claim 1 or 2, it is characterised in that described BMI is N, N '-
4.4 '-diphenyl methane dimaleimide, N, one or both of N '-penylene BMI mixture.
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| CN106977717B (en) * | 2017-04-26 | 2019-03-26 | 黑龙江省科学院石油化学研究院 | A kind of ester group compound containing alkenyl and preparation method thereof and the bimaleimide resin being modified using it |
| CN109988305A (en) * | 2017-12-29 | 2019-07-09 | 深圳光启尖端技术有限责任公司 | Modified bismaleimide resin and preparation method thereof |
| CN110684353B (en) * | 2019-09-24 | 2021-12-03 | 江苏立一新材料科技有限公司 | High-performance friction material and application thereof |
| CN110734546B (en) * | 2019-09-24 | 2021-12-10 | 江苏立一新材料科技有限公司 | Self-repairing wear-resistant material and application thereof |
| CN110746776B (en) * | 2019-09-24 | 2021-12-10 | 江苏立一新材料科技有限公司 | Flame-retardant wear-resistant material and application thereof |
| CN110643321B (en) * | 2019-09-24 | 2022-03-29 | 苏州益可泰电子材料有限公司 | Electronic material glue solution and application thereof |
| CN112480669B (en) * | 2020-11-05 | 2022-10-14 | 航天特种材料及工艺技术研究所 | High-toughness and high-temperature-resistant bismaleimide resin and preparation method thereof |
| CN112662178A (en) * | 2020-12-22 | 2021-04-16 | 广东盈骅新材料科技有限公司 | Modified bismaleimide prepolymer and preparation and application thereof |
| CN113831461B (en) * | 2021-09-28 | 2023-11-21 | 泉州师范学院 | Bismaleimide/acrylic acid liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
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| EP1016659B1 (en) * | 1998-12-29 | 2003-09-24 | Dainippon Ink And Chemicals, Inc. | Bismaleimides comprising mesogenic groups and oligomeric liquid crystalline bismaleimides |
| CN101768269B (en) * | 2008-12-29 | 2012-07-18 | 沁阳市天益化工有限公司 | Bismaleimides resin pre-polymer preparation method |
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Application publication date: 20151014 Assignee: Jiangsu Xinyang new material Limited by Share Ltd Assignor: Dalian University of Technology Contract record no.: 2019320010013 Denomination of invention: Preparation method of liquid-crystal allyl-compound-modified bismaleimide resin Granted publication date: 20170711 License type: Exclusive License Record date: 20190328 |
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