CN101353479A - Siloxane oligomer, preparation and use thereof - Google Patents
Siloxane oligomer, preparation and use thereof Download PDFInfo
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- CN101353479A CN101353479A CNA2007101676793A CN200710167679A CN101353479A CN 101353479 A CN101353479 A CN 101353479A CN A2007101676793 A CNA2007101676793 A CN A2007101676793A CN 200710167679 A CN200710167679 A CN 200710167679A CN 101353479 A CN101353479 A CN 101353479A
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Abstract
The invention relates to a special mixture of siloxane oligomerization with chain, side chain, ring and/or crosslinking structure elements, a preparation method thereof and the application. The siloxane oligomerization with chain and/or ring structure elements can be ideally expressed by the said two general formulas I and II. The invention in particular relates to an oligomer mixture of condensed alkyl alkoxyl silane, a preparation method thereof and the application. In a plurality of special embodiments, the invention relates to a special mixture of n propyl ethoxyl siloxane, octyl alkoxyl siloxane, ammonia-alkyl alkoxyl siloxane and/or siloxane oligomerization replaced by unsaturated organic functional groups such as vinyl and other organic groups, and also relates to a preparation method thereof and the application, in particular to the use of matrix hydrophobic treating and the use as a crosslinking agent.
Description
Technical field:
The present invention relates to have chain, the special mixture of the siloxane oligomer of ring-type and/or crosslinking structure key element, its preparation method and application thereof.Its ideal form of siloxane oligomer with chain and/or ring texture key element can be represented by two general formula Is and II.The crosslinking structure key element then can be brought 3 D cross-linked silane low polymer.
The present invention be more particularly directed to the oligomer mixture of the alkylalkoxy silane of condensation, its preparation method and purposes.In special embodiment, the present invention relates to the special mixture of n-propyl oxyethyl group siloxanes, octyl group oxyalkylsiloxane, its preparation method and its application.
According in a certain respect, the present invention relates to have chain, the mixture of the siloxane oligomer of ring-type and/or crosslinking structure key element, wherein, substituting group can also and be chosen wantonly and be made up of other organo-functional groups except alkoxyl group by undersaturated organo-functional group, and is connected with a undersaturated organo-functional group on Siliciumatom at the most.In addition, this invention also relates to a kind of method and application thereof for preparing described mixture.
According on the other hand, the present invention relates to a kind of mixture of siloxane oligomer, and substituent R wherein is made of organo-functional group except alkoxyl group, and wherein on Siliciumatom, is connected with organo-functional group at the most.In addition, of the present invention this also relates to the method for the described mixture of preparation and the purposes of this mixture on the one hand.
In addition, content of the present invention also be the mixture of siloxane oligomer and its low polymerization degree be 2 to 6 and for each silicon unit substituting group corresponding to alkyl, vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl, and also there are methoxyl group and/or oxyethyl group another organic group that can also have when suitable, and alkyl, vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl are 1: 1 to 1: 8 to the mol ratio of alkoxy substituent, and alkyl, vinyl, allyl group, prenyl, methacryloxy alkyl or acryloyloxyalkyl are 1: 0 to 1: 8 to the mol ratio of organic group.In addition, content of the present invention also is a kind ofly to prepare the method for described mixture and these mixtures are used for TPO as linking agent purposes by specific hydrolysis.
Background technology:
The silane of alkyl functional and siloxanes can for example be used for the hydrophobization of absorptivity inorganic materials.
Known C
3-C
18The alkyl alkoxy siloxanes exists with the form of oligomer mixture usually, and is used for the hydrophobization inorganic surfaces as reagent.If this preparation has very high viscosity, then its can to cause activeconstituents to enter the accessibility of base material usually very poor, particularly for the base material of high compaction, as W/Z-than very low concrete.W/Z-is the ratio of water and cement than what describe, and promptly last hole ratio is also just big more in the big more then concrete of water-content.In addition, for activeconstituents with higher low dimerization degree, the situation of substrate surface variable color also can occur making, this is that it is undesirable or have a phenomenon of oiliness outward appearance to find to I haven't seen you for ages that perhaps substrate surface has gloss because the oligopolymer of higher degree can't penetrate in the base material causedly.
The composition that EP0579453A2 discloses is anhydrous and solvent-free, contain hydrolyzable monomer, silanol and alkoxy-functional oligopolymer.It has instructed a kind of method for preparing the alkyl alkoxy siloxanes, and particularly a kind of system based on the isobutyl-Trimethoxy silane is wherein used the water of 0.1 to 0.6 mole in every mole of alkoxy silane for specific hydrolytic action.Here can form the mixture that contains alcohol, and it contains very a high proportion of silane monomer, i.e. raw material, product will have very high-load volatile monomers and also have very low burning-point value in addition when using thus.For the very low product of burning-point, in such as European Union, Japan, some countries and regions of the U.S., very strict transportation and operational safety rules are arranged all.
Instructed sec.-propyl or the different and hydrolytic action normal-butyl Trimethoxy silane among the J.Organometallic Chem.Bd.489 (1995), wherein adopted such as the catalyzer of dibutyl tin laurate and such as the solvent of tetrahydrofuran (THF).
Disclose among the WO92/06101 and had the purposes that 2 to 9 unitary solvent-free organic alkoxy siloxanes of Si are used to give the inorganic building material water repellency, wherein can in silane, add fluorinated organic compound to improve water repellency.As the organic group of organic alkoxy siloxanes is C for example
1-to C
30-alkyl/cycloalkyl/aralkyl/alkaryl or its mixture, also have in addition olefinic or the organic group that replaces with heteroatoms or fluorine atom.Especially preferably have 4 to 8 C atoms and low polymerization degree and be 2 to 4 organic alkoxy siloxanes, and wherein special recommendation 1,3-di-n-octyl-1,1,3, the 3-tetraethoxy-and-the methoxyl group sily oxide.Yet this sily oxide of specific preparation is very expensive.
Disclose among the US5543173, except the polysiloxane alcohols of aminoalkyl and two aminoalkyl functionalizations, can also have, particularly with the functionalized polysiloxane alcohols of octyl group with methyl, ethyl, sec.-propyl and normal-butyl.It prepares by the corresponding organoalkoxysilane of specific hydrolysis, and wherein product has more the hydrolysis alcohol of a large amount or the solvent of significant quantity, and as toluene or methyl iso-butyl ketone (MIBK), special preferred product only has the oligopolymer of 0.05 to 0.5 weight %.
Instruct among the EP0101816B1, can use solvent-free C for carrying out concrete hydrophobization
3-to C
8-alkylalkoxy silane, promptly monomeric alkylalkoxy silane.Such as n-propyl triethoxyl silane (PTEO), isobutyl-triethoxyl silane (IBTEO) or octyltri-ethoxysilane (OCTEO) though the monomer alkylalkoxy silane have accessibility relatively preferably, but it also has following shortcoming, promptly may cause evaporation (verdunsten), and this can cause material unaccounted-for (MUF) and contaminate environment (VOC---" volatile organic compounds ") owing to the vapour pressure of himself.
The amount of the alcohol that discharges by hydrolysis from monomeric alkyltrialkoxysilaneand is about 50 weight % of used trialkoxy silane for for example octyltri-ethoxysilane.---therefore for alkyltrialkoxysilaneand, there are many application all can't to launch or be affected thus, for example generate because of essential explosion protection or because consider to have VOC from environmental protection.But, from the angle of utilisation technology, wish that again material has those character that are similar to pure alkyltrialkoxysilaneand usually, needn't bear above-mentioned those defectives simultaneously again.These materials can be particularly preferred for the hydrophobization of inorganic surfaces.
Also known, can use be dissolved in that alcohol or other can evaporate or the evaporable solvent in C
3-to C
8-alkylalkoxy silane.Here also can determine to have significant vaporization losses.In addition, the described solution in PTEO, IBTEO and the easy volatile solvent has very low burning-point.Moreover monomeric PTEO can give emulsion being lower than 55 ℃ burning-point, so it can incorporate into and be flammable liquid, correspondingly also just is difficult to storage, transportation and operation.
For reducing described defective, the preferred especially in the past organoalkoxysilane that higher molecular weight is arranged that uses, the alkylalkoxy silane that promptly has the alkyl chain that very big carbonatoms is arranged for example can and then carry out esterification by the alkene of hydrosilylation long-chain on trichlorosilane and obtain.This method is very expensive and can brings expensive product.
Though in commercial run, for example n-propyltrichlorosilan (PTS) produces as by product, the demand for PTS and PTEO on the market is but increasing.
The mixture of chain and cyclic siloxane oligomer can be for example organoalkoxysilane by hydrolysis specifically or condensation organic functional obtain.In the process of the multifunctional siloxane oligomer of preparation, hydrolysis or condensation that special problem is each organic alkoxy or organochlorosilane vary.
EP0760372A2 discloses and has for example contained the organosilane of OH group and acrylic acid functionalized or the aqueous solution of organo-siloxane.These organo-siloxanes are actually complete hydrolysis.
The organosilane of amino-functional and hydroxyl or the aqueous solution of organo-siloxane are disclosed among EP0716128A2, EP0716127A2 and the EP0675128A1.According to above-mentioned two patent applications, the pH value is regulated by adding acid, can produce salt effect thus and make alkoxyl group decompose in addition.Therefore, these organosilane systems form with complete hydrolysis of coming down to exists.
Prepare the high-grade cable insulation material for the known high pressure polymerisation thing that is used in combination of vinyltrimethoxy silane.To adopt the crosslinked high-pressure polyethylene of vinyltrimethoxy silane for this reason.The shortcoming of this method has very high volatility particularly in vinyltrimethoxy silane, thereby making to add very high loss can occur man-hour, this be not only environmentally harmful and also since the toxicity of vinyltrimethoxy silane its also be Hazard Factor.On the other hand because vinyltrimethoxy silane adds the volatility in man-hour, so can dielectricity and depend on cross-linking density and the mechanical value of uniformity coefficient aspect, in crosslinked, bring unwelcome quality fluctuation.Therefore, use vinyl-three-2-methoxy ethoxy silane to replace vinyltrimethoxy silane in also existing tests, and obtained better effect of part.But an outstanding especially shortcoming is that formed 2-methyl cellosolve is extremely toxic in the crosslinking reaction here.Therefore, to make great efforts to abandon this cross-linking method owing to too high long-term poisoning risk.In addition, electronic industry has also proposed the higher requirement that can realize out of so far in dielectric, heat and mechanical properties for crosslinked cable insulation material.
For a series of application (for example hot-water line) that higher heat request is arranged especially, the crosslinked of low pressure polyethylene has very important meaning for improving formability.But, so far this but be there is no actual solution.
The invention task:
Task of the present invention is to provide other siloxane oligomers, its have enough stability to hydrolysiies especially and environmental pollution less.
Also particularly in a kind of product that the inorganic substrate hydrophobization is handled and safety evaporation under normal condition that is applicable to is provided, this product should have higher burning-point and good using or action effect to task of the present invention especially.
Especially, the product of safety evaporation should have burning-point and good the using or action effect that is higher than PTEO or IBTEO.Special duty of the present invention is to provide the compound based on PTS or PTEO, and it also has enough stability to hydrolysiies in addition.
In addition, according on the other hand, task of the present invention provides a kind of liquid, it is particularly suitable for being coated on the inorganic surfaces and at utmost avoids because such as the water seeking liquid of water and wetting inorganic surfaces, even inorganic surfaces hydrophobization, and in the time of on being coated on inorganic surfaces and under the condition of adding water, its alcohol that discharges uses the situation of the alkyltrialkoxysilaneand that concentrates attitude to compare obviously still less down with corresponding conditions.
Task on the other hand is to provide the mixture of siloxane oligomer, it also should have undersaturated organo-functional group and choose other wantonly except alkoxyl group organo-functional group.This special duty on the one hand of the present invention provides the mixture that also can be used for the siloxane oligomer of pigment and japanning as binding agent.
Other organic functional mixtures based on the siloxane oligomer of amino-functional compounds also are provided to provide especially the present invention's task in a certain respect.
According to a further aspect of the invention, be problematic in that and look for defective that does not show above-mentioned those vinyltrimethoxy silanes and the cross-linked material that can improve material physical property ideally.
Invention is described:
Task of the present invention can be finished by content as claimed in claim.
Oligomer mixture of the present invention, its remarkable characteristics be economy, preparation process shockingly easy with have tolerance and particularly in its favourable and relative low viscosity and be good hydrolytic resistance, higher burning-point or better bridging property.
The mixture of siloxane oligomer of the present invention comprises chain, side chain, ring-type and/or crosslinked textural element, and the chain of described ideal form and cyclic textural element be corresponding to general formula I and II,
Wherein, in the crosslinking structure key element-it is not to be ideal form-substituent R, and be made of organic group and/or hydroxyl suc as formula the substituent R of the ideal structure key element shown in I and/or the II, and oligomeric degree is 0≤m≤30 and/or is 2≤n≤30 for the oligopolymer n scope of general formula I I in 2 to 30 scope and/or for the oligopolymer m scope of general formula I.
The oligomeric degree of oligopolymer with chain, ring-type, side chain and/or crosslinking structure key element is corresponding to the unitary number of the Si-of per molecule.If the then oligomeric degree of formula I is with respect to high two the Si-unit of digital m, if the then high Si-unit of II.
The composition of each siloxane oligomer all will be considered the following fact, and promptly each Sauerstoffatom of monomer siloxane unit can play the effect that forms bridged bond between the Siliciumatom.Therefore, also can determine the functionality of each siloxane unit via the Sauerstoffatom number that may have; Therefore the organo-siloxane unit be one, two, trifunctional with part be four functional.Thus, be the siloxane oligomer that formation has chain, ring-type and/or crosslinking structure key element, existing tectonic element comprises (R) of mark with the simple function of M
3-Si-O-, mark is with two functional-O-Si (R) of D
2-O-, mark with the trifunctional of T (O-)
3SiR and mark are with the four functional Si of Q (O-)
4The label symbol M of tectonic element, D, T and Q get according to its functionality.
According to oligopolymer is which kind of tectonic element to constitute this understanding by, can infer textural element.This wherein, textural element can corresponding to can for the oligopolymer overall structure of considering or mixture in the fragment of the Utopian overall structure of oligopolymer.Thus, oligopolymer can be by chain and by ring-type and/or also be made of crosslinked textural element simultaneously.As an alternative, oligopolymer also can be just be made of chain or ring-type or crosslinked textural element.
For example, mark can be just be made of the tectonic element of simple function with the dimer of M2.For the structure chain, need combination simple function and two functional tectonic elements, can construct tripolymer (M2D), the tetramer (M2D2) and like this thus until straight chain shape oligopolymer with M2Dn.For the structure cyclic oligomer needs two functional tectonic elements (D).Can construct the ring that for example has D3, D4, D5 or higher form in this way.If hydrolysis and/or condensation trifunctional and/or four functional tectonic elements under the condition that is with or without simple function and/or two sense tectonic elements then also just can obtain comprising the crosslinked textural element of spiralization compound.The crosslinking structure that can consider can be with for example Tn that is worth mentioning (n 〉=4); DnTm (m＜n); DnTm (n＞＞m); D3T2; M4Q; Forms such as D4Q exist.The functional tectonic element of M is also referred to as terminator or conditioning agent, and the D-unit is called the chaining agent or become the ring agent, and T-and optional Q-unit are called linking agent.
Organic group R of the present invention is particularly including straight chain, side chain and/or cyclic and to have the alkyl of 1 to 18 C atom and/or have the C atomicity be 1 to 18 straight chain, side chain and/or cyclic alkoxyl group, alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based, alkenyl, alkoxyalkyl, alkynyl group, epoxy group(ing), methacryloyl oxyalkyl and/or acryloyloxyalkyl and/or C atomicity are that 6 to 12 aryl and/or C atomicity are 1 to 18 urea alkyl, mercaptoalkyl, the organo-functional group of cyano group alkyl and/or isocyano-alkyl.
Preferred organic group R comprises that formula is-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein is straight chain, side chain or cyclic and has the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms; Wherein chain length n equal 1 to 300, particularly 1 to 30, preferred especially 1 to 12 have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O; And/or has an iso-alkyl of 1 to 18 C atom; Cycloalkyl with 1 to 18 C atom; The 3-methacryloxypropyl; 3-acryloyl-oxy propyl group; Methoxyl group; Oxyethyl group; Propoxy-; Fluoro-alkyl; Vinyl; 3-glycidyl oxygen propyl group and/or allyl group.
And be 〉=0.5 particularly preferably in the quotient of Si/ alkoxyl group mol ratio in the oligomer mixture, extremely preferred this quotient 〉=1.
Siloxane oligomer mixture of the present invention also can make according to following general method.Comprise have chain, the siloxane oligomer mixture mixture of the present invention of ring-type and/or crosslinking structure key element can make by method as described later, the chain of wherein said siloxane oligomer and ring texture key element meet Utopian general formula I and II
In the formula, the substituent R of chain, side chain, ring-type and/or crosslinked textural element is made of organic group and/or hydroxyl, and low dimerization degree in 2 to 30 scope and/or for the oligopolymer m of general formula I in the scope of 0≤m＜30 and/or for the oligopolymer n of general formula I I in the scope of 2≤n≤30
Above-mentioned preparation method is,
A) choose wantonly and have tetraalkoxysilane and choosing wantonly under the condition that has hydrolysis and/or condensation catalyst, with the monoalkoxy silane of three organic groups replacements, with the dialkoxy silicane of two organic groups replacements and/or the trialkoxy silane that replaces with an organic group, perhaps
B) under the condition that has hydrolysis and/or condensation catalyst, the halogenated silanes that in alcoholic solution, replaces with one to three organic group, as chloro or bromosilane,
-and be under the condition of the water that adds calculated amount with respect to 1mol silicon, mix and
Elevated temperature hydrolysis and/or condensated silanes are also removed alcohol and the optional Catalyst And Method b that uses from reaction system) the middle hydrogenchloride that forms.Especially preferably add at least 0.6 to the water that surpasses 1mol, more preferably add 0.6 to 1.2mol water, and in 10 to 120 ℃ temperature range, be hydrolyzed and condensation for every mol Si for every mol silicon.
For all methods of the present invention, described Total Water is always in all exist in the reaction mixture water-content.This just means that the water-content of alcohol also calculates in the water-content of all existence in reaction.
As preferred substituted R, can select organic group and/or hydroxyl.Can consider to have straight chain, side chain and/or the cyclic alkyl of 1 to 18 C atom especially and/or have the organo-functional group that the C atomicity is 1 to 18 straight chain, side chain and/or cyclic alkoxyl group, alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based, alkenyl, alkynyl group, epoxy group(ing), methacryloyl oxyalkyl and/or acryloyloxyalkyl as organic group, and/or have the aryl of 6 to 12 C atoms, and/or has the organo-functional group of urea alkyl, mercaptoalkyl, cyano group alkyl and/or the isocyano-alkyl of 1 to 18 C atom.
Particularly preferred organic group is to have formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein is straight chain, side chain or cyclic and has the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms; Wherein chain length n equal 1 to 300, particularly 1 to 30, preferred especially 1 to 12 have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O; And/or has an iso-alkyl of 1 to 18 C atom; Cycloalkyl with 1 to 18 C atom; The 3-methacryloxypropyl; 3-acryloyl-oxy propyl group; Methoxyl group; Oxyethyl group; Propoxy-; Fluoro-alkyl; Vinyl; 3-glycidyl oxygen propyl group and/or allyl group.
According in a certain respect, start the oligomer mixture of described siloxane oligomer particularly including n-propyl oxyethyl group siloxanes.According to this aspect of the invention, be surprisingly found out that, can obtain a kind of special oligomer mixture of n-propyl oxyethyl group siloxanes by method described later, wherein to have oligomeric degree be the n-propyl oxyethyl group siloxanes of 2 to 6 80 to 100 weight %, particularly 90 to 100 weight % and/or wherein equal 0 to 4 and/or equal 1 to 5 for general formula I In for the oligopolymer m of general formula I; Aforesaid method promptly, make n-propyl Trimethoxy silane or n-propyltrichlorosilan in ethanolic soln and under hydrolysis or condensation catalyst existence condition, preferably under hydrogenchloride (HCl) existence condition, carry out specific hydrolysis and condensation, wherein add 0.65 to 0.85Mol water and will be under good thorough mixing condition with respect to every Mol Si, temperature of reaction is in 40 to 120 ℃ scope, preferably at 60 to 100 ℃, particularly preferably in 70 to 90 ℃, extremely preferably at 80 ℃, simultaneously also preferably at 30 minutes to 24 hours, preferred 3 to 6 hours, after the preferred especially 4 hours reaction times, will comprise the alcohol moiety of volatile catalyst or fully from system, remove.
Usually, the mixture of the present invention that so makes contains≤ethanol of 5 weight %, be 0.001 to less than 0.5 weight % less than 2 weight % and special preferred alcohol content preferably, promptly down until reaching detection limits, wherein remaining enriched material component then is an oligopolymer of the present invention.It is main in this process that what obtain is straight chain, ring-type and/or crosslinked textural element, three-dimensional crosslinking structure then except.
The oligomer mixture of n-propyl oxyethyl group siloxanes of the present invention, its outstanding characteristics are economy for example, easy astoundingly preparation and tolerance, useful and relatively low viscosity, good hydrolytic resistance and apparently higher than 60 ℃ burning-point that is to say that enriched material of the present invention and/or composition are also like this.
Oligomer mixture of the present invention also is particularly suitable for slick, porous and/or granular base material, particularly inorganic substrate, and particularly the inorganic outer facade material of concrete and porous is refused the water modification again.In addition, mixture of the present invention also has outstanding use properties.When using oligomer mixture of the present invention or use the composition of the water miscible liquid form that wherein is mixed with oligomer mixture, can in concrete, obtain fabulous depth of penetration and therefore also can be easy and obtain remarkable deep layer dipping effect economically.Base material according to the present invention after the processing can not show colour-change usually yet.In addition, oligomer mixture of the present invention also be usually evaporation safety and storage stable especially, itself is for water miscible liquid, 50% water miscible liquid still can be used after through 1 year.Described oligomer mixture also can be valuably, particularly is used in combination as the form of final composition and monomeric organofunctional silane and/or siloxanes and/or silicon ester.
Preferably-but and not exclusive-chain n-propyl oxyethyl group siloxanes can come more at large to describe by following general formula III usually:
Wherein x represents the low polymerization degree of formula III.Low polymerization degree has reacted the unitary number of Si-of each molecule.In order to determine low polymerization degree, to adopt gel permeation chromatography (GPC method) and 29Si-NMR-method for described work.If for example be described in the oligopolymer 100 weight % of corresponding definition for oligomer mixture, then this about 1% the detection limits that institute refers to the present corresponding oligopolymer that obtains with described method described here.
In order more in depth to describe siloxanes of the present invention, then to as described in starting, refer to so-called M-, D-and T-structure again.For the proprietary term of this class siloxane structure of accurate description can with reference to "
Chemielexikon "-this entry of Silicone.
Content in a certain respect according to the present invention, the mixture that siloxane oligomer of the present invention constitutes refers to the oligomer mixture that comprises n-propyl oxyethyl group siloxanes, and n-propyl oxyethyl group siloxanes is 80 to 100 weight %, and the low polymerization degree with oligopolymer of chain, side chain, ring-type and/or crosslinking structure key element be 2 to 6 and/or for the oligopolymer n of general formula I and/or II equal 1 to 5 and/or m equal 0 to 4, preferred n equal 2 to 5 and/or m equal 1 to 4.
Preferred oligomer mixture of the present invention has the n-propyl oxyethyl group siloxanes of 90 to 100 weight %, and the low polymerization degree of oligopolymer is 2 to 6, be preferably especially 3 to 6 and/or for the oligopolymer n of general formula I or II equal 1 to 5 and/or m equal 0 to 4, preferred n equal 2 to 5 and/or m equal 1 to 4.
Preferred especially oligomer mixture of the present invention has the n-propyl oxyethyl group siloxanes of at least 95 weight %, and the low polymerization degree of oligopolymer is 2 to 6, be preferably especially 3 to 6 and/or for the oligopolymer n of general formula I or II equal 1 to 5 and/or m equal 0 to 4, preferred n equal 2 to 5 and/or m equal 1 to 4.
Preferred oligomer mixture of the present invention contains the n-propyl oxyethyl group siloxanes of following content, and umber wherein all passes through other compositions, promptly also is n-propyl oxyethyl group siloxanes and supply 100 weight % basically:
-0 to 30 weight %, especially preferably less than 5 weight %, extremely preferred 0.001 to the dimerization n-propyl oxyethyl group siloxanes less than 1 weight %, and its low polymerization degree is 2 and m equals 0, meets to have M
2The general formula I of-structure,
-10 to 40 weight %, the n-propyl oxyethyl group siloxanes of preferred especially 15 to 35 weight %, it has M
2D-and/or D
3-structure, and chain and/or cyclic structure are made of three n-propyl Ethoxysilane molecules altogether and low polymerization degree is 3 wherein equals 2 and/or equal 1 according to general formula I m according to general formula I In,
-30 to 60 weight %, preferred especially 35 to 50 weight %, the n-propyl oxyethyl group siloxanes of preferred especially 35 to 45 weight %, it has M
2D
2-and/or M
3T-and/or D
4-structure, and described chain, ring-type and/or branched structure are made of 4 n-propyl oxyethyl group siloxane molecule altogether and corresponding low polymerization degree is 4 wherein equals 2 and/or equal 3 for the textural element n of general formula I I for the textural element m of general formula I.
-5 to 30 weight %, preferred especially 10 to 25 weight %, the n-propyl oxyethyl group siloxanes of extremely preferred 15 to 24 weight %, it has M
2D
3-and/or M
3DT-and/or D
5-structure, and described chain, ring-type and/or branched structure to be constituted and had low polymerization degree by 5 n-propyl oxyethyl group siloxane molecule altogether be 5, wherein equal 3 and/or equal 4 for the textural element n of general formula I I for the textural element m of general formula I.
-0.1 to 25 weight %, preferred especially 0.5 to 20 weight %, the n-propyl oxyethyl group siloxanes of extremely preferred 5 to 20 weight %, it has M
2D
4-and/or M
3D
2T-and/or M
4T
2-and/or D
6-structure, and described chain, ring-type and/or branched structure are made of 6 n-propyl oxyethyl group siloxane molecule altogether and its low polymerization degree is 6.
In some cases suitably the time, the oligomer mixture of n-propyl oxyethyl group siloxanes of the present invention can contain low polymerization degree be higher than 6 less than 10 weight %, preferred 0 to 8 weight, preferred especially 0.001 to n-propyl oxyethyl group siloxanes less than 5 weight %.
Oligomer mixture of the present invention contain preferably 0 to the low polymerization degree less than 5 weight % be 7 to 20 n-propyl oxyethyl group siloxanes.
Oligomer mixture of the present invention also can contain 0 valuably and be higher than 20 n-propyl oxyethyl group siloxanes to the low polymerization degree less than 1 weight %.
---promptly can detect and have only itself---if the oligomer mixture of n-propyl oxyethyl group siloxanes of the present invention contains but be not preferred and have low polymerization degree and be 2 to 6 n-propyl oxyethyl group siloxanes, especially preferably just have chain, ring-type and/or crosslinking structure key element have 3 to 6 Si unitary those, be the chain oligopolymer of general formula I have m equal 0 to 4, particularly m equal 1 to 4 and/or the ring texture key element of general formula I I have n and equal 1 to 5, particularly n equals 2 to 5.
In addition, it is 0 to less than 5 weight % that oligomer mixture of the present invention can contain with respect to its amount of whole mixture, and preferred 0.001 to less than 2 weight %, extremely preferably less than the free alcohol of 1 weight %.
In addition, oligomer mixture of the present invention also preferably has 3 to 20mPas, preferred especially 3 to 10mPas, extremely preferred 4 to 8mPas viscosity, particularly 4 to 7mPas viscosity.The measurement of viscosity is carried out according to DIN 53015 usually.
In addition, content of the present invention is a kind of method of the general method according to aforesaid preparation siloxane oligomer mixture of the present invention, particularly a kind of method for preparing n-propyl oxyethyl group siloxane oligomer mixture, wherein make n-propyl triethoxyl silane or n-propyltrichlorosilan in ethanolic soln and under the hydrolysis or condensation catalyst existence condition of hydrogenchloride preferably, carrying out specific hydrolysis and/or condensation under the condition of adding 0.65 to 0.85mol water for every mol Si and in 40 to 120 ℃ the temperature range, and will be suitably at experience volatile catalyst with pure and mild optional existence after 5 minutes to 24 hours reaction times, for example hydrogenchloride is removed from reaction system.
Alcohol and hydrogenchloride (HCl) are preferably under the condition of protection product and particularly reduce pressure in the distillatory mode and remove.
The method according to this invention, obtain meeting the described oligomer mixture of first aspect present invention content as the product mixture form, and its can be suitably as the condenses form, with solubilized form or as emulsion, and optional to use in conjunction with other composition of active components forms.
Content of the present invention equally also is the siloxane oligomer mixture of the n-propyl oxyethyl group siloxanes that a kind of the method according to this invention obtains.
In addition, content of the present invention also is the oligomer mixture of n-propyl oxyethyl group siloxanes of the present invention or the purposes of composition of the present invention, be used to handle the substrate surface of particularly smooth, porous and/or particulate state base material, be particularly preferred for constructing inorganic surfaces and make it to refuse water (hydrophobic), refuse oil (oleophobic) and anti-soil, and avoid biological attack and/or corrosion.Suitable, oligomer mixture of the present invention can also be used for anti-scratch application or be used for preparation, in anti-scratch composition, and special preferred combination is used fluorinated organic compound or functional silane of fluorine or siloxanes.
Especially, n-propyl oxyethyl group siloxane oligomer mixture of the present invention is applicable to deep layer dipping material of construction or buildings, is particularly preferred for inorganic building material, as concrete, lime sandstone, grouan, lime, marble, perlite, lime-ash, fragment of brick, multiporous fiber net and ceramic tile, terracotta, lithotome, honeycombed cement, fibrocement, concrete formation spare, mineral lime-ash, the jointless floor, clay-ware, but also can be rostone, materials for wall, outer facade does not have fixed and buildings, as bridge, port facilities, dwelling house, Industrial buildings and utilities building, as the garage, railway station or school, but also can be profiled member, as sleeper or L type stone material---above some examples that these just are worth mentioning.
The resulting siloxane oligomer mixture of the present invention can also be used for to fabric, leather, Mierocrystalline cellulose and starch product carry out hydrophobization, refuse water, anti-soil and/or anti-dyeing handles, make it reduce biological attack and/or corrosion or bonding be provided and/or carry out surface modification; Be used for coated glass and mineral fibre; As binding agent or as the additive of binding agent; The surface modification that is used for filler; Be used to improve the rheological of dispersion liquid and emulsion; As cementing medium, for example be used to improve the cohesiveness of organic polymer on inorganic substrate; As separant; As linking agent or as pigment and painted additive.
In addition, content of the present invention also is the purposes of n-propyl oxyethyl group siloxane oligomer mixture of the present invention, be used to handle smooth, porous and/or granular base material, the powder of for example inorganic or organic substrate, dust, sand, fiber, thin slice, these base materials are just like quartz, silicic acid, calcining silicic acid, the mineral of silicon oxide-containing, titanium oxide and other oxygen containing titanium minerals, aluminum oxide and other salic mineral, aluminium hydroxide is as three aluminium hydroxides, magnesium oxide and contain magnesian mineral, magnesium hydroxide such as magnesium dihydroxide, lime carbonate and mineral calciferous, glass fibre, mineral wool fibre, but also ceramic powder in particular is as silicon carbide, silicon nitride, norbide, boron nitride, aluminium nitride, wolfram varbide, metal or metal-powder, special in aluminium, magnesium, silicon, copper, iron and metal alloy, carbon black.
Oligomer mixture of the present invention will be suitably especially with composition forms, conc forms, the alcoholic solution form of dilution or use with the form that is dissolved in hydrocarbon.Especially, working concentration be 0.1 to 100 weight %, be preferably the oligomer mixture of the present invention of 1 to 40 weight %, preferred especially 20 to 40 weight %.Can for example use methyl alcohol, ethanol, Virahol, n-propyl alcohol, just, the different and trimethyl carbinol, preferably ethanol as alcohol; That then use the aliphatic series of straight or branched or aromatics as hydrocarbon and have the system of 5 to 20 C atoms, as pentane, hexane, hexanaphthene, heptane, octane, decane, toluene, dimethylbenzene, paraffin or white oil, preferably gasoline.
Content of the present invention also is the purposes of siloxane oligomer of the present invention in conjunction with the mixture of following compound, and comprises the composition that is selected from as the oligomer mixture of the present invention of the organoalkoxysilane of next group based at least a:
Alkyl silane, as methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, just-and different-butyl trimethoxy silane, just-and different-butyl triethoxyl silane, just-and different-amyltrimethoxysilane, just-and different-amyl triethoxysilane, just-and different-hexyl triethoxyl silane, just-and different-hexyl Trimethoxy silane, just-and different-octyltri-ethoxysilane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, just-and different-butyl methyl dimethoxy silane, just-and different-butyl methyl diethoxy silane, cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane and isobutyl--sec.-propyl dimethoxy silane, vinyl silanes, as vinyltrimethoxy silane, vinyltriethoxysilane and vinyl three-(2-methoxy ethoxy silane), aminoalkoxy silane, as the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, N-(normal-butyl)-3-TSL 8330,3-aminopropyl methyldiethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-aminoethyl-3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, functional propyl trimethoxy silicane of triamino and 3-(4,5-glyoxalidine base) propyl-triethoxysilicane
Glycidyl ether-or the organoalkoxysilane of glycidyl alkyl functional, as 3-glycidyl oxygen propyl trimethoxy silicane and 3-glycidyl oxygen propyl-triethoxysilicane,
The functional organoalkoxysilane of fluoro-alkyl, as 13 fluoro octyltri-ethoxysilane and 13 fluoro octyl group Trimethoxy silanes,
The functional organoalkoxysilane of acryloyl or methacryloyl; as acryloyl-oxy propyl trimethoxy silicane, acryloyl-oxy propyl-triethoxysilicane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl-2-methyl-propyl trimethoxy silicane and 3-methacryloxypropyl-2-methyl-propyl-triethoxysilicane
The organoalkoxysilane of Mercaptofunctional, as sulfydryl propyl trimethoxy silicane and sulfydryl propyl-triethoxysilicane,
The functional organoalkoxysilane of sulfane or polythioalkane, two-(triethoxysilylpropyltetrasulfide)-four sulfane for example, two-(trimethoxy-silylpropyl)-four sulfane, two-(triethoxysilylpropyltetrasulfide)-disulphanes, two-(trimethoxy-silylpropyl)-disulphanes, two-(triethoxysilylpropyltetrasulfide)-sulfane, two-(trimethoxy-silylpropyl)-sulfane, two-(triethoxysilylpropyltetrasulfide)-five sulfane and two-(trimethoxy-silylpropyl)-five sulfane
Wherein organo-siloxane can exist with the concentration with respect to composition 0.5 to 99.5%, and/or in preparation, can use the siloxanes that is selected from vinyl functional, the siloxanes of vinyl-alkyl functional (cocondensation compound), the methacryloyl functional siloxane, the siloxanes of amino-functional, the siloxanes of aminoalkyl group-alkyl functional, aminoalkyl-fluoro-alkyl functional siloxane or corresponding cocondensation compound and condenses---for example can be with reference to EP0590270A, EP0748357A, EP0814110A, EP0879842A, EP0846715A, EP0930342A, DE19818923A, among DE19904132A and the DE19908636A those---at least a organo-siloxane, and/or at least a silicon ester, tetramethoxy-silicane for example, tetraethoxysilane, four-n-propyl silicon ester, four butyleneglycol silicon ester and ethyl polysilicates, and/or at least a oligomeric silicic acid ester, for example DYNASYLAN
40 or also can be referring among DE2744726C and the DE2809871C those.
Especially, can clearly be present in the siloxane oligomer in the described composition or the mixture of cocondensation compound with reference to disclosed among whole the present invention.
More suitable, under the condition that has hydrolysis and/or condensation catalyst, use oligomer mixture of the present invention and/or composition.Can further improve drippage effect (Abperleffekt) thus.The example of this hydrolysis or condensation catalyst is the mineral acid as hydrogenchloride, sulfuric acid, nitric acid, organic acid as formic acid, acetic acid, such as the tetrabutyl-, tetrapropyl-, the titanate (Titanate) of tetraethyl--titanate, as the tetrabutyl-, tetrapropyl-, the zirconate (Zirkonate) of tetraethyl--zirconate, such as the organo-tin compound of DBTL=dibutyl tin laurate.Can be for example with the aqueous solution or dilution, but also can use these acid with conc forms.
The oligomer mixture of n-propyl oxyethyl group siloxanes of the present invention, its feature be particularly in there being good stability to hydrolysis, thereby make it possible to prepare valuably therefrom the stable water miscible liquid that obtains having very high burning-point.
Oligomer mixture of the present invention preferably is suitable for makes aqueous, the low viscosity oil phase to the paste emulsion of high viscosity, for example put down in writing among the EP0538555A1 like that.Therefore, oligomer mixture of the present invention can be jointly, especially preferably as composition forms and for example emulsifying agent, and such as the damping fluid of yellow soda ash, the sterilant one of thickening material, particularly mycocide, algicide is used from the water miscible liquid.
Especially, oligomer mixture of the present invention also can be common, especially preferably as composition and at least a water miscible silane cocondensation compound---DE1518551A for example, EP0587667A, EP0716127A, EP0716128A, EP0832911A, EP0846717A, EP0846716A, EP0885895A, described in DE19823390A and the DE19955047A those---and/or fluorinated organic compound of at least a optional water soluble---are US5112393 for example, those that put down in writing among US3354022 or the WO92/06101---and/or the silicone wax of emulsifying water uses together.
In addition, content of the present invention also is preferably to contain the composition or the preparation of oligomer mixture of the present invention, oligomer mixture promptly of the present invention can itself or be used to prepare composition or preparation as the form of material composition.
In addition, content of the present invention also is a kind of by being coated on the substrate surface preparation of the present invention or composition of the present invention and optional method of for example carrying out the processing base material of heat and/or photochemistry aftertreatment by IR-or UV-irradiation.
Content of the present invention also is a kind of layer that can obtain according to the present invention, promptly be coated on the base material or dipping base material and obtaining, and it is to obtain under the condition of using the present composition or reagent.
Equally, content of the present invention also is with useful, method of the present invention and the surperficial treated base material that obtains for example has concrete, lime sandstone, lime-ash, fragment of brick, terracotta, rostone, natural rock, honeycombed cement, fibrocement and the clay-ware handled through the inventive method.
Therefore, content of the present invention also is the article based on the base material surface-treated according to the present invention.For example, by the article made of concrete formation spare behind dipping, as Prefabricated buildings, tunnel, bridge and container according to the present invention.
Generally speaking, can make the mixture of siloxane oligomer of the present invention as described below.
At first, can be from n-propyltrichlorosilan, just such as everyone knows, the esterification general formula decomposes and removes HCl to utilize ethanol to pass through completely, thereby makes the n-propyl triethoxyl silane.Then make ester carry out the partial hydrolysis effect.Usually to add appropriate catalyst, react as HCl.Preferably in dilute solution, operate.Can use excess ethanol for this reason.Want specific n-propyl triethoxyl silane to use preferred 0.65 to 0.85mol water for being hydrolyzed for every mol.Hydrolytic action is preferably carried out under higher temperature, and is common in 40 to 120 ℃ scope, and the carrying out of reaction usually also will make all water react.Formed hydrolysis alcohol can be distilled from reaction mixture with volatile catalyst more suitably and be removed.Usually, be for this reason and elevated temperature is generally 40 to 180 ℃, and will under vacuum, operate, be generally＜10 millibars.Use inert gas to make the distillation purification process carry out preferably selecting exsiccant nitrogen for use fully as the towing agent for this reason.Colourless neutral bottom product can need not to purify further and directly as the building protection agent or as the oil phase of water miscible liquid system, perhaps be used for other described application scenarios.
On the other hand, also can be directly by n-propyltrichlorosilan, water and the ethanol synthetic n-propyl oxyalkylsiloxane of setting out.For hydrolysis also will be used 0.65 to 0.85mol water for the used n-propyltrichlorosilan of every mol.Preferably water and ethanol are mixed together, add to and go and make it reaction in the n-propyltrichlorosilan, the wherein preferred stoichiometry excess ethanol of using with respect to reaction.Wherein, preferably HCl is removed from reaction system.Reaction is preferably carried out under comparatively high temps, on seeing.Remaining HCl can remove by vacuum distilling under further adding ethanol and the comparatively high temps.As another selection,,, will adopt alkali from reaction mixture such as sodium methylate or ammoniacal liquor even HCl reacts and removes in order to neutralize.Usually, can separate out corresponding salt---sodium-chlor or ammonium chloride---its can from reaction mixture, remove by filtering.
1. embodiment
1. general embodiment:
Aforesaid method provides a kind of product of the present invention, and it has for example following physicochemical property and following oligomer distribution situation:
Burning-point: 118 ℃
Boiling point: 268 ℃
Viscosity: 4.5mPas
Water-content :≤0.05%
Free ethanol :≤0.1%
| Low polymerization degree (structure type) | The umber that weight % represents |
| 3(M 2D，D 3) | 32 |
| 4(M 2D 2，M 3T，D 4) | 43 |
| 5(M 2D 3，M 3DT，D 5) | 15 |
| 6(M 2D 4，M 3D 2T，M 4T 2，D 6) | 5 |
Fig. 1 has reflected the burning-point performance of reversed-phase emulsion with storage time.
As can be seen from Figure 1 each monomeric n-propyl triethoxyl silane (the PTEO aqueous solution of 50 weight %), monomeric isobutyl-triethoxyl silane (the IBTEO aqueous solution of 50 weight %), the burning-point of the test products 9892 of monomeric n-octyl triethoxyl silane (WS405, the OCTEO aqueous solution of 50 weight %) and embodiment 1.1 (the n-propyl triethoxy silica alkane aqueous solution of 50 weight %).Its burning-point is lower than 55 ℃ product and meets German chemical regulation.Pictorialization, along with the increase of temperature (40 ℃) the following shelf-time that raises, burning-point also can be owing to the free hydrolysis alcohol descends.Product VPS 9892 of the present invention and have substantially the same burning-point performance based on the WS405 of OCTEO, but product based on the PTEO condenses of the present invention is obviously more cheap.Can determine that in addition emulsion and instability by PTEO and IBTEO form just descended strongly after one day.This emulsion can not be used for the security application of building materials.In this case, all to after strong homogenizing, could determine burning-point.
The present invention also comes further at large to set forth by following examples.
Embodiment 1.1:
By the mixture of n-propyl triethoxyl silane and the oligomeric n-propyl siloxanes of water (water of 0.8mol/mol Si) preparation, product code numbering VPS 9892
In a 2-1-chuck whipping appts, insert n-propyl triethoxyl silane (PTEO) in advance and be heated to about 80 ℃.Under this temperature, utilize dropping funnel to drip the mixture that ethanol, water and hydrochloric acid are formed.Then all reaction mixtures of boiling extremely refluxed in four hours.Then, at first under environmental stress, also then under vacuum, heat up in a steamer ethanol input and that in hydrolytic process, discharge.The liquid of staying at the bottom of the tower promptly is VPS 9892.
Consumption:
PTEO 1120.5g
Water 76.5g
Ethanol 321g
HCl (the 32 weight % aqueous solution) 1.5g
Isolating product:
VPS 9892 (yield: 97% theoretical value) 780.81g
Embodiment 1.2:
The mixture (coming hydrolysis) for preparing oligomeric n-propyl siloxanes with every mol Si 0.6mol water
In a 4-1-chuck whipping appts, insert n-propyl triethoxyl silane (PTEO) in advance and be heated to about 80 ℃.Under this temperature, utilize dropping funnel to drip the mixture that ethanol, water and hydrochloric acid are formed.Then all reaction mixtures of boiling extremely refluxed in four hours.Then, at first under environmental stress, also then under vacuum, heat up in a steamer ethanol input and that in hydrolytic process, discharge.The liquid of staying at the bottom of the tower promptly is the ideal propyl-siloxane.
Consumption:
PTEO 1442.7g
Water 75.6g
Ethanol 1518g
HCl (the 32 weight % aqueous solution) 1.58g
Isolating product:
Propyl-siloxane (yield: 91% theoretical value) 1030.9g
The component that records according to GPC (=gel permeation chromatography).Utilize GPC can separate the mixture of different molecular weight size.Can determine each molecular weight by comparing with reference substance:
Monomer 5%
M2 63％
M2D，D3 27％
M2D2，M3T，D4 3％
M2D3, M3DT, D5 and Geng Gao oligopolymer 2%
Viscosity 2.8mPas (DIN 53015)
97 ℃ of burning-points (EN 22719)
Comparative examples A:
Preparation propyl-siloxane oligomer mixture (coming hydrolysis) with every mol Si 1.6mol water
In a 4-1-chuck whipping appts, insert n-propyl triethoxyl silane (PTEO) in advance and be heated to about 80 ℃.Under this temperature, utilize dropping funnel to drip the mixture that ethanol, water and hydrochloric acid are formed.Then all reaction mixtures of boiling extremely refluxed in four hours.Then, at first under environmental stress, also then under vacuum, heat up in a steamer ethanol input and that in hydrolytic process, discharge.The liquid of staying at the bottom of the tower promptly is the ideal propyl-siloxane.
Alcohol through heating up in a steamer is carried out the water that analysis revealed has significant quantity, and this makes the water of effective level be reduced to the used Si of about 1.33mol water/mol.
Consumption:
PTEO 2473.2g
Water 345.9g
Ethanol 593.6g
HCl (the 32 weight % aqueous solution) 2.34g
Isolating product:
Propyl-siloxane (yield: 95% theoretical value) 1222g
The composition that records according to GPC:
M2 0％
M2D，D3： 0％
M2D2，M3T，D4： 8％
M2D3，M3DT，D5： 8％
M2D4，M2D2T，M4T2，D6： 14％
More the high-grade oligopolymer 70%
Viscosity: 165mPas (DIN 53015)
Burning-point: 136 ℃ (EN 22719)
Embodiment 1.4:
The perviousness of VPS 9892 on the lime sandstone
Lime sandstone sample body (the commercially available lime sandstone of sawing cuts into the size of 5 * 5 * 5cm, is placed in 60 ℃ the air seasoning cabinet until constant weight, then cools off in test about 3 hours to room temperature) be impregnated among the VPS 9,892 twice of 5 second.Between impregnation steps, make sample body dropping liquid 30 seconds.After flooding for the second time, the absorbent fabric of apparatus wipes out excessive soaker.Then make the sample body at room temperature place isolated about 1 week of reaction of test.Utilize hammer and chisel that the sample body is cut into 2 half then.(Azorubin S) handles fresh section with aqueous pigment solution.It is red that hydrophilic area can show, and it is colourless that hydrophobic region then keeps, because should the zone not be that aqueous ink is wetting.The degree of depth of infiltrating has been embodied in taint-free zone.Utilize suitable yardstick to measure different zone and calculating mean value.Be 5mm and therefore be enough to keep persistent hydrophobic interaction for the average depth of penetration of handling with VPS 9892 of sample body.Depth of penetration less than 1mm is then hinting the hydrophobic interaction deficiency.Sample body with VPS 9892 dippings does not have the surface variation of obvious visible.After isolated reaction (placing 1 week of laboratory), the surface is not sticking.Therefore, VPS 9892 extremely is suitable for hydrophobicity dipping porous inorganic building material.
Comparative example B
The accessibility of n-propyl siloxane oligomer mixture (with the hydrolysis of every mol Si 1.6mol water) on the lime sandstone
(the commercially available lime sandstone of sawing cuts into the size of 5 * 5 * 5cm with lime sandstone sample body, be placed in 60 ℃ the air seasoning cabinet until constant weight, then cool off in test about 3 hours to room temperature) impregnated in twice of 5 second in the propyl-siloxane oligopolymer of every mol Si 1.6mol water hydrolysis.Between impregnation steps, make sample body dropping liquid 30 seconds.After flooding for the second time, the absorbent fabric of apparatus wipes out excessive soaker.Then make the sample body at room temperature place isolated about 1 week of reaction of test.Utilize hammer and chisel that the sample body is cut into 2 half then.(Azorubin S) handles fresh section with aqueous pigment solution.It is red that hydrophilic area can show, and it is colourless that hydrophobic region then keeps, because should the zone not be that aqueous ink is wetting.The degree of depth of infiltrating has been embodied in taint-free zone.Utilize suitable yardstick to measure different zone and calculating mean value.For the sample body of handling in order to the propyl-siloxane oligopolymer of every mol Si 1.6mol water hydrolysis, average depth of penetration is for＜1mm and therefore show and be not enough to keep for a long time hydrophobic interaction.Depth of penetration less than 1mm is then hinting the hydrophobic interaction deficiency.
Revealed obvious visible surface color with sample body surface and deepened phenomenon with the propyl-siloxane oligopolymer of every mol Si 1.6mol water hydrolysis dipping.This is unfavorable for hydrophobic dipping.After isolated reaction (placing 1 week of laboratory), the surface is not sticking.Therefore, this product is not suitable for hydrophobicity dipping porous inorganic building material.
Below the embodiment shown in reference to the accompanying drawings sets forth the present invention in more detail.Accompanying drawing is:
Fig. 1: according to the burning-point (about 50 ± 10 ℃ of * storage-temp) of the reversed-phase emulsion of storage time
According to a further aspect in the invention, mixture comprise have chain, the siloxane oligomer of the condensation alkylalkoxy silane of ring-type and/or cross-linked structure key element.
Have now found that, for example from octyltri-ethoxysilane by controlled hydrolysis and condensation reaction under the acidic catalyst existence condition and then decompression distillation remove hydrolysis alcohol---carrying out in very harsh conditions the distilation reactant mixture simultaneously---can make the low viscosity mixtures of octyl group ethyoxyl siloxanes, and the content of the content of ethyoxyl free alcohol less than 20 % by weight is less than 1.5 % by weight in this mixture, and it has 125 ℃ burning-point---in comparison: pure octyltri-ethoxysilane has 109 ℃ burning-point. Oligomer mixture of the present invention also surpassingly is suitable for the hydrophobization inorganic surfaces,---compares with the alkyltrialkoxysilaneand of using concentrated attitude---simultaneously and can not discharge owing to hydrolysis again the alcohol of significant quantity.
Therefore, content of the present invention is a kind of mixture of siloxane oligomer, the mixture that particularly has the condensation alkylalkoxy silane of chain, ring-type and/or cross-linked structure key element, and oligomer mixture wherein contains the free alcohol less than 2 % by weight, and particularly preferably the structural element of structural element ring-type corresponding to the alkoxy silane of the condensation of general formula I of chain corresponding to general formula I I
And wherein one or two substituent R is the alkyl with 3 to 18 C atoms on the silicon of each chain, ring-type and/or cross-linked structure key element, and remaining substituting group is corresponding to methoxyl group, ethyoxyl and/or hydroxyl, low polymerization degree is in 2 to 30 scope, be preferably 2 to 20, and/or particularly preferably for the oligomer m of general formula I in the scope of 0≤m≤18 and/or for the oligomer n of general formula I I in the scope of 2≤n≤30, and especially, the quotient of the mol ratio of Si/ alkoxyl 〉=1.
Oligomer mixture of the present invention preferably has and surpasses 0.01 % by weight and less than the alkoxyl of 20 % by weight, and these numerical value are all with the weighing scale of described oligomer mixture.
In addition, according to this on the one hand, oligomer mixture of the present invention preferably contains and has the separately alkyl of identical chain length---for example in general formula I and II as shown in the R. Particularly preferably alkyl is octyl group.
In addition, this oligomer mixture on the one hand preferably has the viscosity less than 100mPas.
So the content of this aspect of the present invention also a kind of prepare have chain, the method for the oligomer mixture of ring-type and/or cross-linked structure key element, and wherein said low polymerization degree is in 2 to 30 scope, and/or be 0≤m≤18 for the oligomer m of general formula I especially and/or be 2≤n≤30 for the oligomer n of general formula I I, and also has especially the mol ratio quotient of Si/ alkoxyl 〉=1, the method be use every 1mol Si surpass the water of 1mol, particularly preferably under the condition of the water of every mol Si1.0 to 1.2mol and use particularly hydrolysis or the condensation catalyst of HCl, make the hydrolysis of alkyltrialkoxysilaneand and/or dialkyl dialkoxy silicane and/or condensation, and under less than 95 ℃ column bottom temperature the decompression distillation resulting reactant mixture of purifying.
Preferably at the Water Under solution and/or used alkyltrialkoxysilaneand and/or the dialkyl dialkoxy silicane of condensation that use methyl alcohol and/or ethanol as diluent and solvent. Usually want the selective solvent amount so that form single-phase mixture.
Be preferably the hydrolysis octyltri-ethoxysilane and can for example use the water yield of every mol silane 1.2mol.
Preferred hydrolyst should almost be removed again quantitatively when distilation reactant mixture thereafter, therefore the preferred HCl that uses. But also can use other acid as catalyst.
According to the present invention in a certain respect, hydrolysis and condensation reaction will be carried out under harsh environment usually, preferably 10 to 80 ℃, particularly preferably carry out under 30 to 78 ℃ the temperature. Reaction also can be carried out under protective atmosphere. In addition, reaction will be carried out under normal pressure more suitably.
In the method for the invention, the hydrolysis and condensation reaction is preferably carried out under stirring condition and the time is 1 to 2 hour.
The reactant mixture that in the methods of the invention decompression distillation is purified and so obtained. And, under careful as far as possible condition, remove equally the free alcohol of most of amount, in the time of suitably also general formula catalyst component is discharged together. When distilation, should make especially column bottom temperature be no more than 90 ℃. Preferred purified reaction mixture under importing such as the inert gas condition of nitrogen. As the residue of distilation, the product of the present invention of the low-viscosity (mobile) liquid form that obtains clarifying.
According to this aspect of the present invention, a special advantage of oligomer mixture is the burning-point that its burning-point is higher than corresponding pure alkyltrialkoxysilaneand or its alcoholic solution. The burning-point of oligomer mixture of the present invention preferably is higher than 100 ℃, particularly preferably is higher than 110 ℃.
Another aspect of the present invention content is the purposes that the oligomer mixture that obtains with oligomer mixture of the present invention and according to the inventive method is used for the inorganic surfaces hydrophobic treatments.
Material with this class inorganic surfaces for example is: construction material such as concrete, cement, mortar, the lime sandstone, fragment of brick or various lithotome, perhaps inorganic powder such as conventional packing or pigment, the trihydrate of aluminium oxide or hydrated alumina such as aluminium, silicic acid, quartz, mica, titanium oxide, zirconia, hafnium oxide or titanium oxide hydrate, Zirconium oxide hydrate, the hafnium oxide hydrate, iron oxide or iron oxide hydrate or cobalt or cobalt oxide hydrate or also have lime and clay material and bloodstone, talcum, trbasic zinc phosphate and calcium metaphosphate.
Oligomer mixture of the present invention also can be fit to prepare the inorganic material with hydrophobic performance, is used in particular for dusty material, and preferably after having applied the oxide intermediate layer, particularly silica and/or alumina layer.
Come more at large to set forth this one side of the present invention by following examples:
2. embodiment
Embodiment 2.1
With the 2208g octyltri-ethoxysilane place one 4-1's and with glass stirred reactor processed of vacuum, reinforced and distilling apparatus and nitrogen ingress pipe, and then add in advance 168g and the HCl aqueous solution of 6.9g 32 % by weight and the water that 400g ethanol mixes under the temperature of normal pressure and 30-70 ℃ again. Descend and under the gentle reflux condition, keep the about 2h of clarified mixture at about 77 ℃. Obtain at last the reactant mixture clarified. Then apply vacuum and drop to by 400 millibars under the condition that about 5 millibars and column bottom temperature be lower than 95 ℃ at pressure, import simultaneously nitrogen and flow to remove ethanol (about 7h). Separate and obtain the product that 1550g has following character:
Free ethanol (gas chromatography): 1.3 % by weight
0.8mol ethyoxyl/mol Si (1H-NMR)
Viscosity: 38.8mPas (DIN53015)
Boiling point: 280 ℃
Burning-point: 125 ℃
Density: 0.95g/ml
Cl-content: 66 weight-ppm
Low polymerization degree: 3-20, average molar mass 1160g/mol (GPC: gel permeation chromatography, SFC: the supercritical liq chromatography)
According to a further aspect of the invention, now be surprised to find, can obtain a kind of mixture with siloxane oligomer of chain, ring-type and/or cross-linked structure key element as described below, the chain of wherein said siloxane oligomer and circulus key element are corresponding to Utopian general formula I and II
The substituent R of chain wherein, side chain, ring-type and/or crosslinked structural element be (i) have the straight chain of 1 to 18 C atom and/or side chain acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or alkenyl oxyalkyl and
-(ii) have an alkoxyl of the straight chain of 1 to 4 C atom and/or side chain and optional
-(iii) organic group, and it is selected from the alkyl of straight chain, side chain and/or ring-type with 1 to 18 C atom and/or with the organo-functional group of alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or the epoxy radicals of straight chain, side chain and/or ring-type with 1 to 18 C atom and/or urea alkyl, mercapto alkyl, cyano group alkyl and/or the isocyanide alkyl that has the aryl of 6 to 12 C atoms and/or have 1 to 18 C atom, and wherein on silicon atom to acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or the alkenyl oxyalkyl of a multi-link straight chain and/or side chain and
-low polymerization degree is 2＜m＜25 and/or is 2≤n≤8 for the compound n of general formula I I in 4 to 27 scope and/or for the compound m of general formula I, and especially, the quotient of the mol ratio of Si/ alkoxyl 〉=0.5.
Particularly preferably can obtain a kind of silane low polymer mixture with chain, ring-type and/or cross-linked structure key element as described below by specific reaction, wherein, the substituent R of chain, ring-type and/or cross-linked structure key element comprises
(i) be selected from 3-methacryloxypropyl or 3-acryloyl-oxy propyl group or vinyl, pi-allyl or isoprene and
(ii) methoxyl group, ethyoxyl and/or propoxyl group and optional
(iii) have alkyl, fluoro-alkyl, isoalkyl, the cycloalkyl of 1 to 18 C atom and/or have the aryl of 6 to 12 C atoms,
And, be connected with at the most a 3-methacryloxypropyl or 3-acryloyl-oxy propyl group or vinyl, pi-allyl or prenyl and low polymerization degree in 4 to 27 scope at silicon atom, be 2＜m＜25 for the compound m of general formula I especially and/or be 2≤n≤8 for the compound n of general formula I I, and the quotient of the mol ratio of Si/ alkoxyl 〉=0.5
Described method is, use 3-methacryloxypropyl-trialkoxy silane or 3-acryloyl-oxy propyl group-trialkoxy silane or 3-methacryloxypropyl-methyl dialkoxy silicane or 3-acryloyl-oxy propyl group-methyl-dialkoxy silicane or vinyl, the trialkoxy silane that pi-allyl or prenyl replace or the methyl dialkoxy silicane of corresponding replacement---alkoxyl wherein is preferably methoxy or ethoxy---are as composition A, with the optional alkyl with 1 to 18 C atom, fluoro-alkyl, isoalkyl, cycloalkyl or have phenyl trialkoxy silane or the alkyl of 1 to 18 C atom, fluoro-alkyl, isoalkyl, the mixture of cycloalkyl or benzyl dialkoxy silicane or described alkoxy silane is as composition B, with the tetraalkoxysilane of choosing any one kind of them as composition C, and at the water that adds every mol Si 0.6 to 1.0mol with when being equivalent to 0.1 to 5 times of methyl alcohol of used alkoxy silane and/or ethanol weight portion, in organic or inorganic acid as catalyst, particularly preferably be under the condition that exists of HCl---wherein said catalyst simultaneously preferred and water add together or add in the reactant mixture after this---and when temperature is 10 to 95 ℃, specifically be hydrolyzed and/or condensation reaction, and follow and reducing pressure and column bottom temperature is distilation product mixture under 30 to 110 ℃ the condition. Preferably, simultaneously with catalyst, free alcohol and residual monomer, unhydrolysed raw material is removed away from product basically quantitatively. Can use for example acetic acid or formic acid as catalyst. Preferably use in the methods of the invention hydrogen chloride (HCl) as catalyst.
The siloxane oligomer mixture that the present invention who so obtains has chain, ring-type and/or a cross-linked structure key element normally uniformly, clarification, colourless to little Huang low viscosity and can stablize the liquid of depositing, and have preferred＞burning-point of 100 ℃.
Can make valuably siloxane oligomer of the present invention by above-mentioned preparation method, it preferably has [Si (R) is O-(R)] unit of the different functional groups of random distribution.
Especially, can be preferably in pigment and japanning, will of the present inventionly have the mixture of siloxane oligomer of chain, ring-type and/or cross-linked structure key element as binding agent or for to the binder system modification.
The boiling point of preferred siloxane oligomer mixture of the present invention is generally＞and 200 ℃.
Therefore, this content on the one hand of the present invention is a kind of siloxane oligomer mixture with chain, ring-type and/or cross-linked structure key element, and the structural element of the chain of described siloxane oligomer and ring-type is corresponding to Utopian general formula I and II,
Wherein the substituent R of chain, side chain, ring-type and/or cross-linked structure key element corresponding to
(i) have the straight chain of 1 to 18 C atom and/or side chain acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or alkenyl oxyalkyl and
(ii) alkoxyl with 1 to 4 C atom of straight chain and/or side chain and optional
(iii) organic group, it is selected from the alkyl of straight chain, side chain and/or ring-type with 1 to 18 C atom, and/or has organic functional base straight chain, side chain and/or ring-type and that have alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or the epoxy radicals of 1 to 18 C atom, and/or has an aryl of 6 to 12 C atoms, and/or have urea alkyl, mercaptoalkyl, cyanoalkyl and/or an isocyano group alkyl of 1 to 18 C atom
-wherein, on silicon atom, be connected with at the most a straight chain with 1 to 18 C atom and/or side chain acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or alkenyl oxyalkyl and
-low polymerization degree is 2＜m＜25 and/or is 2≤n≤8 for the compound n of general formula I I in 4 to 27 scope and/or for the compound m of general formula I, and particularly preferably the quotient of the mol ratio of Si/ alkoxyl is 〉=0.5.
Therefore, the present invention's content in a certain respect especially also is a kind of mixture with siloxane oligomer of chain, ring-type and/or cross-linked structure key element, and wherein the substituent R of chain, ring-type and/or crosslinked structural element is to having
(i) vinyl, pi-allyl, prenyl, 3-methacryloxypropyl or 3-acryloyl-oxy propyl group and
(ii) methoxyl group, ethyoxyl and/or propoxyl group and optional
(iii) organic group, optional is alkyl, fluoro-alkyl, isoalkyl, the cycloalkyl with 1 to 18 C atom, and/or has the aryl of 6 to 12 C atoms, has formula-(CH2)
3-NH
2，-
(CH
2)
3-NHR’，-(CH
2)
3-NH(CH
2)
2-NH
2And/or-(CH2)
3-NH(CH
2)
2-
NH(CH
2)
2-NH
2And R ' equals to have the aminopropyl functional group of the alkyl of 1 to 4 C atom, has formula HC3-(O-CH
2-CH
2-)
nO-CH
2-，H
3C-(O-CH
2-CH
2-CH
2-)
nO-CH
2-or H3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and chain length n equals 1 to 30, special n equals 1 to 20, extremely preferred 1 to 12 polyethers, and/or 3-glycidyl oxygen propyl group, and/or 3-glycidyl oxygen propyl group,
-wherein, on silicon atom, be connected with at the most a vinyl, pi-allyl, prenyl, 3-methacryloxypropyl or 3-acryloyl-oxy propyl group, and
-low polymerization degree is 2＜m＜25 and/or is 2≤n≤8 for the compound n of general formula I I in 4 to 27 scope and/or for the compound m of general formula I, and, particularly preferably
The quotient of the mol ratio of-Si/ alkoxyl is 〉=0.5.
Therefore, the particularly preferred one side content of the present invention is the mixture with siloxane oligomer of chain, ring-type and/or cross-linked structure key element, substituent R wherein is made of 3-methacryloxypropyl or 3-acryloyl-oxy propyl group or vinyl, pi-allyl or prenyl and methoxyl group, ethyoxyl and/or propoxyl group and optional alkyl, fluoro-alkyl, isoalkyl, cycloalkyl with 1 to 18 C atom and/or aryl with 6 to 12 C atoms, and be connected with at the most a 3-methacryloxypropyl or 3-acryloyl-oxy propyl group or vinyl, pi-allyl or prenyl and low polymerization degree on the silicon atom in 4 to 27 scope and/or be 2＜m＜25 and/or be 2≤n≤8 for the compound n of general formula I I for the compound m of general formula I, and particularly preferably the quotient of the mol ratio of Si/ alkoxyl is 〉=0.5.
According to this aspects, siloxane oligomer mixture with chain, ring-type and/or cross-linked structure key element of the present invention preferably has and surpasses 0.1 % by weight and less than 30 % by weight, the alkoxy group content of 5 to 25 % by weight particularly preferably, with the weighing scale of described siloxane oligomer.
Preferably in mixture of the present invention, substituent R by (i) methacryloxypropyl and (ii) methoxy or ethoxy form. For preparing this mixture, use preferably 3-methyl allyl acyloxypropyl trimethoxysilane or 3-methacryloxypropyl triethoxysilane. But also can use the mixture of 3-methyl allyl acyloxypropyl trimethoxysilane and tetramethoxy-silicane for its preparation.
Equally also preferably in mixture of the present invention, substituent R is by (i) 3-methacryloxypropyl, vinyl, pi-allyl or prenyl and (ii) methoxy or ethoxy and (iii) methyl, propyl group, isobutyl group, octyl group, cetyl or phenyl, aminopropyl, polyether-based or 3-glycidyl oxygen propyl group form.
The initial thing that can below for example, be worth mentioning for preparing this mixture, it is the mixture that 3-methyl allyl acyloxypropyl trimethoxysilane and n-pro-pyl trimethoxy silane form, or the mixture of 3-methyl allyl acyloxypropyl trimethoxysilane and octyl group trimethoxy silane composition, or by the 3-methyl allyl acyloxypropyl trimethoxysilane, the mixture that octyl group trimethoxy silane and tetramethoxy-silicane form, it perhaps also can be the mixture that 3-methyl allyl acyloxypropyl trimethoxysilane and n-pro-pyl trimethoxy silane form, or the mixture of 3-methyl allyl acyloxypropyl trimethoxysilane and isobutyl group trimethoxy silane composition, or 3-methyl allyl acyloxypropyl trimethoxysilane and 13 fluoro-1,1,2, the mixture that 2-tetrahydrochysene octyl group-1-trimethoxy silane forms, or the mixture of 3-methyl allyl acyloxypropyl trimethoxysilane and phenyltrimethoxysila,e composition, or the mixture of vinyl propyl trimethoxy silicane and 3-glycidyl oxygen propyl trimethoxy silicane composition, perhaps pi-allyl-propyl group-trimethoxy silane, the mixture that glycidyl oxygen propyl trimethoxy silicane and tetramethoxy-silicane form, or vinyl propyl trimethoxy silicane, the mixture that octyl group trimethoxy silane and tetramethoxy-silicane form, perhaps pi-allyl propyl trimethoxy silicane, the mixture that octyl group trimethoxy silane and tetramethoxy-silicane form, or prenyl-propyl group-trimethoxy silane, the mixture that octyl group trimethoxy silane and tetramethoxy-silicane form.
The substituent R of preferred chain of the present invention and annular siloxane oligomer mixture also can be by (i) 3-methacryloxypropyl and (ii) methoxy or ethoxy and (iii) methyl and (iiii) propyl group, isobutyl group, octyl group, cetyl, phenyl form. For preparing this mixture, can for example be set out by following material, i.e. 3-methyl allyl acyloxypropyl trimethoxysilane and n-pro-pyl-MTMS or 3-methacryloxypropyl-methyl dimethoxysilane and octyl group trimethoxy silane or 3-methacryloxypropyl-methyl dimethoxysilane and n-pro-pyl-methyldiethoxysilane or 3-methyl allyl acyloxypropyl trimethoxysilane, n-pro-pyl-trimethoxy silane and MTMS or 3-methacryloxypropyl-methyl dimethoxysilane, octyl group trimethoxy silane and tetramethoxy-silicane or 3-methacryloxypropyl-methyl dimethoxysilane, n-pro-pyl-methyldiethoxysilane.
Siloxane oligomer mixture with chain, ring-type and/or crosslinking structure key element of the present invention preferably has 3 to 80mPas, preferred especially 4 to 40mPas viscosity.
As an example, below enumerate some and preferably had the system of the siloxane oligomer of chain, ring-type and/or crosslinking structure key element:
The 3-methacryloxypropyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/propyl group-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/isobutyl--/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/octyl group-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/hexadecyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/phenyl-/alkoxyl group-siloxanes, 3-methacryloxypropyl-/-seven fluoro hexyl-/-alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/phenyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/octyl group-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/propyl group-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/octyl group-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/methyl-/seven fluoro hexyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/propyl group-/seven fluoro hexyl-/alkoxyl group-siloxanes, the 3-methacryloxypropyl-/octyl group-/seven fluoro hexyl-/alkoxyl group-siloxanes, and wherein said alkoxyl group is methoxy or ethoxy preferably, but also can have oxyethyl group and methoxyl group successively.
In addition, another aspect of the present invention content is that a kind of preparation has the method for the siloxane oligomer mixture of chain, ring-type and/or crosslinking structure key element, this method trialkoxy silane that to be hydrolysis replace as composition A, with acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or the alkenyl oxyalkyl of straight chain with 1 to 18 C atom and/or side chain or have the methyl dialkoxy silicane of alkoxyl group that the C atomicity is 1 to 4 straight chain and/or side chain and optional
-as composition B's and to have the straight chain of 1 to 18 C atom, side chain and cyclic alkyl and fluoro-alkyl and/or to have the straight chain of 1 to 18 C atom, side chain and cyclic alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, the trialkoxy silane that cyano group alkyl and/or isocyano-alkyl replace or have the methyl dialkoxy silicane that the C atomicity is the alkoxyl group of 1 to 4 straight chain and/or side chain, perhaps its mixture and optional
-as composition C have the C atomicity be 1 to 4 straight chain and/or side chain alkoxyl group tetraalkoxysilane and
-at the water of the every 1mol Si 0.6 to 1.0mol of interpolation with under in 0.1 to 5 times of weight part methyl alcohol of used organoalkoxysilane and/or alcoholic acid condition, and choose wantonly to exist as the acid of catalyzer and in the also condensation that is hydrolyzed under 10 to 95 ℃ the temperature and also follow underpressure distillation refined product mixture under 60 to 110 ℃ column bottom temperature.
Especially, this content on the one hand of the present invention relates to the preparation method with siloxane oligomer mixture of chain, ring-type and/or crosslinking structure key element of the present invention, and this method is hydrolysis specifically
-as composition A's, has the C atomicity and is 1 to 4 the straight chain and/or the 3-methacryloxypropyl trialkoxy silane of branched alkoxy, 3-acryloyl-oxy propyl trialkoxy silane, 3-methacryloxypropyl-methyl-dialkoxy silicane, 3-acryloyl-oxy propyl group methyl dialkoxy silicane, the methyl dialkoxy silicane that trialkoxy silane that vinyl, allyl group or prenyl replace or vinyl, allyl group or prenyl replace and optional
-as composition B's, have the alkyl of 1 to 18 C atom-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-or the phenyl trialkoxy silane or have the alkyl of 1 to 18 C atom-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-or phenyl-methyl dialkoxy silicane and its to have the C atomicity be 1 to 4 the straight chain and/or the alkoxyl group of side chain, perhaps have the C atomicity and be 1 to 4 straight chain and/or branched alkoxy the aminopropyl official can and the trialkoxy silane or the functional methyl dialkoxy silicane of aminopropyl of Polyetherfunctional, wherein said aminopropyl functional group is formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2One of and R ' equal to have the alkyl of 1 to 4 C atom, and polyether group is formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-one of and n equals 1 to 30, special n equals 1 to 20, extremely preferred 1 to 12, perhaps 3-glycidyl oxygen propyl group, perhaps their mixture and optional
-have the C atomicity and be 1 to 4 straight chain and/or side chain alkoxyl group tetraalkoxysilane as composition C and
-at the water of the every 1mol Si 0.6 to 1.0mol of interpolation with under in 0.1 to 5 times of weight part methyl alcohol of used organoalkoxysilane and/or alcoholic acid condition, and choose wantonly to exist as the acid of catalyzer and in the also condensation that is hydrolyzed under 10 to 95 ℃ the temperature and also follow underpressure distillation refined product mixture under 60 to 110 ℃ column bottom temperature.
If use the organoalkoxysilane of aminofunctional, the water that then adds specified quantitative can enough be hydrolyzed and condensation, and in most of the cases can separately add catalyzer.In addition, the interpolation of an acidic catalyst also forms unfavorable salt easily.
Particularly preferred a kind of method, wherein hydrolysis specifically as the 3-methacryloxypropyl trialkoxy silane of composition A or 3-acryloyl-oxy propyl trialkoxy silane or 3-methacryloxypropyl-methyl-dialkoxy silicane or 3-acryloyl-oxy propyl group-methyl dialkoxy silicane and optional alkyl with 1 to 18 C atom as composition B-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-phenyl-trialkoxy silane or have the alkyl of 1 to 18 C atom-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-or the mixture of phenyl-methyl-dialkoxy silicane or described organoalkoxysilane, with optional tetraalkoxysilane as composition C, and at the water of the every 1mol Si 0.6 to 1.0mol of interpolation with under in 0.1 to 5 times of weight part methyl alcohol of used organoalkoxysilane and/or alcoholic acid condition, and existence is also followed underpressure distillation refined product mixture under 60 to 110 ℃ column bottom temperature as the acid of catalyzer and in the also condensation that is hydrolyzed under 10 to 95 ℃ the temperature.
Common following enforcement method of the present invention:
Usually, insert composition A at first in advance, optional ingredients B and optional ingredients C.Can in alkoxysilane mixture, add solvent or thinner, for example methyl alcohol or ethanol.In addition, also add the water yield of calculating at reaction more suitably.Catalyzer can add with water or then sneak into together, preferably under good thorough mixing condition, for example stirs.Can the reacting by heating mixture before or after adding water or catalyzer and the distillation purification so obtains after reaction product mixture.
In the methods of the invention, the usage quantity of composition A, B and C is that mol ratio A: B: C is preferably 1: 0: 0 to 1: 10: 0, more preferably 1: 0: 0 to 1: 4: 0, perhaps 1: 0: 0 to 1: 0: 10, more preferably 1: 0: 0 to 1: 0: 4, perhaps 1: 0: 0 to 1: 10: 10, more preferably 1: 0: 0 to 1: 4: 4.And, especially preferably use alkyl-or phenyl-organoalkoxysilane or alkyl-and the mixture of fluoro-alkyl-organoalkoxysilane or alkyl-and the mixture of phenyl-organoalkoxysilane as composition B.Can use the functional organoalkoxysilane of the fluoro-alkyl with single, low or fluoridized alkyl for this reason, preferably have those of 1 to 9 C atom especially.
In addition, in the methods of the invention, according to the organoalkoxysilane that has methoxyl group and oxyethyl group as the preferred use of the alcohol of solvent and thinner.As solvent and thinner, more suitable methyl alcohol and ethanol or methyl alcohol and the alcoholic acid mixture of being to use.But also can use other pure and mild alcohol mixture.
In a certain respect the method according to the present invention, preferably normal pressure and under under 10 to 85 ℃ the temperature, particularly preferably in 20 to 50 ℃ temperature hydrolysis and the used organoalkoxysilane of condensation.Usually, under normal pressure, react.But reaction also can be carried out under decompression and overpressure condition.Reaction mixture can react 0.5 to 3 hour preferably, and then distillation refined product mixture.
After distillation was purified, product of the present invention preferably contained less than composition A, the B of 0.5 weight % and C and preferred especially less than 2 weight %, extremely preferred free alcohol less than 1 weight %.
Siloxane oligomer mixture with chain, side chain, ring-type and/and crosslinking structure key element of the present invention and the siloxane oligomer mixture that obtains according to the inventive method with chain, side chain, ring-type and/and crosslinking structure key element, can preference as but be not to be incorporated into uniquely in the following application to go:
Therefore, content of the present invention be will the described siloxane oligomer of beginning mixture as the purposes of additive, be used for highly-filled fine inorganic filler, go based on casting resin with flow capacity and curable methacrylic ester.Thus, than similar casting resin, need not to add required composition and can make casting resin obtain tangible viscosity reduction.
Therefore, content of the present invention also is the described siloxane oligomer mixture of beginning is used for the purposes of modification and crosslinked organic resin.
In addition, content of the present invention also is the described siloxane oligomer mixture of beginning is used to improve the physical strength of plastic article and molding and the purposes of optical property.
Content of the present invention also is the described siloxane oligomer mixture of beginning is used to handle purposes with the modified glass-fiber surface, especially for better provide bonding in glass fibre enhanced plastics.
In addition, content of the present invention is the described siloxane oligomer mixture of beginning is used as the purposes that helps binding agent in the japanning and be used as composition in the varnish.By adopting the mixture of chain of the present invention and/or annular siloxane oligopolymer, can obviously improve use properties, particularly better weather resistance, higher scratch resistance and better chemical resistant properties.
Content of the present invention also is the described siloxane oligomer mixture of beginning is used to prepare the purposes of coating, and this coating is by thermal treatment under 40 to 200 ℃, preferred 80 to 150 ℃ temperature and/or pass through radiotreatment, for example, solidify in known manner by UV or microwave.
In addition, content of the present invention also is the described siloxane oligomer mixture of beginning is used to handle or apply the purposes of mineral or metallic surface.By this processing, can carry out modification to surface property valuably.For example can for example be used for filler or pigment, be used in particular for the pigment, pearly pigment of mica, aluminium, brass, copper etc. with the described siloxane oligomer mixture of beginning especially as hydrophilization reagent and/or cementing medium.
Therefore, content of the present invention is the described siloxane oligomer mixture of beginning is used for the purposes of silanization powdery substance, preferably also is used for TiO
2, kaolin, aluminium hydroxide, CaCO
3, talcum and silica powder or cristobalite powder.
Come more at large to set forth this one side of the present invention by following examples:
3. embodiment:
Embodiment 3.1
992g 3-methyl allyl acyloxypropyl trimethoxysilane is inserted in the glass 2-1-stirred reactor that has vacuum, a reinforced and water distilling apparatus in advance, and then under the room temperature condition of normal pressure, add 57.6g and mix water and 256g methyl alcohol in advance with the moisture HCl of 0.2g 37 weight %.Heated mixt is to boiling and kept gentle reflux one hour.Then normal pressure boils off most methyl alcohol and HCl in 2 hours.Apply vacuum tightness then for reducing to 1 millibar pressure and remove remaining methyl alcohol, HCl and initial thing under 80 ℃ the column bottom temperature and kept bottom product under these conditions 2 hours being lower than from 900 millibars.Obtain having the siloxane oligomer of the 840g of following character:
Free methanol (gas-chromatography): 0.3 weight %
Viscosity: 35mPas (DIN53015)
Boiling point: 257 ℃ (ASTM D-11209)
Burning-point: 152 ℃ (DIN51755)
Density: 1.117g/ml (DIN 51757)
Cl-content: 100mg/kg
Average molar mass: 650g/mol (gel permeation chromatography)
Embodiment 3.2
744g 3-methyl allyl acyloxypropyl trimethoxysilane and 492.9g propyl trimethoxy silicane are inserted in the glass 2-1-stirred reactor that has vacuum, a reinforced and water distilling apparatus in advance, and then under the room temperature condition of normal pressure, add 86.4g and mix water and 192g methyl alcohol in advance with the moisture HCl of 0.3g 37 weight %.Heated mixt is to boiling and kept gentle reflux one hour.Then normal pressure boils off most methyl alcohol and HCl in 3 hours.Apply vacuum tightness then for reducing to about 1 millibar pressure and remove remaining methyl alcohol, HCl and initial thing under 954 ℃ the column bottom temperature and kept bottom product under these conditions 2 hours being lower than from 900 millibars.Obtain having the siloxane oligomer of the 1020g of following character:
Free methanol (gas-chromatography): 0.6 weight %
Viscosity: 14.3mPas (DIN53015)
Boiling point: 277 ℃ (ASTM D-11209)
Burning-point: 110 ℃ (DIN51755)
Density: 1.083g/ml (DIN 51757)
Cl-content: 200mg/kg
Average molar mass: 570g/mol (gel permeation chromatography)
According to another aspect of the present invention, now be surprised to find, by specific hydrolysis can obtain having chain, the mixture of the siloxane oligomer of ring-type and/or crosslinking structure key element, and wherein said chain and ring texture key element can be represented by ideal general formula I and II.
Mixture with siloxane oligomer of chain, ring-type and/or crosslinking structure key element can obtain by specific reaction, and at first therein substituent R corresponding to
(i) has formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have 6 to 12 C atoms aryl and
(ii) has the alkoxyl group of the straight chain of 1 to 4 C atom and/or side chain and optional
(iii) organic group, urea alkyl, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl that it is selected from straight chain, side chain and/or cyclic alkenyl and/or the alkyl with 1 to 18 C atom and/or the straight chain with 1 to 18 C atom, side chain and/and cyclic alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or has the aryl of 6 to 12 C atoms and/or have 1 to 18 C atom
-wherein be connected with at the most an aminopropyl functional group and low polymerization degree on the Siliciumatom between 4 to 32, and/or for the compound m of general formula I in the scope of 2＜m＜30 and/or for the compound n of general formula I I in the scope of 3≤n≤30, and merchant 〉=0.5 of the mol ratio of preferred especially Si/ alkoxyl group, and method is to use
-as composition A, the functional methyl dialkoxy silicane of functional trialkoxy silane of at least a aminopropyl or aminopropyl, and wherein alkoxyl group be straight or branched and have 1 to 4 C atom and optional
-as composition B's, at least a trialkoxy silane or methyl dialkoxy silicane, and wherein alkoxyl group be straight or branched and have 1 to 4 C atom, and has a straight chain with 1 to 18 C atom as other groups, side chain and/or cyclic alkenyl and/or alkyl and/or have the straight chain of 1 to 18 atom, side chain and/or cyclic alkoxyalkyl, aralkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl and optional
-as the tetraalkoxysilane of composition C,
-and, under 10 to 95 ℃ temperature and at the water that uses every 1mol Si 0.6 to 1.2mol with in the alcohol of 0.1 to 5 times of weight part of used organoalkoxysilane, particularly under methyl alcohol and/or the alcoholic acid precursor, specifically successively or mix ground hydrolysis or condensation composition A, optional B and optional C, and then under normal pressure or the reduced pressure and be no more than distillation refined product mixture under 120 ℃ the column bottom temperature.Simultaneously, preferably the unhydrolysed initial thing of monomer of free alcohol and possible remnants is removed from product.Therefore can make the siloxane oligomer mixture of another kind of amino-functional.
A special advantage is, can be hydrolyzed or condensation under the condition of not adding with the different additive of system such as hydrolysis or condensation catalyst.
By above-mentioned preparation method, can make siloxane oligomer valuably, it preferably has different functional [Si (R) is O-(R)]-unit of random distribution.
The boiling point that the present invention has the siloxane oligomer mixture of chain, side chain, ring-type and/or crosslinking structure key element also can be＞200 ℃ usually valuably.
Therefore, another aspect of the present invention content is the mixture with siloxane oligomer of chain, side chain, ring-type and/or crosslinking structure key element, and wherein said chain and cyclic textural element be corresponding to Utopian general formula I and II,
Radicals R wherein is selected from
(i) has formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have 6 to 12 C atoms aryl and
(ii) have the straight chain of 1 to 4 C atom and/or the alkoxyl group of side chain, and preferably methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-and optional
(iii) organic group, it is selected from the straight chain with 1 to 18 C atom, side chain and/or cyclic alkenyl and/or alkyl, and/or has a straight chain that carbonatoms is 1 to 18 C atom, side chain and/or cyclic alkoxyalkyl, aralkyl, halo ten thousand machines, the group of polyether-based and/or epoxy group(ing), and/or has an aryl of 6 to 12 C atoms, and/or has a urea alkyl of 1 to 18 C atom, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl, with preferred can be when (iii) organic group is suitable corresponding to alkyl with 1 to 18 C atom, alkenyl, fluoro-alkyl, iso-alkyl, cycloalkyl and/or have the aryl of 6 to 12 C atoms has formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and wherein chain length n equal 1 to 30, particularly n equal 1 to 20, extremely preferred 1 to 12 polyethers, and/or 3-glycidyl oxygen propyl group,
-wherein be connected with at the most an aminopropyl functional group and low polymerization degree on the Siliciumatom between 4 to 32, and/or for the compound m of general formula I in the scope of 2＜m＜30 and/or for the compound n of general formula I I in the scope of 3≤n≤30, and merchant 〉=0.5 of the mol ratio of preferred especially Si/ alkoxyl group.
Mixture with siloxane oligomer of chain, ring-type and/or crosslinking structure key element has preferably that weight in this siloxane oligomer surpasses 0.1 weight % and less than the alkoxyl group of 30 weight %, preferred especially 5 to 25 weight %.
In mixture of the present invention, substituent R is made up of following:
(i) aminopropyl, aminoethyl aminopropyl, aminoethyl aminoethyl aminopropyl, methyl aminopropyl, normal-butyl aminopropyl, cyclohexyl aminopropyl and/or phenylamino propyl group and
(ii) methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-and
(iii) Ren Xuan methyl, vinyl, ethyl, propyl group, isobutyl-, octyl group, hexadecyl or phenyl.
Can mention following these preferred chains and annular siloxane oligopolymer system as an example: the 3-aminopropyl-/n-propyl-/alkoxyl group-siloxanes; N-aminoethyl-3-aminopropyl-/n-propyl-/alkoxyl group-siloxanes; N-butyl aminopropyl-/methyl-/alkoxyl group-siloxanes, and alkoxyl group methoxy or ethoxy preferably wherein, but also can have oxyethyl group and methoxyl group successively.
In addition, content of the present invention is a kind of by specific hydrolysis, prepares the method with siloxane oligomer mixture of chain, side chain, ring-type and/or crosslinking structure key element of the present invention,
-wherein use as composition A, the functional methyl dialkoxy silicane of functional trialkoxy silane of at least a aminopropyl or aminopropyl, and wherein alkoxyl group be straight or branched and have 1 to 4 C atom and optional
-as composition B's, at least a trialkoxy silane or methyl dialkoxy silicane, and wherein alkoxyl group be straight or branched and have 1 to 4 C atom, and has a straight chain with 1 to 18 C atom as other groups, side chain and/or cyclic alkenyl and/or alkyl and/or have the straight chain of 1 to 18 atom, side chain and/or cyclic alkoxyalkyl, aralkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl and optional
-as the tetraalkoxysilane of composition C,
-and, under 10 to 95 ℃ the temperature and under the water and methyl alcohol or alcoholic acid precursor of the every 1mol Si 0.6 to 1.2mol of use in 0.1 to 5 times of weight part of used organoalkoxysilane, specifically successively or mix ground hydrolysis or condensation composition A, optional B and optional C, and then under normal pressure or reduced pressure and be no more than to distill under 120 ℃ the column bottom temperature alcohol used and that discharge in reaction is removed from product mixture.
Preferred a kind of method for preparing chain and annular siloxane oligomer mixture wherein is hydrolysis specifically,
-composition A, it is corresponding to functional trialkoxy silane of at least a aminopropyl or the functional methyl dialkoxy silicane of aminopropyl, and wherein said aminopropyl functional group is corresponding to formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2, and R ' wherein is straight chain, side chain or cyclic alkyl with 1 to 18 C atom or the aryl with 6 to 12 C atoms, and wherein said alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxyl group and/or propoxy-and optional
-composition B, it is corresponding at least a trialkoxy silane or methyl dialkoxy silicane, wherein alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-, and comprise alkyl, alkenyl, fluoro-alkyl, iso-alkyl, cycloalkyl and/or have the aryl of 6 to 12 C atoms to have formula H with 1 to 18 C atom as other groups
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and wherein chain length n equal 1 to 30, particularly n equal 1 to 20, preferred especially 1 to 12, polyethers that extremely preferred n equals 1, and/or 3-glycidyl oxygen propyl group and optional
-composition C, tetraalkoxysilane, and wherein said alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-,
-and, under 10 to 95 ℃ the temperature and under the water and methyl alcohol or alcoholic acid precursor of the every 1mol Si 0.6 to 1.2mol of use in 0.1 to 5 times of weight part of used organoalkoxysilane, specifically successively or mix ground hydrolysis or condensation composition A, optional B and optional C, and then under normal pressure or reduced pressure and be no more than to distill under 120 ℃ the column bottom temperature alcohol used and that discharge in reaction is removed from product mixture.
As composition A, particularly preferred composition is functional trialkoxy silane of at least a aminopropyl or the functional methyl dialkoxy silicane of aminopropyl, and optional preferred component as composition B be at least a alkyl with 1 to 18 C atom-, alkenyl-, iso-alkyl-, cycloalkyl tri-alkoxy-silane and/or phenyl trialkoxy silane and/or have the alkyl of 1 to 18 C atom-, alkenyl-, iso-alkyl-, methyl cycloalkyl dialkoxy silicane and/or phenyl methyl dialkoxy silicane and optional preferred component as composition C be tetraalkoxysilane.
For preparing the mixture of siloxane oligomer of the present invention, can be for example but not uniquely from following compound or from the mixture of described compound:
For composition A:
3-aminopropyl trialkoxy silane, N-aminoethyl-3-aminopropyl trialkoxy silane, N-aminoethyl-N-aminoethyl-3-aminopropyl trialkoxy silane, N-methyl-aminopropyl trialkoxy silane, N-normal-butyl-aminopropyl trialkoxy silane, N-cyclohexyl-aminopropyl trialkoxy silane, N-phenyl-aminopropyl trialkoxy silane, 3-aminopropyl-methyl dialkoxy silicane, N-aminoethyl-3-aminopropyl-methyl dialkoxy silicane, N-aminoethyl-N-aminoethyl-3-aminopropyl-methyl dialkoxy silicane, N-methyl-aminopropyl-methyl dialkoxy silicane, N-normal-butyl-aminopropyl-methyl dialkoxy silicane, N-cyclohexyl-aminopropyl-methyl dialkoxy silicane, N-phenyl-aminopropyl-methyl dialkoxy silicane.
For composition B:
Methyl trialkoxysilane, ethyl trialkoxy silane, n-propyl trialkoxy silane, isobutyl-trialkoxy silane, n-octyl trialkoxy silane, isobutyl-trialkoxy silane, n-octyl trialkoxy silane, iso-octyl-trialkoxy silane, hexadecyl trialkoxy silane, phenyl trialkoxy silane, vinyl trialkyl oxysilane.
For composition C:
Tetraalkoxysilane, and aforesaid alkoxyl group preferably methoxyl group and oxyethyl group.
Usually, implement method of the present invention as described below:
Generally, insert composition A at first in advance, optional ingredients B and optional ingredients C.Can in alkoxysilane mixture, add such as methyl alcohol or alcoholic acid solvent or thinner.In addition, be added into the water of reaction calculated amount preferably, and more suitably will be at thorough mixing, for example under the stirring condition.The product mixture of can the reacting by heating mixture before or after adding water and will so obtain after reaction is with described method distillation purification.Preferably in 50 to 120 ℃ temperature range and under normal pressure and/or reduced pressure, distill the refined product mixture.
In the methods of the invention, preferably with A: the mol ratio of B: C is 1: 0: 0 to 1: 10: 0, preferred 1: 0: 0 to 1: 4: 0, perhaps 1: 0: 0 to 1: 0: 10, more preferably 1: 0: 0 to 1: 0: 4, perhaps 1: 0: 0 to 1: 10: 10, more preferably 1: 0: 0 to 1: 4: 4 ratio was used composition A, B and C.
In addition, also want preferred in the inventive method and use organoalkoxysilane with methoxy or ethoxy according to alcohol as solvent or dispersion agent.What be suitable as solvent or thinner is methyl alcohol or ethanol or methyl alcohol and alcoholic acid mixture.But also can use other alcohol or alcohol mixture.
According to the present invention, preferably normal pressure and under 10 to 95 ℃, preferred especially 60 to 80 ℃ temperature hydrolysis and the used organoalkoxysilane of condensation, and normally under condition of normal pressure, carry out.But reaction also can be carried out under reduced pressure or overpressure condition.Preferably can make reaction mixture reaction 2 to 8 hours, distill the refined product mixture then.
After distillation was purified, product of the present invention contained preferred composition A, B and C and the preferred especially free alcohol less than 1 weight % less than 5 weight %.
Siloxane oligomer mixture of the present invention can preference as, but be not limited to following application:
Therefore, the content of one aspect of the present invention also be the siloxane oligomer mixture and the mixture that obtains according to the inventive method as the purposes of preparation or be used for composition, in order to powdery substance is carried out surface modification, be used for the mineral filler and the pigment of fine distribution are carried out silanization, also be used to handle mineral, inorganic and metallic surface in addition, as concrete, aluminium, steel and plastics (example of for example being worth mentioning has PVC, PMMA).Therefore, the mixture of chain of the present invention and annular siloxane oligopolymer also can be used for surface-hydrophobicized preferably.
In addition, the content of one aspect of the present invention also is the siloxane oligomer mixture and is used as the purposes of filling cementing medium in thermoplasticity formulation such as the HFFR-formulation (halogen release fire retardant) according to the mixture that the inventive method obtains, to obtain better mechanical strength and better electrical insulating property.
In addition, an aspect of of the present present invention content also is siloxane oligomer mixture and the purposes that is used as cementing medium in binding agent and the sealing agent according to the mixture that the inventive method obtains, to obtain better use properties, particularly control curing action, better mechanical strength and better moisture resistance.
Therefore, an aspect of of the present present invention content also is the siloxane oligomer mixture and is used for the purposes of modification and crosslinked organic resin according to the mixture that the inventive method obtains, as the purposes of binding agent in pigment with better use properties and the japanning and be used for coated glass fiber, be used to improve this glass fibre in the cohesiveness of its enhanced plastics be used to obtain the purposes of better physical strength.
The monomeric amino-functional silane that the siloxane oligomer mixture uses with respect to standard, its useful especially performance are that boiling point is higher, burning-point is higher, vapour pressure is lower, the amount of the hydrolysis alcohol (VOC) of release still less and particularly has chemistry " multifunctionality " when using.
These aspects of the present invention also can more at large be set forth by following examples:
4. embodiment:
Embodiment 4.1
In the glass 4-1-stirred reactor that has vacuum, reinforced and water distilling apparatus, insert 1791g3-aminopropyl trimethoxysilane (AMMO) and 820.5g n-propyl Trimethoxy silane (PTMO) in advance.Mix 216.0g water and 300.0g methyl alcohol and in 20 minutes, be added into mixture via feeding device.Heated mixt from room temperature to about 70 ℃.Then stirred 5 hours and then boiled off in about 2 hours under the vacuum methyl alcohol (50 to 70 ℃ of column bottom temperatures, pressure are reduced to 10hPa from 400) down at about 65 ℃.Obtain the achromaticity and clarification liquid that 1924g has following character:
Free MeOH (gas-chromatography): 0.3 weight %
Silicon: 20.8 weight %
Nitrogen: 6.9 weight %
Viscosity: 35mPas (DIN53015)
Burning-point: 115 ℃ (DIN 51755)
Density: 1.103g/ml (DIN51757)
Average molar mass (gel permeation chromatography): 1000g/mol
Embodiment 4.2
In the glass 2-1-stirred reactor that has vacuum, reinforced and water distilling apparatus, insert 246g n-propyl Trimethoxy silane (PTMO) in advance and be heated to 80 ℃.Mixing 21.6g water and 144.2g methyl alcohol also was added into via feeding device in 30 minutes.Reaction mixture is temperature-resistant in this process.After finishing to add water/carbinol mixture, stirred 2 hours down at 80 ℃.Then descend to add 667g ethene-two aminopropyl trimethoxysilane (DAMO) and stirred 30 minutes at 80 ℃.In 30 minutes, add mixture that 43.2g water and 288.4g methyl alcohol forms then and 80 ℃ of following stirred reaction mixtures 1 hour.
The methyl alcohol that in reaction mixture, is contained at first barometric point (3 hours about 300g) down and then nubbin (70 to 90 ℃ of column bottom temperatures, pressure drops to 1hPa from 450) under vacuum distilled away through 3 hours.The vacuum aftertreatment is 1 hour under 1hPa and about 110 ℃ column bottom temperature.Obtain the yellow clarified liq that 690g has following character:
Free MeOH (gas-chromatography):＜0.1 weight %
Silicon: 17.3 weight %
Nitrogen: 10.8 weight %
Viscosity: 208mPas (DIN 53015)
Boiling point: 267 ℃ (ASTM D-1120)
Burning-point: 136 ℃ (DIN 51755)
Density: 1.096g/ml (DIN51757)
Total chloride content: 88mg/kg
Average molar mass (gel permeation chromatography): about 1000g/mol
According to another aspect of the present invention, the crosslinking mixture of preparation siloxane oligomer, it detects according to test can confirm to have ideal better material physical properties.Astoundingly, it can improve the physicals of material with itself than required working concentration still less so far, and allows to clean and harmless lost territory processing and significantly reduced toxicity risk.
Siloxanes with chain, ring-type and/or crosslinking structure key element is referred to as the mixture of siloxane oligomer, and wherein, general formula I and II represent ideal chain and cyclic textural element.
The low polymerization degree of oligopolymer with chain, side chain, ring-type and/or crosslinking structure key element is corresponding to the Si-unit number of per molecule.If formula I, then low polymerization degree is wanted high two Si-unit than the numerical value of m, if formula II then wants a high Si-unit.According to this aspect of the invention, low polymerization degree in 2 to 10 scope, and/or for the compound m of general formula I be 0 to 8, preferred m equals 0 to 2, preferred especially m equals 0, for the compound of general formula I I then n be 2 to 8, be preferably 2 to 4 especially.
The mixture of siloxane oligomer of the present invention, as chain, the substituent R of ring-type and/or crosslinking structure key element contains vinyl, methoxyl group and/or oxyethyl group and/or optional alkyl with 1 to 18 C atom, iso-alkyl or cycloalkyl, and wherein occur to many vinyl for each Siliciumatom, vinyl is 1: 1 to 1: 8 and vinyl to the mol ratio of alkyl substituent to the mol ratio of alkoxy substituent is that the low polymerization degree of 1: 0 to 1: 8 and siloxanes is in 2 to 10 scope, and/or be integer in 0 to 8 scope for the oligopolymer m of general formula I, preferred m equals 0 to 2, preferred especially m equals 0, and/or is 2 to 8 integer for the oligopolymer n of general formula I I.
The mixture of preferred siloxane oligomer of the present invention, as chain, the substituent R of ring-type and/or crosslinking structure key element contains vinyl, allyl group, prenyl, the methacryloyl oxyalkyl, acryloyloxyalkyl, methoxyl group and/or oxyethyl group and/or optional being selected from have the alkyl of 1 to 18 C atom, iso-alkyl or cycloalkyl, alkoxyalkyl with 1 to 18 C atom, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, the organic group of cycloalkyl and/or isocyano-alkyl, and wherein occur to many vinyl for each Siliciumatom, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl, and vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl are 1: 1 to 1: 8 and vinyl to the mol ratio of alkoxy substituent, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl to the mol ratio of organic group be the low polymerization degree of 1: 0 to 1: 8 and siloxanes in 2 to 10 scope, and/or be 0 to 8 for the oligopolymer m of general formula I especially and/or be 2 to 8 for the oligopolymer n of general formula I I.
Preferred embodiment contain alkyl as organic group in the oligomer mixture according to one, have formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2Aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms, wherein chain length n equal 1 to 30, particularly 1 to 20, extremely preferred 1 to 12 and have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O, fluoro-alkyl and/or 3-glycidyl oxygen propyl group.
From vinyl trialkyl oxysilane and choose mixed alkyl trialkoxy silane and/or tetraalkoxysilane wantonly, under the acidic catalyst condition of the hydrogenchloride that is used as catalyzer, by hydrolysis or synergetic hydrolysis effect in the pure and mild solution that forms for the water that reaches required low polymerization degree calculated amount of corresponding alkoxyl group and then use distillating method to come pure and mild catalyzer of separated free and optional rectification purified product, prepare mixture of the present invention with this such as routine.
In preferred embodiment, can and choose the mixture of preparation siloxane oligomer under the catalyzer existence condition wantonly by hydrolysis specifically or synergetic hydrolysis.For this reason, can adopt vinyl trialkyl oxysilane, allyl group trialkoxy silane, prenyl trialkoxy silane, methacryloxypropyl alkyltrialkoxysilaneand or acryloyloxyalkyl trialkoxy silane and the optional trialkoxy silane that replaces with organic group and/or tetraalkoxysilane as raw produce, and in the water of calculated amount and in the methyl alcohol of 0.2 to 8 times of weight of silane or ethanolic soln and under 20 to 80 ℃, carry out condensation, the catalyzer of removing free alcohol simultaneously and may using.
Organic group as trialkoxy silane, can consider to have alkyl, iso-alkyl or the cycloalkyl of 1 to 18 C atom especially, have alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or the epoxy group(ing) of 1 to 18 C atom and/or have the aryl of 6 to 12 C atoms and/or have urea alkyl, mercaptoalkyl, cyano group alkyl and/or the isocyano-alkyl of 1 to 18 C atom.
The organic group of preferred trialkoxy silane can particularly have formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or wherein chain length n equal 1 to 30, particularly 1 to 20, extremely preferred 1 to 12 and have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O, fluoro-alkyl and/or 3-glycidyl oxygen propyl group.
If use catalyzer, can preferably make concentration in water/alcohol mixture is 3 to 3000ppm HCl.
As vinyl trialkyl oxysilane, use vinyltrimethoxy silane or vinyltriethoxysilane.The used alkyltrialkoxysilaneand of the present invention is for example ethyl triethoxysilane, propyl trimethoxy silicane, isobutyl-Trimethoxy silane, cyclohexyl triethoxyl silane, cyclopentyl Trimethoxy silane, octyl group Trimethoxy silane, dodecyl Trimethoxy silane, tetradecyl Trimethoxy silane, octadecyl Trimethoxy silane.
Use tetramethoxy-silicane or tetraethoxysilane as tetraalkoxysilane.
More satisfactory ground makes preferably premix at room temperature of silane, and dilutes and 20 to 80 ℃ of following condensations with the alcohol of 0.2 to 8 times of weight part (its contain promising reach required low polymerization degree and the water and the optional hydrogenchloride as acid catalyst of calculated amount).The concentration of HCl is 3 to 3000ppm in preferably water/alcohol mixture.Finish after the condensation, the pure and mild hydrogenchloride of free is removed in distillation.The neutral mixture of the siloxane oligomer of residual general formula I with chain, ring-type and/or crosslinking structure key element, particularly chain and ring texture key element and II in reactor, and it needn't further be purified usually again but can be used as linking agent immediately.
Be linking agent, will utilize mixture grafting of the present invention that superoxide will make according to aforementioned material again on the TPO and hydrolytic crosslinking, the particularly graftomer of condensation gained in known manner as CABLE MATERIALS.The material property of products obtained therefrom has surpassed according to the resulting effect of traditional method.
Following embodiment according to the cocondensation compound for preparing vinyl alkoxy silane comes more at large to set forth the present invention, but is not limited to these embodiment.The corresponding scheme of migrating of carrying out condensation on the organoalkoxysilane that allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl replace all is conspicuous to those skilled in the art.
5. embodiment:
Embodiment 5.1
Prepare the cocondensation compound by vinyltrimethoxy silane and methyltrimethoxy silane, its molar ratio vinyl: methoxyl group is about 1: 3, with and be used for the purposes of polyethylene crosslinking
A) preparation cocondensation compound:
In the stirred reactor that has water distilling apparatus and vacuum Link Port and in mixing 74kg vinyltrimethoxy silane and 44.2kg methyltrimethoxy silane under 20 ℃ the temperature at the most.Mixture is mixed with the solution that the 9.28kg distilled water of the hydrogenchloride that contains 2400ppm forms in 61.9kg methyl alcohol.Temperature was elevated to 38 ℃ in 31 minutes.Altogether after 16 hours, under about 300 millibars of conditions, in about 3 hours, all methyl alcohol (about 85kg) and HCl composition are all boiled off.In then between 48 ℃ to 92 ℃ boiling section and under about 1 millibar at the most pressure condition oligomer mixture is distilled until almost there not being residue (yield is about 93kg).The boiling point of product is about 214 ℃ under normal pressure.
B) be used for crosslinked polyethylene:
182 ℃ down the oligomer product (from embodiment 1a) of the high-pressure polyethylene of plasticizing 100 weight parts (T) and 2T and 0.2T dicumyl peroxide and mixing the dibutyl tin laurate of 0.05T after extrude and be the standard testing body, and its under 95 ℃ by water treatment crosslinked 24 hours for a long time.
Degree of crosslinking: gel content APPROX 100% (do not have to extract solvent components).
From these numerical value as can be seen, still has good performance after under comparatively high temps, depositing in the water with the crosslinked polyethylene of mixture of the present invention.
Embodiment 5.2 (Comparative Examples)
180 ℃ down the dicumyl peroxide of vinyltrimethoxy silane, the 0.2T of the high-pressure polyethylene of plasticizing 100 weight parts (T) and 5T and 0.05T dibutyl tin laurate and extrude and be the standard testing body, and its 95 ℃ crosslinked 24 hours down by water treatment.
Degree of crosslinking: about 72% (about 20% the extracted solvent components) of gel content.
Poly degree of crosslinking is incomplete among this comparative example.Dielectricity after depositing in the water compares to that the exsiccant analog value has remarkable deterioration under the room temperature.
Embodiment 5.3 (Comparative Examples)
183 ℃ down the dicumyl peroxide of vinyl-three-(2-methoxy ethoxy)-silane, the 0.2T of the high-pressure polyethylene of plasticizing 100 weight parts (T) and 2T and 0.05T dibutyl tin laurate and extrude and be the standard testing body, and its 95 ℃ crosslinked 24 hours down by water treatment.
Degree of crosslinking: about 82 to 83% (about 17% the extracted solvent components) of gel content.
Here, after depositing in the water, dielectricity compare to have in the past significantly unfavorable.
Embodiment 5.4
Prepare the cocondensation compound by vinyltriethoxysilane, octyltri-ethoxysilane and tetraethoxysilane, its molar ratio vinyl: oxyethyl group is about 1: 3.7, with and be used for the purposes of polyethylene crosslinking
A) preparation cocondensation compound:
In the stirred reactor that has water distilling apparatus and vacuum Link Port and under 20 ℃ temperature, mix 57kg vinyltriethoxysilane, 12.5kg tetraethoxysilane and 41.4kg octyltri-ethoxysilane, and mixture is mixed with the solution that the 11.61kg distilled water of the hydrogenchloride that contains 1700ppm forms in 51.4kg ethanol.Temperature was elevated to 34 ℃ in 53 minutes.Altogether after 18 hours, in 2 to 3 hours all ethanol (about 81kg) and HCl composition are all boiled off under the condition of 160 ℃ nucleation temperature and perfect vacuum when about 200 millibars pressure and terminal point (about 1 millibar).Obtain the nonvolatile oligomer mixture of about 92kg.
B) be used for crosslinked polyethylene:
Plastify the highdensity low pressure polyethylene of 100 weight parts (T) and the oligomer product (from embodiment 4a) of 3T and the dicumyl peroxide of 0.2T down at 239 ℃.They after mixing the dibutyl tin laurate of 0.05T, be the standard testing body, and it was at 95 ℃ times by water treatment crosslinked 24 hours with the homogeneous polymer melt extrusion.
Degree of crosslinking: gel content APPROX 100% (do not have to extract solvent components).
Has basically degree of crosslinking completely with the crosslinked polyethylene of this mixture.Dielectric radio is not surveyed.
Embodiment 5.5 (Comparative Examples)
Plastify the highdensity low pressure polyethylene of 100 weight parts (T) and the vinyltrimethoxy silane of 5T, the dicumyl peroxide of 0.2T and the dibutyl tin laurate of 0.05T down at 236 ℃, occur caking in this process.The test body of extruding is uneven and contains caking and " flake ".
Degree of crosslinking: gel content about 16%.
Poly degree of crosslinking is incomplete.Dielectric radio is not surveyed.
Embodiment 5.6
Prepare condenses by vinyltrimethoxy silane, its molar ratio vinyl: methoxyl group is about 1: 1.75, with and be used for the purposes of polyethylene crosslinking
A) preparation condenses:
In the stirred reactor that has water distilling apparatus and vacuum Link Port and in mixing the 44.4kg vinyltrimethoxy silane under 20 ℃ the temperature and contain the solution that the 3.38kg distilled water of 1100ppm hydrogenchloride forms in 22.5kg methyl alcohol.Temperature was elevated to 36 ℃ in 26 minutes.Altogether after 13 hours, in about 2 to 3 hours, all methyl alcohol (about 34.5kg) and HCl composition are all being boiled off under about 300 millibars of conditions.In then between 45 ℃ to 90 ℃ boiling section and under about 1 millibar of pressure oligomer mixture is distilled until almost there not being residue (yield is about 32kg).The boiling point of product is about 202 ℃ under normal pressure.
B) be used for crosslinked polyethylene:
At 195 ℃ of high-pressure polyethylene and the oligomer product (from embodiment 6a) of 1.4T and dicumyl peroxides of 0.14T that plastify 100 weight parts (T) down, the viscosity of material significantly raises in this process, and after mixing the dibutyl tin laurate of 0.05T, extrude and be the standard testing body, and make it at 95 ℃ times crosslinked 24 hours by water treatment.
Degree of crosslinking: about 97% (2 to 3% the solvent components that extract) of gel content.
Than embodiment 10 (Comparative Examples), the oligomer mixture that obtains can be used for crosslinked high-pressure polyethylene.
Embodiment 5.7
With the crosslinked low pressure polyethylene of vinyl methoxyl group siloxane oligomer (vinyl: methoxyl group-mol ratio 1: 1.75)
Plastify the highdensity low pressure polyethylene of 100 weight parts (T) and the oligomer product (from embodiment 6a) of 1T and the ditertiary butyl peroxide of 0.1T down at 252 ℃, and after mixing the dibutyl tin laurate of 0.05T, extrude and be the standard testing body, and make it at 95 ℃ times crosslinked 24 hours by water treatment.
Degree of crosslinking: gel content about 100% (almost do not have to extract solvent components).
Comment: referring to embodiment 5.4b).
Embodiment 5.8
The cocondensation compound of vinyltriethoxysilane and tetraethoxysilane, and vinyl: the mol ratio of oxyethyl group is about 1: 2.8
Be similar to embodiment 5.6a), make the mixture of 38kg vinyltriethoxysilane and 16.4kg tetraethoxysilane and the solution reaction that the 3.24kg water that contains 2600ppm hydrogenchloride forms in 38.2kg ethanol generate about 40kg oligopolymer.
This embodiment is used according to the invention tetraethoxysilane.
Embodiment 5.9
The cocondensation compound of vinyltrimethoxy silane, isobutyl-Trimethoxy silane and tetramethoxy-silicane, the mol ratio vinyl: methoxyl group is about 1: 2.3
Be similar to embodiment 5.1, make the mixture of 29.6kg vinyltrimethoxy silane, 20.2kg isobutyl-Trimethoxy silane and 9.1kg tetramethoxy-silicane and solution reaction that 6.66kg water forms in 71kg methyl alcohol generate about 40.8kg oligopolymer.
This embodiment is used according to the invention iso-alkyl trialkoxy silane.
Embodiment 5.10 (Comparative Examples)
Be similar to embodiment 5.6, under 20 ℃ the 44.4g vinyltrimethoxy silane mixed mutually with the solution that the 3.38g water that contains 1100ppm hydrogenchloride forms in 22.5g methyl alcohol, and 40 ℃ of long-time down stirrings 36 hours.Distillation obtains the solid polymer residue of about 30g methyl alcohol, about 21g vinyltrimethoxy silane and about 12g.
Catalyzer in this Comparative Examples (HCl) remains in the reaction mixture.Condenses mixture and monomer and superpolymer are disproportionate.
Claims (102)
1. the mixture that has the siloxane oligomer of chain, side chain, ring-type and/or crosslinking structure key element, wherein the chain of siloxane oligomer and cyclic textural element be corresponding to ideal general formula I and II,
The substituent R of chain wherein, side chain, ring-type and/or crosslinking structure key element is made of organic group and/or hydroxyl,
It is characterized in that,
Low polymerization degree is 0≤m＜30 and/or is 2≤n≤30 for the oligopolymer n of general formula I I in 2 to 30 scope and/or for the oligopolymer m of general formula I.
2. oligomer mixture as claimed in claim 1, it is characterized in that organic group is corresponding to straight chain, side chain and/or cyclic and to have the alkyl of 1 to 18 C atom and/or have the C atomicity be 1 to 18 straight chain, side chain and/or cyclic alkoxyl group, alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based, alkenyl, alkynyl group, epoxy group(ing), methacryloyl oxyalkyl and/or acryloyloxyalkyl and/or C atomicity are that 6 to 12 aryl and/or C atomicity are 1 to 18 urea alkyl, mercaptoalkyl, the organo-functional group of cyano group alkyl and/or isocyano-alkyl.
3. oligomer mixture as claimed in claim 2 is characterized in that organic group corresponding to formula is-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2Aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms; Wherein chain length n equal 1 to 300 have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O; And/or has an iso-alkyl of 1 to 18 C atom; Cycloalkyl with 1 to 18 C atom; The 3-methacryloxypropyl; 3-acryloyl-oxy propyl group; Methoxyl group; Oxyethyl group; Propoxy-; Fluoro-alkyl; Vinyl; 3-glycidyl oxygen propyl group and/or allyl group.
4. oligomer mixture as claimed in claim 1 is characterized in that, the quotient of the mol ratio of Si/ alkoxyl group 〉=0.5.
5. oligomer mixture as claimed in claim 1 is characterized in that, the quotient of the mol ratio of Si/ alkoxyl group 〉=1.
6. the oligomer mixture that comprises n-propyl oxyethyl group siloxanes as claimed in claim 1 especially, it is characterized in that, the low polymerization degree that oligopolymer is arranged in the oligomer mixture is the n-propyl oxyethyl group siloxanes of 2 to 6 80 to 100 weight %, and wherein especially for the oligopolymer n of general formula I and/or general formula I I equal 1 to 5 and/or m equal 0 to 4.
7. oligomer mixture as claimed in claim 6 is characterized in that, it is the n-propyl oxyethyl group siloxanes of 3 to 6 90 to 100 weight % that low polymerization degree is arranged in the oligomer mixture, and wherein preferred especially n equal 2 to 5 and/or m equal 1 to 4.
8. oligomer mixture as claimed in claim 6 is characterized in that, it is the n-propyl oxyethyl group siloxanes of 2 to 6 at least 95 weight % that low polymerization degree is arranged in the oligomer mixture, and wherein preferred especially n equal 1 to 5 and/or m equal 0 to 4.
9. oligomer mixture as claimed in claim 6 is characterized in that, it is the n-propyl oxyethyl group siloxanes of 3 to 6 at least 95 weight % that low polymerization degree is arranged in the oligomer mixture, and wherein preferred especially n equal 2 to 5 and/or m equal 1 to 4.
10. oligomer mixture as claimed in claim 6 is characterized in that, it is the n-propyl Ethoxysilane of 20 to 30 weight % that oligomer mixture has low polymerization degree, and m equals 0.
11. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture contains the M that has of 10 to 40 weight %
2D and/or D
3The n-propyl oxyethyl group siloxanes of structure.
12. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture contains the M that has of 30 to 60 weight %
2D
2And/or M
3T and/or D
4The n-propyl oxyethyl group siloxanes of structure.
13. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture contains the M that has of 5 to 30 weight %
2D
3And/or M
3DT and/or D
5The n-propyl oxyethyl group siloxanes of structure.
14. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture contains the M that has of 0.1 to 25 weight %
2D
4And/or M
3D
2T and/or M
4T
2And/or D
6The n-propyl oxyethyl group siloxanes of structure.
15. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture has less than the low polymerization degree of 10 weight % greater than 6 n-propyl oxyethyl group siloxanes, and wherein particularly n greater than 5 and/or m greater than 4.
16. oligomer mixture as claimed in claim 15, it is characterized in that, oligomer mixture has the n-propyl oxyethyl group siloxanes of low polymerization degree in 7 to 20 scopes less than 5 weight %, and wherein particularly n in 6 to 19 scope and/or m in 5 to 18 scope.
17. oligomer mixture as claimed in claim 15 is characterized in that, oligomer mixture has less than the low polymerization degree of 1 weight % greater than 20 n-propyl oxyethyl group siloxanes, and preferred especially n greater than 19 and/or m greater than 18.
18. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture contains≤and the free ethanol of 5 weight %.
19. oligomer mixture as claimed in claim 6 is characterized in that, oligomer mixture has 3 to 20mPas viscosity.
20. the oligomer mixture of the alkylalkoxy silane with chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 1 especially, as to comprise condensation, it is characterized in that, oligomer mixture contains the free alcohol less than 2 weight %, and wherein the chain of the organoalkoxysilane of condensation and ring texture key element are corresponding to general formula I and II
Wherein, one or two substituent R of each silicon of chain, side chain, ring-type and/or crosslinking structure key element is the alkyl with 3 to 18 C atoms, and the corresponding methoxyl group of all the other substituting groups, oxyethyl group and/or hydroxyl, low polymerization degree is in 2 to 30 scope, and/or for the oligopolymer m of general formula I in the scope of 0≤m≤18 and/or for the oligopolymer n of general formula I I in the scope of 2≤n≤30, and the merchant of the mol ratio of Si/ alkoxyl group 〉=1.
21. oligomer mixture as claimed in claim 20 is characterized in that, alkoxy group content is greater than 0.01 weight % and less than 20 weight %, in oligomer mixture weight.
22., it is characterized in that all alkyl all have identical C atomicity as claim 20 or 21 described oligomer mixtures.
23. oligomer mixture as claimed in claim 22 is characterized in that alkyl is an octyl group.
24. oligomer mixture as claimed in claim 20 is characterized in that, viscosity is less than 100mPas.
25. oligomer mixture as claimed in claim 20 is characterized in that burning-point is higher than 100 ℃.
26. the mixture with siloxane oligomer of chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 1 especially, the chain of wherein said siloxane oligomer and ring texture key element be corresponding to ideal general formula I and II,
It is characterized in that,
The substituent R of chain, side chain, ring-type and/or crosslinking structure key element corresponding to
(i) have the straight chain of 1 to 18 C atom and/or side chain acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or alkenyl oxyalkyl and
(ii) has the alkoxyl group of the straight chain of 1 to 4 C atom and/or side chain and optional
(iii) organic group, and urea alkyl, mercapto alkyl, cyano group alkyl and/or isocyanide alkyl that it is selected from straight chain, side chain and/or the cyclic alkyl with 1 to 18 C atom and/or has the organo-functional group of straight chain, side chain and/or cyclic alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) with 1 to 18 C atom and/or have the aryl of 6 to 12 C atoms and/or have 1 to 18 C atom
-and wherein on Siliciumatom to acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or the alkenyl oxyalkyl of multi-link one straight chain with 1 to 18 C atom and/or side chain and
-low polymerization degree is 2＜m＜25 and/or is 2≤n≤8 for the compound n of general formula I I in 4 to 27 scope and/or for the compound m of general formula I.
27. the mixture of siloxane oligomer as claimed in claim 26,
It is characterized in that,
The substituent R of chain, side chain, ring-type and/or crosslinking structure key element corresponding to
(i) vinyl, allyl group, prenyl, 3-methacryloxypropyl or 3-acryloyl-oxy propyl group and
(ii) methoxyl group, oxyethyl group and/or propoxy-and optional
(iii) organic group has alkyl, fluoro-alkyl, iso-alkyl, the cycloalkyl of 1 to 18 C atom, and/or has the aryl of 6 to 12 C atoms, has formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2And R ' equals to have the aminopropyl functional group of the alkyl of 1 to 4 C atom, has formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and the chain length n polyethers that equals 1 to 30, and/or 3-glycidyl oxygen propyl group,
-wherein, on Siliciumatom, be connected with at the most a vinyl, allyl group, prenyl, 3-methacryloxypropyl or 3-acryloyl-oxy propyl group and
-low polymerization degree is 2＜m＜25 and/or is 2≤n≤8 for the compound n of general formula I I in 4 to 27 scope and/or for the compound m of general formula I, and especially
The quotient of the mol ratio of-Si/ alkoxyl group is 〉=0.5.
28., it is characterized in that the content of alkoxyl group is greater than 0.1 weight % and less than 30 weight %, in the weight of described alkoxyl group oligopolymer as claim 26 or 27 described siloxane oligomer mixtures.
29. the mixture of siloxane oligomer as claimed in claim 26 is characterized in that, substituent R is corresponding to (i) 3-methacryloxypropyl and (ii) methoxy or ethoxy.
30. the mixture of siloxane oligomer as claimed in claim 26, it is characterized in that substituent R is corresponding to (i) 3-methacryloxypropyl or vinyl, allyl group or prenyl and (ii) methoxy or ethoxy and (iii) methyl, propyl group, isobutyl-, octyl group, hexadecyl or phenyl.
31. siloxane oligomer mixture as claimed in claim 26 is characterized in that, substituent R is corresponding to (i) 3-methacryloxypropyl and (ii) methoxy or ethoxy and (iii) fluoro-alkyl, aminoalkyl or glycidyl oxygen propyl group.
32. the mixture of siloxane oligomer as claimed in claim 26 is characterized in that, viscosity is 3 to 80mPas.
33. the mixture of siloxane oligomer as claimed in claim 26 is characterized in that, burning-point＞100 ℃.
34. the mixture of siloxane oligomer as claimed in claim 26 is characterized in that, boiling point＞100 ℃.
35. the siloxane oligomer mixture with chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 1 especially, the chain of wherein said siloxane oligomer and cyclic textural element is characterized in that corresponding to general formula I and II,
Wherein the substituent R of chain, side chain, ring-type and/or crosslinking structure key element is selected from
(i) has formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have 6 to 12 C atoms aryl and
(ii) has the alkoxyl group of the straight chain of 1 to 4 C atom and/or side chain and optional
(iii) organic group, urea alkyl, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl that it is selected from straight chain, side chain and/or cyclic alkenyl and/or the alkyl with 1 to 18 C atom and/or the straight chain with 1 to 18 C atom, side chain and/and cyclic alkoxyalkyl, aralkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or has the aryl of 6 to 12 C atoms and/or have 1 to 18 C atom
-wherein be connected with at the most an aminopropyl functional group and low polymerization degree on the Siliciumatom between 4 to 32, and/or for the compound m of general formula I in the scope of 2＜m＜30 and/or for the compound n of general formula I I in the scope of 3≤n≤30, and the merchant of the mol ratio of Si/ alkoxyl group 〉=0.5 particularly.
36. the mixture with siloxane oligomer of chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 35 especially, the chain of wherein said siloxane oligomer and ring texture key element is characterized in that corresponding to general formula I and II,
The substituent R of chain, side chain, ring-type and/or crosslinking structure key element is selected from
(i) has formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2The aminopropyl functional group, and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have 6 to 12 C atoms aryl and
(ii) methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-and optional
(iii) organic group, it is corresponding to alkyl, alkenyl, fluoro-alkyl, iso-alkyl, cycloalkyl with 1 to 18 C atom and/or have the aryl of 6 to 12 C atoms, has formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and the chain length n polyethers that equals 1 to 30 wherein, and/or 3-glycidyl oxygen propyl group,
-wherein be connected with at the most an aminopropyl functional group and low polymerization degree on the Siliciumatom between 4 to 32, and/or for the compound m of general formula I in the scope of 2＜m＜30 and/or for the compound n of general formula I I in the scope of 3≤n≤30, and merchant 〉=0.5 of the mol ratio of preferred especially Si/ alkoxyl group.
37. the mixture as claim 35 or 36 described siloxane oligomers is characterized in that, alkoxy group content is greater than 0.1 weight % and less than 50 weight %, in the weight of described siloxane oligomer mixture.
38. the mixture of siloxane oligomer as claimed in claim 35 is characterized in that, substituent R is made up of following:
(i) aminopropyl, aminoethyl aminopropyl, aminoethyl aminoethyl aminopropyl, methyl aminopropyl, normal-butyl aminopropyl, cyclohexyl aminopropyl and/or phenylamino propyl group and
(ii) methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-and optional
(iii) methyl, ethyl, vinyl, allyl group, prenyl, propyl group, isobutyl-, octyl group, hexadecyl, phenyl, 3-glycidyl oxygen propyl group or the n H that equals 1
3C-(O-CH
2-CH
2-)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-)
nO-CH
2-group.
39. the mixture of siloxane oligomer as claimed in claim 35 is characterized in that, boiling point＞200 ℃.
40. the mixture of siloxane oligomer as claimed in claim 35 is characterized in that, burning-point＞100 ℃.
41. the mixture with siloxane oligomer of chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 1 especially, wherein the chain of siloxane oligomer and cyclic textural element be corresponding to general formula I and II,
It is characterized in that,
Chain, side chain, the substituent R of ring-type and/or crosslinked textural element is corresponding to vinyl, allyl group, prenyl, the methacryloyl oxyalkyl, acryloyloxyalkyl, methoxyl group and/or oxyethyl group and/or optional being selected from have the alkyl of 1 to 18 C atom, iso-alkyl or cycloalkyl, alkoxyalkyl with 1 to 18 C atom, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, the organic group of cycloalkyl and/or isocyano-alkyl
-and wherein occur to many vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyls for each Siliciumatom, and vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl are 1: 1 to 1: 8 and vinyl, allyl group, prenyl, methacryloyl oxyalkyl or acryloyloxyalkyl to the mol ratio of organic group to the mol ratio of alkoxy substituent is 1: 0 to 1: 8, and
The low polymerization degree of-siloxanes is 0 to 8 integer for the oligopolymer m of general formula I wherein and/or is 2 to 8 integer for the oligopolymer n of general formula I I in 2 to 10 scope.
42. oligomer mixture as claimed in claim 41 is characterized in that, substituting group has formula-(CH corresponding to alkyl
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2Aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms, wherein chain length n equal 1 to 30 and have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O, fluoro-alkyl and/or 3-glycidyl oxygen propyl group.
43. the mixture of siloxane oligomer as claimed in claim 41, it is characterized in that, the substituent R of chain, side chain, ring-type and/or crosslinking structure key element is corresponding to vinyl, methoxyl group and/or oxyethyl group and/or optional alkyl, iso-alkyl or cycloalkyl with 1 to 18 C atom
-and wherein occur to many vinyl for each Siliciumatom, vinyl to the mol ratio of alkoxy substituent be 1: 1 to 1: 8 and vinyl to the mol ratio of alkyl substituent be 1: 0 to 1: 8 and
-wherein the low polymerization degree of siloxanes and is the integer in 0 to 8 scope and/or is 2 to 8 integer for the oligopolymer n of general formula I I for the oligopolymer m of general formula I in 2 to 10 scope.
44. preparation has the method for siloxane oligomer mixture of chain, side chain, ring-type and/or crosslinking structure key element, the chain of wherein said siloxane oligomer and cyclic textural element be corresponding to desirable general formula I and II,
Wherein the substituent R of chain, side chain, ring-type and/or crosslinked textural element is made of organic group and/or hydroxyl, and low dimerization degree in 2 to 30 scope and/or for the oligopolymer m of general formula I in the scope of 0≤m＜30 and/or for the oligopolymer n of general formula I I in the scope of 2≤n≤30
Above-mentioned preparation method is,
A) choose wantonly and have tetraalkoxysilane and choosing wantonly under the condition that has hydrolysis and/or condensation catalyst, with the monoalkoxy silane of three organic groups replacements, with the dialkoxy silicane of two organic groups replacements and/or the trialkoxy silane that replaces with an organic group, perhaps
B) under the condition that has hydrolysis and/or condensation catalyst, the halogenated silanes that replaces with one to three organic group is in alcoholic solution
-and be under the condition of the water that adds calculated amount with respect to 1mol silicon, and elevated temperature hydrolysis and condensation, and from reaction system, remove alcohol and the optional Catalyst And Method b that uses) the middle hydrogenchloride that forms.
45. method as claimed in claim 44 is characterized in that, adds every mol silicon at least 0.6 to the water that surpasses 1mol, the water of particularly every mol Si 0.6 to 1.2mol, and hydrolysis and condensation under 10 to 120 ℃ temperature.
46. method as claimed in claim 44, it is characterized in that, substituent R is selected from organic group and/or hydroxyl, and wherein organic group is corresponding to straight chain, side chain and/or cyclic and have the alkyl of 1 to 18 C atom and/or have that to have the C atomicity be 1 to 18 straight chain, side chain and/or cyclic alkoxyl group, alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based, alkenyl, alkoxyalkyl, alkynyl group, epoxy group(ing), the organic functional base of methacryloyl oxyalkyl and/or acryloyloxyalkyl and/or C atomicity are that 6 to 12 aryl and/or C atomicity are 1 to 18 urea alkyl, mercaptoalkyl, the organo-functional group of cyano group alkyl and/or isocyano-alkyl.
47. method as claimed in claim 46 is characterized in that, organic group corresponding to formula is-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2Aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and have the alkyl of 1 to 18 C atom or have the aryl of 6 to 12 C atoms; Wherein chain length n equal 1 to 300 have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O; And/or has an iso-alkyl of 1 to 18 C atom; Cycloalkyl with 1 to 18 C atom; The 3-methacryloxypropyl; 3-acryloyl-oxy propyl group; Methoxyl group; Oxyethyl group; Propoxy-; Fluoro-alkyl; Vinyl; 3-glycidyl oxygen propyl group and/or allyl group.
48. the oligomer mixture method of preparation as claimed in claim 44 especially n-propyl oxyethyl group particularly as claimed in claim 6 siloxanes, it is characterized in that, n-propyl triethoxyl silane or n-propyltrichlorosilan are hydrolyzed and condensation in ethanolic soln and under hydrolysis or condensation catalyst existence condition, wherein add 0.65 to 0.85Mol water and temperature of reaction in 40 to 120 ℃ scope, and alcohol and hydrogenchloride are removed from system with respect to every Mol Si.
49. the oligomer mixture that contains n-propyl oxyethyl group siloxanes as claimed in claim 6 especially, it obtains by the following method, even n-propyl Trimethoxy silane or n-propyltrichlorosilan are hydrolyzed and/or condensation in ethanolic soln and under hydrolysis or condensation catalyst existence condition, wherein add 0.65 to 0.85Mol water and temperature of reaction in 40 to 120 ℃ scope, and alcohol and hydrogenchloride are removed from system with respect to every Mol Si.
50. be used to handle the purposes on the surface of particularly smooth, porous and/or particulate state base material as claim 6 or 49 described oligomer mixtures.
51. oligomer mixture as claimed in claim 6 is used to make inorganic surfaces to refuse water, refuses oil, anti-soil and/or pigment, and suppresses biological degradation and/or corrosive purposes.
52. the purposes that is used to flood material of construction or building implement as claimed in claim 51.
53. purposes as claimed in claim 51, be used to handle inorganic surfaces, be used for structure such as iron, steel, brick, wall stone, natural rock, concrete, the lime sandstone, marble, fibrous reticulum, rostone, sheet glass, double glazing, compound glass, bridge, top ceiling, the metal of facade, pottery, material of construction and building element make it refuse water, refuse oil, anti-soil and/or pigment also suppress biological degradation and/or corrosion or bonding is provided, be used to make fabric, leather, hydrophobic and the surface modification of Mierocrystalline cellulose and starch product, be used for coated glass and mineral fibre, as binding agent or as the additive of binding agent, the surface modification that is used for filler, be used to improve the rheological of dispersion liquid and emulsion, as cementing medium, be used to improve the cohesiveness of organic polymer on inorganic substrate, as separant, as linking agent or as pigment and painted additive.
54. the purposes of oligomer mixture as claimed in claim 50, wherein with the oligomer mixture of conc forms as the diluting soln of alcohol or as the solution of hydrocarbon.
55. purposes as claimed in claim 50; wherein in preparation, use oligomer mixture; and use (i) at least a organoalkoxysilane together; be selected from alkyl-; vinyl-; amino organoalkoxysilane; glycidyl ether or the functional organoalkoxysilane of glycidyl oxyalkyl; the organoalkoxysilane of fluoro organic functional; the functional organoalkoxysilane of acryloyl or methacryloyl; the organoalkoxysilane of Mercaptofunctional; functional organoalkoxysilane of sulfane or polythioalkane and/or (ii) at least a organo-siloxane; be selected from the siloxanes of vinyl functional; glycidyl oxyalkyl functional siloxane; the siloxanes of alkyl functional; methacryloyl functional siloxane, the siloxanes of fluoro-alkyl or fluoro organic functional and corresponding cocondensation compound and/or (iii) at least a silicon ester and/or (iv) at least a oligomeric silicon ester.
56. the purposes under hydrolysis and/or condensation catalyst existence condition as claimed in claim 50.
57. purposes as claimed in claim 50 is wherein used oligomer mixture as the form of oil phase in the water miscible liquid.
58. purposes as claimed in claim 50 is wherein used oligomer mixture, and uses the silicone wax of at least a water-soluble silane cocondensation compound and/or at least a water miscible fluorinated organic compound and/or at least a emulsifying water together.
59. comprise in the preparation as claim 6 or 49 described oligomer mixtures and (i) at least a organoalkoxysilane; and its be selected from alkyl-; vinyl-; amino organoalkoxysilane; glycidyl ether or the functional organoalkoxysilane of glycidyl oxyalkyl; the organoalkoxysilane of fluoro organic functional; the functional organoalkoxysilane of acryloyl or methacryloyl; the organoalkoxysilane of Mercaptofunctional; functional organoalkoxysilane of sulfane or polythioalkane and/or (ii) at least a organo-siloxane; be selected from the siloxanes of vinyl functional; glycidyl oxyalkyl functional siloxane; the siloxanes of alkyl functional; the methacryloyl functional siloxane, the siloxanes of fluoro-alkyl or fluoro organic functional and corresponding cocondensation compound and/or (iii) at least a silicon ester and/or the (iv) composition of at least a oligomeric silicon ester.
60. the purposes of composition as claimed in claim 59 under hydrolysis and/or condensation catalyst existence condition.
61. comprise composition in the water miscible liquid as claim 6 or 49 described oligomer mixtures and at least a emulsifying agent, buffer reagent, thickening material and/or biocide.
62. handle the method for base material, be that composition as claimed in claim 59 is coated on substrate surface and optional heat and/or photochemistry aftertreatment again.
63. as the coating on the base material that obtains as described in the claim 62 or the dipping body of base material.
64. as the surperficial treated base material that obtains as described in the claim 62.
65. based on article as the treated base material in claim 63 or 64 described surfaces.
66. as claimed in claim 44ly especially be used for that preparation is as claimed in claim 20 especially to have a chain, side chain, the method of the oligomer mixture of ring-type and/or crosslinking structure key element, wherein be by hydrolysis and condensation alkyltrialkoxysilaneand and/or dialkyl dialkoxy silicane, wherein used silane has alkyl with 3 to 18 C atoms and as the methoxyl group and/or the oxyethyl group of alkoxyl group, and uses every 1mol Si more than the water of 1mol with use hydrolysis and/or condensation catalyst and the resulting reaction mixture of underpressure distillation aftertreatment under less than 95 ℃ column bottom temperature.
67. as the described method of claim 66, it is characterized in that, add 1.0 to 1.2mol water at the most with respect to every mol Si.
68., it is characterized in that catalyzer is HCl as the described method of claim 66.
69., it is characterized in that the used alkyltrialkoxysilaneand and/or the hydrolysis of dialkyl dialkoxy silicane and/or condensation exist methyl alcohol and/or ethanol to carry out under as the condition of thinner and solvent as the described method of claim 66.
70., it is characterized in that the hydrolysis of used alkyltrialkoxysilaneand and/or dialkyl dialkoxy silicane and/or condensation normal pressure under 10 to 80 ℃ temperature carries out as the described method of claim 66.
71. as the described method of claim 66, it is characterized in that, import inert gas aftertreatment reaction mixture.
72. oligomer mixture as claimed in claim 20 is used for the purposes of hydrophobically modified inorganic surfaces.
73. be used for the purposes of hydrophobically modified powdered material as the described oligomer mixture of claim 72.
74. be used to prepare special as claim 26 or 27 described methods with siloxane oligomer mixture of chain, ring-type and/or crosslinking structure key element, this method trialkoxy silane that to be specific hydrolysis replace as composition A, with acryloyloxyalkyl, alkynyl group, alkynyl group oxyalkyl, alkenyl or the alkenyl oxyalkyl of straight chain with 1 to 18 C atom and/or side chain or have the methyl dialkoxy silicane of alkoxyl group that the C atomicity is 1 to 4 straight chain and/or side chain and optional
-as composition B's and to have the straight chain of 1 to 18 C atom, side chain and cyclic alkyl and fluoro-alkyl and/or to have the straight chain of 1 to 18 C atom, side chain and cyclic alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, the trialkoxy silane that cyano group alkyl and/or isocyano-alkyl replace or have the methyl dialkoxy silicane that the C atomicity is the alkoxyl group of 1 to 4 straight chain and/or side chain, perhaps its mixture and optional
-as the tetraalkoxysilane that the C atomicity is the alkoxyl group of 1 to 4 straight chain and/or side chain that has of composition C, and
-at the water that adds every 1mol Si 0.6 to 1.0mol with under in 0.1 to 5 times of weight part methyl alcohol of used organoalkoxysilane and/or alcoholic acid condition, and exist as the acid of catalyzer and carrying out specific hydrolysis and condensation and then underpressure distillation aftertreatment products mixture under 60 to 110 ℃ column bottom temperature under 10 to 95 ℃ the temperature.
75. as the described method of claim 74, this method is that hydrolysis specifically is as composition A's, has the C atomicity and is 1 to 4 the straight chain and/or the 3-methacryloxypropyl trialkoxy silane of branched alkoxy, 3-acryloyl-oxy propyl trialkoxy silane, 3-methacryloxypropyl-methyl-dialkoxy silicane, 3-acryloyl-oxy propyl group methyl dialkoxy silicane, the methyl dialkoxy silicane that trialkoxy silane that vinyl, allyl group or prenyl replace or vinyl, allyl group or prenyl replace and optional
-as composition B's, have the alkyl of 1 to 18 C atom-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-or the phenyl trialkoxy silane or have the alkyl of 1 to 18 C atom-, fluoro-alkyl-, iso-alkyl-, cycloalkyl-or phenyl-methyl dialkoxy silicane and its to have the C atomicity be 1 to 4 the straight chain and/or the alkoxyl group of side chain, perhaps have the C atomicity and be 1 to 4 straight chain and/or branched alkoxy the aminopropyl official can, the trialkoxy silane or the functional methyl dialkoxy silicane of aminopropyl of Polyetherfunctional, wherein said aminopropyl functional group is formula-(CH
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2One of and R ' equal to have the alkyl of 1 to 4 C atom, and polyether group is formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-one of and n equal 1 to 30, perhaps 3-glycidyl oxygen propyl group, perhaps their mixture and optional
-have the C atomicity and be 1 to 4 straight chain and/or side chain alkoxyl group tetraalkoxysilane as composition C and
-at the water that adds every 1mol Si 0.6 to 1.0mol with under in 0.1 to 5 times of weight part methyl alcohol of used organoalkoxysilane and/or alcoholic acid condition, and exist as the acid of catalyzer and carrying out specific hydrolysis and condensation and then underpressure distillation aftertreatment products mixture under 60 to 110 ℃ column bottom temperature under 10 to 95 ℃ the temperature.
76., it is characterized in that the used molar ratio of composition A, B and C is that A: B: C is 1: 0: 0 to 1: 10: 0 or 1: 0: 0 to 1: 0: 10 or 1: 0: 0 to 1: 10: 10 as the described method of claim 74.
77. as the described method of claim 74, it is characterized in that, use organoalkoxysilane with methoxy or ethoxy according to alcohol as solvent or thinner.
78. as the described method of claim 74, it is characterized in that, use hydrogenchloride as catalyzer.
79. as the described method of claim 74, it is characterized in that, under the temperature of normal pressure and 10 to 85 ℃, be hydrolyzed and condensation.
80., it is characterized in that the product of distillation after the aftertreatment contains less than composition A, the B of 0.5 weight % and C with less than the free alcohol of 2 weight % as the described method of claim 74.
81. as the purposes of the mixture of claim 26 or 27 described siloxane oligomers, as highly-filled with the fine dispersion mineral filler and based on the additive of casting resin with flow capacity and curable methacrylic ester.
82., be used to improve the physical strength and the optical property of plastic article and molding as the purposes of claim 26 or 27 described siloxane oligomer mixtures.
83. the purposes as claim 26 or 27 described siloxane oligomer mixtures is used for surface-treated glass fiber.
84., be used for modification and crosslinked organic resin as the purposes of claim 26 or 27 described siloxane oligomer mixtures.
85. as the purposes of claim 26 or 27 described siloxane oligomer mixtures, as binding agent in the japanning and the composition in the varnish.
86. the purposes as claim 26 or 27 described siloxane oligomer mixtures is used to prepare coating, and it is by the thermal treatment under 40 to 200 ℃ and/or by solidifying with known method radiotreatment own.
87., be used for handling or applying mineral or metallic surface as the purposes of claim 26 or 27 described siloxane oligomer mixtures.
88. the purposes as claim 26 or 27 described siloxane oligomer mixtures is used for the surface treatment powdered material.
89. as claimed in claim 44ly especially be used to prepare the method with siloxane oligomer mixture of chain, ring-type and/or crosslinking structure key element as claimed in claim 35 especially, this method be with
-as functional trialkoxy silane of at least a aminopropyl or the functional methyl dialkoxy silicane of aminopropyl of composition A, and wherein alkoxyl group be straight or branched and have 1 to 4 C atom and optional
-as at least a trialkoxy silane or the methyl dialkoxy silicane of composition B, wherein alkoxyl group be straight or branched and have 1 to 4 C atom, and has a straight chain with 1 to 18 C atom as other groups, side chain and/or cyclic alkenyl and/or alkyl and/or have the straight chain of 1 to 18 atom, side chain and/or cyclic alkoxyalkyl, aralkyl, haloalkyl, polyether-based and/or epoxy group(ing) and/or have the aryl of 6 to 12 C atoms and/or have the urea alkyl of 1 to 18 C atom, mercaptoalkyl, cyano group alkyl and/or isocyano-alkyl and optional
-as the tetraalkoxysilane of composition C,
-under 10 to 95 ℃ the temperature and under the water and methyl alcohol and/or ethanol of the every 1mol Si 0.6 to 1.2mol of use in 0.1 to 5 times of weight part of used organoalkoxysilane, specifically successively or mix ground hydrolysis and condensation composition A, optional B and optional C, and then under normal pressure or reduced pressure and at the most under 120 ℃ the column bottom temperature alcohol will be used and that from react, discharge from product mixture, remove.
90. preparation is as the method for the mixture of described chain of claim 89 and annular siloxane oligopolymer, this method is to use
-composition A, it is corresponding to functional trialkoxy silane of at least a aminopropyl or the functional methyl dialkoxy silicane of aminopropyl, and wherein said aminopropyl functional group is corresponding to formula-(CH
2)
3-NH
2Or-(CH
2)
3-NHR ' or-(CH
2)
3-NH (CH
2)
2-NH
2Or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2, R ' wherein is straight chain, side chain or cyclic alkyl with 1 to 18 C atom or the aryl with 6 to 12 C atoms, and wherein said alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-and optional
-composition B, it is corresponding at least a trialkoxy silane or methyl dialkoxy silicane, wherein alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-, and comprise alkyl, alkenyl, fluoro-alkyl, iso-alkyl, cycloalkyl and/or have the aryl of 6 to 12 C atoms to have formula H with 1 to 18 C atom as other groups
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-and wherein chain length n equal 1 to 30 and/or 3-glycidyl oxygen propyl group and optional
-composition C, it is a tetraalkoxysilane, wherein alkoxyl group is corresponding to methoxyl group, oxyethyl group, 2-methoxy ethoxy and/or propoxy-,
-and, under 10 to 95 ℃ the temperature and under the water and methyl alcohol or ethanol of the every 1mol Si 0.6 to 1.2mol of use in 0.1 to 5 times of weight part of used organoalkoxysilane, specifically successively or mix ground hydrolysis and condensation composition A, optional B and optional C, and then distill under 120 ℃ the column bottom temperature under normal pressure or reduced pressure and at the most alcohol used and that discharge in reaction is removed from product mixture.
91., it is characterized in that the used molar ratio of composition A, B and C is that A: B: C is 1: 0: 0 to 1: 10: 0 or 1: 0: 0 to 1: 0: 10 or 1: 0: 0 to 1: 10: 10 as the described method of claim 89.
92. as the described method of claim 89, it is characterized in that,, use organoalkoxysilane with methoxy or ethoxy according to alcohol as solvent or thinner.
93. as the described method of claim 89, it is characterized in that, under the temperature of normal pressure and 10 to 95 ℃, be hydrolyzed and condensation.
94., it is characterized in that distillation aftertreatment products mixture in 50 to 120 ℃ temperature range and under normal pressure and/or reduced pressure as the described method of claim 89.
95., it is characterized in that the product of distillation after the aftertreatment contains less than used composition A, the B of 5 weight % and C with less than the free alcohol of 1 weight % as the described method of claim 89.
96. as claim 35, the purposes with siloxane oligomer mixture of chain, side chain, ring-type and/or crosslinking structure key element as claimed in claim 36 especially, cementing medium as binding agent and sealing agent, be used for modification and crosslinked organic resin, as the binding agent in pigment and the japanning, be used for coated glass fiber, as the cementing medium in the fillibility thermoplasticity formulation, be used to handle mineral, organic and metallic surface, be used for the hydrophobization surface, be used for the surface modification powdered material and be used for silanization filler and pigment.
97. the method that is used for preparing siloxane oligomer mixture as claimed in claim 41 especially as claimed in claim 44 especially by specific hydrolysis, it is characterized in that, randomly use catalyzer, vinyl trialkyl oxysilane, the allyl group trialkoxy silane, the prenyl trialkoxy silane, methacryloxypropyl alkyltrialkoxysilaneand or acryloyloxyalkyl trialkoxy silane, optional trialkoxy silane that replaces with organic group and/or tetraalkoxysilane are as raw produce, and the water that adopts calculated amount is in the methyl alcohol of 0.2 to 8 times of weight of silane or ethanolic soln and carry out condensation under 20 to 80 ℃ temperature, simultaneously the catalyzer of the pure and mild optional use of free is removed.
98. as the described method of claim 97, it is characterized in that, by specific acidic catalyst hydrolysis and utilize HCl as catalyzer, vinyl trialkyl oxysilane, optional alkyltrialkoxysilaneand and/or tetraalkoxysilane are as initial product, and the water that adopts calculated amount is removed catalyzer and free alcohol in the methyl alcohol of 0.2 to 8 times of weight of silane or ethanolic soln and carry out condensation under 20 to 80 ℃ temperature simultaneously.
99. as the described method of claim 97, it is characterized in that, organic group is corresponding to alkyl, iso-alkyl or cycloalkyl with 1 to 18 C atom, has alkoxyalkyl, aralkyl, aminoalkyl, haloalkyl, polyether-based and/or the epoxy group(ing) of 1 to 18 C atom and/or has the aryl of 6 to 12 C atoms and/or have urea alkyl, mercaptoalkyl, cycloalkyl and/or the isocyano-alkyl of 1 to 18 C atom.
100., it is characterized in that organic group is corresponding to having formula-(CH as the described method of claim 99
2)
3-NH
2,-(CH
2)
3-NHR ' ,-(CH
2)
3-NH (CH
2)
2-NH
2And/or-(CH
2)
3-NH (CH
2)
2-NH (CH
2)
2-NH
2Aminopropyl functional group and R ' wherein be straight chain, side chain or cyclic and alkyl with 1 to 18 C atom, wherein chain length n equal 1 to 30 and have a formula H
3C-(O-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2)
nO-CH
2-, H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nO-CH
2-, H
3C-(O-CH
2-CH
2-)
nO-, H
3C-(O-CH
2-CH
2-CH
2-)
nO-and/or H
3C-(O-CH
2-CH
2-CH
2-CH
2-)
nThe polyethers of O, fluoro-alkyl and/or 3-glycidyl oxygen propyl group.
101., it is characterized in that making concentration in water/alcohol mixture as catalyzer is 3 to 3000ppm HCl as the described method of claim 97.
102. as the purposes of claim 41 or 43 described mixtures, as the linking agent of TPO and by known way graft polymerization own and hydrolytic condensation.
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| CNA2007101676793A CN101353479A (en) | 2007-07-27 | 2007-07-27 | Siloxane oligomer, preparation and use thereof |
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