CN101619073A - Cage type silsesquioxane sulphonate with potential catalytic action and thermosetting resin composite thereof - Google Patents
Cage type silsesquioxane sulphonate with potential catalytic action and thermosetting resin composite thereof Download PDFInfo
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- CN101619073A CN101619073A CN200910163123A CN200910163123A CN101619073A CN 101619073 A CN101619073 A CN 101619073A CN 200910163123 A CN200910163123 A CN 200910163123A CN 200910163123 A CN200910163123 A CN 200910163123A CN 101619073 A CN101619073 A CN 101619073A
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Abstract
The invention provides a cage type silsesquioxane sulphonate with potential catalytic action and a thermosetting resin composite thereof, in particular to a cage type oligomeric silsesquioxane containing ammonium sulphonate and the thermosetting resin composite obtained by mixing the cage type oligomeric silsesquioxane containing the ammonium sulphonate with thermosetting resins such as benzoxazine, oxadiazoline, an ethoxyline resin and a composition of the benzoxazine, the oxadiazoline and the ethoxyline resin. The obtained thermosetting resin composite can be solidified under lower temperature, and an obtained solidified product has higher modulus and better heat resistance.
Description
Technical field
The present invention relates to cage type silsesquioxane sulfonate and compositions of thermosetting resin thereof that a class has latent katalysis.Specifically, relate to the polyhedral oligomeric silsesquioxane that contains sulfonic acid ammonium salt and use such silicious sesquioxane and thermosetting resin,, mix back gained compositions of thermosetting resin as benzoxazine, bisoxazoline, Resins, epoxy and composition thereof; This gained compositions of thermosetting resin can solidify under lower temperature, and the gained cured article has higher modulus and better heat-resisting.
Background technology
Polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane, POSS) monomer is at present unique inorganic-organic hybridization nano chemistry filler, it not only combines organic constituent and inorganic component high-performance separately, but also has the new capability that is produced by both synergistic effects.Its molecular formula can be expressed as (RSiO
1.5)
n(n generally can be 6,8,10,12 etc.), the nano grade inorganic kernel that the rigidity that it is made up of silicon and oxygen, structure are determined is the hybrid compounds that shell is formed with the organic group that is connected by covalent linkage, these organic groups can be designed to nonactive groups such as straight chained alkyl, cycloalkyl as required, also can be active group, as alkylene, alkoxyl group, epoxy alkyl, alcohol radical, acrylate-based, amino etc.Some active group can make the POSS molecule have acidity or thereby alkalescence can catalytic reaction process.
Benzoxazine colophony is a class novel hot setting resin that grows up on the basis of traditional resol, it is to be the intermediate that raw material synthetic one class contains heterocycle structure with phenolic compound, aldehydes and aminated compounds, and the reticulation that ring-opening polymerization generates nitrogenous similar resol takes place under heating and/or catalyst action.03146797.0) and " phenolphthalein type benzoxazine intermediate and composition and method of making the same " (Chinese patent application number: the content 200510087724.5) background technology of its main synthetic method can be with reference to the inventor in " containing allylic benzoxazine intermediate of N-and composition and method of making the same " (Chinese patent application number:.In various disclosed documents, the advantage of the benzoxazine colophony of pointing out is except the excellent properties that comprises traditional resol such as high heat resistance, flame retardant resistance, good electricity, chemical property, low water absorbable, low cost etc., and in solidification process, there is not small molecules to emit, goods zero shrink or slight expansion are arranged, polymkeric substance has low thermal expansivity, good resistance to elevated temperatures and mechanical property, special benefits such as moisture resistance is good.But also there is shortcoming in benzoxazine colophony, molecular weight as polymkeric substance is low, solidification value is high, cross-linking density is low, property is crisp, toughness is relatively poor etc., and reported method all is to have done a series of improvement research at these shortcomings of benzoxazine in existing literature, the patent.
Because the special construction of POSS and benzoxazine, the investigator passes through the whole bag of tricks gradually, the POSS molecule is combined with benzoxazine colophony improve its performance.200610114117.8) and " 2-oxazoline-Ben Bing Evil compounds and its composition and method of making the same " (Chinese patent application number: the content 200610114118.2) technology Beijing of POSS Dui benzoxazine colophony method of modifying specifically can be with reference to the inventor in " containing the silicious sesquioxane of benzoxazinyl group and its composition and preparation method " (Chinese patent application number:.In various disclosed documents and the patent, point out that the adding of POSS can improve performances such as the second-order transition temperature of benzoxazine colophony, storage modulus, thermostability, dielectricity, do not relate to the research that POSS reduces the benzoxazine colophony solidification value.
Hajime Kimura etc. has studied the influence of the solidification process of salt pair benzoxazine/bisoxazoline resin that the reaction of tosic acid and organic amine (as diethanolamine) obtains, benzoxazine/Resins, epoxy, the result shows, these organic ammonium salts of tosic acid can reduce the solidification value of resin system to a certain extent, shorten set time, but in thermogravimetric analysis, this ammonium salt does not improve the remaining carbon of cured resin.(specifically referring to 1, Hajime Kimura, Akihiro Matsumoto, Keiko Ohtsuka, Journal of Applied PolymerScience, 2008,107:710-718; 2, Hajime Kimura, Akihiro Matsumoto, Keiko Ohtsuka.Journal of Applied Polymer Science, 2008,109:1248-1256)
Research does not at present all relate to the study on the modification of the cage type silsesquioxane Dui benzoxazine/bisoxazoline resin that contains sulfonic acid ammonium salt, benzoxazine/Resins, epoxy, benzoxazine/compositions of thermosetting resin such as Resins, epoxy/bisoxazoline.The cage type silsesquioxane that the applicant then finds to contain sulfonic acid ammonium salt can reduce the solidification value of benzoxazine/bisoxazoline resin, benzoxazine/Resins, epoxy, benzoxazine/compositions of thermosetting resin such as Resins, epoxy/bisoxazoline, improves the modulus and the remaining carbon of cured product.
Summary of the invention
The objective of the invention is to propose the polyhedral oligomeric silsesquioxane that a class contains the katalysis of diving, and it and the composition and method of making the same of thermosetting resins compositions such as benzoxazine, bisoxazoline and Resins, epoxy.This method is to make after the composition that will contain the ammonium sulphonate polyhedral oligomeric silsesquioxane of the catalytic group of diving and benzoxazine, bisoxazoline and Resins, epoxy mixes, reduce the solidification value of resulting composition, improved the modulus and the remaining carbon of cured product.
The objective of the invention is to propose to utilize the polyhedral oligomeric silsesquioxane and the sulfonic acid reaction of amino-contained, or contain polyhedral oligomeric silsesquioxane and the primary amine or the secondary amine reaction of Phenylsulfonic acid group, make the polyhedral oligomeric silsesquioxane that contains the katalysis of diving; With this polyhedral oligomeric silsesquioxane that contains the katalysis of diving with blend under molten state or in solvent prepares compositions of thermosetting resin with benzoxazine, bisoxazoline and Resins, epoxy.
The polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, the group that wherein has latent katalysis is an ammonium sulphonate.
The polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, the group that wherein has latent katalysis is paratoluenesulfonic acid ammonium salt or ammonium benzene sulfonate.
The preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes is: the polyhedral oligomeric silsesquioxane of amino-contained is dissolved in the certain amount of solvent, tetrahydrofuran (THF) for example, add sulfonic acid according to amido and sulfonic group molar ratio 1/1～1/2, the polyhedral oligomeric silsesquioxane that contains ammonium sulphonate that generates is separated out from solution gradually, makes through separating drying.
The preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes is: the polyhedral oligomeric silsesquioxane of amino-contained is dissolved in the certain amount of solvent, tetrahydrofuran (THF) for example, according to amido and sulfonic group molar ratio 1/1～1/2, add tosic acid, the polyhedral oligomeric silsesquioxane that contains paratoluenesulfonic acid ammonium salt that generates is separated out from solution gradually, makes through separation, washing, drying.
Among the preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, used sulfonic acid comprises chlorsulfonic acid, and alkylsulphonic acid is methylsulphonic acid for example, and aryl sulfonic acid is tosic acid for example.
Among the preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, used sulfonic acid is tosic acid.
The basic polyhedral oligomeric silsesquioxane that contains amine that adopts among the preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes comprises cage type aminocarbonyl phenyl silicious sesquioxane, for example cage type eight aminophenyl silicious sesquioxanes, cage type hexamine base phenyl silicious sesquioxane, cage type ten aminocarbonyl phenyl silicious sesquioxanes, cage type amino dodecane base phenyl silicious sesquioxane; Cage modle eight aminocarbonyl propyl silicious sesquioxanes; Cage modle monoamine base silicious sesquioxane, cage modle monoamine base propyl group seven phenyl silicious sesquioxanes for example, cage modle monoamine base propyl group seven isobutyl-silicious sesquioxanes; The single anilino silicious sesquioxane of cage modle, single anilino seven isobutyl-silicious sesquioxanes of cage modle for example, wherein amido can be contraposition, a position, ortho position and their mixture; And the mixture of above-mentioned different amido oligomer silasesquioxaness.
The polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes comprises the sulfonate of cage type aminocarbonyl phenyl silicious sesquioxane, for example tosilate of the tosilate of the tosilate of tosilate, metilsulfate and the chlorosulfonate of cage type eight aminophenyl silicious sesquioxanes, cage type hexamine base phenyl silicious sesquioxane, cage type ten aminocarbonyl phenyl silicious sesquioxanes, cage type amino dodecane base phenyl silicious sesquioxane; The tosilate of cage modle eight aminocarbonyl propyl silicious sesquioxanes; The tosilate of cage modle monoamine base silicious sesquioxane, the tosilate of cage modle monoamine base propyl group seven phenyl silicious sesquioxanes for example, the tosilate of cage modle monoamine base propyl group seven isobutyl-silicious sesquioxanes; The tosilate of the single anilino silicious sesquioxane of cage modle, the tosilate of the single anilino seven isobutyl-silicious sesquioxanes of cage modle for example, wherein amido can be contraposition, a position, ortho position and their mixture; And the above-mentioned different mixture that contains the polyhedral oligomeric silsesquioxane of the katalysis of diving.
The preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes is: will contain sulfonic polyhedral oligomeric silsesquioxane and be dissolved in the certain amount of solvent, tetrahydrofuran (THF) for example, add primary amine or secondary amine according to amido and sulfonic group molar ratio 2/1～1/1, for example ethamine or diethanolamine, the polyhedral oligomeric silsesquioxane that contains ammonium sulphonate that generates is separated out from solution gradually, makes through separation, washing, drying.
Among the preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, described amido is the Armeen that this area researchist knows, for example methylamine, ethamine etc., the alicyclic ring primary amine, hexahydroaniline for example, primary aromatic amine, for example aniline; The binary aliphatic primary amine, quadrol for example, aromatic dicarboxylic primary amine, for example Ursol D; Secondary aliphatic amine, diethylamine for example, Diisopropylamine, diethanolamine.
The sulfonic polyhedral oligomeric silsesquioxane that contains that adopts among the preparation method of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes comprises cage type sulfonic group phenyl silicious sesquioxane, for example cage type eight sulfonic group phenyl silicious sesquioxanes, cage type six sulfonic group phenyl silicious sesquioxanes, cage type ten sulfonic group phenyl silicious sesquioxanes, cage type ten disulfonic acid base phenyl silicious sesquioxanes; Partly sulfonated cage type phenyl silicious sesquioxane, for example cage type tetrasulfonic acid base phenyl tetraphenyl-silicon sesquioxyalkane; And their mixture.
The polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes comprises the ammonium salt of sulfonic group phenyl silicious sesquioxane, the ammonium salt of sulfonic group phenyl silicious sesquioxane for example, the ammonium salt that comprises cage type sulfonic group phenyl silicious sesquioxane, for example cage type eight sulfonic group phenyl silicious sesquioxane ethylamine salts, cage type six sulfonic group phenyl silicious sesquioxane ethylamine salts, cage type ten sulfonic group phenyl silicious sesquioxane ethylamine salts, cage type ten disulfonic acid base phenyl silicious sesquioxane ethylamine salts; Partly sulfonated cage type octaphenyl silicious sesquioxane ammonium salt, for example cage type tetrasulfonic acid base phenyl tetraphenyl-silicon sesquioxyalkane ethylamine salt; And their mixture.
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, the composition with benzoxazine monomer, bisoxazoline and Resins, epoxy mixes the back preparation under fusion or solution state respectively.It is characterized in that: the quality percentage composition that contains the polyhedral oligomeric silsesquioxane of the katalysis of diving is 0.5%～15%.
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, scorification and the solution method be familiar with for those skilled in the art.The concrete grammar of scorification is: with benzoxazine Yu at least a in the bisoxazoline, Resins, epoxy mix under 140 ℃ according to certain molar ratio example or mass ratio, after the temperature for the treatment of system is reduced to 100 ℃, the polyhedral oligomeric silsesquioxane that will contain the catalytic group of diving joins in the resin compound according to the ratio of 0.5%～15% (mass content), obtains corresponding compositions of thermosetting resin after mixing.The concrete grammar of solution method is: with benzoxazine Yu the prepolymer of bisoxazoline be dissolved in a certain amount of tetrahydrofuran (THF), add the polyhedral oligomeric silsesquioxane that contains the catalytic group of diving according to certain quality per-cent, after mixing, remove and desolvate, obtain corresponding mixture.
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, the thermosetting resin matrix of employing is a composition at least a in benzoxazine, bisoxazoline, the Resins, epoxy.
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, the thermosetting resin matrix of employing is at least two kinds a composition in benzoxazine, bisoxazoline, the Resins, epoxy.
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, used benzoxazine colophony is the benzoxazine that this area researchist knows in the thermosetting resin matrix that adopts, comprise N-alkyl benzoxazine, N-Ben base benzoxazine, N-alicyclic radical benzoxazine, the allylic benzoxazine of N-, wherein modal is dihydroxyphenyl propane-aniline type benzoxazine, specifically can be with reference to the inventor in " containing allylic benzoxazine intermediate of N-and composition and method of making the same " (Chinese patent application number: 03146797.0), " phenolphthalein type benzoxazine intermediate and composition and method of making the same " (Chinese patent application number: 200510087724.5), 200610114117.8) and " 2-oxazoline-Ben Bing Evil compounds and its composition and method of making the same " (Chinese patent application number: the content 200610114118.2) (the Chinese patent application number: that " contains the silsesquioxane of benzoxazinyl group and its composition and preparation method ".。
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, used bisoxazoline is the compound that contains the bisoxazoline group that this area researchist knows in the thermosetting resin matrix that adopts, for example 1,3-pair-(2-oxazolinyl) benzene (PBO), 1,4-pair-(2-oxazolinyl) benzene, 2,2 '-two-(2-oxazoline) is (BOZ).
The preparation method of the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes, used Resins, epoxy can be the various Resins, epoxy that this area researchist knows in the thermosetting resin matrix that adopts, comprise monofunctional epoxy resin and polyfunctional epoxy resin, for example bifunctional epoxy resin, trifunctional epoxy resin, four sense Resins, epoxy, modal E51 etc.
The present invention adopts scorification and solution method can obtain a series of benzoxazine/bisoxazoline, benzoxazine/Resins, epoxy and benzoxazine/compositions of thermosetting resin such as Resins, epoxy/bisoxazoline that contain the polyhedral oligomeric silsesquioxane of the katalysis of diving, the solidification value of the compositions of thermosetting resin of this polyhedral oligomeric silsesquioxane that contains the katalysis of diving reduces, and over-all properties improves.
The thermosetting resin that the compositions of thermosetting resin of the polyhedral oligomeric silsesquioxane that contains the katalysis of diving that the present invention proposes is familiar with applicable to those skilled in the art and the various contour machining procedures of matrix material thereof are as sprayup process, resin transfer molding technology (RTM technology), die press technology for forming, casting molding process, impregnation technology, winding process, pultrusion molding process etc.; The strongthener that the preparation matrix material uses can be that various fibers or nanometer strengthen particle; The porosity of resulting product or matrix material is low, shrinks little; Can be used as high-performance tackiness agent and coating,, and can replace traditional resol, Resins, epoxy to be used for electronic industry as the matrix resin of high performance composite.
Embodiment
The initial solidification value of compositions of thermosetting resin, peak value solidification value adopt differential scanning calorimeter (DSC) method to measure, storage modulus adopts dynamic thermomechanical analysis apparatus (DMA) method to measure, and decomposition temperature and remaining carbon adopt thermogravimetric analyzer (TGA) to measure.The benzoxazine that Comparative Examples and embodiment adopt is that (BZ) ， bisoxazoline is 1 to dihydroxyphenyl propane-aniline type benzoxazine, and 3-pair-(2-oxazolinyl) benzene (PBO), Resins, epoxy is E51.
Comparative Examples 1
With benzoxazine Yu bisoxazoline according to 1: 1 mol ratio at 140 ℃ of following melt blendings, after the temperature of system to be mixed drops to 100 ℃, the mixture of molten state is poured in the good mould of cleaning in advance, put into vacuum drying oven and be cured, obtain Polybenzoxazine (PBZ)/dioxazole quinoline (PBO) matrix material batten according to 120 ℃/1h, 140 ℃/1h, 160 ℃/2h, 180 ℃/3h, 200 ℃/1h, the curing process of 220 ℃/1h.The initial solidification value of benzoxazine monomer and dioxazole quinoline composition is 192.7 ℃, and the peak value solidification value is 233.7 ℃.The storage modulus of PBZ/PBO in the time of 100 ℃ (E ') be 1.25GPa, weightless 10% decomposition temperature is 374.1 ℃, remaining carbon is 42.98%.
Embodiment 1
Eight aminophenyl POSS (OAPS) are reacted with quantitative tosic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/1, generate cage modle eight aminophenyl silicious sesquioxane tosilate (OPAAS), after separation, washing, drying, productive rate 95.4%.
Embodiment 2
Eight aminophenyl POSS (OAPS) are reacted with quantitative tosic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/2, generate cage modle eight aminophenyl silicious sesquioxane tosilate (OPAAS), after separation, washing, drying, productive rate 95.7%.
Embodiment 3
Eight aminophenyl POSS (OAPS) are reacted with quantitative methylsulphonic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/1, generate cage modle eight aminophenyl silicious sesquioxane metilsulfates (OAPS-MS), after separation, washing, drying, productive rate 94.1%.
Embodiment 4
Eight aminophenyl POSS (OAPS) are reacted with quantitative chlorsulfonic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/1, generate cage modle eight aminophenyl silicious sesquioxane chlorosulfonates (OAPS-CS), after separation, washing, drying, productive rate 96.1%.
Embodiment 5
Eight aminopropyl POSS (OAS) are reacted with quantitative tosic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/1, generate cage modle eight aminopropyl silicious sesquioxane tosilate (OAS-TS), after separation, washing, drying, productive rate 97.1%.
Embodiment 6
Cage modle monoamine base propyl group seven phenyl silicious sesquioxanes are reacted with quantitative tosic acid in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/2, generate cage modle monoamine base propyl group seven phenyl silicious sesquioxane tosic acid (MAPS-TS), after separation, washing, drying, productive rate 96.1%.
Embodiment 7
Eight sulfonic group phenyl POSS (OSPS) are reacted with quantitative ethamine in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 1/1, generate cage modle eight sulfonic group phenyl silicious sesquioxane ethylamine salts (OSPS-EAS), after separation, washing, drying, productive rate 94.1%.
Embodiment 8
Eight sulfonic group phenyl POSS (OSPS) are reacted with quantitative ethamine in THF solution in molar ratio, wherein amido and sulfonic group mol ratio 2/1, generate cage modle eight sulfonic group phenyl silicious sesquioxane ethylamine salts (OSPS-EAS), after separation, washing, drying, productive rate 95.8%.
Embodiment 9
With benzoxazine Yu bisoxazoline according to the ratio and the method melt blending of Comparative Examples 1, after the temperature of system to be mixed drops to 100 ℃, be 1% according to the quality percentage composition, join benzoxazine Yu in the bisoxazoline co-mixing system with OPAAS, after mixing, promptly obtain composition; The composition of molten state is poured in advance in the good mould of cleaning, put into vacuum drying oven and be cured, obtain Polybenzoxazine (PBZ)/dioxazole quinoline (PBO)/OPAAS matrix material batten according to the curing process of Comparative Examples 1.The initial solidification value of BZ/PBO/OPAAS composition is 183.2 ℃, and the peak value solidification value is 228.2 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 1.83GPa, and weightless 10% decomposition temperature is 387.3 ℃, and remaining carbon is 46.81%.
Embodiment 10
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 2%, and curing makes PBZ/PBO/OSAS matrix material batten.The initial solidification value of BZ/PBO/OPAAS composition is 181.6 ℃, and the peak value solidification value is 227 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 1.89GPa, and weightless 10% decomposition temperature is 380.7 ℃, and remaining carbon is 42.95%.
Embodiment 11
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 3%, and curing makes PBZ/PBO/OPAAS matrix material batten.The initial solidification value of BZ/PBO/OPAAS composition is 171.2 ℃, and the peak value solidification value is 218.2 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 1.95GPa, and weightless 10% decomposition temperature is 387.9 ℃, and remaining carbon is 48.89%.
Embodiment 12
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 4%, and curing makes PBZ/PBO/OPAAS matrix material batten.The initial solidification value of BZ/PBO/OPAAS composition is 177.5 ℃, and the peak value solidification value is 224.5 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 2.00GPa, and weightless 10% decomposition temperature is 390.0 ℃, and remaining carbon is 47.33%.
Embodiment 13
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 5%, and curing makes PBZ/PBO/OPAAS matrix material batten.The BZ/PBO/OPAAS composition is that initial solidification value is 177.5 ℃, and the peak value solidification value is 222.1 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 1.8GPa, and weightless 10% decomposition temperature is 384.4 ℃, and remaining carbon is 47.91%.
Embodiment 14
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the percentage composition of OPAAS is 10%, and curing makes PBZ/PBO/OPAAS matrix material batten.The initial solidification value of BZ/PBO/OPAAS composition is 177.8 ℃, and the peak value solidification value is 215.9 ℃.The E ' of PBZ/PBO/OPAAS matrix material is 1.74GPa, and weightless 10% decomposition temperature is 380.3 ℃, and remaining carbon is 43.99%.
Embodiment 15
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 0.5%.The initial solidification value of BZ/PBO/OPAAS composition is 190.2 ℃, and the peak value solidification value is 230.8 ℃.
Embodiment 16
According to embodiment 9 described methods, OPAAS and BZ/PBO composition are carried out melt blending, the quality percentage composition of OPAAS is 15%.The initial solidification value of BZ/PBO/OPAAS composition is 174.1 ℃, and the peak value solidification value is 213.2 ℃.
Embodiment 17
According to embodiment 9 described methods, cage modle eight aminophenyl silicious sesquioxane metilsulfates (OAPS-MS) and BZ/PBO composition are carried out melt blending, the quality percentage composition of OAPS-MS is 2%.The initial solidification value of BZ/PBO/OAPS-MS composition is 179 ℃, and the peak value solidification value is 223 ℃.
Embodiment 18
According to embodiment 9 described methods, cage modle eight aminophenyl silicious sesquioxane chlorosulfonates (OAPS-CS) and BZ/PBO composition are carried out melt blending, the quality percentage composition of OAPS-CS is 2%.The initial solidification value of BZ/PBO/OAPS-CS composition is 185.3 ℃, and the peak value solidification value is 228 ℃.
Embodiment 19
According to embodiment 9 described methods, cage modle eight aminopropyl silicious sesquioxane tosilate (OAS-TS) and BZ/PBO composition are carried out melt blending, the quality percentage composition of OAS-TS is 2%.The initial solidification value of BZ/PBO/OAS-TS composition is 181 ℃, and the peak value solidification value is 225 ℃.
Embodiment 20
According to embodiment 9 described methods, cage modle monoamine base propyl group seven phenyl silicious sesquioxane tosic acid (MAPS-TS) and BZ/PBO composition are carried out melt blending, the quality percentage composition of MAPS-TS is 10%.The initial solidification value of BZ/PBO/MAPS-TS composition is 191 ℃, and the peak value solidification value is 229 ℃.
Embodiment 21
According to embodiment 9 described methods, cage modle eight sulfonic group phenyl silicious sesquioxane ethylamine salts (OSPS-EAS) and BZ/PBO composition are carried out melt blending, the quality percentage composition of OSPS-EAS is 2%.The initial solidification value of BZ/PBO/OSPS-EAS composition is 186 ℃, and the peak value solidification value is 226 ℃.
Embodiment 22
According to the method for embodiment 9 with BZ and Resins, epoxy (E51) melt blending, wherein the BZ/E51 mol ratio is 1: 1, after the temperature of system to be mixed drops to 100 ℃, OPAAS is joined among the BZ/E51, the mass percent of OPAAS is 4%, mixes to obtain the BZ/E51/OPAAS composition.The initial solidification value of BZ/E51/OPAAS composition is 168 ℃, and the peak value solidification value is 226 ℃.
Embodiment 23
According to the method for embodiment 9 with BZ, E51 and PBO melt blending, wherein the BZ/E51/PBO mol ratio is 1: 1: 1, after the temperature of system to be mixed drops to 100 ℃, OPAAS is joined in the BZ/E51/PBO mixture, the mass percent of OPAAS is 4%, mixes to obtain the BZ/E51/PBO/OPAAS composition.The initial solidification value of BZ/E51/PBO/OPAAS composition is 178 ℃, and the peak value solidification value is 223 ℃.
Claims (10)
1, the present invention proposes polyhedral oligomeric silsesquioxane alkyl sulfonate and the compositions of thermosetting resin thereof that a class has latent katalysis, it is characterized in that: utilize the polyhedral oligomeric silsesquioxane and the sulfonic acid reaction of amino-contained, or contain the polyhedral oligomeric silsesquioxane and the primary amine reaction of Phenylsulfonic acid group, make the polyhedral oligomeric silsesquioxane that contains the katalysis of diving; With this polyhedral oligomeric silsesquioxane that contains the katalysis of diving with blend under molten state or in solvent prepares compositions of thermosetting resin with benzoxazine, bisoxazoline and Resins, epoxy.
2, the polyhedral oligomeric silsesquioxane that contains the katalysis of diving according to claim 1, the group that it is characterized in that having latent catalytic is an ammonium sulphonate.
3, the polyhedral oligomeric silsesquioxane that contains the katalysis of diving according to claim 1, the group that it is characterized in that having latent catalytic is paratoluenesulfonic acid ammonium salt or ammonium benzene sulfonate.
4, the preparation method who contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 1 is characterized in that: the polyhedral oligomeric silsesquioxane of amino-contained is dissolved in the certain amount of solvent according to amido with sulfonic group molar ratio 1/1～1/2 adding sulfonic acid and prepare.
5, the preparation method who contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 1, it is characterized in that: will contain sulfonic polyhedral oligomeric silsesquioxane and be dissolved in the certain amount of solvent, and add primary amine or secondary amine and prepare according to amido and sulfonic group molar ratio 2/1～1/1.
6, the preparation method who contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 4 is characterized in that used sulfonic acid is chlorsulfonic acid, alkylsulphonic acid, aryl sulfonic acid.
7, the preparation method who contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 4, it is characterized in that: the polyhedral oligomeric silsesquioxane of amino-contained comprises cage type aminocarbonyl phenyl silicious sesquioxane, cage modle eight aminocarbonyl propyl silicious sesquioxanes, cage modle monoamine base silicious sesquioxane, the single anilino silicious sesquioxane of cage modle, and the mixture of above-mentioned different amido oligomer silasesquioxaness.
8, the preparation method who contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 5, it is characterized in that: contain sulfonic polyhedral oligomeric silsesquioxane and comprise cage type sulfonic group phenyl silicious sesquioxane, partly sulfonated cage type phenyl silicious sesquioxane, and their mixture.
9, the composition and method of making the same that contains the polyhedral oligomeric silsesquioxane of the katalysis of diving according to claim 1 is, to contain composition blend preparation under molten state or in solvent of polyhedral oligomeric silsesquioxane and the benzoxazine monomer, bisoxazoline and the Resins, epoxy of the katalysis of diving, it is characterized in that: the quality percentage composition that contains the polyhedral oligomeric silsesquioxane of the katalysis of diving is 0.5%～15%.
10, the compositions of thermosetting resin that contains the polyhedral oligomeric silsesquioxane alkyl sulfonate with latent katalysis according to claim 1, it is characterized in that: the thermosetting resin matrix is a composition at least a in benzoxazine, bisoxazoline, the Resins, epoxy.
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| CN200910163123A CN101619073A (en) | 2009-08-18 | 2009-08-18 | Cage type silsesquioxane sulphonate with potential catalytic action and thermosetting resin composite thereof |
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| CN200910163123A CN101619073A (en) | 2009-08-18 | 2009-08-18 | Cage type silsesquioxane sulphonate with potential catalytic action and thermosetting resin composite thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013521243A (en) * | 2010-03-01 | 2013-06-10 | エボニック デグサ ゲーエムベーハー | Polyhedral oligomeric silsesquioxane (POSS) binding ligand |
| CN108727831A (en) * | 2018-05-23 | 2018-11-02 | 湖南博隽生物医药有限公司 | A kind of medical antibacterial silica gel material and preparation method thereof |
| CN112126194A (en) * | 2020-09-15 | 2020-12-25 | 江南大学 | Preparation method of toughened and modified epoxy resin composite material |
-
2009
- 2009-08-18 CN CN200910163123A patent/CN101619073A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013521243A (en) * | 2010-03-01 | 2013-06-10 | エボニック デグサ ゲーエムベーハー | Polyhedral oligomeric silsesquioxane (POSS) binding ligand |
| CN108727831A (en) * | 2018-05-23 | 2018-11-02 | 湖南博隽生物医药有限公司 | A kind of medical antibacterial silica gel material and preparation method thereof |
| CN112126194A (en) * | 2020-09-15 | 2020-12-25 | 江南大学 | Preparation method of toughened and modified epoxy resin composite material |
| CN112126194B (en) * | 2020-09-15 | 2021-11-02 | 江南大学 | Preparation method of toughened and modified epoxy resin composite material |
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