CN103881069B - The manufacture of low-k bimaleimide resin - Google Patents
The manufacture of low-k bimaleimide resin Download PDFInfo
- Publication number
- CN103881069B CN103881069B CN201410130088.9A CN201410130088A CN103881069B CN 103881069 B CN103881069 B CN 103881069B CN 201410130088 A CN201410130088 A CN 201410130088A CN 103881069 B CN103881069 B CN 103881069B
- Authority
- CN
- China
- Prior art keywords
- aryl
- resin
- substituted
- unsubstituted
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *c(c(*)c1N)c(*)c(CC=CN)c1N Chemical compound *c(c(*)c1N)c(*)c(CC=CN)c1N 0.000 description 1
Abstract
The invention provides the preparation method of a kind of low-k BMI, specifically, described method is by bismaleimide monomer and the fluorinated aromatic hydrocarbon copolymerization containing pi-allyl, it is thus achieved that modified bismaleimide resin.Prepared resin not only shows relatively low dielectric constant, and has relatively low solidification temperature, can be as high-temperature-resistant adhesive and electric industry as the encapsulating material of electronic devices and components and lamination matrix resin.
Description
Technical field
The invention belongs to high-performance polymer material and manufacture field, be specifically related to a kind of low-k span and come
Imide resin manufacture method.
Background technology
BMI because of when it heats can autohemagglutination, can't release little molecule volatile matter, polymerizate has
There are higher heat resisting temperature and preferable electrical insulation capability, are that in existing thermosetting resin, performance and price valency compares
High kind.But, BMI autohemagglutination purely the material fragility formed is relatively big, therefore,
It must be carried out toughening modifying.It is modified double that the most business-like modified resin is mainly diallyl bisphenol
Maleimide resin and binary Modified by Aromatic Amines bimaleimide resin.I.e. virgin resin is carried out chain extension,
Thus reduce the crosslink density of resin.Comparing with virgin resin, the toughness of the modified resin after chain extension significantly carries
High.So the bimaleimide resin of modification is as fibrous composite matrix resin, encapsulating material etc.,
It is widely used in the industry such as Aero-Space and electronic apparatus.
Except toughness not in addition to, the dielectric constant of pure bimaleimide resin is the highest, generally reaches 3.5.
Along with a large amount of manufactures of high frequency printed circuit board, the demand of low-k matrix resin is got over by relevant industries
Come the biggest, thus modified bismaleimide resin traditionally can not fully meet requirement, need to develop low
The kind of dielectric constant.
Known fluorine-containing organic material is generally of relatively low dielectric constant, and fluoro-containing group is introduced bismaleimide
In amine molecule, low-k BMI can be obtained in theory.It practice, have been reported entirely
Fluoroalkyl or trifluoromethyl introduce in bimaleimide resin, it is thus achieved that fluorine-containing bimaleimide resin tool
There are low dielectric constant and preferable heat resistance.But, these attempt the system of the fluorine-bearing modifier used
Standby process is loaded down with trivial details, cost of material is higher, limits its application.
In sum, this area still lacks one and prepares simplicity, and cost of material is low, has good thermostability
Can be with the bimaleimide resin of low-k.
Summary of the invention
It is an object of the invention to provide one and prepare simplicity, cost of material is low, have good heat resistance and
The bimaleimide resin of low-k.
A first aspect of the present invention, it is provided that a kind of side preparing low-k bimaleimide resin
Method, described method includes step:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
To low-k bimaleimide resin:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
In another preference, described R1Group selected from being constituted with the substituent group shown in following formula 1-16:
In another preference, in described step, described compound of formula I and described Formula II chemical combination
The mol ratio of thing is 1:0.1～15, preferably 1:1～12.
In another preference, described compound of formula I is 1 with the mol ratio of described Formula II compound:
1～9.
In another preference, in described step, described reaction temperature is 10 (room temperatures)～180 DEG C.
In another preference, in described step, the described response time is 5～20 hours.
In another preference, in described step, described polyreaction is polymerisation in bulk, or described
Polyreaction is carried out in the presence of an organic；It is preferred that described organic solvent be toluene, dimethylbenzene,
Trimethylbenzene, diphenyl ether, Ketohexamethylene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl are sub-
Sulfone or N-Methyl pyrrolidone, or a combination thereof.
In another preference, in described step, described compound of formula I is prepared by the following method:
In atent solvent, react with phenyl-pentafluoride and halogenated allyl compound, obtain compound of formula I；
In formula, R=H or phenyl；X is halogen, preferably Cl and/or Br.
In another preference, described reaction is deposited at n-BuLi and/or N, N, N, N-tetramethylethylenediamine
Under carry out.
In another preference, described reaction is carried out in organic solvent；It is preferred that described is organic molten
Agent is selected from lower group: oxolane, methyltetrahydrofuran, dioxane, or a combination thereof.More preferably, described
The consumption of solvent and the ratio of phenyl-pentafluoride be 10～100:1 (milliliter: gram).
In another preference, described reaction is carried out under inert gas shielding.
In another preference, described reaction is carried out under-78～30 DEG C (room temperature).
In another preference, the described response time is 10～25 hours.
In another preference, described method also includes: be purified product by decompression distillation mode.
In another preference, in the process, described phenyl-pentafluoride, n-BuLi, N, N, N, N-tetra-
The mol ratio of methyl ethylenediamine and halogenated allyl compound is 1:1～5:1～5:1～5.
A second aspect of the present invention, it is provided that a kind of low-k bimaleimide resin, described tree
Fat is to prepare by method as described in the first aspect of the invention.
In another preference, described resin is insoluble and insoluble.
In another preference, described resin has a repetitive shown in following formula III:
In formula, Ar=
In another preference, described resin is prepared by the following method:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
Low-k bimaleimide resin to as shown in formula III:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Represent multiple cross-linked unit；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
In another preference, described resin is prepared by the following method:
(1) under solvent-free state, or in polar solvent, enter with Formula II compound by compound of formula I
Row reaction, obtains Formula II a compound；It is preferred that described reaction is ene reaction；
(2) under solvent-free state, or in polar solvent, enter with compound of formula I with Formula II a compound
Row reaction, obtains Formula II b compound；It is preferred that described reaction is Diels-Alder reaction；
(3) under solvent-free state, or in polar solvent, carry out with compound of formula I with Formula II b compound
Reaction, obtains the low-k bimaleimide resin shown in formula III:
In formula, each group is as defined above.
In another preference, described resin has one or more features selected from lower group:
The dielectric constant of described resin is 2.4-2.9；
The dielectric loss angle tangent of described resin is≤6 ‰, preferably≤5.8 ‰；More preferably, described tree
The dielectric loss angle tangent of fat is 3-5.8 ‰.
5% weight loss temperature of described resin is >=350 DEG C, preferably >=400 DEG C；More preferably, described
5% weight loss temperature of resin is >=450 DEG C.
A third aspect of the present invention, it is provided that a kind of goods, described goods contain such as second aspect present invention institute
The resin stated, or described goods are standby by resin-made as described in respect of the second aspect of the invention.
In another preference, described goods are selected from lower group: microelectronics and/or printed circuit board (PCB) encapsulating material,
Lamination matrix resin.
In another preference, described goods are fibre-reinforced composite products.
In another preference, described goods are prepared by the following method:
Resin as described in respect of the second aspect of the invention is shaped, obtains described goods；
Preferably, described goods are by being prepared selected from (a), (b), any one method of (c):
A resin as described in respect of the second aspect of the invention is carried out heating and mould pressing molding by (), obtain described goods；
Or (b): provide the organic solvent solution of a resin as described in respect of the second aspect of the invention, with described solution pair
Fiber impregnates, and obtains fibre-reinforced material prepreg；
Described prepreg is shaped, obtains described goods；
In another preference, described organic solvent be selected from lower group: toluene, dimethylbenzene, trimethylbenzene, two
Phenylate, Ketohexamethylene, chloroform, acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, two
Methyl sulfoxide, N-Methyl pyrrolidone, or a combination thereof.
Or (c):
By resin as described in respect of the second aspect of the invention, the method in employing perfusion resin to fiber preform body is (i.e.
Common RTM technique), obtain fibre-reinforced prepreg；
Prepreg is shaped, obtains described goods.
In should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and below (such as embodiment)
Can be combined with each other between each technical characteristic of middle specific descriptions, thus constitute new or preferred technical side
Case.As space is limited, the most tired at this state.
Detailed description of the invention
The present inventor is through in-depth study for a long time, it has unexpectedly been found that, use containing phenyl-pentafluoride construction unit
Allyl deriv and bismaleimide aminated compounds react, a class can be prepared with low cost,
Preparation method is simple, and have low dielectric constant and good heat resistance (5% weight loss temperature for >=
350 DEG C, preferably >=400 DEG C；Be more preferably >=450 DEG C) bimaleimide resin.Based on above-mentioned
Existing, inventor completes the present invention.
Term
Unless stated otherwise, in the application, shape is such asOrWays of writing, all
Represent, on any one carbon atom (1,2,3,4,5,6) of this aromatic ring (preferably phenyl ring), there is this change
Learn key or this R base substituent group.
As used herein, term " alkyl of C1-C30 " refers to the straight or branched with 1-30 carbon atom
Alkyl (including alkylidene), such as methyl, ethyl, propyl group, normal-butyl, isobutyl group, the tert-butyl group, or class
Like group.
Term " aryl of C1-C30 " refers to the aryl (including arlydene) with 1-30 carbon atom or contains
Aryl as heteroatomic in S, N, O etc. (includes arlydene), as phenyl, phenylene, pyridine radicals, furyl,
Naphthyl, or similar group.
Term " aryl-carbonyl-aryl of C3-C30 " refers to have 3-30 carbon atom, and have aryl-
The group of carbonyl-heteroaryl structure, wherein, aryl defined as described above, representational example is such as
Term " aryl-oxygen-aryl of C2-C30 " refers to have 2-30 carbon atom, and have aryl-oxygen-
The group of heteroaryl structure, wherein, aryl defined as described above, representational example is such as
Term " aryl-sulfur-aryl of C2-C30 " refers to have 2-30 carbon atom, and have aryl-sulfur-
The group of heteroaryl structure, wherein, aryl defined as described above, representational example is such as
Term " aryl-sulfuryl-aryl of C2-C30 " refers to have 2-30 carbon atom, and have aryl-
The group of oxygen-heteroaryl structure, wherein, aryl defined as described above, representational example is such as
Term " haloalkyl of C1-C4 " refers to have 1-4 carbon atom, and the one or more hydrogen on group
The alkyl that atom is substituted with halogen atoms, such as trifluoromethyl, Dichloroethyl, or similar group.
Term " aryl-epoxide of C1-C10 " refers to have 1-10 carbon atom, and has such as " aryl-O-"
The substituent group of structure, such asOr similar group.
Term " halo " refers to that the one or more hydrogen atoms on group are substituted with halogen atoms, wherein, described
Halogen atom selected from lower group: fluorine, chlorine, bromine, iodine.
The bimaleimide resin of low-k
The invention provides the bimaleimide resin of a class low-k, described resin is with as follows
Shown compound of formula I (the substituted fluorine-containing aromatic hydrocarbons of pi-allyl) and Formula II compound (bismaleimide amine chemical combination
Thing) carry out copolymerization acquisition:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
In another preference, described R1Group selected from being constituted with the substituent group shown in following formula 1-16:
The end-state of resin of the present invention is not melt and insoluble solid.
The structure of the resin of the present invention is likely to be of multiple version, in a preference, and described tree
Fat has a repetitive shown in following formula III:
Wherein,Represent multiple cross-linked unit；
Or described resin has following formula III ' shown in formula:
In formula,
The degree of polymerization (i.e. n) of described resin is >=2, preferably >=5；
In another preference, preparing of described resin is as follows:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
Low-k bimaleimide resin to as shown in formula III:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
The preparation process of described resin has no particular limits, and generally carries out copolymerization i.e. according to the condition of the present invention
Can obtain.Especially, under a kind of preferable case of the present invention, the preparation of described resin includes following step
Rapid:
(1) under solvent-free state, or in polar solvent, enter with Formula II compound by compound of formula I
Row reaction, obtains Formula II a compound；It is preferred that described reaction is ene reaction；
(2) under solvent-free state, or in polar solvent, enter with compound of formula I with Formula II a compound
Row reaction, obtains Formula II b compound；It is preferred that described reaction is Diels-Alder reaction；
(3) under solvent-free state, or in polar solvent, carry out with compound of formula I with Formula II b compound
Reaction, obtains the low-k bimaleimide resin shown in formula III:
In formula, each group is as defined above.
Described resin has relatively low dielectric constant, in a preference of the present invention, and described resin
There are the one or more features selected from lower group:
The dielectric constant of described resin is 2.4-2.9；
The dielectric loss angle tangent of described resin is≤6 ‰, preferably≤5.8 ‰；More preferably, described tree
The dielectric loss angle tangent of fat is 3-5.8 ‰.
5% weight loss temperature of described resin is >=350 DEG C, preferably >=400 DEG C；More preferably, described
5% weight loss temperature of resin is >=450 DEG C.
The method preparing low-k bimaleimide resin
Present invention also offers a kind of method preparing low-k bimaleimide resin, including step
Rapid:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
To low-k bimaleimide resin:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
In another preference, described R1Group selected from being constituted with the substituent group shown in following formula 1-16:
In another preference, in described step, described compound of formula I and described Formula II chemical combination
The mol ratio of thing is 1:0.1～15, preferably 1:0.5～12.
In another preference, in described step, described reaction temperature is 10 (room temperatures)～180 DEG C.
In another preference, in described step, the described response time is 10～20 hours.
In described step, described polyreaction is polymerisation in bulk, or described polyreaction is organic molten
Carry out in the presence of agent；It is preferred that when described polyreaction is carried out in the presence of an organic, described
Organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, N,N-dimethylformamide, N, N-
Dimethyl acetylamide, dimethyl sulfoxide or N-Methyl pyrrolidone, or a combination thereof.
Described each raw material can be prepared by any approach, such as commercially available or conventional method.It is preferred that
In described step, described compound of formula I is prepared by the following method:
In atent solvent, react with phenyl-pentafluoride and halogenated allyl compound, obtain compound of formula I；
In formula, R=H or phenyl；X is halogen, preferably Cl and/or Br.
In another preference, described reaction is deposited at n-BuLi and/or N, N, N, N-tetramethylethylenediamine
Under carry out.
In another preference, described reaction is carried out in organic solvent；It is preferred that described is organic molten
Agent is selected from lower group: oxolane, methyltetrahydrofuran, dioxane, or a combination thereof.More preferably, described
The consumption of solvent and the ratio of phenyl-pentafluoride be 10～100:1 (milliliter: gram).
In another preference, described reaction is carried out under inert gas shielding.
In another preference, described reaction is carried out under-78～30 DEG C (room temperature).
In another preference, the described response time is 10～25 hours.
In another preference, described method also includes: be purified product by decompression distillation mode.
In another preference, in the process, described phenyl-pentafluoride, n-BuLi, N, N, N, N-tetra-
The mol ratio of methyl ethylenediamine and halogenated allyl compound is 1:1～5:1～5:1～5.
Main advantages of the present invention include:
(1) provide fluorine modified bismaleimide resin, due to the present invention containing fluorine richness span
Bismaleimide resin does not use fluorine-containing dianhydride or diamidogen synthesis (the fluorine-containing BMI of intrinsic), therefore
Low cost, is suitable for industrialized production.
(2) present invention uses the mode of additional fluorine-bearing modifier to improve the dielectricity of bimaleimide resin
Can, reducing while cost, its dielectric constant is maintained at 2.4-2.9, and has reported
The dielectric constant of the fluorine-containing bimaleimide resin of intrinsic in road is suitable.
(3) fluorine-bearing modifier that the present invention is additional can be by commercially available phenyl-pentafluoride and pi-allyl halides one
Step synthesis, method is simple, and source is wide, with low cost.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate
The present invention rather than restriction the scope of the present invention.The experiment side of unreceipted actual conditions in the following example
Method, generally according to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise
Percentage ratio and number are calculated by weight.
The synthesis of embodiment 1 cinnamene phenyl-pentafluoride
Under dry ice acetone bath (-78oC) cools down, add in the 1000 milliliters of bottle with two necks substituting gas 3 times
100 milliliters of oxolanes and 5.8g N, N, N, N-tetramethylethylenediamine (TMEDA) (0.05mol).Stir evenly
After, in mixture, drip 20 milliliters of n-BuLis (0.05mol).After stirring 30 minutes, to mixture
In be slowly added dropwise phenyl-pentafluoride 8.4g (0.05mol).Drip off, after mixture continues stirring 30 minutes, to mixed
Compound drips 14.8 grams of Cortex Cinnamomi bromides (0.075mol) solution in oxolane (100 milliliters), drips
Complete, stir 1 hour under-78oC, then, remove cryostat, reaction system is warmed to room temperature naturally, and
Stir 15 hours under room temperature.Reactant liquor goes out with 200 milliliters of shrends, then with 20 milliliters of ethyl acetate extractions
Reactant liquor, collects organic facies, uses Na2SO4Remove solvent, crude product column chromatography (60～90oC stones after drying
Oil ether eluting), yield 60%.1H NMR(400MHz,CDCl3): 7.32～7.19 (m, 5H), 6.47～
6.43 (d, 1H), 6.23～6.16 (m, 1H), 3.59～3.57 (d, 2H).19F NMR(376MHz,
CDCl3) :-143.90～-143.98 (dd, 2F) ,-157.21～-157.32 (t, 1F),
-162.39(ddd,2F).MS(EI,m/z):284.2[M]+.Anal.Calcd for C15H9F5:C,
63.39,H,3.19,F,33.42;found:C,63.62,H,3.18,F,33.56.
The preparation of embodiment 2 modified bismaleimide solidification resin and dielectric constant test thereof
Cinnamyl five fluorine that 3.2 grams of g (9mmol) diphenyl methane dimaleimides and embodiment 1 are obtained
Benzene (0.28g, 1mmol) is finely ground, mix homogeneously, adds in reaction tube, substitutes gas 3 times.Press from room temperature
50 DEG C are warming up to 180 DEG C per hour, keep 10 hours, obtain the modified double maleoyl of transparent buff
Imines solidification resin.
Utilizing the dielectric constant of capacitance method test solidification resin, result shows, in 10kHz～30MHz scope,
The dielectric constant range of resin is 2.90-2.75, and corresponding dielectric loss angle tangent is 5.8/1000ths.
The preparation of embodiment 3 modified bismaleimide solidification resin and dielectric properties test thereof
Cinnamyl five fluorine that 1.79g (5mmol) diphenyl methane dimaleimide and embodiment 1 are obtained
Benzene (1.42g, 5mmol) is finely ground, mix homogeneously, adds in reaction tube, substitutes gas 3 times.From room temperature
50 DEG C are warming up to 160 DEG C on an hourly basis, keep 20 hours, obtain transparent yellow modified bismaleimide
Amine solidification resin.
Utilizing the dielectric constant of capacitance method test solidification resin, result shows, in 10kHz～30MHz scope,
The dielectric constant range of resin is 2.62-2.54, and corresponding dielectric loss angle tangent is 3.5/1000ths.
The preparation of embodiment 4 modified bismaleimide solidification resin and dielectric constant test thereof
By 1.8 grams of g (5mmol) Diphenyl Ether Bismaleimides (according to document " diaminodiphenyl ether span
Come imido synthesis and sign ", insulant, 2008,41(2), method synthesis described in 19-21)
Finely ground with the cinnamyl phenyl-pentafluoride (0.28g, 1mmol) that embodiment 1 obtains, mix homogeneously, add reaction
Guan Zhong, substitutes gas 3 times.From room temperature on an hourly basis 50 DEG C be warming up to 180 DEG C, keep 10 hours,
To transparent buff modified bismaleimide solidification resin.
Utilizing the dielectric constant of capacitance method test solidification resin, result shows, in 10kHz～30MHz scope,
The dielectric constant range of resin is 2.86-2.74, and corresponding dielectric loss angle tangent is 5.2/1000ths.
Comparative example: the preparation of pure BMI solidification resin and dielectric properties test thereof
By finely ground for 5g diphenyl methane dimaleimide, add in test tube, substitute gas 3 times.Press from room temperature
50 DEG C are warming up to 180 DEG C per hour, keep 10 hours, obtain transparent buff BMI
Solidification resin.
Utilizing the dielectric constant of capacitance method test solidification resin, result shows, in 10kHz～30MHz scope,
The dielectric constant range of resin is 2.99-2.91, and corresponding dielectric loss angle tangent is 6.2/1000ths.
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each document
It is individually recited as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention,
The present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within this Shen equally
Please appended claims limited range.
Claims (15)
1. the method preparing low-k bimaleimide resin, it is characterised in that include step
Rapid:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
To low-k bimaleimide resin:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10；Described compound of formula I and described Formula II
The mol ratio of compound is 1:0.1～15.
2. the method for claim 1, it is characterised in that in described step, described Formulas I
Compound is 1:1～12 with the mol ratio of described Formula II compound.
3. the method for claim 1, it is characterised in that in described step, described polymerization
Reaction is polymerisation in bulk, or described polyreaction is carried out in the presence of an organic.
4. the method for claim 1, it is characterised in that described organic solvent be toluene, two
Toluene, trimethylbenzene, diphenyl ether, Ketohexamethylene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, two
Methyl sulfoxide or N-Methyl pyrrolidone, or a combination thereof.
5. the method for claim 1, it is characterised in that in described step, described Formulas I
Compound is prepared by the following method:
In atent solvent, react with phenyl-pentafluoride and halogenated allyl compound, obtain compound of formula I；
In formula, R=H or phenyl；X is halogen.
6. method as claimed in claim 5, it is characterised in that X is Cl and/or Br.
7. a low-k bimaleimide resin, it is characterised in that described resin is with such as
Prepared by the arbitrary described method of claim 1-6.
8. resin as claimed in claim 7, it is characterised in that described resin is by the following method
Preparation:
With compound shown in formula I, carry out polyreaction with the compound as shown in Formula II, thus obtain
Low-k bimaleimide resin to as shown in formula III:
In formula, R=H or phenyl；
R1Selected from lower group: the alkyl of substituted or unsubstituted C1-C30, substituted or unsubstituted C1-C30
Aryl, the aryl-alkyl of substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 aryl-
Alkyl-aryl-group, the aryl-carbonyl-aryl of substituted or unsubstituted C3-C30, substituted or unsubstituted C2-C30
Aryl-oxygen-aryl, the aryl-sulfur-aryl of substituted or unsubstituted C2-C30, substituted or unsubstituted
Aryl-sulfuryl-the aryl of C2-C30；
Represent multiple cross-linked unit；
Ar=
Wherein, described replacement refers to be selected from one or more groups of lower group and replaces: the alkyl of C1-C4,
The haloalkyl of C1-C4, the aryl-epoxide of C1-C10.
9. resin as claimed in claim 7, it is characterised in that described resin has selected from lower group
One or more features:
The dielectric constant of described resin is 2.4-2.9；
The dielectric loss angle tangent of described resin is≤6 ‰；
5% weight loss temperature of described resin is >=350 DEG C.
10. resin as claimed in claim 7, it is characterised in that described resin has selected from lower group
One or more features:
The dielectric loss angle tangent of described resin is≤5.8 ‰；
5% weight loss temperature of described resin is >=400 DEG C.
11. resins as claimed in claim 7, it is characterised in that described resin has selected from lower group
One or more features:
The dielectric loss angle tangent of described resin is 3-5.8 ‰；
5% weight loss temperature of described resin is >=450 DEG C.
12. 1 kinds of goods, it is characterised in that described goods contain resin as claimed in claim 7, or institute
The goods stated are standby by resin-made as claimed in claim 7.
13. goods as claimed in claim 12, it is characterised in that described goods are prepared by the following method:
Resin as claimed in claim 7 is shaped, obtains described goods.
14. goods as claimed in claim 13, it is characterised in that described goods by selected from (a), (b),
C any one method of () is prepared:
A resin as claimed in claim 7 is carried out heating and mould pressing molding by (), obtain described goods；
Or (b): the organic solvent solution of a resin as claimed in claim 7 is provided, with described solution, fiber is entered
Row dipping, obtains fibre-reinforced material prepreg；
Described prepreg is shaped, obtains described goods；
Or (c):
By resin as claimed in claim 7, the method in employing perfusion resin to fiber preform body, obtain fibre
The prepreg that dimension strengthens；
Prepreg is shaped, obtains described goods.
15. goods as claimed in claim 14, it is characterised in that in method (b), described organic solvent
Selected from lower group: toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, chloroform, acetone, N, N-
Dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, or a combination thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410130088.9A CN103881069B (en) | 2014-04-01 | 2014-04-01 | The manufacture of low-k bimaleimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410130088.9A CN103881069B (en) | 2014-04-01 | 2014-04-01 | The manufacture of low-k bimaleimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881069A CN103881069A (en) | 2014-06-25 |
| CN103881069B true CN103881069B (en) | 2016-08-17 |
Family
ID=50950223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410130088.9A Expired - Fee Related CN103881069B (en) | 2014-04-01 | 2014-04-01 | The manufacture of low-k bimaleimide resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881069B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060116476A1 (en) * | 2004-12-01 | 2006-06-01 | 3M Innovative Properties Company | Hybrid thermosetting composition |
| CN102363607B (en) * | 2011-11-28 | 2013-01-02 | 中国科学院上海有机化学研究所 | Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium |
-
2014
- 2014-04-01 CN CN201410130088.9A patent/CN103881069B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881069A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1278396C (en) | Polyimide resin composition | |
| KR101953369B1 (en) | Polymerizable composition | |
| Wan et al. | Preparation and properties of a novel polytriazole resin | |
| Nikitin et al. | Restricted rotation in 9-phenyl-anthracenes: A prediction fulfilled | |
| CN104017214B (en) | Light-coloured transparent polyimides based on meta-terphenyl structure diamidogen and its preparation method and application | |
| JP6831012B2 (en) | Dianhydride compounds having a hard alicyclic fluorine-containing structure and their preparation methods and applications | |
| RU2702630C2 (en) | Benzoxazines and compositions containing same | |
| EP3211023A1 (en) | Phthalonitrile monomer modified with organosilicon fragments | |
| TWI705064B (en) | Curable compositions containing benzoxazine epoxy blend and use thereof | |
| CN104628544B (en) | Propenylbenzene oxo-compound of a kind of three branch's aromatic structures and preparation method thereof and the bimaleimide resin utilizing its modification | |
| CN104130409B (en) | A kind of preparation method of phenolphthalein type polyimides | |
| CN111423584B (en) | Preparation method of bismaleimide containing adamantane structure | |
| CN106928116B (en) | Preparation method of 2, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane | |
| CN103131008A (en) | Bismaleimide prepolymer and synthesis method thereof | |
| CN103881069B (en) | The manufacture of low-k bimaleimide resin | |
| JP2759796B2 (en) | Novel bis (maleimide) siloxane and method for producing the same | |
| CN102617857A (en) | Polyimide and preparation process thereof | |
| WO1992012967A1 (en) | Bisimide compounds, polyimide resin composition prepared therefrom, and carbon fiber-reinforced polyimide resin composition | |
| CN101602856A (en) | Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes | |
| CN103524746A (en) | Borazine aryne resin and preparation method thereof | |
| CN106279688A (en) | Thermoset polyimide resin and its preparation method and application | |
| JPH0299508A (en) | Thermosetting bismaleimide resin | |
| CN113402500A (en) | Polyimide modifier and resin composition containing same | |
| CN104311401B (en) | Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof | |
| CN104130412B (en) | A kind of N replaces polybenzimidazoles acid imide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20200401 |