CN101880363A - Allylation hyperbranched polyphenyl ether modified bismaleimide resin and preparation method thereof - Google Patents
Allylation hyperbranched polyphenyl ether modified bismaleimide resin and preparation method thereof Download PDFInfo
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- CN101880363A CN101880363A CN 201010223700 CN201010223700A CN101880363A CN 101880363 A CN101880363 A CN 101880363A CN 201010223700 CN201010223700 CN 201010223700 CN 201010223700 A CN201010223700 A CN 201010223700A CN 101880363 A CN101880363 A CN 101880363A
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Abstract
The invention discloses an allylation hyperbranched polyphenyl ether modified bismaleimide resin and a preparation method thereof. The method for preparing the resin comprises the following steps of: according to the molar ratio, stirring 100 parts of bismaleimide and 30 to 85 parts of diallylphenyl compound at the temperature of between 110 and 140 DEG C until the mixture is transparent; adding 1 to 55 parts of allylation hyperbranched polyphenyl ether into the mixture; and reacting for 20 to 100 minutes at the temperature of between 110 and 140 DEG C and cooling so as to obtain the allylation hyperbranched polyphenyl ether modified bismaleimide resin. The method for synthesizing the allylation hyperbranched polyphenyl ether by adopting dimethyl sulfoxide and other weak polar solvents has the advantages of simple process, rich raw materials, high yield, and the capacity of meeting the requirement on mass production. The prepared modified bismaleimide resin has the advantages of excellent toughness, heat resistance, wet resistance and higher dielectrical property (low dielectric constant and dielectric loss). The preparation method for the modified bismaleimide resin also has the characteristics of simple process and easy control.
Description
Technical field
The present invention relates to a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin and preparation method thereof, belong to polymeric material field.
Background technology
Bismaleimides (BMI) resin has excellent thermotolerance, humidity resistance, dielectric properties, good mechanical performance and dimensional stability, therefore is widely used in numerous high-technology fields such as aerospace, electronic apparatus, communications and transportation as high-performance tackiness agent, advanced composite material resin matrix, insullac etc.But BMI cured article fragility is big, and since the seventies in 20th century, the toughening modifying of BMI is the research emphasis of performance resins just always.Adopting high-performance thermoplastic resin modified thermosetting resin is the toughness reinforcing main path of thermosetting resin, and polyethersulfone, polyaryletherketone, poly-glycolylurea, polyarylether, polyimide and polybenzimidazole etc. have been used for modified BMI resin at present.But problem of these system ubiquities promptly because high-performance thermoplastic resin melt viscosity is big, poor with the consistency of BMI, therefore is difficult for obtaining finely dispersed system.Though people also once improved consistency with thermosetting resin by thermoplastic polymer functionalized, the complex process that thermoplastic polymer is functionalized, industrial prospect is less.Therefore, how to research and develop and a kind ofly be easy to industrialized novel high tenacity BMI resin and have important use and be worth.
Polyphenylene oxide (PPO) is a kind of high-performance thermoplastic engineering plastics, has outstanding dielectric properties (low-k and dielectric loss factor), wet fastness, good thermotolerance and dimensional stability.But there are problems such as melt temperature height, fluidity of molten difference in the PPO resin, is difficult to use in the BMI modification.
Hyper-branched polyphenyl ether (HBPPO) has not only been inherited the advantage of PPO, and has characteristics such as the low melt viscosity of hyperbranched polymer, high rheological, high resolution.In addition, if HBPPO has suitable active function groups, then be expected effectively to solve the shortcoming of existing high-performance thermoplastic polymer modification BMI resin, and obtain novel high-performance BMI resin.
Before the present invention makes, it is solvent with the alkali metal hydrogen oxidation thing aqueous solution that Chinese invention patent " a kind of allylation hyperbranched polyphenyl ether and preparation method thereof " (CN101717503A) discloses a kind of, the method of the hyper-branched polyphenyl ether of preparation allyl capped, characteristics with environmental protection, but the productive rate of the prepared product of this method is lower, is unfavorable for extensive industrialization.For allylation hyperbranched polyphenyl ether being applied to not appearing in the newspapers of BMI modification.
Summary of the invention
The object of the present invention is to provide a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin and preparation method thereof with good consistency and melt viscosity, good manufacturability, outstanding toughness, resistance toheat, wet fastness and more excellent dielectric properties.
For achieving the above object, technical scheme of the present invention is: a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin is provided, by mole, its component ratio is 100 parts of bismaleimidess, 30～85 parts of diallyl phenyl compounds and 1～55 part of allylation hyperbranched polyphenyl ether.
The preparation method of above-mentioned allylation hyperbranched polyphenyl ether modified bismaleimide resin comprises the steps:
(1) by weight, having the hyper-branched polyphenyl ether of phenolic hydroxyl group, 1～100 part of alkali metal hydroxide and 0～10 part of quaternary ammonium salt phase transfer catalyst with 100 parts joins in 50～5000 parts of solvents, in inert atmosphere, be warming up to 50～110 ℃, stirred 0.1～5 hour; Under temperature is 40～90 ℃ condition, dripping 2.5～150 parts of 3-propylene halides again, after dripping off in 0.03～5 hour, is to be incubated 4～12 hours under 50～120 ℃ the condition to react in temperature;
(2) after reaction finishes, be cooled to room temperature, under the agitation condition, the reactant that step (1) is obtained splashes into methyl alcohol or ethanol by volume: water is in 1: 0.5～1: 8 the mixing solutions, after filtering, be that oven dry is handled under 40～80 ℃ the vacuum condition with filter cake, obtain the hyper-branched polyphenyl ether crude product of allylation in temperature;
(3) the hyper-branched polyphenyl ether crude product of the allylation that step (2) is obtained is dissolved in the tetrahydrofuran solution, under agitation condition, it is splashed in the cyclohexane solution again, after filtering, filter cake is that oven dry is handled under 40～120 ℃ the vacuum condition in temperature, promptly obtain a kind of allylation hyperbranched polyphenyl ether, its allyl capped rate is greater than 0, smaller or equal to 100%;
(4), under 110～140 ℃, be stirred to 100 parts of bismaleimidess and 30～85 parts of diallyl phenyl compounds transparent by mole; Adding the allylation hyperbranched polyphenyl ether that 1～55 part of step (3) obtains again, is to react 20～100 minutes postcooling under 110～140 ℃ the condition in temperature, obtains a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
In the technique scheme, described bismaleimides is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether and 4,4 '-a kind of in the dimaleoyl imino sulfobenzide, or their arbitrary combination.Described diallyl phenyl compound is a kind of in diallyl bisphenol, diallyl bisphenol ether and the diallyl bisphenol S, or their arbitrary combination.Described quaternary ammonium salt phase transfer catalyst is benzyltriethylammoinium chloride or Tetrabutyl amonium bromide.Described 3-propylene halide is chlorallylene or 3-bromopropylene.Described solvent is tetrahydrofuran (THF), methyl-sulphoxide, dimethyl formamide or N,N-DIMETHYLACETAMIDE.Described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
Compared with prior art, the beneficial effect that the present invention has is: adopt weak polar solvent synthesis of allyl hyper-branched polyphenyl ethers such as methyl-sulphoxide, this method technology is simple, abundant raw materials, productive rate height, can satisfy the requirement of scale operation.Adopt allylation hyperbranched polyphenyl ether modified BMI resin, overcome shortcomings such as the consistency that traditional hot thermoplastic polymer modified BMI resin exists is poor, melt viscosity is big, prepared modified resin has good manufacturability, outstanding toughness, resistance toheat, wet fastness and more excellent dielectric properties (lower specific inductivity and dielectric loss).The preparation method of modified BMI resin also has the characteristics that technology is simple, be easy to control.
Description of drawings
Fig. 1 is a kind of hyper-branched polyphenyl ether that the embodiment of the invention provides
1H NMR spectrogram;
Fig. 2 is a kind of allylation hyperbranched polyphenyl ether that the embodiment of the invention provides
1H NMR spectrogram;
Fig. 3 is a kind of complete allylation hyperbranched polyphenyl ether that the embodiment of the invention provides
1H NMR spectrogram.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described.
Embodiment one
(1) preparation of hyper-branched polyphenyl ether
Under nitrogen atmosphere, with 2.41g (6.82mmol) 4-bromo-4 ', 4 " dihydroxyl tritane, 1.08g (7.81mmol) anhydrous K
2CO
3Join successively in the 98ml methyl-sulphoxide (DMSO) with 25.0ml toluene, heat up, after the reflux dewatering 3 hours, reaction system be cooled to 45 ℃, add 13.5mg (0.14mmol) Catalysts Cu Cl, be warming up to 170 ℃ and isothermal reaction again 40 hours.After mixed solution is chilled to room temperature, use hcl acidifying, stir after 0.5 hour, splash in first alcohol and water mixing (volume ratio is 1: 8) solution and precipitate, filter 60 ℃ of vacuum-dryings.Crude product is dissolved in a small amount of tetrahydrofuran (THF) (THF), filters, filtrate is precipitated with hexanaphthene, refilter, and the hexanaphthene washing, 90 ℃ of following vacuum-dryings obtain hyper-branched polyphenyl ether.Referring to accompanying drawing 1, it is a kind of hyper-branched polyphenyl ether that present embodiment provides
1H NMR spectrogram, this hyper-branched polyphenyl ether
1H NMR (DMSO-d
6) be: δ 5.29-5.34 (t ,-(Ph)
3CH), δ 6.43-7.63 (br, Ph-H), δ 9.84 (s ,-Ph-OH).As can be seen from FIG. δ=5.29-5.34 be-(Ph)
3Proton peak on the CH, δ=6.43-7.63 corresponds to the proton peak on the phenyl ring, and δ=9.84 correspond to the chemical shift of the proton peak on the phenolic hydroxyl group.
Its structural formula be:
Wherein, 2≤m+n≤12, m and n are positive integer.
Adopt the back titration method, the hydroxyl value of measuring this hyper-branched polyphenyl ether with potassium hydroxide ethanol standardized solution is 15～250mgKOH/g.
(2) preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 1.5g sodium hydroxide and 50g tetrahydrofuran (THF) (THF) that the 100g above-mentioned steps is made drop in the there-necked flask.Be warming up to 50 ℃, stirred 0.1 hour.After being cooled to 40 ℃, begin to drip the 1g3-propenyl chloride, dripped off at 0.03 hour.Then be warming up to 50 ℃, insulation refluxed 10 hours, heated up 60 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into second alcohol and water mixing (volume ratio 1: 8), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 40 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 40 ℃ of following vacuum dryings, and its allyl capped rate is 1%.Because the position of allylation be can not determine, so following just a kind of structural formula of this allylation hyperbranched polyphenyl ether:
(3) preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino ditane and 84 parts of diallyl bisphenols are stirred to transparent under 110 ℃; The allylation hyperbranched polyphenyl ether that adds 1 part of present embodiment step (2) preparation, reaction is after 20 minutes down at 110 ℃, and cooling promptly obtains a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment two
The preparation of allylation hyperbranched polyphenyl ether
Under argon gas atmosphere, under normal temperature, the hyper-branched polyphenyl ether that 100g embodiment one step (1) is made, the potassium hydroxide of 10g, 100g dimethyl formamide (DMF) and 1g Tetrabutyl amonium bromide drop in the there-necked flask.Be warming up to 70 ℃, stirred 1 hour.After being cooled to 40 ℃, begin to drip 10g 3-bromopropylene, dripped off at 0.5 hour; Then be warming up to 60 ℃, insulation refluxed 3 hours, heated up 70 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio is 1: 3), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 50 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 60 ℃ of following vacuum dryings, and its allyl capped rate is 10%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino sulfobenzide and 85 parts of diallyl bisphenol ether are stirred to melt under 125 ℃ transparent; The allylation hyperbranched polyphenyl ether that then adds 18 parts of present embodiment above-mentioned steps preparations reacts 30 minutes postcooling down at 125 ℃, promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment three
The preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 1.5g sodium hydroxide, 150g N,N-DIMETHYLACETAMIDE (DMAc) and 2g benzyltriethylammoinium chloride that 100g embodiment one step (1) is made drop in the there-necked flask.Be warming up to 60 ℃, stirred 0.5 hour.After being cooled to 50 ℃, begin to drip the 20g chlorallylene, dripped off at 2.5 hours.Then be warming up to 60 ℃, insulation refluxed 2 hours, heated up 80 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 1: 2), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 60 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 80 ℃ of following vacuum dryings, and its allyl capped rate is 40%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino sulfobenzide and 85 parts of diallyl bisphenol ether are stirred to melt under 125 ℃ transparent; The allylation hyperbranched polyphenyl ether that then adds 18 parts of present embodiment above-mentioned steps preparations, behind reaction 30min under 125 ℃, cooling promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment four
The preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 50g potassium hydroxide and 2500g DMSO that 100g embodiment one step (1) is made drop in the there-necked flask.Be warming up to 80 ℃, stirred 5 hours.After being cooled to 70 ℃, begin to drip 40g 3-bromopropylene, dripped off at 3 hours.Then be warming up to 80 ℃, insulation refluxed 4 hours, heated up 100 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 1: 0.5), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 70 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains allylation hyperbranched polyphenyl ether at 50 ℃ of following vacuum dryings.
The allyl capped rate of this allylation hyperbranched polyphenyl ether is 85%.Referring to accompanying drawing 2, it is the allylation hyperbranched polyphenyl ether that present embodiment provides
1H NMR spectrogram, its
1H NMR (DMSO-d
6): δ 3.50-4.09 (br ,-CH
2-), δ 4.32-4.69 (br ,=CH
2), δ 4.95-5.66 (br ,-CH=CH
2), δ 5.88-6.14 (t ,-(Ph)
3CH), δ 6.46-7.66 (br, Ph-H), δ 8.48 (s ,-Ph-OH).Can see that from Fig. 2 δ=3.50-4.09 is on the methylene radical-CH
2-proton peak, δ=4.32-4.69 is=CH
2Proton peak, δ=4.95-5.66 is-CH=CH
2Proton peak, δ=5.88-6.14 is-(Ph)
3Proton peak on the CH, the proton peak on the corresponding phenyl ring of δ=6.46-7.66, the chemical shift of the H on the corresponding phenolic hydroxyl group in δ=8.48.Compared to Figure 1, the proton peak of the hydroxyl among Fig. 2 obviously reduces, and allylic proton peak feature is obvious, has proved that hyper-branched polyphenyl ether realized the part allylation.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino ditane and 80 parts of diallyl bisphenol Ss are stirred to melt under 120 ℃ transparent; The hyper-branched polyphenyl ether that then adds the allyl capped of 10 parts of present embodiment above-mentioned steps preparations, behind reaction 40min under 120 ℃, cooling promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment five
The preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 100g sodium hydroxide and 5000g DMSO that 100g embodiment one step (1) is made drop in the there-necked flask.Be warming up to 90 ℃, stirred 2 hours.After being cooled to 45 ℃, begin to drip the 90g chlorallylene, dripped off at 4 hours.Then be warming up to 50 ℃, insulation refluxed 3 hours, heated up 60 ℃ again, and insulation refluxed 2 hours, heated up 110 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 1: 1), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 75 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 80 ℃ of following vacuum dryings, and its allyl capped rate is 90%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino ditane and 69 parts of diallyl bisphenols are stirred to melt under 115 ℃ transparent; The allylation hyperbranched polyphenyl ether that adds 16 parts of present embodiment above-mentioned steps preparations reacts 40 minutes postcooling down at 115 ℃, promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment six
The preparation of allylation hyperbranched polyphenyl ether
Under argon gas atmosphere, under normal temperature, hyper-branched polyphenyl ether, 40g sodium hydroxide and 1000g DMSO that 100g embodiment one step (1) is made drop in the there-necked flask.Be warming up to 80 ℃, stirred 0.5 hour.After being cooled to 40 ℃, begin to drip the 66g chlorallylene, dripped off at 2.5 hours.Then be warming up to 50 ℃, insulation refluxed 2 hours, heated up 60 ℃ again, and insulation refluxed 2 hours, then heated up 80 ℃, and insulation refluxed 2 hours, heated up 100 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 1: 2), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 60 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains allylation hyperbranched polyphenyl ether at 90 ℃ of following vacuum dryings, and its allyl capped rate is 100%.
Referring to accompanying drawing 3, it is the complete allylation hyperbranched polyphenyl ether that present embodiment provides
1H NMR spectrogram, as seen from the figure
1H NMR (CDCl
3): δ 3.60-4.13 (br ,-CH
2-), δ 4.25-4.69 (=CH
2), δ 4.98-5.60 (br ,-CH=CH
2), δ 5.75-6.20 (t ,-(Ph)
3CH), and δ 6.44-7.76 (br, Ph-H).
Correspond to as can be seen from FIG. δ=3.60-4.13 for methylene radical that alkene links to each other on-CH
2-proton peak, δ=4.25-4.69 is=CH
2Proton peak, δ=4.98-5.60 is-CH=CH
2Proton peak, δ=5.75-6.20 is-(Ph)
3Proton peak on the CH, δ=6.44-7.76 corresponds to the proton peak on the phenyl ring, and the spike of δ=7.26 is the residual proton peak of deuterochloroform.Because the chemical shift of the no hydroxyl hydrogen in 8.0-10.0ppm place, can think and the existence of no hydroxyl in the final product promptly realize complete allylation.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 50 part 4,4 '-dimaleoyl imino ditane, 50 part 4,4 '-dimaleoyl imino sulfobenzide and 41 parts of diallyl bisphenols are stirred to melt under 130 ℃ transparent; The hyper-branched polyphenyl ether that adds the allyl capped of 40 parts of present embodiment above-mentioned steps preparations, behind reaction 35min under 130 ℃, cooling promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment seven
(1) preparation of hyper-branched polyphenyl ether
Under the nitrogen environment, add acetone (8mL), 5-(methylol)-1 being equipped with in the circle flask of reflux (because monomer is to photaesthesia, the circle flask needs wrap up with sheet metal), and the 3-dihydroxy-benzene (0.51g, 2.5mmol), K
2CO
3(1.0g, 7.5mmol) (0.04g 0.2mmol), forms suspension with 18-hat (ether)-6.After the reflux 51 hours, add excessive bromotoluene, reheat back flow reaction 12 hours, reaction solution, is dissolved in the methylene dichloride except that after desolvating through underpressure distillation again, through washing 3 times, uses MgSO
4Drying obtains yellow oil.Add diethyl ether, obtain throw out, filtration drying promptly gets the yellow solid hyper-branched polyphenyl ether.Its
1H NMR (DMSO-d
6) δ 3.9-4.3 (br, PhCH
2-Ph), 4.4-5.3 (br, PhCH
2O-), 6.0-7.7 (br, Ar-H), δ 9.50 (s ,-Ph-OH).
The molecular weight of the hyper-branched polyphenyl ether for preparing (Mw) is 500≤Mw≤50000; Adopt the back titration method, the hydroxyl value of measuring this hyper-branched polyphenyl ether with potassium hydroxide ethanol standardized solution is 25～550mgKOH/g.The general formula of this hyper-branched polyphenyl ether is:
Wherein, 2≤x+y≤400, x and y are positive integer.
(2) preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 50g sodium hydroxide and 150g DMF that 100g present embodiment step (1) is made drop in the there-necked flask.Be warming up to 60 ℃, stirred 1 hour.After being cooled to 40 ℃, begin to drip the 13g chlorallylene, dripped off at 0.5 hour.Then be warming up to 55 ℃, insulation refluxed 5 hours, heated up 70 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into second alcohol and water mixing (volume ratio 1: 3), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 50 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 60 ℃ of following vacuum dryings, and its allyl capped rate is 12%.Because the position of allylation be can not determine, only provides a kind of structural formula of this allylation hyperbranched polyphenyl ether below:
(3) preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino phenyl ether and 70 parts of diallyl bisphenols are stirred to melt under 120 ℃ transparent; The allylation hyperbranched polyphenyl ether that adds 15 parts of present embodiment steps (2) preparation reacts 25 minutes postcooling down at 120 ℃, promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment eight
The preparation of the hyper-branched polyphenyl ether of allylation
Under nitrogen atmosphere, under normal temperature, hyper-branched polyphenyl ether, 100g sodium hydroxide, 500gDMAc and 5g Tetrabutyl amonium bromide that 100g embodiment seven steps (1) are made drop in the there-necked flask.Be warming up to 70 ℃, stirred 3 hours.After being cooled to 60 ℃, begin to drip 45g 3-bromopropylene, dripped off at 1 hour.Then be warming up to 75 ℃, insulation refluxed 5 hours, heated up 90 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into second alcohol and water mixing (volume ratio 1: 1), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 75 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 85 ℃ of following vacuum dryings, and its allyl capped rate is 55%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 80 part 4,4 '-dimaleoyl imino ditane, 20 part 4,4 '-dimaleoyl imino phenyl ether, 30 parts of diallyl bisphenols and 10 parts of diallyl bisphenol ether are stirred to melt under 120 ℃ transparent; The allylation hyperbranched polyphenyl ether that adds 45 parts of present embodiment above-mentioned steps preparations reacts 55 minutes postcooling down at 120 ℃, promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment nine
The preparation of the hyper-branched polyphenyl ether of allylation
Under argon gas atmosphere, under normal temperature, hyper-branched polyphenyl ether, 30g sodium hydroxide, 2500g DMSO that 100g embodiment seven steps (1) are made drop in the there-necked flask.Be warming up to 80 ℃, stirred 3 hours.After being cooled to 75 ℃, begin to drip 65g 3-bromopropylene, dripped off at 3 hours.Then be warming up to 80 ℃, insulation refluxed 5 hours, heated up 100 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into second alcohol and water mixing (volume ratio 1: 1), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 80 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 85 ℃ of following vacuum dryings, and its allyl capped rate is 65%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 60 part 4,4 '-dimaleoyl imino ditane, 20 part 4,4 '-dimaleoyl imino phenyl ether, 20 part 4,4 '-dimaleoyl imino sulfobenzide and 31 parts of diallyl bisphenols are stirred to melt under 115 ℃ transparent; The allylation hyperbranched polyphenyl ether that adds 55 parts of embodiment above-mentioned steps preparations reacts 100 minutes postcooling down at 115 ℃, promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment ten
The preparation of the hyper-branched polyphenyl ether of allylation
Under nitrogen atmosphere, under normal temperature, the hyper-branched polyphenyl ether that 100g embodiment seven steps (1) are made, the potassium hydroxide of 50g and 2000g DMSO drop in the there-necked flask.Be warming up to 100 ℃, stirred 2 hours.After being cooled to 45 ℃, begin to drip the 80g chlorallylene, dripped off at 3 hours.Then be warming up to 60 ℃, insulation refluxed 3 hours, heated up 80 ℃ again, and insulation refluxed 2 hours, heated up 100 ℃ again, and insulation refluxed 2 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 1.5: 1), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 70 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 90 ℃ of following vacuum dryings, and its allyl capped rate is 100%.
1H?NMR(CDCl
3)：δ4.27-4.50(br，-CH
2-)，δ4.50-4.69(br，PhCH
2-Ph)，δ4.89-5.32(＝CH
2)，δ5.35-5.65(br，-CH＝CH
2)，5.65-5.89(br，PhCH
2O-)，6.05-7.74(br，Ar-H)。
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 55 part 4,4 '-dimaleoyl imino ditane, 45 part 4,4 '-dimaleoyl imino sulfobenzide, 10 parts of diallyl bisphenols and 20 diallyl bisphenol Ss are stirred to melt under 130 ℃ transparent; The allylation hyperbranched polyphenyl ether that adds 55 parts of present embodiment above-mentioned steps preparations, behind reaction 85min under 130 ℃, cooling promptly gets a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
Embodiment 11
The preparation of allylation hyperbranched polyphenyl ether
Under nitrogen atmosphere, under normal temperature, the hyper-branched polyphenyl ether that 100g embodiment seven steps (1) are made, the potassium hydroxide of 100g and 5000g DMSO drop in the there-necked flask.Be warming up to 110 ℃, stirred 5 hours.After being cooled to 90 ℃, begin to drip 150g 3-bromopropylene, dripped off at 5 hours.Then be warming up to 95 ℃, insulation refluxed 4 hours, heated up 120 ℃ again, and insulation refluxed 3 hours.After reaction finishes, be cooled to room temperature, stir in the solution that splashes into first alcohol and water mixing (volume ratio 2: 1), filter.Filter cake is dissolved in tetrahydrofuran (THF) again behind 80 ℃ of following vacuum dryings, splash in the stirring in the hexanaphthene, filters, and filter cake promptly obtains the hyper-branched polyphenyl ether of allylation at 120 ℃ of following vacuum dryings, and its allyl capped rate is 95%.
The preparation of allylation hyperbranched polyphenyl ether modified bismaleimide resin
By mole, with 100 part 4,4 '-dimaleoyl imino ditane, 18 parts of diallyl bisphenols, 12 parts of diallyl bisphenol ether and 10 parts of diallyl bisphenol Ss are stirred to melt under 140 ℃ transparent; Add 45 parts of allylation hyperbranched polyphenyl ethers that the present embodiment above-mentioned steps prepares, react 95 minutes postcooling down, promptly get a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin at 140 ℃.
Claims (10)
1. allylation hyperbranched polyphenyl ether modified bismaleimide resin, it is characterized in that: by mole, its component ratio is 100 parts of bismaleimidess, 30～85 parts of diallyl phenyl compounds and 1～55 part of allylation hyperbranched polyphenyl ether.
2. allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 1, it is characterized in that: described bismaleimides is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether and 4,4 '-a kind of in the dimaleoyl imino sulfobenzide, or their arbitrary combination.
3. allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 1, it is characterized in that: described diallyl phenyl compound is a kind of in diallyl bisphenol, diallyl bisphenol ether and the diallyl bisphenol S, or their arbitrary combination.
4. the preparation method of an allylation hyperbranched polyphenyl ether modified bismaleimide resin is characterized in that comprising the steps:
(1) by weight, having the hyper-branched polyphenyl ether of phenolic hydroxyl group, 1～100 part of alkali metal hydroxide and 0～10 part of quaternary ammonium salt phase transfer catalyst with 100 parts joins in 50～5000 parts of solvents, in inert atmosphere, be warming up to 50～110 ℃, stirred 0.1～5 hour; Under temperature is 40～90 ℃ condition, dripping 2.5～150 parts of 3-propylene halides again, after dripping off in 0.03～5 hour, is to be incubated 4～12 hours under 50～120 ℃ the condition to react in temperature;
(2) after reaction finishes, be cooled to room temperature, under the agitation condition, the reactant that step (1) is obtained splashes into methyl alcohol or ethanol by volume: water is in 1: 0.5～1: 8 the mixing solutions, after filtering, be that oven dry is handled under 40～80 ℃ the vacuum condition with filter cake, obtain the hyper-branched polyphenyl ether crude product of allylation in temperature;
(3) the hyper-branched polyphenyl ether crude product of the allylation that step (2) is obtained is dissolved in the tetrahydrofuran solution, under agitation condition, it is splashed in the cyclohexane solution again, after filtering, filter cake is that oven dry is handled under 40～120 ℃ the vacuum condition in temperature, promptly obtain a kind of allylation hyperbranched polyphenyl ether, its allyl capped rate is greater than 0, smaller or equal to 100%;
(4), under 110～140 ℃, be stirred to 100 parts of bismaleimidess and 30～85 parts of diallyl phenyl compounds transparent by mole; Adding the allylation hyperbranched polyphenyl ether that 1～55 part of step (3) obtains again, is to react 20～100 minutes postcooling under 110～140 ℃ the condition in temperature, obtains a kind of allylation hyperbranched polyphenyl ether modified bismaleimide resin.
5. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4, it is characterized in that: described bismaleimides is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether and 4,4 '-a kind of in the dimaleoyl imino sulfobenzide, or their arbitrary combination.
6. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4, it is characterized in that: described diallyl phenyl compound is a kind of in diallyl bisphenol, diallyl bisphenol ether and the diallyl bisphenol S, or their arbitrary combination.
7. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4 is characterized in that: described quaternary ammonium salt phase transfer catalyst is benzyltriethylammoinium chloride or Tetrabutyl amonium bromide.
8. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4 is characterized in that: described 3-propylene halide is chlorallylene or 3-bromopropylene.
9. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4 is characterized in that: described solvent is tetrahydrofuran (THF), methyl-sulphoxide, dimethyl formamide or N,N-DIMETHYLACETAMIDE.
10. the preparation method of allylation hyperbranched polyphenyl ether modified bismaleimide resin according to claim 4 is characterized in that: described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
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Cited By (9)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493600A (en) * | 2003-08-19 | 2004-05-05 | 梁国正 | Preparation method and application of modified double maleimide resin |
| CN101717503A (en) * | 2009-12-02 | 2010-06-02 | 苏州大学 | Method for preparing allylation hyperbranched polyphenylene oxide |
| WO2010075006A1 (en) * | 2008-12-16 | 2010-07-01 | Dow Global Technologies Inc. | Homogeneous bismaleimide - triazine - epoxy compositions useful for the manufacture of electrical laminates |
-
2010
- 2010-07-09 CN CN2010102237009A patent/CN101880363B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493600A (en) * | 2003-08-19 | 2004-05-05 | 梁国正 | Preparation method and application of modified double maleimide resin |
| WO2010075006A1 (en) * | 2008-12-16 | 2010-07-01 | Dow Global Technologies Inc. | Homogeneous bismaleimide - triazine - epoxy compositions useful for the manufacture of electrical laminates |
| CN101717503A (en) * | 2009-12-02 | 2010-06-02 | 苏州大学 | Method for preparing allylation hyperbranched polyphenylene oxide |
Non-Patent Citations (1)
| Title |
|---|
| 《中国胶粘剂》 20090430 程雷等 烯丙基化合物改性双马来酰亚胺树脂的研究进展 第18卷, 第4期 2 * |
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