CN103476837A - Process for producing a composite material - Google Patents

Process for producing a composite material Download PDF

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CN103476837A
CN103476837A CN2012800143998A CN201280014399A CN103476837A CN 103476837 A CN103476837 A CN 103476837A CN 2012800143998 A CN2012800143998 A CN 2012800143998A CN 201280014399 A CN201280014399 A CN 201280014399A CN 103476837 A CN103476837 A CN 103476837A
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compd
metal
aryloxy
compound
formaldehyde
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A·朗格
G·考克斯
R·戴利克-布伦岑格
O·格朗瓦尔德
T·史密斯
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BASF SE
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BASF SE
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
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    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Abstract

The present invention relates to a process for producing composite materials which consist essentially of a) at least one oxidic phase and b) at least one organic polymer phase, by copolymerizing at least one compound A selected from aryloxy metallates, aryloxy semimetallates and aryloxy esters of non-metals which form oxo acids and are different from carbon and nitrogen, with at least one compound B selected from formaldehyde and formaldehyde equivalents, in a reaction medium which is essentially anhydrous, the compound B being used in an amount such that the molar ratio of formaldehyde to the aryloxy groups in the compound A is at least 0.9:1.

Description

The method for preparing matrix material
The present invention relates to a kind of method that is prepared matrix material by following material:
A) at least one oxidation phase; With
B) at least one organic polymer phase.
Recently, existing many about the record for preparing matrix material by so-called Dual polymerization (twin polymerization) (referring to, such as people such as Spange, Angew.Chem.Int.Ed., 46 (2007) 628-632, WO2009/083083, WO2009/133086, WO2010/112581 and WO2010/128144).Dual polymerization comprises and carries out polymerization by having a plurality of by one or two heteroatoms---being preferably one or two Sauerstoffatom---with the compound of the arylmethyl of atoms metal or semi-metal atomic linkage.
Dual polymerization provides the matrix material that usually has at least one oxidation phase and at least one organic polymer phase, and wherein region has common continuous arrangement and size is about several nanometers (distance between adjacent phase homophase).Infer that at first the little distance between specific arrangement mutually and adjacent phase is because secondly the Dynamics Coupling of arylmethyl unit polymerization in dual monomer is because formed silicon-dioxide.Therefore, phase component almost forms simultaneously, and just is separated as inorganic phase and organic phase in dual monomer polymerization process.
Preferred dual monomer is the spirocyclic compound be recorded in WO2009/083083.In these spirocyclic compounds, two 1-oxygen-2-(oxygen methyl) thus aryl is connected to atoms metal by their Sauerstoffatom or the semi-metal atom forms spirane structure.An example of this spirocyclic compound is 2,2 '-spiral shell [4H-1,3,2-benzo dioxa silane (benzodioxasilin)].
The method preparation that described spirocyclic compound can be put down in writing in WO2009/083083, prepare in relative simple mode with metal alkoxide or semi-metal alcohol reactant salt by the 1-hydroxyl such as 1-hydroxyl-2-hydroxymethyl benzene (saligenin)-2-hydroxymethyl aromatic hydrocarbon.Yet parent material is the preparation relative complex of 1-hydroxyl-2-hydroxymethyl aromatic hydrocarbon.The form meaning, 1-hydroxyl-2-hydroxymethyl aromatic hydrocarbon is single adduct that formaldehyde is added to the hydroxyaromatic hydrocarbon.But, be added in the process such as the hydroxyaromatic hydrocarbon of phenol and usually can not generate the monoadduct of wanting at formaldehyde, but generate o, o-dihydroxyl methyl compound (referring to Rec.Trav.Chim.Pays-Bas62,57 (1943)).Known equally, can be reduced to suitable reductive agent corresponding 1-hydroxyl-2-hydroxymethyl aromatic hydrocarbon (referring to J.Chem.Soc.PT1 such as salicylic adjacent hydroxyaryl carboxylic acid, (1981) 1942-1952 and Bull.Chem.Soc.Jap.56,719-723,), or phenyl boronate can obtain monoadduct with formaldehyde reaction and the adjacent hydroxymethyl phenyl boronate hydrolyzable that then generates is saligenin (referring to FR2626575) (1983).The common trait of all these methods has obtained well and result repeatably by purification process in laboratory for it, but whole implementation process complexity.Not exclusively conversion or by product cause product loss.Therefore, obtain the spirocyclic compound of putting down in writing in WO2009/083083 and be complicated and still be subject to strict restriction, up to now, this has become the obstruction for the preparation of the industrial application of the Dual polymerization of nano composite material.
DE1816241 discloses the preparation of solubility containing metal or semimetallic phenol-formaldehyde resin, the formaldehyde reaction of specific metal or semi-metal phenates and substoichiometric amount wherein, or phenolic varnish (being the P-F condenses) react with selected inorganic metal or semi metallic compound.Record prepares the matrix material of phase structure that region has the size of nanometer range.
Now have been surprisingly found that, by:
-at least one be selected from aryloxy metallide, aryloxy semi-metal compound and form oxygen acid and be different from carbon and the compd A of the nonmetallic aryloxy ester of nitrogen with
-at least one is selected from the compd B of formaldehyde and formaldehyde equivalent,
Copolymerization in substantially anhydrous reaction medium, can prepare and there is the similar matrix material of nano composite material that region is arranged the Dual polymerization acquisition that can put down in writing in prior art with those, wherein, compd B makes with such amount: in formaldehyde and compd A, the mol ratio of aryloxy is 0.9:1 at least.
Why unexpected this is, be because the formation of having inferred nano composite material so far owing to being present in the structural unit existed in dual monomer, it has via heteroatoms covalently bound to metal or semimetallic aryl methylene.Infer so far, these structural units cause the Dynamics Coupling of the formation of the Dynamics Coupling of polymerization of organic molecule part of dual monomer and " inorganic polymer " (being inorganic phase), this is that formation due to polymerization and inorganic phase has common reactions steps, i.e. the mesomethylene carbon of aryl methylene and with the bond rupture between the heteroatoms of (partly) metal.Think that the Dynamics Coupling caused thus is the reason that in Dual polymerization, the feature nanostructure forms.Yet the feature structure unit of dual monomer does not have aryloxy metallide, aryloxy semi-metal compound and nonmetallic aryloxy ester.
Therefore, the present invention relates to a kind of method for preparing the matrix material substantially formed by following material:
-at least one oxidation phase; With
-at least one organic polymer phase;
Described method comprises:
-at least one be selected from aryloxy metallide, aryloxy semi-metal compound and form oxygen acid and be different from carbon and the compd A of the nonmetallic aryloxy ester of nitrogen with
-at least one is selected from the compd B of formaldehyde and formaldehyde equivalent,
Copolymerization in substantially anhydrous reaction medium, wherein, compd B makes with such amount: the mol ratio of the aryloxy in the formaldehyde in compd B or formaldehyde equivalent and compd A is at least 0.9: 1, especially at least 1: 1, particularly at least 1.01: 1 and be at least 1.05: 1 especially.
Method of the present invention has a plurality of advantages.At first, method of the present invention provides the matrix material as obtained in Dual polymerization, by the following matrix material formed:
A) at least one oxidation phase; With
B) at least one organic polymer phase,
Described oxidation phase and described organic polymer phase are comprised of region basically, and wherein the mean distance between the adjacent region of phase homophase is very little.Yet, different from the situation of Dual polymerization, be the matrix material that acquisition is wanted, do not need to be difficult to the parent material obtained, as spirocyclic compound or unsettled arylmethyl (partly) metallide of mentioning at this paper introductory song, as four (furyl methoxyl group) silane.In contrast, may use and can hold the facile and metastable parent material with aryloxy metallide, aryloxy semi-metal compound and nonmetal aryloxy ester-formin, this makes it possible to prepare more on a large scale matrix material.
In addition, method of the present invention can---by selecting suitable compd A or the mixture of compd A---be carried out controlled modification (controlled modification) to substance characteristics that can thus obtained matrix material.The mixture of the different compd As that for example, may differ from one another by copolymerization metal, semi-metal or nonmetal type is modified the characteristic of inorganic polymer phase.For example, may by the mixture copolymerization of different compd As that the aryl type is differed from one another, to the characteristic of organic polymer phase, be modified with similar method.For example, can also to characteristic organic and the inorganic polymer phase, be modified by the mixture copolymerization by metal, semi-metal or the different compd As that nonmetal type differs from one another and aryl differs from one another.
As previously mentioned, method of the present invention provides the matrix material by least one oxidation phase and at least one organic polymer phase composite, and described oxidation phase and described organic polymer phase are comprised of the very little region of mean distance between the adjacent region of phase homophase basically.Mean distance between the adjacent region of phase homophase is less than 200 nanometers usually, usually is less than 100 nanometers or is less than 50 nanometers, and especially being less than 10 nanometers.The adjacent region of phase homophase should be understood two regions that refer to two phase homophases that separated by a region of another phase, two regions of the oxidation phase for example separated by a region of organic polymer phase, or two regions of the polymer phase that separates of a region of oxidized phase.
Aryloxy metallide, aryloxy semi-metal compound and aryloxy ester be interpreted as referring to based on the monohydroxy aromatic hydrocarbon and from the form meaning say have one or more (especially 1,2,3,4,5 or 6) from the monohydroxy aromatic hydrocarbon by the derivative aryloxy obtained of aromatic hydroxy functional group deprotonation or the compound of negatively charged ion, should via the Sauerstoffatom of the deprotonation of the hydroxy functional group of monohydroxy aromatic hydrocarbon, be bonded in from the derivative aryloxy obtained of monohydroxy aromatic hydrocarbon or negatively charged ion metal, semi-metal or nonmetal on.This atoms metal, semi-metal atom or form oxygen acid and be different from C and the non-metallic atom of N hereinafter also referred to as central atom.Compd A can have one or more central atoms, and, for situation about having more than a central atom, compd A can have linearity, side chain, monocycle or polynuclear plane.
Suitable monohydroxy aromatic hydrocarbon is specially phenol, naphthyl alcohol or 2-Naphthol, and it is unsubstituted or for example, usually is selected from alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and NR containing one or more---1,2,3 or 4--- ar b(R wherein aand R bbe hydrogen, alkyl or cycloalkyl independently of one another) substituting group.
Herein and hereinafter, the collective term that term " alkyl ", " thiazolinyl ", " cycloalkyl ", " alkoxyl group ", " cycloalkyloxy " and " aryl " are rolled into a ball for any monovalent organic radical with its usual definition, wherein alkyl and alkoxyl group usually containing 1 to 20, usually containing 1 to 10 and especially containing 1 to 4 carbon atom, cycloalkyl and cycloalkyloxy usually containing 3 to 20, usually containing 3 to 10 and especially containing 5 or 6 carbon atoms.Carbonatoms possible in group is usually with prefix C n-C mmean, wherein n is minimum carbonatoms and m is maximum carbonatoms.
In the context of this article, alkyl be usually containing 1 to 20, usually containing 1 to 10 and especially containing saturated, the straight or branched alkyl of 1 to 4 carbon atom, it be such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 1-methyl butyl, 3-amyl group, n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 2-ethylhexyl, n-nonyl, 1-methyl nonyl, just decyl, 3-propylheptyl etc.
Thiazolinyl is usually containing 2 to 20, usually containing 2 to 10 and especially undersaturated containing the olefinic of 2 to 6 carbon atoms, the straight or branched alkyl, it is for example vinyl, the 1-propenyl, the 2-propenyl, the 1-methyl ethylene, 1-methyl-1-propylene base, 2-methyl-1-propylene base, 1-methyl-2-propenyl, 2-methyl-2-propenyl, the 1-pentenyl, pentenyl, the 3-pentenyl, the 4-pentenyl, 1-methyl isophthalic acid-butenyl, the 2-methyl-1-butene thiazolinyl, the 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, the 1-hexenyl, the 2-hexenyl, the 3-hexenyl, the 4-hexenyl, the 5-hexenyl, 1-methyl-1-pentene thiazolinyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, the 4-methyl-1-pentene base, 1-methyl-pentenyl, 2-methyl-pentenyl, 3-methyl-pentenyl, 4-methyl-pentenyl, the 1-methyl-3-pentenyl, the 2-methyl-3-pentenyl, the 3-methyl-3-pentenyl, the 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-crotyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butylene base, 1,2-dimethyl-crotyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butylene base, 1,3-dimethyl-crotyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butylene base, 2,3-dimethyl-crotyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butylene base, 3,3-dimethyl-crotyl, 1-ethyl-1-butylene base, 1-ethyl-crotyl, 1-ethyl-3-butenyl, 2-ethyl-1-butylene base, 2-ethyl-crotyl, 2-ethyl-3-butenyl, 1,1,2-trimethylammonium-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-Ethyl-2-Methyl-1-propenyl and 1-Ethyl-2-Methyl-2-propenyl.
Alkoxyl group is the alkyl as defined above via a Sauerstoffatom bonding, its usually containing 1 to 20, usually containing 1 to 10 and especially containing 1 to 4 carbon atom and its be such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-methyl butoxy, 1-methyl butoxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, 1-methyl oxygen in heptan base, 2-methyl oxygen in heptan base, 2-ethyl oxygen in heptan base, just the ninth of the ten Heavenly Stems oxygen base, 1-methyl oxygen in ninth of the ten Heavenly Stems base, n-decyloxy, 3-propyl group oxygen in heptan base etc.
Cycloalkyl be usually containing 3 to 20, usually containing 3 to 10 and especially containing monocycle, dicyclo or the three ring filling alicyclic groups of 5 or 6 carbon atoms, its for cyclopropyl for example, cyclobutyl, cyclopentyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, dicyclo [2.2.1] heptan-1-base, dicyclo [2.2.1] heptan-2-base, dicyclo [2.2.1] heptan-7-base, dicyclo [2.2.2] suffering-1-base, dicyclo [2.2.2] suffering-2-base, 1-adamantyl or 2-adamantyl.
Cycloalkyloxy is via the monocycle of a Sauerstoffatom bonding, dicyclo or three ring filling alicyclic groups, its usually have 3 to 20, usually have 3 to 10 and especially there are 5 or 6 carbon atoms and for for example encircle propoxy-, cyclobutoxy group, cyclopentyloxy, cyclopentyloxy, cyclohexyloxy, ring oxygen in heptan base, ring octyloxy, dicyclo [2.2.1] heptan-1-base oxygen base, dicyclo [2.2.1] heptan-2-base oxygen base, dicyclo [2.2.1] heptan-7-base oxygen base, dicyclo [2.2.2] suffering-1-base oxygen base, dicyclo [2.2.2] suffering-2-base oxygen base, 1-Buddha's warrior attendant alkoxyl group or 2-Buddha's warrior attendant alkoxyl group.
Aryl is monocycle or polycyclic aromatic alkyl, for example phenyl, 1-naphthyl or 2-naphthyl.
Except aryloxy, other groups also can be bonded to central atom, and other groups for example are selected from 1,2 or 3 organic group of alkyl, thiazolinyl, cycloalkyl or aryl, or 1 or 2 Sauerstoffatom.The valency that the sum of binding groups is usually by central atom---being atoms metal, semi-metal atom or the non-metallic atom of these group institute bondings---is determined.
Usually, the central atom of compd A is to be selected from the de-carbon of the following family of the periodic table of elements and the element beyond nitrogen: IA is as Li, Na or K, IIA is as Mg, Ca, Sr or Ba, IIIA is as B, Al, Ga or In, IVA is as Si, Ge, Sn or Pb, and VA is as P, As or Sb, VIA as S, Se or Te, IVB as Ti or Zr, VB is as V, VIB as Cr, Mo or W and VIIB as Mn.The central atom of compd A preferably is selected from the de-carbon of IIIA, IVA, VA and IVB family of the periodic table of elements and the element beyond nitrogen, and especially is selected from the element of second, third and period 4 in these elements.This central atom more preferably is selected from B, Al, Si, Sn, Ti and P.
In a specific embodiments of the present invention, compound used is aryloxy semi-metal compound, such as semimetallic compound of B or Si.In a specific embodiments of the present invention, compd A is selected from the aryloxy semi-metal compound that semi-metal contains at least 90 % by mole of (the total amount meter based on the semi-metal atom) silicon.
According to the present invention, suitable compd A can specifically be described with following general formula I:
[(ArO) mMO nR p] q (I)
Wherein
M is metal, semi-metal or forms oxygen acid and be different from carbon and nitrogen nonmetal;
M is 1,2,3,4,5 or 6,
N is 0,1 or 2,
P is 0,1 or 2,
Q be 1 or>1 integer, for example 2 to 20 integer, especially 3 to 6 integer,
M+2n+p is 1,2,3,4,5 or 6 and be equivalent to the valency of M,
Ar is phenyl or naphthyl, and wherein phenyl ring or naphthalene nucleus are unsubstitutedly maybe can for example, be selected from alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and NR containing one or more---1,2 or 3--- ar b(R wherein aand R bbe hydrogen, alkyl or cycloalkyl independently of one another) substituting group;
R is alkyl, thiazolinyl, cycloalkyl or aryl, and wherein aryl is unsubstituted or for example, is selected from alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and NR containing one or more---1,2 or 3--- ar b(R wherein aand R bsubstituting group separately as defined above).
When the m in formula I is 2,3,4,5 or 6, the Ar base can be identical or different certainly, and wherein different Ar can be the difference of the different of aromatic ring type and/or the mode of replacement type.When the p in formula I is 2, the R base can be identical or different certainly.
Formula I is interpreted as empirical formula; It means type and the number feature of the structural unit of compd A, i.e. central atom M and be bonded in the group on central atom, for example the R base of aryloxy ArO, Sauerstoffatom O and bond with carbon; And the quantity of these unit.When q>1, [(ArO) mmO nr p] unit can form monocycle or polynuclear plane or linear structure.
In formula I, M is metal or semi-metal or forms oxygen acid and be different from carbon and nitrogen nonmetal, this metal, semi-metal and nonmetal usually be selected from the following family of the periodic table of elements denitrogenate and carbon beyond element: IA is as Li, Na or K, IIA is as Mg, Ca, Sr or Ba, and IIIA is as B, Al, Ga or In, and IVA is as Si, Ge, Sn or Pb, VA is as P, As or Sb, VIA is as S, Se or Te, IVB as Ti or Zr, and VB is as V, VIB as Cr, Mo or W and VIIB as Mn.M preferably is selected from the de-carbon of IIIA, IVA, VA and IVB family of the periodic table of elements and the element beyond nitrogen, and especially is selected from the element of second, third and period 4 in these elements.M more preferably is selected from B, Al, Si, Sn, Ti and P.In a particularly preferred embodiment according to the invention, M is B or Si and is especially Si.
In a preferred embodiment of the invention, the p in formula I is 0, and it refers to that atom M is not with any R base.In another preferred embodiment of the present invention, at least two kinds of different compd As and formaldehyde or formaldehyde equivalent copolymerization, wherein variable p=0 in the compound of variable p=0 and at least another kind of formula I in the compound of at least one formula I.
Do not consider these, variable m, n, p, Ar and the R in formula I (independent or combination, and especially with one of preferred and particularly preferred definition of M in conjunction with) preferably be defined as follows separately:
M is 2,3 or 4;
N is 0 or 1;
P is 0,1 or 2, especially 0;
Ar is that unsubstituted phenyl maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl), cycloalkyl (C especially 3-C 10cycloalkyl), alkoxyl group (C especially 1-C 4alkoxyl group), cycloalkyloxy (C especially 3-C 10cycloalkyloxy) and NR ar b(R wherein aand R bbe hydrogen, alkyl (C especially independently of one another 1-C 4alkyl) or cycloalkyl (C especially 3-C 10cycloalkyl)) substituent phenyl;
R, as existed, is C 1-C 6alkyl, C 2-C 6thiazolinyl, C 3-C 10cycloalkyl or phenyl, especially C 1-C 4alkyl, C 5-C 6cycloalkyl or phenyl.
More specifically, variable m, n, p, Ar and the R in formula I (independent or combination, and especially with one of preferred and particularly preferred definition of M in conjunction with) preferably be defined as follows separately:
M is 1,2,3 or 4;
N is 0 or 1;
P is 0;
Ar is that unsubstituted phenyl maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.
A preferred embodiment of compd A is those compounds of the formula I that wherein q is 1.The visual ortho ester of making the parent oxygen acid of central atom M of this compounds.In these compounds, that variable m, n, p, M, Ar and R have separately as defined above and especially is independent or combination, especially with the definition of one of preferred or particularly preferred definition combination.
Those compounds that a particularly preferred embodiment of compd A is formula I: the M in formula I is selected from B, Si, Sn, Ti and P, m be 3 or 4, n be 0 or 1, p be 0 and q=1.Wherein Ar have above-mentioned definition and especially as preferably mention those, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.
Those compounds that an embodiment very particularly preferably of compd A is formula I: the M in formula I is selected from B, Si and Sn, m be 3 or 4, n be 0 and p be 0 and q=1.Wherein Ar have above-mentioned definition and especially as preferably mention those, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.
Those compounds that a specific embodiments of compd A is formula I: the M in formula I is Si, m be 4, n be 0 and p be 0.Wherein Ar have above-mentioned definition and especially as preferably mention those, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.
According to the present invention, the example of the formula I compound of preferred q=1 is tetraphenoxy-silicane alkane, four (4-methylphenoxy) silane, triphenyl borate, triphenylphosphate, tetraphenyl titanate, metatitanic acid tetramethyl phenyl ester and stannic acid four phenyl esters.
Those compounds that other embodiments of compd A are the general formula I that differs from one another of Ar group.Therefore, the fusing point of compd A reduces usually, and this can be favourable to polymerization.
There is different Ar and the example of preferred formula I compound is triple phenoxyl (4-methylphenoxy) silane, two phenoxy groups two (4-methylphenoxy) silane, phenylbenzene (4-aminomethyl phenyl) boric acid ester, triphenyl (4-aminomethyl phenyl) titanic acid ester and phenylbenzene two (4-aminomethyl phenyl) titanic acid ester and composition thereof according to the present invention.
Those compounds that another specific embodiments of compd A is formula I: the M in formula I is Si, m be 1,2 or 3, n be 0 and p be 4-m.Wherein Ar has above-mentioned definition and especially as the definition preferably mentioned, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.In these compounds, the definition of R is suc as formula I; More specifically, R is methyl, ethyl, phenyl, vinyl or allyl group.The example of the preferred compound A of this embodiment is methyl (triple phenoxyl) silane, dimethyl (two phenoxy groups) silane, trimethylammonium (phenoxy group) silane, phenyl (triple phenoxyl) silane and phenylbenzene (two phenoxy groups) silane.
As compd A same suitable be " condensation product " of the formula I compound of q=1.These compounds formula I that usually sees service, the integer that wherein q is>1, for example 2 to 20 integer and especially 3,4,5 or 6.Say from the form meaning, thereby slough separately 2 ArO unit on the formula I compound form of this compounds by q=1, form Ar-O-Ar molecule and M (OAr) m-2(O) n+1r pthe condensation course of unit and obtaining.Therefore, it is formed by the structural element of following formula I a basically:
-[-O-A-]- (Ia)
Wherein-A-is>M (ArO) m-2(O) n(R) pgroup, on wherein M, Ar and R have separately
The definition of stating, especially as preferably or particularly preferably mention those.
M is 3 or 4,
N is 0 or 1 and especially 0,
P is 0 or 1 and especially 0,
M+2n+p is 3,4,5 or 6 and be equivalent to the valency of M.
M in formula A is preferably Si, Sn, B and P.
In a preferred embodiment, condensation product is ring-type and q is 3,4 or 5.This compounds can be especially with following structrual description:
Figure BDA0000385113190000101
Wherein, k be 1,2 or 3 and-A-is>M (ArO) m-2(O) n(R) pgroup, wherein M, Ar and R have the definition of above-mentioned formula I, and m, n have the above-mentioned definition relevant with structure I a with p.
In another preferred embodiment, that condensation product is straight chain and for saturated, end is with the ArO unit.In other words, the structure I c that this compounds can be following describes:
Ar-[-O-A-] q-OAr (Ic)
Wherein, the integer that q is 2 to 20 and-A-is>M (ArO) m-2(O) n(R) pgroup, wherein M, Ar and R have the definition of above-mentioned formula I, and m, n have the above-mentioned definition relevant with structure I a with p.(while existing with different q), particularly preferably this embodiment when compound has the distribution with regard to the repeating unit number.For example, may have mixture, wherein at least 99%, 90%, 80% or 60% quality exists as oligomer mixture (wherein q=2 to 6 or q=4 to 9 or q=6 to 15 or q=12 to 20).
The example of this class condensation product is metaboric acid triphenylmethyl methacrylate, six phenoxy group cyclotrisiloxane or eight phenoxy group cyclotetrasiloxanes.
Compd A is known or can be similar to the known method preparation for preparing phenates; Referring to, O.F.Senn for example, WADC Technical Report54-339, SRI (1955), DE1816241, Z.Anorg.Allg.Chem.551,61-66 (1987), Houben-Weyl, volume VI-235-41, Z.Chem.5,122-130 (1965).
In another embodiment of the invention, compd A comprises at least two kinds of different compd As 1 and A2, compd A 1 is selected from wherein M and is B, Si, Sn, Ti or P and is especially B, Si or Sn, m be 1,2,3 or 4, n be 0 or 1 especially 0, p is 0 and the compound of the q formula I that is 0,1,3 or 4, compd A 2 is selected from wherein M and is selected from Si and Sn, m is the compound that 2, n is 0, q=0 and the p formula I that is 2.Ar in compd A 1 and A2 can be identical or different, wherein Ar have above-mentioned definition and especially as preferably mention those, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.Here R is preferably C 1-C 6alkyl, C 3-C 10cycloalkyl or phenyl, especially C 1-C 4alkyl, C 5-C 6cycloalkyl or phenyl.
In another specific embodiment of the present invention, compd A comprises at least two kinds of different compd As 1 and A2, it is Si that compd A 1 is selected from wherein M, m is 2 or 4, n is that 0, p is 0 and the compound of the q formula I that is 1,3 or 4, and it is Si that compd A 2 is selected from wherein M, m is that 2, n is 0 and the compound of the p formula I that is 2.Ar in compd A 1 and A2 can be identical or different, wherein Ar have above-mentioned definition and especially as preferably mention those, and especially for unsubstituted phenyl, maybe can be selected from alkyl (C especially containing 1,2 or 3 1-C 4alkyl) and alkoxyl group (C especially 1-C 4alkoxyl group) substituent phenyl.Here R is preferably C 1-C 6alkyl, C 3-C 10cycloalkyl or phenyl, especially C 1-C 4alkyl, C 5-C 6cycloalkyl or phenyl.
In the method for the invention, compd A and formaldehyde or formaldehyde equivalent (compd B) make with such amount: the formaldehyde in chemical combination B---being the amount of the formaldehyde that maybe exists in formaldehyde equivalent when using formaldehyde equivalent of the amount of monomer formaldehyde used---with the mol ratio of the aryloxy ArO existed in compd A at least 0.9: 1, be preferably at least 1: 1, be at least 1.01: 1 especially, be more preferably at least 1.05: 1 and be especially at least 1.1: 1.Generally speaking, higher excess formaldehyde is harmless but non-essential, therefore formaldehyde or formaldehyde equivalent make with such amount usually: formaldehyde or the mol ratio that is present in the formaldehyde in formaldehyde equivalent and is present in the aryloxy ArO in compd A are no more than 10: 1, are preferably 5: 1 and the numerical value of 2: 1 especially.The such amount of preferably take is used formaldehyde or formaldehyde equivalent to make: formaldehyde or the formaldehyde be present in formaldehyde equivalent are 1: 1 to 10: 1 with the mol ratio that is present in the aryloxy ArO in compd A, are 1.01: 5: 1 especially and are especially 1.05: 1 to 5: 1 or 1.1: 1 to 2: 1.
Formaldehyde equivalent is interpreted as referring to the compound that discharges formaldehyde under polymerizing condition.This formaldehyde equivalent is preferably oligopolymer or the polymkeric substance of formaldehyde, the formula that sees service (CH 2o) xmaterial, the x in this formula means the polymerization degree.These are particularly including trioxane (3 formaldehyde units) and paraformaldehyde (higher oligomers (CH 2o) x).
Preferably use the compd B (hereinafter also referred to as formaldehyde source) that is selected from gaseous formaldehyde, trioxane and paraformaldehyde to implement polyreaction.This compound is the Wei trioxane especially.
In a preferred embodiment of the inventive method, under existing, the acid of catalytic amount implements the polyreaction of compd A and formaldehyde source.Usually, acid is with the amount use, particularly 0.2 % by weight to 5 % by weight of 0.1 % by weight to 10 % by weight, based on the compd A meter.Preferred acid herein is
Figure BDA0000385113190000111
acid, for example carboxylic acid (as trifluoroacetic acid, oxalic acid or lactic acid) and organic sulfonic acid, especially C 1-C 20alkylsulphonic acid (as methylsulphonic acid, octyl group sulfonic acid, decyl sulfonic acid or dodecyl sodium sulfonate), haloalkyl sulfonic acid (as trifluoromethane sulfonic acid), Phenylsulfonic acid or C 1-C 20alkyl benzene sulphonate (ABS), toluenesulphonic acids, nonyl benzene sulfonic acid or Witco 1298 Soft Acid.Same suitable is inorganic
Figure BDA0000385113190000121
acid, as HCl, H 2sO 4or HClO 4.Louis (Lewis) acid of using can be BF for example 3, BCl 3, SnCl 4, TiCl 4or AlCl 3.Also may use form complexed or be dissolved in the Lewis acid of ionic liquid.
Also can react with base catalyzed polymerization.The oxyhydroxide that example is amine (as triethylamine or xylidene(s)), alkali and alkaline earth metal ions and basic salt are (as LiOH, NaOH, KOH, Ca (OH) 2, Ba (OH) 2or Na 3pO 4) and the alkoxide (as sodium methylate, sodium ethylate, potassium tert.-butoxide or magnesium ethylate) of alkali and alkaline earth metal ions.
Also can thermal-initiated polymerization react, do not add the mixture by heating compound A and B in sour situation to implement polyreaction.
The required temperature of polyreaction is usually in the scope of 50 to 250 ℃, particularly in the scope of 80 to 200 ℃.In the polyreaction of acid catalysis or base catalysis, polymerization temperature is usually in 50 to 200 ℃ of scopes and particularly in the scope of 80 to 150 ℃.In the thermal-initiated polymerization reaction, polymerization temperature is usually in 120 to 250 ℃ of scopes and particularly in the scope of 150 to 200 ℃.
In principle, can so-called batch process (batch process) or addition method (addition process) enforcement polyreaction.With regard to implementing with batch process, at first compd A and B are added to reactor with required amount and make it reach the condition of polyreaction needs.In addition method, supply with at least in part at least one (being compd A and/or B) in two kinds of components until reach the ratio of wanting of compd A and compd B during polyreaction.It after adding, is optionally the reacting phase continued.Preferably with batch process, implement.
Have now found that, it is favourable implementing polyreaction with single stage method (one stage), this means to treat that the total amount of the compd A of polymerization and B is as a collection of enforcement polyreaction, or the use addition method, wherein compd A and B add and make by this way: before the compd As of whole amounts and B add reactor, do not interrupt polymerizing condition.
The polyreaction of compd A and B can be carried out in body or inert diluent.Suitable thinner is for example halohydrocarbon, as methylene dichloride, trichloromethane, ethylene dichloride; Or hydrocarbon, aromatic hydrocarbons for example, as list-C 1-C 4the benzene of alkyl-replacement or naphthalene or many-C 1-C 4the benzene of alkyl-replacement or naphthalene (for example toluene, dimethylbenzene, isopropyl benzene or sym-trimethylbenzene) or list-alkylnaphthalene and C 1-C alkylnaphthalene, and aliphatic hydrocrbon and clicyclic hydrocarbon, as hexane, hexanaphthene, heptane, suberane, octane and isomer thereof, nonane and isomer thereof, decane and isomer thereof; And their mixture.
The polyreaction of compd A and B is preferably carried out under substantially water-free condition, this means that the concentration of water when polyreaction starts is lower than 0.1 % by weight.
With regard to preparing particulate composite, have now found that, compd A is favourable with reacting in inert diluent of compd B.Preferred inert diluent those that the above-mentioned hydrocarbon of total amount meter at least 80 volume %, particularly at least 90 volume % and especially at least 99 volume % based on thinner or 100 volume % forms of serving as reasons, described hydrocarbon comprises aromatic hydrocarbon, as list-C 1-C 4the benzene of alkyl-replacement or naphthalene or many-C 1-C 4the benzene of alkyl-replacement or naphthalene (for example toluene, dimethylbenzene, isopropyl benzene or sym-trimethylbenzene) or list-alkylnaphthalene and C 1-C 4alkylnaphthalene, and aliphatic hydrocrbon and clicyclic hydrocarbon, as hexane, hexanaphthene, heptane, suberane, octane and isomer thereof, nonane and isomer thereof, decane and isomer thereof; And their mixture.
With regard to preparing particulate composite, also find compd A and compd B react under at least one surfactant exists, preferably in inert diluent, be favourable.
Suitable surfactant is specially anionic emulsifier and nonionic emulsifier.
Anionic emulsifier has at least one hydrophobic grouping (for example at least one is containing at least 6 carbon atoms, especially containing aliphatic group or araliphatic group or at least one oligomeric (alkylsiloxane) group or poly-(alkylsiloxane) group of at least 10 carbon atoms) and at least one anionic group (for example 1 or 2 is selected from for example anionic group of sulfonate group and phosphonate groups, wherein said sulfonate group and phosphonate groups can also sulfate groups or phosphate groups existence) usually.Preferred inorganic anion emulsifying agent contains 1 or 2 sulfonate group or sulfate groups.
Anionic emulsifier comprises sulfuric acid monoester and salt (particularly its ammonium salt and an alkali metal salt) and alkyl, aralkyl and the aryl phosphate ester that usually contains aliphatic series, araliphatic, aromatic sulfonic acid and salt thereof (particularly its ammonium salt and an alkali metal salt), ethoxylation alkanol and the alkylphenol of at least 6 carbon atoms, comprises phosphate monoester and the salt (particularly its ammonium salt and an alkali metal salt) thereof of alkanol and alkylphenol.
Preferred anionic emulsifier is:
An alkali metal salt of-dialkyl sulfosuccinate and ammonium salt (alkyl: C 8to C 16),
An alkali metal salt of-alkyl sulfuric ester and ammonium salt (alkyl: C 8to C 18),
An alkali metal salt of-alkyl sulfonic ester and ammonium salt (alkyl: C 8to C 18),
An alkali metal salt of-alkyl aryl sulphonic acid and ammonium salt (alkyl: C 8to C 18),
The compound of-following general formula
R wherein 1and R 2hydrogen or C respectively do for oneself 4-to C 18-alkyl and be hydrogen when different, and X and Y can respectively do for oneself alkalimetal ion and/or ammonium ion.R 1, R 2preferably respectively do for oneself containing straight or branched alkyl or the hydrogen of 6 to 14 carbon atoms, particularly contain the straight or branched alkyl of 6,12 and 16 carbon atoms, wherein R 1and R 2when different, be hydrogen.X and Y are preferably sodium ion, potassium ion or ammonium ion, particularly preferably sodium ion.Particularly advantageous compound is that X and Y are sodium, R 1for branched-chain alkyl and the R containing 12 carbon atoms 2for hydrogen or R 1those compounds of one of definition (beyond dehydrogenation).Usually, the cuts of the monoalkylation product that usage ratio is 50 % by weight to 90 % by weight, for example
Figure BDA0000385113190000142
2A1 (trade mark of Dow Chemical Company).
Anionic emulsifier can also its sour form be used, and now it is as initiator.
The example of suitable nonionic emulsifier is generally in alkyl in ethoxylation alkanol containing 8 to 36 carbon atoms, alkyl usually ethoxylation monoalkyl phenol, ethoxylation dialkyl group phenol and the ethoxylation trialkyl phenol containing 4 to 12 carbon atoms, wherein the ethoxylation degree of ethoxylation alkanol and alkylphenol is generally 2 to 100, and particularly 3 to 50.The example of suitable non-ionic surfactant compound is also ethoxylation oligomeric (dialkylsiloxane) and poly-(dialkylsiloxane), especially ethoxylation oligomeric (dimethyl siloxane) and poly-(dimethyl siloxane), wherein these compounds have at least 2---for example 2 to 50---dialkylsiloxane unit and ethoxylation degree are 2 to 100, particularly 3 to 50.
Can after the polyreaction of compd A and B, implement purification step and optional drying step.
Can after the polyreaction of compd A and B, implement calcining step.It comprises that the organic polymer materials carbonization formed in the polyreaction that makes monomeric unit B is the carbon phase.
Can after the polyreaction of compd A and B, implement the oxidation removal step of organic polymer phase.It comprises that the organic polymer materials oxidation formed in the polyreaction that makes organic constituent is to obtain nanoporous oxidation material or nanoporous nitride material.
The matrix material that can obtain by method of the present invention has at least one and comprises metal, semi-metal or the nonmetallic oxidation phase except C and N and the organic polymer phase that at least one is obtained by the polyreaction of aryloxy and formaldehyde.The size of the region in thus obtained matrix material is generally approximately several nanometers, but may obtain the material of region size maximum to the 100-200 nanometer.In addition, the region of oxidation phase and the region of organic phase are generally common continuous arrangement, i.e. organic phase and inorganic phase or organo-metallic infiltration and basically do not form any discontinuity zone each other mutually.Distance between adjacent phase border or the distance between adjacent identical region are minimum and on average be no more than 100 nanometers, usually be no more than 50 nanometers, be no more than especially 10 nanometers or be no more than 5 nanometers and especially be no more than 2 nanometers, but may obtain the material of area size's maximum to the 100-200 nanometer.There do not is microscopic separation phenomenon in the discontinuous zone of specific phase.
Mean distance between adjacent identical region can be measured (measurement of 20 ℃ of lower transmitances, monochromatic CuK by Scattering of Vector q by combination (combined) small angle X ray scattering (SAXS) αradiation, 2D detector (image plate), slit collimation).
About term " external phase zone ", " discontinuous phase zone " and " external phase zone altogether ", equally can be referring to people Definitions of Terms Related to Polymer Blends such as W.J.Work, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations2004), Pure Appl.Chem., 76 (2004), 1985-2007 page, particularly the 2003rd page.Accordingly, the common continuous arrangement of two-component mixture is interpreted as referring to the arrangement that is separated of two-phase, wherein in a zone of specific phase, through a continuous path of arbitrary region, can be extended down to all phases border and not with any region boundary-intersected.
The organic constituent that the matrix material that can obtain according to the present invention can known method itself be removed nano composite material of the present invention by oxidation is converted into Porous Inorganic Nanostructure Materials.This can remain resident in the nanostructure of the inorganic phase in nano composite material of the present invention, and according to selected compd A, result obtains (partly) metal or nonmetallic oxide compound or a kind of mixed form.Put down in writing in the people's such as Spange that quote as introductory song article, usually by heating under oxygen-containing atmosphere, implement oxidation.Generally speaking, 400 to 1500 ℃, especially pass into oxygen at the temperature of 500 to 1000 ℃ and heated.Heating is carried out usually under oxygen-containing atmosphere, for example in air or other oxygen/nitrogen mixtures, carries out, and the ratio of oxygen can change in wider scope, for example, in scope 5 volume % to 50 volume %.
The matrix material that can obtain according to the present invention also can be converted into electroactive nano composite material, and it,, except can be oxidation state or this inorganic phase as (partly) metal of (partly) metallic state, also has carbon phase C.This class material can be by the matrix material to obtaining according to the present invention in being calcined and obtain in fact or under complete oxygen-free environment.Containing in carbon nano-composite material, carbon phase C and inorganic phase form basically continuous region altogether, and wherein the mean distance between two of the phase homophase adjacent areas is no more than 10 nanometers usually.Generally speaking, calcining 400 to 2000 ℃, especially at the temperature of 500 to 1000 ℃, carry out.Calcining is subsequently carried out usually under the environment of essence anaerobic.In other words, in calcination process, in the conversion zone of being calcined, oxygen partial pressure is very low, and preferably is no more than 20 millibars, especially is no more than 10 millibars.Calcining is preferably carried out under inert atmosphere, as carried out under nitrogen or argon gas.Inert atmosphere preferably comprises the oxygen that is less than 1 volume %, especially is less than 0.1 volume %.In a same preferred embodiment of the present invention, calcining is carried out under reductive condition, is for example comprising hydrogen (H 2), appropriate hydrocarbon gas (as methane, ethane or propane) or ammonia (NH 3), optionally in the atmosphere as the mixture mixed with rare gas element such as nitrogen or argon gas, carry out.For removing volatile constituent, calcining is carried out in can or comprising the air-flow such as the reducing gas of hydrogen, appropriate hydrocarbon gas or ammonia at inert gas.
The porous of the obtainable matrix material of the present invention and preparation thus particularly can successfully be used to solve known problem or improve performance in many application by Porous Inorganic Nanostructure Materials and electroactive nano composite material---it also has carbon phase C except the inorganic phase of (partly) metal that can be oxidation state or (partly) metallic state---.
The matrix material that for example, can obtain according to the present invention is applicable to for the preparation of gas storage (H especially 2storage) porous carbon materials, for example, to be similar to the method preparation of putting down in writing in WO2009/083082.To this, the full text of WO2009/083082 is included this specification sheets in the mode of reference.
The matrix material that can obtain according to the present invention---especially comprise silicon those---also is suitable for preparing elastomerics or rubber blend, in particular for manufacturing airtyred rubber blend, for example,, to be similar to the method preparation of putting down in writing in US2011-0240197.To this, the full text of US2011-0240197 is included this specification sheets in the mode of reference.
The matrix material that can obtain according to the present invention also be applicable to preparation as so-called low-the porous oxidation material of k dielectric medium---dielectric medium that there are low-k (k<3.7)---, for example, to be similar to the method preparation of putting down in writing in WO2009/133082.To this, the full text of WO2009/133082 is included this specification sheets in the mode of reference.
The matrix material that can obtain according to the present invention---especially comprise silicon those---also is suitable for electroactive material, the especially anode material that preparation is suitable for lithium ion battery, for example, and to be similar to the method preparation of putting down in writing in WO2010/112580.To this, the full text of WO2010/112580 is included this specification sheets in the mode of reference.
In addition, matrix material of the present invention can be similar to the method put down in writing in the WO2011/000858 barrier film for the preparation of electrochemical cell, in particular for preparing the barrier film of lithium cell.To this, the full text of WO2011/000858 is included this specification sheets in the mode of reference.
In addition, matrix material of the present invention can be similar to the method put down in writing in the WO2011/039139 film for the preparation of sepn process.To this, the full text of WO2011/039139 is included this specification sheets in the mode of reference.
Following examples and accompanying drawing are for explaining the present invention.
i. analyze:
With TEM, the sample obtained in copolyreaction is analyzed: utilize Tecnai F20 transmission electron microscope (FEI, Eindhoven, the Netherlands) adopt superthin layer technology (sample is embedded in the synthetic resins of matrix) to be 200 kilovolts in operating voltage and carry out tem analysis with HAADF-STEM.The results are shown in following Fig. 1 a, 1b, 2a, 2b, 3 and 4.Arrow in figure means the special characteristic zone of sample, and it shows that region distance is for approximately several nanometers (<10 nanometer).
iI. accompanying drawing:
The HAADF-STEM of the sample of Fig. 1 a: embodiment 1 analyzes, and ratio of enlargement is 2x10 5.
The HAADF-STEM of the sample of Fig. 1 b: embodiment 1 analyzes, and ratio of enlargement is 10 6.
The HAADF-STEM of the sample of Fig. 2 a: embodiment 2 analyzes, and ratio of enlargement is 2x10 4.Black region is owing to embedded material uniformly.
The HAADF-STEM of the sample of Fig. 2 b: embodiment 2 analyzes, and ratio of enlargement is 10 6.
The HAADF-STEM of the sample of Fig. 3: embodiment 3 analyzes, and ratio of enlargement is 10 6.
The HAADF-STEM of the sample of Fig. 4: embodiment 4 analyzes, and ratio of enlargement is 10 6.
The HAADF-STEM of the sample of Fig. 5: embodiment 9 analyzes, and ratio of enlargement is 10 6.
The HAADF-STEM of the sample of Fig. 6: embodiment 20 analyzes, and ratio of enlargement is 10 6.
iII. the compd A used:
Tetraphenyl-silicon (compound of formula I, M=Si wherein, m=4, n=p=0, q=1, Ar=phenyl)
At first add the phenol of 498 grams 70 ℃ of lower meltings to being equipped with in glassed agitator and sleeve pipe, 2 liter of four neck flask with the prolong of bubble meter and washing tower.By 270 gram SiCl 4dropwise add so that washing tower can be in conjunction with a certain amount of formed HCl.When the release of HCl reduces, internal temperature raises (approximately 6 hours) gradually to 250 ℃.Obtain thus the light color clarification oily matter of at room temperature crystallization of 550 grams.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 7.25ppm (2H, triplet (triplet)), 7.05ppm (1H, triplet), 7.03ppm (2H, doublet)
Six phenoxy group cyclotrisiloxane (compound of formula I, M=Si wherein, m=2, n=1, p=0, q=3, or the compound of formula Ib, M=Si wherein, m=4, n=0, p=0, k=1, Ar=phenyl)
A) at first to being equipped with in glassed agitator and sleeve pipe, 1 liter of four neck flask with the prolong of bubble meter and washing tower, add the phenol of 188 grams 50 ℃ of lower meltings.By 170 gram SiCl 4dropwise add so that washing tower can be in conjunction with a certain amount of formed HCl.When the release of HCl reduces, internal temperature raises (approximately 6 hours) gradually to 250 ℃.Obtain thus 310 gram light color clarification oily matter.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 2 groups of fignal center 7.4.-7.2ppm (2X2H), 6.95-7.15ppm (2X3H)
B) at first to being equipped with in glassed agitator and sleeve pipe, 0.5 liter of four neck flask with the prolong of bubble meter and washing tower, add by the solution of 57 gram affixtures in 200 milliliters of toluene a) obtained.Dropwise add the solution of 3.2 gram water in 50 milliliters of dry THF and mixture is stirred 1 hour again under 25 ℃.Solution is carried out to suction filtration and anhydrate to remove, and concentrated under 80 ℃/10 millibars on Rotary Evaporators.Obtain thus the light color clarification oily matter of 38 gram crystallizations.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 7.25ppm (triplet, 3X2H); 7.04ppm (triplet, 3X1H); 7.03ppm (doublet, 3X2H)
Metaboric acid triphenylmethyl methacrylate (compound of formula I, M=B wherein, m=1, n=1, p=0, q=3 and Ar=phenyl, or the compound of formula Ib, M=B wherein, m=3, n=0, p=0, k=1 and Ar=phenyl)
At first add 156 gram boric acid and 400 milliliters of dimethylbenzene in 2 liter of four neck flask that glassed agitator, thermometer and prolong are housed.Mixture is heated to reflux.After 2 hours, remove condenser, load onto water trap.
In 3 hours, at internal temperature, be to collect altogether 41 ml waters under 122-138 ℃.Then, reaction mixture is heated to reflux and added wherein the solution of 226 gram phenol in 300 milliliters of dimethylbenzene in 1 hour.After this, by mixture return stirring 5 hours again, isolate again the water that total amount is 22 milliliters.The reaction mixture obtained is concentrated into to drying under 100 ℃ and 5 millibars.Obtain thus the solid-state title compound of 230 gram.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 7.29ppm (2H, triplet), 7.12ppm (1H, triplet), 7.05ppm (2H, doublet)
P-methylphenyl phenylbenzene metaboric acid ester (M=B wherein, m=1, n=1, p=0, the mixture of the formula I compound of q=3 and Ar=phenyl and p-methylphenyl, or M=B wherein, m=3, n=0, p=0, the mixture of the formula Ib compound of k=1 and Ar=phenyl and 4-aminomethyl phenyl)
Figure BDA0000385113190000191
At first add 185 gram boric acid and 500 milliliters of dimethylbenzene in 2 liter of four neck flask that glassed agitator, thermometer and prolong are housed.Mixture is heated to reflux.After 2 hours, remove condenser, load onto water trap.
In 3 hours, at internal temperature, be to collect altogether 52 ml waters under 122-137 ℃.Then, reaction mixture is heated to reflux and added wherein 198 gram phenol and the solution of 108 gram p-cresols in 300 milliliters of dimethylbenzene in 1 hour.After this, by mixture return stirring 5 hours again, collect again the water that total amount is 46 milliliters.The reaction mixture obtained is concentrated into to drying under 100 ℃ and 5 millibars.Obtain thus the solid mixt of 340 gram three p-methylphenyl metaboric acid esters (1), di-p-tolyl phenyl metaboric acid ester (2), p-methylphenyl phenylbenzene metaboric acid ester (3) and metaboric acid triphenylmethyl methacrylate (4).
1h NMR (500MHz, 16 scanning, CD 2cl 2):
(7.4-6.6ppm 14H, the aromatic signal of various stacks)
(2.31ppm 3H, unimodal)
Tetraphenyl titanate (compound of formula I, M=Ti wherein, m=4, n=p=0, q=1, Ar=phenyl)
By the method preparation of putting down in writing in DE1816241.
Metatitanic acid tetramethyl phenyl ester (compound of formula I, M=Ti wherein, m=4, n=p=0, q=1, Ar==4-aminomethyl phenyl)-commercially available prod
Triphenylphosphate (compound of formula I, M=P wherein, m=3, n=1, p=0, q=1, Ar=phenyl)-commercially available prod
Phenol aluminium (compound of formula I, M=Al wherein, m=3, n=p=0, q=1, Ar=phenyl)
At first add the phenol of 188 grams 50 ℃ of lower meltings to being equipped with in agitator, 0.5 liter of four neck flask with the prolong of bubble meter and washing tower.Add 30 gram AlCl in 50-70 ℃ of lower minute 3 parts 3, then add all temperature to be risen to approximately 180 ℃ afterwards at every turn, and temperature kept until select without HCl.Then, slough excessive phenol bathing under 180 ℃ of temperature, and use endways water-jet vacuum pump (water-jet vacuum).By the method, obtain 95 grams and approximately usining the title compound obtained as oily matter that crystal habit solidifies under 130 ℃.This title compound is insoluble to methylene dichloride, acetone, trichloromethane or toluene, and is dissolved in DMSO.
1h NMR (500MHz, 16 scanning, DMSO-D 6): 9.36ppm (1H, unimodal), 7.16ppm (2H, triplet), 6.76ppm (1H, triplet), 6.75ppm (2H, doublet) is approximately 5% free-phenol and water and DMSO-D under 3.34ppm 5
Four (4-aminomethyl phenyl) silicon ester (compound of formula I, M=Si wherein, m=4, n=p=0, q=1, Ar=4-aminomethyl phenyl)
At first add the p-cresol of 229 grams 50 ℃ of lower meltings to being equipped with in glassed agitator, 1 liter of four neck flask with the prolong of bubble meter and washing tower.By 107 gram SiCl 4dropwise add and make the washing tower can be in conjunction with a certain amount of formed HCl with this speed.When the release of HCl reduces, internal temperature raises (approximately 6 hours) gradually to 250 ℃.Obtain thus the light color clarification oily matter of at room temperature crystallization of 210 grams.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 7.04ppm (2H, doublet), 6.89ppm (2H, doublet)
Two phenoxy group dimethylsilane (compound of formula I, M=Si wherein, m=2, n=0, p=2, q=1, Ar=phenyl, R=methyl)
At first add the phenol of 344 grams 50 ℃ of lower meltings to being equipped with in glassed agitator, 1 liter of four neck flask with the prolong of bubble meter and washing tower.By 227 gram (CH 3) 2siCl 2dropwise add and make the washing tower can be in conjunction with a certain amount of formed HCl with this speed.When the release of HCl reduces, internal temperature raises (approximately 6 hours) gradually to 250 ℃.Obtain thus 440 gram light color clarification oily matter.
1h NMR (500MHz, 16 scanning, CD 2cl 2): 7.24ppm (2x2H, triplet), 6.98ppm (2x1H, triplet), 6.94ppm (2x2H, doublet), 0.36ppm (2x3H, unimodal)
iV. the embodiment of the present invention:
Embodiment 1: silicic acid four phenyl ester mass polymerizations
3 Ke trioxanes and 10 gram silicic acid four phenyl esters are obtained to even settled solution in 65 ℃ of meltings in 100 milliliters of round-bottomed flasks on Rotary Evaporators.Add wherein 100 milliliters of trifluoroacetic acids, by mixture homogenization.5 gram mixtures are moved into to penicillin bottle (penicillin bottle), with jaw lid (crimp cap), cover tightly bottleneck and be heated to 90-100 ℃ in loft drier.After 15 hours, obtain 4.4 gram clear resins.
The resin sample obtained is carried out to the HAADF-STEM analysis.Phase structure is shown in Fig. 1 a and 1b and shows to exist the area size of approximately several nanometers (<10nm).
Embodiment 2: the precipitation polymerization of silicic acid four phenyl esters in solution
In 250 milliliter of four neck flask, make 20.0 gram silicic acid four phenyl esters and 6.6 Ke trioxanes in nitrogen in 40-50 ℃ of lower melting, and diluted with 80 gram dimethylbenzene.Add wherein 0.2 gram methylsulfonic acid under 50 ℃, make mixture homogenization.Then under the stirring velocity of 500-600rpm, mixture is stirred 30 minutes under 80 ℃, stir 30 minutes under 100 ℃, stir 30 minutes under 120 ℃.Mixture becomes pasty state, then adds 60 gram dimethylbenzene, makes the mixture boiling, then refluxes 30 minutes.Mixture is cooled to room temperature, filters with D4 frit (frit), with dimethylbenzene washing dry in vacuum drying oven.Obtain thus the pink fine powder that 22.5 gram median sizes are 14 microns, its spherical primary particle by 1 micron of diameter forms (sees Fig. 2 a).This primary particle shows the representative region structure of Dual polymerization, is of a size of 2-5 nanometer (seeing Fig. 2 b).
Embodiment 3: the mass polymerization of triphenylphosphate
33 Ke trioxanes and 109 gram triphenylphosphates are obtained to even settled solution in 50 ℃ of meltings in the round-bottomed flask on Rotary Evaporators.
Experiment a)
This solution of 5 grams is introduced in 50 milliliters of ampoules that wherein add 51 milligrams of trifluoroacetic acids, makes mixture homogenization.Ampoule covers tightly and is heated in loft drier 90-140 ℃ with jaw.After 5 days, obtain 4.2 gram chocolate resins.
Experiment b)
This solution of 5 grams is introduced in 50 milliliters of ampoules that wherein add 55 milligrams of lactic acid, makes mixture homogenization.Ampoule covers tightly and is heated in loft drier 90-140 ℃ with jaw.After 5 days, obtain 4.1 gram chocolate resins.
The resin sample obtained is carried out to the HAADF-STEM analysis.Phase structure is shown in Fig. 3 and shows to exist the area size of approximately several nanometers (<10nm).
Embodiment 4: the mass polymerization of metatitanic acid tetramethyl phenyl ester
27.8 gram trioxanes and 100 gram metatitanic acid tetramethyl phenyl esters are obtained to even settled solution in 50 ℃ of meltings in the round-bottomed flask on Rotary Evaporators.This solution of 5 grams is introduced in 50 milliliters of ampoules and adds wherein 61 milligrams of trifluoroacetic acids, make mixture homogenization.Ampoule covers tightly and is heated in loft drier 120-140 ℃ with jaw.After 6 days, obtain 4 gram reddish-brown brittle resins.
The resin sample obtained is carried out to the HAADF-STEM analysis.Phase structure is shown in Fig. 3 and shows to exist the area size of approximately several nanometers (<10nm).
Embodiment 5: the mass polymerization of metaboric acid triphenylmethyl methacrylate
By 4 gram boric acid esters in 20 milliliters of ampoules in 90-100 ℃ of lower melting.Add wherein 1.1 Ke trioxanes.Sample is stored to 1 day in the loft drier of 100 ℃, obtain thus 5 gram polymkeric substance.
Embodiment 6: the precipitation polymerization of metaboric acid triphenylmethyl methacrylate in solution
In 250 milliliter of four neck flask, make 20.0 gram triphenyl borates and 5.5 Ke trioxanes in nitrogen in 50-55 ℃ of lower melting, and diluted with 80 gram dimethylbenzene.Add wherein 0.2 gram methylsulfonic acid under 55 ℃, and make mixture homogenization.Then under the stirring velocity of 600rpm, mixture is stirred 30 minutes under 80 ℃, stir 30 minutes under 100 ℃, stir 30 minutes under 120 ℃.Mixture becomes muddy and form the sand shape precipitation on flask walls.Mixture is cooled to room temperature, filters with the D4 frit, with dimethylbenzene washing dry in vacuum drying oven.Obtain thus 20.5 gram pink colour powder.
Embodiment 7: the precipitation polymerization of p-methylphenyl phenylbenzene metaboric acid ester in solution
In 500 milliliters of HWS containers of Ultra-Turrax agitator and reflux exchanger are housed, make 60.0 gram p-methylphenyl phenylbenzene metaboric acid esters and 40 gram dimethylbenzene and 19.5 Ke trioxanes in nitrogen in 50-55 ℃ of lower melting, and dilute this melts with 200 gram dimethylbenzene.Add 0.8 gram methylsulfonic acid under 55 ℃, make mixture homogenization.Then under the stirring velocity of 8000rpm, mixture is stirred 30 minutes under 80 ℃, stir 30 minutes under 100 ℃, stir 30 minutes under 120 ℃.Mixture becomes muddy and forms the sand shape precipitation.Reaction mixture is cooled to room temperature, with D4 frit suction filtration, dimethylbenzene washing dry in vacuum drying oven for resistates.Obtain thus 58.5 gram red powder.
Utilizing the median size (average surface area) of the powder of light scattering method (Mastersizer2000) mensuration is 27 microns.
Ultimate analysis (thermally-stabilised oxide compound can cause low end value):
C 19H 178 3O 6 C H O B Total amount
Theoretical value 61.1 4.6 25.7 8.7 100.0
Observed value 54.9 5.4 26.0 6.8 93.1
Embodiment 8-1 to 8-12:
Make compound and the trioxane of the formula I of table 1 appointment mix and be incorporated in 60 to 70 ℃ of lower meltings in 20 ml penicillin bottles with the amount of table 1 appointment.Then add 0.05 gram trifluoroacetic acid in melts, metal-Teflon for penicillin bottle (Teflon) covers tightly and heats 48 hours under 110 ℃.The mixture of embodiment 1 to 7 obtains red to brown clear matrix material, and the mixture of embodiment 8 to 12 obtains red to brown opaque matrix material.
Table 1 (embodiment 8-1 to 8-12)
Embodiment Monomer A [gram] Monomers B [gram] Monomer C[gram] Trioxane [gram]
1 5.00 1.00 0.00 1.78
2 4.00 2.00 0.00 1.92
3 3.00 3.00 0.00 1.86
4 2.00 4.00 0.00 1.90
5 1.00 5.00 0.00 1.94
6 5.00 0.00 0.00 1.45
7 0.00 0.00 0.00 1.65
8 5.00 1.00 2.00 2.32
9 4.00 2.00 2.00 2.36
10 3.00 3.00 2.00 2.40
11 2.00 4.00 2.00 2.44
12 1.00 5.00 2.00 2.48
Monomer A: four (4-aminomethyl phenyl) silicon ester
Monomers B: silicic acid four phenyl esters
Monomer C: two phenoxy group dimethylsilane
Embodiment 9:
At first 1.00 gram tetraphenyl titanates and 0.32 Ke trioxane are added in penicillin bottle, and add 1.3 gram toluene to make it become solution.Penicillin bottle is covered tightly and is heated to 90 ℃.After 1 hour, polyreaction finishes.Obtain thus powder.
Embodiment 10 to 16: prepare the particle nano composite material
By Malvern Master Sizer S (module: MS7 sample pool, analytical model: polydispersion) utilize Fraunhofer diffraction method (Fraunhofer diffraction) to measure the size distribution of the powder made in embodiment 10 to 16 under 23 ℃.
Ultimate analysis: after sample and strong sulfuric acid response are also cleared up (digestion) with soda/borax, with emission spectrometer (ICP-OES; Purchased from Varian, pattern: Varian Vista Pro) measure Si.Utilize conventional elemental analysis method (Dumas) (F.Ehrenberger " Quantitative organische Elementaranalyse " [Quantitative organic elemental analysis] ISBN3-527-28056-1) to carry out the carbon analysis.Instrument: purchased from Elementar, instrument type: elemental analyser, pattern: Vario EL Cube or Vario Micro Cube.
Embodiment 10:
At first at room temperature with under nitrogen atmosphere in 2 liters of glass flask that agitator, reflux exchanger and measuring apparatus are housed, add silicic acid four phenyl esters (100 gram), 1,3,5-trioxane (45 gram) and dimethylbenzene (isomer mixture, 850 grams), under atmospheric pressure under stirring (100rpm), mixture is heated to 80 ℃.While arriving this temperature, stirring velocity is adjusted to 400rpm and continues to be stirred to formation settled solution (approximately 5 minutes).Dimethylbenzene (isomer mixture, the 40 grams) solution that added wherein 4-Witco 1298 Soft Acid (5.2 gram) in 10 minutes.Then temperature is increased to 135 ℃ (bathing temperature) and polyreaction is carried out 3 hours under specified requirements.After cooling, get the suspension sample to measure size distribution (weighted average (D 50)=115 micron).Matrix material, by filtering separation, then carries out drying (productive rate 142 grams).
Embodiment 11:
At first at room temperature with under nitrogen atmosphere in 250 milliliters of glass flask that magnetic stirring apparatus, reflux exchanger are housed, add silicic acid four phenyl esters (18.4 gram), 1,3,5-trioxane (8.3 gram) and dimethylbenzene (isomer mixture, 123 grams), under atmospheric pressure under stirring (325rpm), mixture is heated to 70 ℃.While arriving this temperature, add 0.34 gram methylsulfonic acid.Then temperature is increased to 135 ℃ and polyreaction is carried out 3 hours under specified requirements.After cooling, by filtering from liquid reaction, isolate matrix material mutually, then carry out drying (productive rate 14.0 grams).Ultimate analysis: C69.7%, Si5.9%.
Embodiment 12:
At first at room temperature with under nitrogen atmosphere in 250 milliliters of glass flask that magnetic stirring apparatus, reflux exchanger are housed, add four (4-aminomethyl phenyl) silicon ester (10.8 gram), 1,3,5-trioxane (4.2 gram) and dimethylbenzene (isomer mixture, 85.0 gram), under atmospheric pressure under stirring (325rpm), mixture is heated to 70 ℃.While arriving this temperature, add 0.23 gram methylsulfonic acid.Then temperature is increased to 135 ℃ and polyreaction is carried out 3 hours under specified requirements.After cooling, by filtering from liquid reaction, isolate matrix material mutually, then carry out drying (productive rate 3.60 grams).Ultimate analysis: C48.6%, Si15.3%.
Embodiment 13:
At first at room temperature with nitrogen atmosphere under to homogenizer is housed
Figure BDA0000385113190000261
add silicic acid four phenyl esters (48.3 gram), 1 in 2 liters of glass flask of baffle plate, reflux exchanger and measuring apparatus, 3,5-trioxane (21.7 gram) and n-decane (400 gram) under atmospheric pressure are heated to 80 ℃ by mixture under stirring (1000rpm).While arriving this temperature, stirring velocity is adjusted to 7000rpm and was metered into n-decane (40 gram) solution of 4-Witco 1298 Soft Acid (7.0 gram) in 10 minutes.After this, temperature is increased to 135 ℃ (bathing temperature) and polyreaction is carried out 3 hours under specified requirements.After cooling, get the suspension sample to measure size distribution (weighted average (D 50)=11 micron).Isolate matrix material by filtering from liquid reaction mutually, then carry out drying (productive rate 58.2 grams).
Embodiment 14:
At first at room temperature with nitrogen atmosphere under to homogenizer is housed
Figure BDA0000385113190000262
add silicic acid four phenyl esters (48.3 gram), 1 in 2 liters of glass flask of baffle plate, reflux exchanger and measuring apparatus, 3,5-trioxane (21.7 gram) and n-decane (400 gram) under atmospheric pressure are heated to 80 ℃ by mixture under stirring (1000rpm).While arriving this temperature, stirring velocity is adjusted to 7000rpm and adds Sodium dodecylbenzene sulfonate (7.0 gram).After this, be metered into n-decane (40 gram) solution of methylsulfonic acid (1.1 gram) in 10 minutes.Temperature is increased to 135 ℃.Polyreaction is carried out 3 hours under specified requirements.After cooling, get the suspension sample to measure size distribution (weighted average (D 50)=11 micron).Isolate matrix material by filtering from liquid phase, then carry out drying (productive rate 57.5 grams).
Embodiment 15:
At first at room temperature with nitrogen atmosphere under to homogenizer is housed add silicic acid four phenyl esters (48.3 gram), 1 in 2 liters of glass flask of baffle plate, reflux exchanger and measuring apparatus, 3,5-trioxane (21.7 gram) and n-decane (400 gram) under atmospheric pressure are heated to 80 ℃ by mixture under stirring (1000rpm).While arriving this temperature, stirring velocity is adjusted to 7000rpm.Add wherein Sodium dodecylbenzene sulfonate (7.0 gram), and be metered into n-decane (40 gram) solution of tin tetrachloride (2.5 gram) in 10 minutes.After this, temperature is increased to 135 ℃ and polyreaction is carried out 3 hours under specified requirements.After cooling, get the suspension sample to measure size distribution (weighted average (D 50)=18 micron).Isolate matrix material by filtering from liquid reaction mutually, then carry out drying (productive rate 28.8 grams).
Embodiment 16:
At first at room temperature with nitrogen atmosphere under to homogenizer is housed
Figure BDA0000385113190000271
add four phenoxide titaniums (50.7 gram), 1 in 2 liters of glass flask of baffle plate, reflux exchanger and measuring apparatus, 3,5-trioxane (21.7 gram) and n-decane (400 gram) under atmospheric pressure are heated to 80 ℃ by mixture under stirring (1000rpm).While arriving this temperature, stirring velocity is adjusted to 7000rpm and adds Sodium dodecylbenzene sulfonate (7.0 gram).After this, temperature is increased to 135 ℃ and polyreaction is carried out 3 hours under specified requirements.After cooling, get the suspension sample to measure size distribution (weighted average (D 50)=14 micron).Isolate matrix material by filtering from liquid reaction mutually, then carry out drying (productive rate 50.7 grams).
Purposes embodiment
Embodiment 17: preparation B 2o 3/ C hybrid material
The powder that 8.9 gram embodiment 7 are made is calcined in tube furnace under argon gas stream, selects following temperature/time to distribute:
Be heated to 800 ℃ with 3-4 ℃/minute
Time of lag under 800 ℃, (delay time) was 120 minutes
Be cooled to ambient temperature overnight.
Obtain thus the black block sprills that 4.9 grams are easy to be ground into powder.
Ultimate analysis:
C H O B Total amount
Observed value 59.1 1.1 27.5 11.1 98.8
Embodiment 18: prepare high porosity carbon
The powder that 4 gram embodiment 17 are made and 70 ml waters stir 2 hours under 70 ℃.Then mixture being cooled to 23 ℃ also filters with the 4D frit.A small amount of water washing dry under 60 ℃ in vacuum drying oven for resistates.By this method, obtain 2.6 gram black fine powders, it is comprised of carbon basically.
Ultimate analysis:
C H O B Total amount
Observed value 92.3 1.3 7.3 0.4 101.3
In the BET test, measured the surface property of carbon dust:
Surface-area (Langmuir evaluation): 715m 2/ g
Surface-area (multiple spot evaluation): 517m 2/ g
Total pore size volume 0.442ml/g
Average pore radius 16.2 dusts
Embodiment 19: reclaim boric acid
The water that embodiment 18 is obtained (filtrate) is concentrated in being up under 100 ℃/15 millibars on Rotary Evaporators.By this method, obtain 2.2 gram white powders, find that by ultimate analysis it is boric acid B (OH) 3.
Ultimate analysis:
B(OH) 3 C H O B Total amount
Theoretical value 0 4.9 77.8 17.5 100.0
Observed value ＜0.5 4.8 78 17.4 100.7
Embodiment 20: prepare nano porous titanium dioxide
The powder that embodiment 9 is made is heated to 500 ℃ and keep at this temperature 4 hours in tube furnace under airflow.By this method, obtain white fine powder, it is accredited as titanium dioxide based on ultimate analysis.The X-ray powder diffraction pattern shows that it is anatase octahedrite polymorphic titanium dioxide.Tem analysis is shown in Fig. 6.

Claims (20)

1. one kind is passed through
-at least one be selected from aryloxy metallide, aryloxy semi-metal compound and form oxygen acid and be different from carbon and the compd A of the nonmetallic aryloxy ester of nitrogen with
-at least one is selected from the compd B of formaldehyde and formaldehyde equivalent,
In substantially anhydrous reaction medium, the copolymerization preparation comprises the method for the matrix material of following material:
A) at least one oxidation phase; With
B) a kind of organic polymer phase;
Wherein, described compd B makes with such amount: in formaldehyde and compd A, the mol ratio of aryloxy is at least 0.9: 1.
2. method according to claim 1, wherein, the metal of described compd A, semi-metal or the de-carbon of nonmetal IA, IIA, IIIA, IVA, VA, VIA, IVB, VB, VIB and the VIIB family that is selected from the periodic table of elements and the element beyond nitrogen.
3. method according to claim 1 and 2, wherein, the metal of described compd A, semi-metal or nonmetal Li, Na, K, Mg, Ca, Sr, Ba, B, Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Ti, Zr, V, Cr, Mn and the W of being selected from.
4. method according to claim 3, wherein, the metal of described compd A, semi-metal or nonmetal B, Si, Sn, Ti and the P of being selected from.
5. according to the described method of the claims any one, wherein, compd A is selected from the aryloxy semi-metal compound that semi-metal comprises at least 90 % by mole of silicon of total amount meter based on the semi-metal atom.
6. according to the described method of the claims any one, wherein, described compd B be take such amount and made: the formaldehyde in described compd B and the mol ratio of the aryloxy in compd A are 1: 1 to 10: 1 and particularly 1.05: 1 to 2: 1.
7. according to the described method of the claims any one, wherein, described compd A is described with general empirical formula I:
[(ArO) mMO nR p] q (I)
Wherein
M is metal, semi-metal or forms oxygen acid and be different from carbon and nitrogen nonmetal;
M is 1,2,3,4,5 or 6,
N is 0,1 or 2,
P is 0,1 or 2,
Q is integer, for example 1,2,3,4,5 or 6,
M+2n+p is 1,2,3,4,5 or 6 and be equivalent to the valency of M,
Ar is phenyl or naphthyl, and wherein phenyl ring or naphthalene nucleus are unsubstitutedly maybe can contain one or more alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and NR of being selected from ar b---R wherein aand R bbe hydrogen, alkyl or cycloalkyl independently of one another---substituting group;
R is alkyl, thiazolinyl, cycloalkyl or aryl, and wherein aryl is unsubstitutedly maybe can contain one or more alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and NR of being selected from ar b---R wherein aand R bseparately as defined above---substituting group.
8. method according to claim 7, wherein, M is selected from B, Si, Sn, Ti and P, m be 1,2,3 or 4, n be 0 or 1 and p be 0.
9. according to the described method of claim 7 or 8, wherein, described compd A comprises at least two kinds of different compd As 1 and A2, described compd A 1 is selected from wherein M and is selected from B, Si, Sn, Ti and P, m be 1,2,3 or 4, n be 0 or 1 and the compound of the p empirical formula I that is 0, described compd A 2 is selected from wherein M and is selected from Si and Sn, m is that 2, n is 0 and the compound of the p empirical formula I that is 2.
10. according to claim 6,7 or 8 described methods, wherein, described compd A is selected from tetraphenoxy-silicane alkane, six phenoxy group cyclotrisiloxane, eight phenoxy group cyclotetrasiloxanes, four (4-methylphenoxy) silane, methyl (triple phenoxyl) silane, dimethyl (two phenoxy groups) silane, trimethylammonium (phenoxy group) silane, phenyl (triple phenoxyl) silane, phenylbenzene (two phenoxy groups) silane, triphenyl borate, metaboric acid triphenylmethyl methacrylate, ortho-phosphoric acid triphenylmethyl methacrylate, tetraphenyl titanate, metatitanic acid tetramethyl phenyl ester and stannic acid four phenyl esters.
11., according to the described method of the claims any one, wherein, described compd B is selected from paraformaldehyde, trioxane and gaseous formaldehyde.
12., according to the described method of the claims any one, wherein, described polyreaction is carried out under sour existence.
13. method according to claim 12, wherein, described acidic group is 0.1 % by weight to 10 % by weight in the consumption of compd A meter.
14., according to the described method of the claims any one, wherein, described polyreaction is carried out with single stage method.
15., according to the described method of the claims any one, wherein, described polyreaction is carried out in inert solvent.
16., according to the described method of the claims any one, wherein, described polyreaction is carried out in body.
17. the matrix material that can be obtained by the described method of claim 1 to 16 any one is for the preparation of the purposes of gas storage material.
18. the matrix material that can be obtained by the described method of claim 1 to 16 any one is for the preparation of the purposes of rubber blend.
19. the matrix material that can be obtained by the described method of claim 1 to 16 any one is for the preparation of the dielectric purposes of low-K.
20. the matrix material that can be obtained by the described method of claim 1 to 16 any one is for the preparation of the purposes of the electrode materials for lithium ion battery.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755269A (en) * 1952-01-14 1956-07-17 Dow Corning Phenol-aldehyde type organosilicon resins
US3489783A (en) * 1966-09-06 1970-01-13 Hooker Chemical Corp Alkaryloxy substituted hydroxy silanes and siloxanes
US5856583A (en) * 1997-05-21 1999-01-05 Allco Chemical Corp. Synthesis of 2-hydroxyarylaldehydes
WO2000040534A1 (en) * 1998-12-30 2000-07-13 Cognis Deutschland Gmbh Salicylaldoximes and method of preparation
WO2009083082A2 (en) * 2007-12-27 2009-07-09 Merck Patent Gmbh Porous monolithic materials
WO2010112580A1 (en) * 2009-04-03 2010-10-07 Basf Se Electroactive material, and use thereof in anodes for lithium-ion cells
WO2011000858A1 (en) * 2009-07-01 2011-01-06 Basf Se Porous film material, comprising at least one carbonaceous semimetal oxide phase, and the use thereof as a separator material for electrochemical cells
US20110240197A1 (en) * 2010-04-02 2011-10-06 Ralf Mruk Pneumatic tire and rubber composition containing twin polymerization structures

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2623866A (en) * 1951-05-26 1952-12-30 Chrysler Corp Resinous material from a phenyl borate and an aldehyde
DE1233606B (en) * 1960-09-30 1967-02-02 Dynamit Nobel Ag Process for the preparation of polymeric boron compounds
US3367996A (en) * 1964-06-22 1968-02-06 Nat Polychemicals Inc Phosphorus-containing polymers
BE670773A (en) * 1964-10-16
FR1566195A (en) 1967-12-20 1969-05-09
US4055546A (en) * 1971-10-29 1977-10-25 Hitachi Chemical Company, Ltd. Novel thermosetting resins and process for preparing the same
FR2626575B1 (en) 1988-02-01 1990-08-10 Rhone Poulenc Chimie PROCESS FOR THE PREPARATION OF ARYL METABORATE AND ITS APPLICATION TO THE PREPARATION OF ORTHOHYDROXYBENZYL ALCOHOLS
JP2006083318A (en) * 2004-09-17 2006-03-30 Sumitomo Bakelite Co Ltd Phenol resin composition and method for producing the same
DE102007063284A1 (en) 2007-12-27 2009-07-02 Basf Se spiro compounds
US8476368B2 (en) * 2008-04-28 2013-07-02 Basf Se Low-k dielectrics obtainable by twin polymerization
ATE544375T1 (en) 2008-04-30 2012-02-15 Goldeck Textil Gmbh SPRING ELEMENT FOR SUPPORTING CAVITIES
CA2754718A1 (en) 2009-04-03 2010-10-07 Basf Se Method for the production of composite materials
CN102459285A (en) * 2009-05-08 2012-05-16 巴斯夫欧洲公司 Process for producing a particulate nanocomposite material
JP2013506543A (en) 2009-10-01 2013-02-28 ビーエーエスエフ ソシエタス・ヨーロピア Method for separating substance mixtures using multiphase polymer films

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755269A (en) * 1952-01-14 1956-07-17 Dow Corning Phenol-aldehyde type organosilicon resins
US3489783A (en) * 1966-09-06 1970-01-13 Hooker Chemical Corp Alkaryloxy substituted hydroxy silanes and siloxanes
US5856583A (en) * 1997-05-21 1999-01-05 Allco Chemical Corp. Synthesis of 2-hydroxyarylaldehydes
WO2000040534A1 (en) * 1998-12-30 2000-07-13 Cognis Deutschland Gmbh Salicylaldoximes and method of preparation
WO2009083082A2 (en) * 2007-12-27 2009-07-09 Merck Patent Gmbh Porous monolithic materials
WO2010112580A1 (en) * 2009-04-03 2010-10-07 Basf Se Electroactive material, and use thereof in anodes for lithium-ion cells
WO2011000858A1 (en) * 2009-07-01 2011-01-06 Basf Se Porous film material, comprising at least one carbonaceous semimetal oxide phase, and the use thereof as a separator material for electrochemical cells
US20110240197A1 (en) * 2010-04-02 2011-10-06 Ralf Mruk Pneumatic tire and rubber composition containing twin polymerization structures

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