CN1944441A - Sesqui-siloxane containing benzoxazinyl group and its composition and preparing method - Google Patents
Sesqui-siloxane containing benzoxazinyl group and its composition and preparing method Download PDFInfo
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- CN1944441A CN1944441A CN 200610114117 CN200610114117A CN1944441A CN 1944441 A CN1944441 A CN 1944441A CN 200610114117 CN200610114117 CN 200610114117 CN 200610114117 A CN200610114117 A CN 200610114117A CN 1944441 A CN1944441 A CN 1944441A
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Abstract
The present invention is one kind of sesqui-siloxane containing benzoxazinyl group and its preparation process and composition. The sesqui-siloxane containing benzoxazinyl group is prepared with sesqui-siloxane containing primary amido phenyl radical as amine source, and through condensation cyclization with phenol and aldehyde. The sesqui-siloxane containing benzoxazinyl group may be mixed with epoxy resin, phenolic resin, bismaleimide resin, or other thermosetting resin or their composition to form benzoxazinyl group-containing sesqui-siloxane composition. The benzoxazinyl group-containing sesqui-siloxane composition can form cured matter with obviously raised heat resisting property.
Description
Technical field
The present invention relates to the synthetic method of a class silsesquioxane.More particularly, relate to silsesquioxane and its composition and the preparation method who contains benzoxazinyl group.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane is called for short POSS) is a member in the silsesquioxane family, is the novel nano material of a class.The molecular diameter of POSS is very little, and about 1～3 nanometer, its cage structure exactly like silicon-dioxide (Si: O=1: 1.5).Can be regarded as silicon-dioxide (silica) or " the molecule silica " of least unit.POSS has can bear very high temperature and intensity, flame retardant properties excellence, low-density characteristics; Eight summits of its cage structure (or claim " angle ") but the various organo-functional groups of keyed jointing become POSS organic functional monomer, can regard a class organic inorganic hybridization molecule as.Known organo-functional group such as amido, epoxy group(ing), ester group, phenyl, vinyl, cyclohexyl, methyl, isobutyl-etc., and the organic group at each angle can be identical, and also can be different.This has given POSS the organic materials matrix has been had good consistency, even can enter high molecular main chain and cross-linked network at high molecular side chain or direct polymerization by the chemical bond grafting, prepare commixed type, copolymerization or crosslinked hybridized polymer or polymer composites.
U.S. Hybridplastics company is in China application, and one of authorized patent (Chinese patent application number: 00813875.3), contained multiple synthetic method; One of Japan's Nippon Steel Chemical Co., Ltd application relates to POSS synthetic patent, and (Chinese patent application number: 03154435.5), main preparation contains the base-catalyzed method of epoxy group(ing), POSS such as acrylate-based." preparation method of amino-contained phenyl silsesquioxane " that the inventor proposes (Chinese patent application number 200610080871.4) disclosed the novel method of preparation amino-contained phenyl silsesquioxane.
Taiwan Zhang Fengzhi professor seminar has taken the lead in preparing the nano composite material of benzoxazine colophony and POSS, and they at first synthesize the POSS molecule (BZ-POSS) that band has the oxazine ring structure by following two kinds of routes: one by the POSS molecule with si-h bond and the oxazine monomer that has an allyl group carry out the addition of silicon hydrogen; The 2nd, the POSS molecule and the formaldehyde that have a kiber alkyl amine group, phenol are Chenged the oxazine ring structure according to certain molar mass than anti-Xing of answering.Then BZ-POSS is mixed with Chun De oxazine monomer, heat up again and solidify, make the nano composite material of POSS/ benzoxazine colophony.The result shows, compare with matrix resin, the second-order transition temperature and the thermal degradation temperature of the introducing Ti Gao oxazine resin of POSS molecule, but find simultaneously, the consistency of BZ-POSS molecule and benzoxazine monomer is bad, easily reunites, and forms the structure that is separated in cured product, when the content of BZ-POSS is increased to a certain degree, the thermal characteristics of compound system can descend on the contrary.They also attempt selecting for use the POSS of the isobutyl group that has anergy and benzoxazine directly to carry out melt blending under study for action, the preparation matrix material, the result shows that this class POSS molecule is compatible with matrix resin very poor, so its introducing makes the degradation of matrix resin.(specifically referring to Y.J.Lee 1,, S.W.Kuo, T.C.Su, J.K.Chen, C.W.Tu, F.C.Chang, Syntheses, thermal properties, and phase morphologies ofnovel benzoxazine functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites, Polymer, 2004,45 (18): 6321-6331; 2, Y.J.Lee, J.M.Huang, S.W.Kuo, J.K.Chen, F.C.Chang, Synthesis and characterizations of a vinyl-terminatedbenzoxazine monomer and its blending with polyhedral oligomeric silsesquioxane (POSS), Polymer, 2005,46 (7): 2320-2330)
The relevant technologies background of benzoxazine 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) and " phenolphthalein type benzoxazine intermediate and composition and method of making the same " (Chinese patent application number: the content 200510087724.5).In various open source literatures, reported between the benzoxazine, benzoxazine and other thermosetting resins prepare composition, wherein other thermosetting resins comprise that benzoxazine intermediate, Resins, epoxy, unsaturated polyester resin, Vinylite, bimaleimide resin, resol, urethane resin, cyanate ester resin or Thermocurable polyimide etc. all are thermosetting resin well known to those skilled in the art and composition thereof.The introducing of benzoxazine can improve the resistance toheat of composition, or reduces cost, or improves processing characteristics.Benzoxazine and composition thereof have broad application prospects in many fields such as matrix material, printed circuit board (PCB), Electronic Packaging, coating.
But do not utilize the preparation of primary amine groups phenyl silsesquioxane to contain the report of the silsesquioxane of benzoxazinyl group so far, do not utilize it to prepare the report of composition yet.
Summary of the invention
The objective of the invention is to propose a kind of preparation method and composition thereof that contains the silsesquioxane of benzoxazinyl group.This method is to be the amine source to contain primary amine groups phenyl silsesquioxane compound, carries out cyclic condensation with phenol, aldehyde, obtains containing the silsesquioxane of benzoxazinyl group.This compounds can mix with thermosetting resins such as Resins, epoxy, resol, bimaleimide resin, cyanate ester resin, benzoxazine colophony, oxazoline resin, polyimide resin or their composition, obtains containing the composition of the silsesquioxane of benzoxazinyl group.
The structural formula of the silsesquioxane that contains benzoxazinyl group of the present invention is as follows:
(RSiO
1.5)n
Wherein n is 6,8,12
Wherein R is following structure:
R1, R2, R3, R4 all are hydrogen in the formula; Or R1, R2, R3, R4 one of them be alkyl or the allyl group or the vinyl of carbonatoms 1～10, its excess-three is a hydrogen; R2, R4 are carbonatoms 1～10 alkyl, and R1, R3 are hydrogen.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the silsesquioxane that silsesquioxane, phenol and the aldehyde of amino-contained is contained benzoxazinyl group with solution or flux synthesis procedure preparation, it is characterized in that: amine adopts the silsesquioxane, particularly eight aminocarbonyl phenyl silsesquioxanes of amino-contained; The mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group is (1～15) in the reactant: 1: (2～4).
The silsesquioxane that contains benzoxazinyl group that the present invention proposes, its preparation method can adopt the synthetic method of benzoxazine well known to those skilled in the art, comprises following two kinds of methods:
(1) solution synthetic method: with the silsesquioxane of phenol, amino-contained, the mol ratio (1～15) that aldehyde (formalin or Paraformaldehyde 96) is pressed phenolic hydroxyl group, amido, aldehyde radical functional group: 1: (2～4) are quantitative, earlier phenol and primary amine are dissolved in mix in the solvent after, gradation adds aldehyde again, and the temperature rising reflux reaction finishes reaction after 2～10 hours; Use deionized water wash,, in hexane, precipitate, filter, remove the silsesquioxane that obtains containing benzoxazinyl group after remaining solvent, the drying the gained solution concentration.
(2) flux synthesis procedure: with the silsesquioxane of phenol, amino-contained, the mol ratio (1～15) that aldehyde (Paraformaldehyde 96 or formalin) is pressed phenolic hydroxyl group, amido, aldehyde radical functional group: 1: (2～4) are quantitative, at low temperatures (0 ℃～5 ℃) in advance the silsesquioxane with phenol and amino-contained mix, add aldehyde then, the temperature rising reflux reaction finishes reaction after 2～10 hours; Use deionized water wash, dissolution with solvents precipitates in hexane, filters, removes the silsesquioxane that obtains containing benzoxazinyl group after remaining solvent, the drying.
The present invention adopts solution synthetic method or flux synthesis procedure can obtain a series of silsesquioxanes that contain benzoxazinyl group.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the amido silsesquioxane that adopts comprises eight aminocarbonyl phenyl silsesquioxanes, hexamine base phenyl silsesquioxane, amino dodecane base phenyl silsesquioxane, polyamines base phenyl oligomeric silsesquioxane.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the phenol of employing comprises phenol, the monoalkyl fortified phenol, for example p-cresol, meta-cresol, ortho-cresol, nonyl phenol, many alkyl substituted phenols, for example 3,5-dimethyl phenol etc., the unsaturated group fortified phenol, for example adjacent allyl phenol, 4-vinyl phenol etc., halogenated phenol, para-chlorophenol etc. for example, p methoxy phenol can also be other single phenolic compounds well known to those skilled in the art.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the phenol of employing comprises phenol, p-cresol, meta-cresol, ortho-cresol, nonyl phenol, 3,5-dimethyl phenol, adjacent allyl phenol, 4-vinyl phenol, para-chlorophenol.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the aldehyde of employing is formalin well known to those skilled in the art or Paraformaldehyde 96.
The preparation method of the silsesquioxane that contains benzoxazinyl group that the present invention proposes, the solvent of employing is benzene,toluene,xylene well known to those skilled in the art, dioxane, tetrahydrofuran (THF) (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), ethanol, butanols, Virahol etc.
The composition that the silsesquioxane that contains benzoxazinyl group that the present invention proposes and other thermosetting resins are mixed with, other thermosetting resins comprise at least a in: benzoxazine intermediate, Resins, epoxy, unsaturated polyester resin, Vinylite, bimaleimide resin, oxazoline resin, resol, urethane resin, cyanate ester resin, Thermocurable polyimide, aryl ethane resin or the furane resin; The silsesquioxane weight content that contains benzoxazinyl group is 1%～15% of a composition.
The preparation of compositions method that the silsesquioxane that contains benzoxazinyl group that the present invention proposes and other thermosetting resins are mixed with comprises that mechanically mixing, solution mixing or melting mixing etc. well known to a person skilled in the art blending means and obtain composition.
The prepared cured article of composition that the silsesquioxane that contains benzoxazinyl group that the present invention proposes and other thermosetting resins are mixed with, POSS is uniformly dispersed in its matrix, and cured article has higher heat resistance.
The composition that the silsesquioxane that contains benzoxazinyl group that the present invention proposes and other thermosetting resins are mixed with is applicable to the complete processing of various thermosetting resins well known to those skilled in the art and the moulding process of matrix material.For example: coating process, impregnation technology, pultrude process also can adopt rotational molding moulding process (RTM) etc.; The strongthener that the preparation matrix material uses comprises various fibers well known to those skilled in the art such as glass fibre, carbon fiber, can also use carbon nanotube, nanometer inorganic filler nanometer reinforcing fillers such as (as nano titanium oxide, organo-clay etc.); The thermotolerance of resulting product or matrix material, flame retardant resistance be improved significantly; Can be applied to many fields such as matrix material, printed circuit board (PCB), Electronic Packaging, coating.
Embodiment
Embodiment 1
Get 2 gram (0.173mmol) eight aminocarbonyl phenyl silsesquioxanes (being called for short OAPS), p-cresol, Paraformaldehyde 96 are quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 1: 1: 2, earlier p-cresol and OAPS are dissolved in mix in the dioxane after, gradation adds aldehyde again, and the temperature rising reflux reaction finishes reaction after 2～10 hours; Use deionized water wash,, in hexane, precipitate, obtain p-cresol type eight benzoxazinyl silsesquioxanes (cBZ-POSS) 0.3 gram, productive rate 8% after filtering, remove remaining solvent, drying the gained solution concentration.
Embodiment 2
Described according to embodiment 1, just that p-cresol, Paraformaldehyde 96 is quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 2: 1: 2, finally obtain about 0.5 gram of cBZ-POSS, productive rate 13%.
Embodiment 3
Described according to embodiment 1, just that p-cresol, Paraformaldehyde 96 is quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 5: 1: 3, finally obtain about 0.84 gram of cBZ-POSS, productive rate 22%.
Embodiment 4
Described according to embodiment 1, just that p-cresol, Paraformaldehyde 96 is quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 10: 1: 3, finally obtain about 1.22 grams of cBZ-POSS, productive rate 32%.
Embodiment 5
Described according to embodiment 1, just that p-cresol, Paraformaldehyde 96 is quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 15: 1: 4, finally obtain about 1.07 grams of cBZ-POSS, productive rate 28%.
Embodiment 6
Get 5 gram (0.173mmol) OAPS, p-cresol, Paraformaldehyde 96 are quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 1: 1: 2, earlier p-cresol and OAPS are mixed, after OAPS dissolves fully, cool to 0～5 ℃, gradation adds aldehyde again, and the temperature rising reflux reaction finishes reaction after 6 hours; Behind acetic acid ethyl dissolution, in hexane, precipitate, obtain eight benzoxazinyl silsesquioxanes (cBZ-POSS), 0.57 gram, productive rate 15% after filtering, remove remaining solvent, drying.
Embodiment 7
Described according to embodiment 6, just get 2 gram (0.173mmol) OAPS, p-cresol, Paraformaldehyde 96 are quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 13.4: 1: 2.89, finally obtain about 2.9 grams of cBZ-POSS, productive rate 75%.
Embodiment 8
Described according to embodiment 6, just get 2 gram (0.173mmol) OAPS, p-cresol, Paraformaldehyde 96 are quantitative according to the mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group 15: 1: 4, finally obtain about 2.6 grams of cBZ-POSS, productive rate 68%.
Embodiment 9
Described according to embodiment 7, just phenol replaces p-cresol, finally obtains about 1.56 grams of phenol type eight benzoxazinyl silsesquioxanes (BZ-POSS), productive rate 43%.
Embodiment 10
Described according to embodiment 7, just nonyl phenol is replaced p-cresol, finally obtain about 3.06 grams of nonyl phenol type eight benzoxazinyl silsesquioxanes (nBZ-POSS), productive rate 57%.
Embodiment 11
Described according to embodiment 7, just o-allyl phenol replaces p-cresol, finally obtains about 2.63 grams of nonyl phenol type eight benzoxazinyl silsesquioxanes (nBZ-POSS), productive rate 63%.
Embodiment 12
Adopt the dihydroxyphenyl propane aniline type benzoxazine (BA) of dihydroxyphenyl propane, aniline, prepared formaldehyde to be cured, solidify the segmentation temperature and time: following 1 hour at 100 ℃, following 1 hour at 130 ℃, following 1 hour at 160 ℃, 180 ℃ following 3 hours, following 3 hours at 200 ℃, 220 ℃ following 1 hour, promptly obtain cured article; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 177 ℃.
Embodiment 13
99 parts of BA and 1 part of eight benzoxazinyl silsesquioxane (writing a Chinese character in simplified form cBZ-POSS) are dissolved in THF under the room temperature, mix after 1 hour, and vacuum removal THF obtains the BA/cBZ-POSS composition, is cured according to embodiment 12 described conditions of cure, obtains cured article; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 177.5 ℃.
Embodiment 14
95 parts of BA and 5 parts of cBZ-POSS obtain cured article according to embodiment 13 described methods; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 180 ℃.
Embodiment 15
90 parts of BA and 10 parts of cBZ-POSS obtain cured article according to embodiment 13 described methods; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 183 ℃.
Embodiment 16
85 parts of BA and 15 parts of cBZ-POSS obtain cured article according to embodiment 13 described methods; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 194 ℃.
Embodiment 17
15 parts of E-51 type Resins, epoxy, 60 parts of BA and 15 parts of cBZ-POSS obtain cured article according to embodiment 13 described methods; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 185 ℃.
Embodiment 18
40 part 2,2 '-(1, the 3-phenylene)-two (4,5-dihydro-oxazolines) (PBO), 45 parts of BA and 15 parts of cBZ-POSS mix, and are warming up to 140 ℃, and the PBO/BA/cBZ-POSS system is mixed, cooling obtains composition.Be cured according to embodiment 12 described conditions of cure, obtain cured article; Measure through dynamic viscoelastic analyser (being called for short DMA), its second-order transition temperature (Tg) is 190 ℃.
Claims (3)
1, it is as follows to contain the structural formula of silsesquioxane of benzoxazinyl group:
(RSiO
1.5)n
Wherein n is 6,8,12
Wherein R is following structure:
R1, R2, R3, R4 all are hydrogen in the formula; Or R1, R2, R3, R4 one of them be alkyl or the allyl group or the vinyl of carbonatoms 1～10, its excess-three is a hydrogen; R2, R4 are carbonatoms 1～10 alkyl, and R1, R3 are hydrogen.
2, the preparation method who contains the silsesquioxane of benzoxazinyl group according to claim 1, the silsesquioxane that silsesquioxane, phenol and the aldehyde of amino-contained is contained benzoxazinyl group with solution or flux synthesis procedure preparation, it is characterized in that: amine adopts the silsesquioxane, particularly eight aminocarbonyl phenyl silsesquioxanes of amino-contained; The mol ratio of phenolic hydroxyl group, amido, aldehyde radical functional group is (1～15) in the reactant: 1: (2～4).
3, contain the silsesquioxane of benzoxazinyl group and the composition that other thermosetting resins are mixed with, other thermosetting resins comprise at least a in: benzoxazine intermediate, Resins, epoxy, unsaturated polyester resin, Vinylite, bimaleimide resin, oxazoline resin, resol, urethane resin, cyanate ester resin, Thermocurable polyimide, aryl ethane resin or the furane resin; The silsesquioxane weight content that contains benzoxazinyl group is 1%～15% of a composition.
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| CN102775614A (en) * | 2011-05-13 | 2012-11-14 | 北京化工大学 | Double-decker-shaped silsesquioxane-containing benzoxazine resin |
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