CN101062970A - Polysiloxane toughening allyl group linear pnenolic aldehyde/bimaleimide resin - Google Patents
Polysiloxane toughening allyl group linear pnenolic aldehyde/bimaleimide resin Download PDFInfo
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Abstract
The invention discloses an allyl group linear pnenolic aldehyde/bimaleimide resin of toughened polysiloxane, which comprises the following steps: (1) mixing poly dimethyl oxosilane 1 of hydrogen sealing end and poly dimethyl oxosilane 2 of hydrogen sealing end and allyl group linear pnenolic aldehyde resin solution evenly; reacting under the function of metallic catalyst at 50-80 deg. c; getting allyl group linear pnenolic aldehyde resin of toughened polysiloxane; (2) adding bimaleimide monomer into the product of the step (1); refluxing in the dissolvent; removing the dissolvent; getting the product. This resin possesses good processing property and simple preparing method, which can be used to basal body resin of high property composite.
Description
Technical field
The present invention relates to allyl group linear phenolic aldehyde/bimaleimide resin, relate in particular to the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening.
Background technology
Resol is widely used in numerous areas such as aerospace, the vehicles with its good thermotolerance and heat ablative.But resol body viscosity is big, discharge a large amount of low-molecular materials in the solidification process, makes traditional resol can not satisfy the requirement of resin transfer moulding (RTM) technology.And the fragility of phenolic resin curing thing is also bigger, has limited the use range of resol to a certain extent.In the resol molecular structure, introduce the viscosity that allyl group not only can reduce resin, make it be suitable for the requirement of RTM moulding process; And, allyl group also can by and maleimide base group between reaction, the bismaleimides (BMI) that will have outstanding over-all properties is introduced in the resol molecular structure.Allyl group linear phenolic aldehyde/BMI resin system has more excellent thermotolerance, and mechanical property also has raising by a relatively large margin, is expected to become the high performance composite matrix resin.But, exist a large amount of benzene ring structures and cured article to have high cross-linking density in allyl group linear phenolic aldehyde/BMI resin system molecular structure, therefore, the toughness of allyl group linear phenolic aldehyde/BMI resin cured matter still awaits further raising.The polysiloxane molecule main chain has excellent kindliness and better heat-resisting, is a kind of properties-correcting agent of good modified heat convertible resin.But the consistency of polysiloxane and general organic polymer is relatively poor, and therefore the consistency that improves between them is very important.Adopt functionalized polysiloxane as properties-correcting agent, polysiloxane is introduced in the organic macromolecule molecular structure, can improve consistency between the two to a certain extent by the reaction between the functional group.Tsung-Han Ho etc. introduce the hydrogen functional polysiloxane thermal stresses that reduces system in the phenolic epoxy resin system, obtain effect preferably, [1.Polymer 38 (1997), 1997-2003 but the introducing of not mentioning polysiloxane influences the resin system flexible; 2.European PolymerJournal 37 (2001), 267-274].
Summary of the invention
The object of the present invention is to provide the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening.
The present invention adopts two-component polysiloxane as plasticized modifier, utilize addition reaction of silicon with hydrogen, allyl group linear resol molecular chain and polysiloxane molecule chain are tied allyl group linear phenolic aldehyde/BMI resin that a kind of polysiloxane toughening is provided by chemical bond.Wherein, the less component of molecular weight improves the consistency of polysiloxane and allyl group linear resol as expanding material, enlarges the molecular weight ranges of operable polysiloxane.This resin processing performance is good, compares with pure allyl group linear phenolic aldehyde/BMI resin system, and shock strength has significantly lifting, and thermotolerance is suitable, and the preparation method is easy.
Allyl group linear phenolic aldehyde/the bimaleimide resin of polysiloxane toughening of the present invention, can adopt following method preparation:
(1) end capped polydimethylsiloxane 1 of 1～5 weight part hydrogen and the end capped polydimethylsiloxane 2 of 5 weight part hydrogen are mixed with the solution that contains 90～94 weight part allyl group linear resol, in 50 ℃～80 ℃, reaction under the metal catalyst effect of catalytic amount (preferred 4～12h), obtain the allyl group linear resol of polysiloxane toughening.
The general formula of the end capped polydimethylsiloxane of described hydrogen is:
Wherein, the several 6≤p of repeating segment≤8 of the end capped polydimethylsiloxane 1 of hydrogen, number-average molecular weight is 500～800; Several 20≤the p of repeating segment≤40 of the end capped polydimethylsiloxane 2 of hydrogen, number-average molecular weight is 1500～3000.
The structural formula of described allyl group linear resol is:
Wherein, m+n＞1, number-average molecular weight scope 550～900.
The solvent of the solution of described allyl group linear resol can be toluene, 4-methyl-2 pentanone or tetrahydrofuran (THF).
Described metal catalyst can be H
2PtCl
6Aqueous isopropanol or H
2PtCl
6Xylene solution.
Described H
2PtCl
6The volumetric molar concentration of aqueous isopropanol be 0.004～0.008M;
Described H
2PtCl
6Xylene solution in the content of Pt be 3～5wt%;
Described H
2PtCl
6The preparation reference literature of xylene solution: J.V.Crivello etal., Journal of Polymer Science:Part A:Polymer Chemistry 24 (1986), 1197-1215.
(2) the bismaleimide amine monomers is joined in the product of step (1), wherein the mol ratio of maleimide base group and allyl group is 0.3～0.6: 1; In solvent, reflux (preferred 1～2h), remove the allyl group linear phenolic aldehyde/bimaleimide resin that obtains polysiloxane toughening after desolvating.Described solvent can be 4-methyl-2 pentanone or butanone.
The monomeric structural formula of described bismaleimides is:
The synthetic reference literature of described allyl group linear resol: Yehai Yan, et al., Journalof Applied Polymer Science 83 (2002), 1651-1657.
The synthetic reference literature of the end capped polydimethylsiloxane of described hydrogen: Chen Li, master thesis, Institute of Chemistry, Academia Sinica, 1994.With the vitriol oil as catalyzer, with tetramethyl disiloxane (M
HM
H) as end-capping reagent, octamethylcyclotetrasiloxane (D
4) ring-opening polymerization makes the end capped polydimethylsiloxane of hydrogen; The ratio of adjusting octamethylcyclotetrasiloxane and tetramethyl disiloxane can obtain to have the end capped polydimethylsiloxane 1 of hydrogen or the end capped polydimethylsiloxane 2 of hydrogen of different molecular weight respectively.The concentration of the wherein said catalyzer vitriol oil is 95-98%, and consumption is the 1-5wt% of octamethylcyclotetrasiloxane quality; Temperature of reaction is 10-30 ℃; Relation between ratio of octamethylcyclotetrasiloxane and tetramethyl disiloxane (mol ratio) and the number-average molecular weight sees the following form:
| Number-average molecular weight | 750 | 1700 | 3000 |
| D 4∶M HM H | 1∶1 | 4.6∶1 | 7.3∶1 |
The method that structural characterization of the present invention adopts is that magnetic nuclear resonance method (comprises
1H-NMR,
29Si-NMR).What mechanical property characterizing method of the present invention adopted is shock strength test (according to ISO179-1982 (E)).It is thermal gravimetric analyzer (TGA) that thermotolerance of the present invention characterizes the method that adopts, and wherein the quality retention rate of 5% weightless temperature of TGA and 900 ℃ characterizes resistance toheat.
The present invention adopts the end capped polydimethylsiloxane of hydrogen as properties-correcting agent, improves the toughness of allyl group linear phenolic aldehyde/BMI resin system.Experimental result shows.Polysiloxane can improve the toughness of allyl group linear phenolic aldehyde/BMI resin system.But, the molecular weight of polysiloxane there is strict requirement, otherwise, be difficult to obtain gratifying toughening effect.The present invention adopts two-component polysiloxane as plasticized modifier, and wherein, the polysiloxane of small molecular weight improves the consistency of the polysiloxane and the matrix resin of macromolecule as expanding material, enlarges the molecular weight ranges of operable polysiloxane.
The resin that the present invention obtains is with the advantage that existing resin is compared:
(1) the present invention has polysiloxane than small molecular weight by adding, improved the consistency of polysiloxane and allyl group linear resol, enlarge the molecular weight ranges of operable polysiloxane, obtained transparent, the stable allyl group linear resol that contains the polysiloxane segment.This resin has the favorable manufacturability energy, and viscosity is suitable with pure allyl group linear resol, satisfies the requirement of RTM technology.
(2) adopt the allyl group linear phenolic aldehyde/bimaleimide resin pour mass shock strength and the pure allyl group linear phenolic aldehyde/BMI resin of the polysiloxane toughening of the present invention's preparation that significantly raising is relatively arranged, shock strength improves 2-2.6 doubly than unmodified resin, simultaneously, thermotolerance and pure allyl group linear phenolic aldehyde/BMI resin remain basically stable.The matrix resin that can be used for high performance composite.
Embodiment
Embodiment 1
Step 1: in the 500ml there-necked flask that is equipped with mechanical stirring, prolong and thermometer, add linear phenolic resin 90.00g (0.21mol), propyl carbinol 135g, treat that linear phenolic resin dissolves the back fully and adds potassium hydroxide 29.87g (0.44mol), after the reaction 2h, drip chlorallylene 42.41g (0.44mol), reaction 6h.Reaction finishes the back filtered while hot, and collection filtrate is adopted Rotary Evaporators to remove to desolvate and obtained allyl group linear resol.
Adopt
1H-NMR characterizes its structure:
1H-NMR (with the deuterated dimethyl sulfoxide that contains TMS as solvent, dimethyl sulfoxide (DMSO) in the chemical shift at 2.5ppm place as standard): 7.1,7.0,6.9,6.8ppm phenyl (phenyl), 6.0,5.9ppm (Φ-OCH
2CH=CH
2And Φ-CH
2CH=CH
2), 5.2,5.4ppm (Φ-OCH
2CH=CH
2), 4.95ppm (Φ-CH
2CH=CH
2), 4.5ppm (Φ-OCH
2CH=CH
2), 3.9,3.8,3.7ppm (Φ-CH
2-Φ), 3.3ppm (Φ-CH
2CH=CH
2).
According to
1Among the H-NMR 3.7～3.9ppm, 4.95ppm and 5.2～5.4ppm place integral area to calculate number-average molecular weight be 707.
Step 2: in being equipped with churned mechanically 500ml there-necked flask, add octamethylcyclotetrasiloxane (D
4) 200.00g (0.68mol), tetramethyl disiloxane (M
HM
H) 19.56g (0.15mol), stir; Drip vitriol oil 6.32g under the vigorous stirring, behind 30 ℃ of following reaction 6h; Add deionized water 3.79g, continue reaction 6h.After reaction stops, reaction solution is transferred in the separating funnel, divides the disacidify layer, be washed till pH=7 with a large amount of deionized waters then; At last, adopt the method for underpressure distillation, remove low-boiling-point substance, obtain the end capped polydimethylsiloxane of hydrogen (2).
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 0.08ppm[(CH
3)
2SiO], 0.19ppm[HSi (CH
3)
2], 4.71ppm (SiH).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard) :-5.47ppm (Si-H) ,-18.58ppm ,-20.54ppm[(CH
3) SiO].
According to
1To calculate the number-average molecular weight of above-mentioned polydimethylsiloxane (2) be 1700 to the integral area at 0.08ppm and 0.19ppm place among the H-NMR.
Step 3: in being equipped with churned mechanically 250ml there-necked flask, add octamethylcyclotetrasiloxane (D
4) 40.00g (0.14mol), tetramethyl disiloxane (M
HM
H) 18.09g (0.14mol), stir; Drip vitriol oil 0.4g under the vigorous stirring, behind 25 ℃ of following reaction 6h; Add deionized water 0.76g, continue reaction 6h.After reaction stops, reaction solution is transferred in the separating funnel, divides the disacidify layer, be washed till pH=7 with a large amount of deionized waters then; At last, adopt the method for underpressure distillation, remove low-boiling-point substance, obtain the end capped polydimethylsiloxane of hydrogen (1).
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 0.08ppm[(CH
3)
2SiO], 0.19ppm[HSi (CH
3)
2], 4.71ppm (SiH).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard) :-5.47ppm (Si-H) ,-18.58ppm ,-20.54ppm[(CH
3) SiO].
According to
1To calculate the number-average molecular weight of above-mentioned polydimethylsiloxane (1) be 750 to the integral area at 0.08ppm and 0.19ppm place among the H-NMR.
Step 4: be equipped with mechanical stirring, N
2Add allyl group linear resol 94.00g (0.22mol) in the four-hole boiling flask of inlet, thermometer and spherical condensation tube, above-mentioned number-average molecular weight is that 1700 the end capped polydimethylsiloxane of hydrogen (2) 5.00g (0.0029mol), number-average molecular weight are 750 the end capped polydimethylsiloxane of hydrogen (1) 1.00g (0.0013mol) and toluene 150.00g, and 1h refluxes under nitrogen protection; Then, reduce to 25 ℃, add H
2PtCl
6Aqueous isopropanol 2.52ml, wherein, H
2PtCl
6The volumetric molar concentration of aqueous isopropanol be 0.0077M.Elevated temperature to 80 ℃, reaction 4h; Reaction is transferred to reaction solution in the 500ml single port bottle after finishing, remove with Rotary Evaporators and to desolvate, obtain the 5wt% number-average molecular weight and be 1700 and the 1wt% number-average molecular weight be 750 polysiloxane-modified allyl group linear resol, outward appearance is a burgundy transparence liquid.
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 7.1,7.0,6.9,6.8ppm phenyl (phenyl), 6.0,5.9ppm (Φ-OCH
2CH=CH
2And Φ-CH
2CH=CH
2), 5.2,5.4ppm (Φ-OCH
2CH=CH
2), 4.95ppm (Φ-CH
2CH=CH
2), 4.5ppm (Φ-OCH
2CH=CH
2), 3.9,3.8,3.7ppm (Φ-CH
2-Φ), 3.3ppm (Φ-CH
2CH=CH
2), 1.8ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si), 0.7ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard): 9.58ppm (Φ-CH
2CH
2CH
2-Si and Φ-OCH
2CH
2CH
2-Si) ,-19.63ppm and-20.18ppm[(CH
3)
2SiO].
Step 5: in the 500ml there-necked flask that is equipped with mechanical stirring, spherical condensation tube and thermometer, add the above-mentioned allyl group linear resol 90.00g (allyl group 0.60mol) that contains polysiloxane that obtains, bismaleimide amine monomers 31.95g (maleimide base group 0.17mol) and 4-methyl-2 pentanone 280ml, reflux 1h, adopting Rotary Evaporators to remove then desolvates, obtain polysiloxane-modified allyl group linear phenolic aldehyde/BMI resin blend, its outward appearance is a scarlet transparence liquid.
Step 6: the above-mentioned polysiloxane-modified allyl group linear resol/BMI blend that obtains is poured in the mould, and the program according to 160 ℃ of 4h+200 ℃ of 4h+250 ℃ of 6h is heating and curing in a conventional oven, obtains the resin-cast body.
The TGA analysis revealed, cured resin 5wt% weightless temperature is 415.1 ℃, is 33.90% at 900 ℃ quality retention rates.Impact experiment shows that the shock strength of resin-cast body is 4.78kJ/m
2, be 2 times of unmodified allyl group linear phenolic aldehyde/BMI resin shock strength.
Embodiment 2
Step 1: with step 1 among the embodiment 1.
Step 2: with step 2 among the embodiment 1.
Step 3: with step 3 among the embodiment 1.
Step 4: be equipped with mechanical stirring, N
2Add allyl group linear resol 92.00g (0.22mol) in the four-hole boiling flask of inlet, thermometer and spherical condensation tube, above-mentioned number-average molecular weight is that 1700 the end capped polydimethylsiloxane of hydrogen (2) 5.00g (0.0029mol), number-average molecular weight are 750 the end capped polydimethylsiloxane of hydrogen (1) 3.00g (0.0040mol) and 4-methyl-2 pentanone 150.00g, and 1h refluxes under nitrogen protection; Then, reduce to 25 ℃, add H
2PtCl
6Xylene solution 2.00ml, wherein, the content of Pt is 3wt% in the xylene solution.Elevated temperature to 80 ℃, reaction 6h; Reaction is transferred to reaction solution in the 500ml single port bottle after finishing, remove with Rotary Evaporators and to desolvate, obtain the 5wt% number-average molecular weight and be 1700 and the 3wt% number-average molecular weight be 750 polysiloxane-modified allyl group linear resol, outward appearance is a burgundy transparence liquid.
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 7.1,7.0,6.9,6.8ppm phenyl (phenyl), 6.0,5.9ppm (Φ-OCH
2CH=CH
2And Φ-CH
2CH=CH
2), 5.2,5.4ppm (Φ-OCH
2CH=CH
2), 4.95ppm (Φ-CH
2CH=CH
2), 4.5ppm (Φ-OCH
2CH=CH
2), 3.9,3.8,3.7ppm (Φ-CH
2-Φ), 3.3ppm (Φ-CH
2CH=CH
2), 1.8ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si), 0.7ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard): 9.58ppm (Φ-CH
2CH
2CH
2-Si and Φ-OCH
2CH
2CH
2-Si) ,-19.63ppm and-20.18ppm[(CH
3)
2SiO].
Step 5: in the 500ml there-necked flask that is equipped with mechanical stirring, spherical condensation tube and thermometer, add the above-mentioned allyl group linear resol 85.00g (allyl group 0.56mol) that contains polysiloxane that obtains, bismaleimide amine monomers 60.86g (maleimide base group 0.34mol) and butanone 280ml, reflux 1h, adopting Rotary Evaporators to remove then desolvates, obtain polysiloxane-modified allyl group linear phenolic aldehyde/BMI resin blend, its outward appearance is a scarlet transparence liquid.
Step 6: the above-mentioned polysiloxane-modified allyl group linear resol/BMI blend that obtains is poured in the steel die, and the program according to 160 ℃ of 4h+200 ℃ of 4h+250 ℃ of 6h is heating and curing in a conventional oven, obtains the resin-cast body.
The TGA analysis revealed, cured resin 5wt% weightless temperature is 418.5 ℃, is 34.14% at 900 ℃ quality retention rates.Impact experiment shows that the shock strength of resin-cast body is 5.68kJ/m
2, be 2.4 times of unmodified allyl group phenolic aldehyde/BMI resin shock strength.
Embodiment 3
Step 1: with the step 1 among the embodiment 1.
Step 2: with the step 2 among the embodiment 1.
Step 3: with the step 3 among the embodiment 1.
Step 4: be equipped with mechanical stirring, N
2Add allyl group linear resol 100.00g (0.24mol) in the four-hole boiling flask of inlet, thermometer, the above-mentioned number-average molecular weight that obtains is that 1700 the end capped polysiloxane of hydrogen (2) 5.500g (0.0032mol), number-average molecular weight are 750 the end capped polysiloxane of hydrogen (1) 5.5g (0.0073mol) and toluene 150.00g, and 1h refluxes under nitrogen protection; Then, reduce to 25 ℃, add H
2PtCl
6Aqueous isopropanol 5.10ml, wherein, H
2PtCl
6The volumetric molar concentration of aqueous isopropanol be 0.004M, elevated temperature to 80 ℃, reaction 6h; Reaction is transferred to reaction solution in the 500ml single port bottle after finishing, remove with Rotary Evaporators and to desolvate, obtain the 5wt% number-average molecular weight and be 1700 and the 5wt% number-average molecular weight be 750 polysiloxane-modified allyl group linear resol, outward appearance is a burgundy transparence liquid.
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 7.1,7.0,6.9,6.8ppm phenyl (phenyl), 6.0,5.9ppm (Φ-OCH
2CH=CH
2And Φ-CH
2CH=CH
2), 5.2,5.4ppm (Φ-OCH
2CH=CH
2), 4.95ppm (Φ-CH
2CH=CH
2), 4.5ppm (Φ-OCH
2CH=CH
2), 3.9,3.8,3.7ppm (Φ-CH
2-Φ), 3.3ppm (Φ-CH
2CH=CH
2), 1.8ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si), 0.7ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard): 9.58ppm (Φ-CH
2CH
2CH
2-Si and Φ-OCH
2CH
2CH
2-Si) ,-19.63ppm and-20.18ppm[(CH
3)
2SiO].
Step 5: in the 500ml there-necked flask that is equipped with mechanical stirring, spherical condensation tube and thermometer, add the above-mentioned allyl group linear resol 85.00g (allyl group 0.55mol) that contains polysiloxane that obtains, bismaleimide amine monomers 28.46g (maleimide base group 0.16mol) and 4-methyl-2 pentanone 280ml, reflux 1h, adopting Rotary Evaporators to remove then desolvates, obtain polysiloxane-modified allyl group linear phenolic aldehyde/BMI resin blend, its outward appearance is a scarlet transparence liquid.
Step 6: the above-mentioned polysiloxane-modified allyl group linear resol/BMI blend that obtains is poured in the mould, and the program according to 160 ℃ of 4h+200 ℃ of 4h+250 ℃ of 6h is heating and curing in a conventional oven, obtains the resin-cast body.
The TGA analysis revealed, cured resin 5wt% weightless temperature is 419.8 ℃, is 32.43% at 900 ℃ quality retention rates.Impact experiment shows that the shock strength of resin-cast body is 6.12kJ/m
2, be 2.6 times of unmodified allyl group phenolic aldehyde/BMI resin.
Embodiment 4
Step 1: with the step 1 among the embodiment 1.
Step 2: in being equipped with churned mechanically 500ml there-necked flask, add octamethylcyclotetrasiloxane (D
4) 150.00g (0.51mol), tetramethyl disiloxane (M
HM
H) 9.25g (0.069mol), stir; Drip vitriol oil 7.50g under the vigorous stirring, behind 10 ℃ of following reaction 6h; Add deionized water 2.84g, continue reaction 6h.After reaction stops, reaction solution is transferred in the separating funnel, divides the disacidify layer, be washed till pH=7 with a large amount of deionized waters then; At last, adopt the method for underpressure distillation, remove low-boiling-point substance, obtain the end capped polydimethylsiloxane of hydrogen (2).
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 0.08ppm[(CH
3)
2SiO], 0.19ppm[HSi (CH
3)
2], 4.71ppm (SiH).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard) :-5.47ppm (Si-H) ,-18.58ppm ,-20.54ppm[(CH
3) SiO].
According to
1To calculate the number-average molecular weight of above-mentioned polydimethylsiloxane (2) be 3000 to the integral area at 0.08ppm and 0.19ppm place among the H-NMR.
Step 3: with the step 3 among the embodiment 1.
Step 4: be equipped with mechanical stirring, N
2Add allyl group linear resol 100.00g (0.24mol) in the four-hole boiling flask of inlet, thermometer and spherical condensation tube, number-average molecular weight is 3000 the end capped polysiloxane of hydrogen (2) 5.44g (0.0019mol), number-average molecular weight is 750 the end capped polysiloxane of hydrogen (1) 3.26g (0.0043mol) and tetrahydrofuran (THF) 150.00g, and 1h refluxes under nitrogen protection; Then, reduce to 25 ℃, add H
2PtCl
6Xylene solution 1.20ml, wherein, the content of Pt is 5wt% in the xylene solution, elevated temperature to 50 ℃, reaction 12h; Reaction is transferred to reaction solution in the 500ml single port bottle after finishing, remove with Rotary Evaporators and to desolvate, obtain containing 5wt% number-average molecular weight 3000 and 3wt% number-average molecular weight and be 750 polysiloxane-modified allyl group linear resol, outward appearance is a burgundy transparence liquid.
Adopt
1H-NMR,
29Si-NMR characterizes its structure:
1H-NMR (with the deuterated acetone that do not contain TMS as solvent, acetone in the chemical shift at 2.05ppm place as standard): 7.1,7.0,6.9,6.8ppm phenyl (phenyl), 6.0,5.9ppm (Φ-OCH
2CH=CH
2And Φ-CH
2CH=CH
2), 5.2,5.4ppm (Φ-OCH
2CH=CH
2), 4.95ppm (Φ-CH
2CH=CH
2), 4.5ppm (Φ-OCH
2CH=CH
2), 3.9,3.8,3.7ppm (Φ-CH
2-Φ), 3.3ppm (Φ-CH
2CH=CH
2), 1.8ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si), 0.7ppm (Φ-CH
2CH
2-CH
2-Si and Φ-O-CH
2CH
2-CH
2-Si).
29Si-NMR (with the deuterated acetone that contains TMS as solvent, TMS in the chemical shift at 0ppm place as standard): 9.58ppm (Φ-CH
2CH
2CH
2-Si and Φ-OCH
2CH
2CH
2-Si) ,-19.63ppm and-20.18ppm[(CH
3)
2SiO].
Step 5: the allyl group linear resol 85.00g (allyl group 0.56mol) that in the 500ml there-necked flask that is equipped with mechanical stirring, spherical condensation tube and thermometer, adds the above-mentioned polysiloxane that obtains, bismaleimide amine monomers 40.09g (maleimide base group 0.22mol) and 4-methyl-2 pentanone 280ml, reflux 1h, adopting Rotary Evaporators to remove then desolvates, obtain polysiloxane-modified allyl group linear phenolic aldehyde/resin B MI blend, its outward appearance is a scarlet transparence liquid resin.
Step 6: the above-mentioned polysiloxane-modified allyl group linear resol/BMI blend that obtains is poured in the mould, and the program according to 160 ℃ of 4h+200 ℃ of 4h+250 ℃ of 6h is heating and curing in a conventional oven, obtains the resin-cast body.
The TGA analysis revealed, cured resin 5wt% weightless temperature is 418.5 ℃, is 34.14% at 900 ℃ quality retention rates.Impact experiment shows that the shock strength of resin-cast body is 4.67kJ/m
2, be 2.0 times of unmodified allyl group phenolic aldehyde/BMI resin shock strength.
Claims (8)
1. the allyl group linear phenolic aldehyde/bimaleimide resin of a polysiloxane toughening is characterized in that: can adopt following method preparation:
(1) end capped polydimethylsiloxane 1 of 1～5 weight part hydrogen and the end capped polydimethylsiloxane 2 of 5 weight part hydrogen are mixed with the solution that contains 90～94 weight part allyl group linear resol, in 50 ℃～80 ℃, under the metal catalyst effect of catalytic amount, react, obtain the allyl group linear resol of polysiloxane toughening;
(2) the bismaleimide amine monomers is joined in the product of step (1), wherein the mol ratio of maleimide base group and allyl group is 0.3～0.6: 1; In solvent, reflux, remove the allyl group linear phenolic aldehyde/bimaleimide resin that obtains polysiloxane toughening after desolvating;
The general formula of the end capped polydimethylsiloxane of described hydrogen is:
Wherein, the several 6≤p of repeating segment≤8 of the end capped polydimethylsiloxane 1 of hydrogen, number-average molecular weight is 500～800; Several 20≤the p of repeating segment≤40 of the end capped polydimethylsiloxane 2 of hydrogen, number-average molecular weight is 1500～3000.
2. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the structural formula of described allyl group linear resol is:
Wherein, m+n＞1, number-average molecular weight scope 550～900.
3. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the metal catalyst in the described step (1) is H
2PtCl
6Aqueous isopropanol or H
2PtCl
6Xylene solution.
4. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 3 is characterized in that: described H
2PtCl
6The volumetric molar concentration of aqueous isopropanol be 0.004～0.008M; Described H
2PtCl
6Xylene solution in the content of Pt be 3～5wt%.
5. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the solvent of the solution of the allyl group linear resol in the described step (1) is toluene, 4-methyl-2 pentanone or tetrahydrofuran (THF).
6. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the solvent in the described step (2) is 4-methyl-2 pentanone or butanone.
7. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the reaction times in the described step (1) is 4～12 hours.
8. the allyl group linear phenolic aldehyde/bimaleimide resin of polysiloxane toughening according to claim 1, it is characterized in that: the return time in the described step (2) is 1～2 hour.
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| JPH03250017A (en) * | 1990-02-27 | 1991-11-07 | Sumitomo Chem Co Ltd | Thermosetting resin composition |
| JP2837503B2 (en) * | 1990-04-23 | 1998-12-16 | 住友ベークライト株式会社 | Resin composition for semiconductor encapsulation |
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| JPH0860132A (en) * | 1994-08-25 | 1996-03-05 | Yokohama Rubber Co Ltd:The | Heat-resistant adhesive, prepreg and resin composition |
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