CN101649051A - Formed organic amino siloxane copolycondensation polymer and preparation methods and application thereof - Google Patents
Formed organic amino siloxane copolycondensation polymer and preparation methods and application thereof Download PDFInfo
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Abstract
The invention discloses an organic siloxane co-condensation polymer crosslinked by an optional crosslinker containing Si, Ti, Zr and/or Al. The co-condensation polymer comprises the units shown in theformula (1), wherein, R<1>-R<5> are shown in the formula (2); R<6> is C1-C10 alkylene directly connected to N or X, or C5-C8 sub-naphthenic base or is shown in the formula (3); X is shown in the formula (4) or is -S-, -S2-, -S3-, -S4- or P-C6H5 and R'' is equal to H or is C1-C5 alkyl. The products are in the form of spherical particles, with diameters being 0.01-3.0mm, specific surface areas being 1000m<2>/g at most, specific pore volumes being 6.0ml/g at most and bulk density being 50-1000g/l. The invention discloses different methods for preparing the formed co-condensation polymer and application of specific components in separating metals from solution and/or in adsorbing gaseous organic mixtures and/or water vapor.
Description
Technical field
The present invention relates to the big ball co-condensation polymer of shaping of uncle's organo-siloxane amine and one or more silicone components, it has good processing and the utilisation technology of organopolysiloxane co-condensation polymer (the German patent application P 38 37 418 on November 4th, 1988) than previous exploitation.On the other hand, the present invention relates to make and have the sphere sizes that is suitable for special applications and shape and have the method for the product innovation of suitable physical properties.In addition, another aspect of the invention is the method for the organo-siloxane amine co-condensation polymer that uses these moulding.
Background technology
Soluble organo-siloxane amine is described in the German Patent 31 20 214, especially with based on organic polymer compares with the similar system of the inorganic polymer system of special modification, it is characterized in that extremely good chemistry and physical properties.These organo-siloxane amine can be used as the carrier of composite catalyst of weak base type ion exchanger, absorption agent, active ingredient carriers, heterogeneousization or the heterogeneous alkali in the base catalysis reaction.The matrix of these products can be based on chemistry and physical properties and customized production, so can be fit to the requirement of for example above-mentioned special use.In order to be suitable for industrial application requirements, also developed shaping or forming method for these novel polymers, not only can be with block or Powdered but also can produce these products with favourable sphere.The organo-siloxane amine of these shapings is described among the German Patent P 38 00 563.8.Confirmed in a kind of polymeric matrix, to mutually combine have different functional groups in the various application of organo-siloxane very favourable after, developed suitable organo-siloxane amine co-condensation polymer and be described among the German Patent P 38 37 418.8.Can be by produce the synergistic function effect of each component effect sum (promptly surpass) in conjunction with different functional groups, simultaneously can be by different functional groups different arrangement scheme and produce other possibility in polymeric system, optional in conjunction with linking agent.Yet, simultaneously having confirmed that these co-condensation polymers are not favourable, this is because these products before only can uncertain relatively geometric format rather than with sphere production, and the sphere with required physics and morphological properties helps industrial application.
Summary of the invention
Therefore, an object of the present invention is to prepare with sphere the organo-siloxane amine co-condensation polymer with required physical properties of type described in the German Patent P 3,837 418.8 in mode repeatably.The present invention has solved this problem by developing the big ball organo-siloxane amine co-condensation polymer that is shaped, and wherein said organo-siloxane amine co-condensation polymer comprises unit of following formula:
And unit of following formula:
Wherein, R
1-R
5Identical or different and represent the group of following formula:
Wherein, R
6Be directly connected in the even X group of (double-bonded) of nitrogen-atoms or two key, and representative has the linearity of 1-10 carbon atom or the alkylidene group of branching, the cycloalkylidene with 5-8 carbon atom or the following unit of general formula:
Wherein, n is the numerical value of 1-6 and the methylene radix that expression is connected in nitrogen or X, and m is the numerical value of 0-6.
Wherein, the Siliciumatom of other groups of free valency through type (III) of Sauerstoffatom that is connected in Siliciumatom is as silicon dioxide skeleton and/or saturated via one or more crosslinked atoms metals of crosslinked bridging type:
Or
Or
M is that Siliciumatom, titanium atom or zirconium atom and R ' they are linearity or branched-alkyl or the phenyl with 1-5 carbon atom, and the ratio of the atoms metal of the Siliciumatom of the middle group of formula (III) and bridging type crosslinked (IV) is 1: 0-1: 20, and
Wherein, R " equal H or for having linearity or the branched-alkyl or the group (CH of 1-5 carbon atom
2)
n-NR
2" ', wherein n represents the numerical value of 1-6, and R " ' have and R " identical meaning.
The diameter of big ball particle is 0.01-3.0mm, preferred 0.05-2.0mm, and specific surface area is at most 1000m
2/ g preferably is at most 700m
2/ g, specific pore volume is long-pending to be that 0-6.0ml/g and bulk density are 50-1000g/l, preferred 100-800g/l.
Of the present invention one more specifically aspect in, described being formed with in the organic siloxane co-condensation polymer, formula (I) unit and the unitary ratio of formula (II) they are 0.03: 99.97-99.99: 0.01 mole of %, preferred 5: 95-95: 5 moles of %.
Of the present inventionly be formed with the form that the organic siloxane co-condensation polymer can be so-called random co-condensation polymer, block copolycondensation thing or mix co-condensation polymer.
Of the present invention also more specifically aspect in, R
1-R
5Represent the group of following general formula:
The ratio of two kinds of components of formula I and formula II can change big and can be within above-mentioned boundary, if not like this, then cause the problem of product of the present invention or cause the problem of production method of the present invention on form, physics or chemical property.
The ratio of actual selection depends primarily on the intended application and the required chemistry and the physical properties of this application of concrete co-condensation polymer, promptly for example depends on the functional group that whether needs highdensity formula II.
The monomer structure of the organo-siloxane amine co-condensation polymer of described shaping is mainly known compound, for example the compound of following formula:
N[(CH
2)
3Si(OC
2H
5)
3]
3
S[(CH
2)
3Si(OCH
3)
3]
2
HN[(CH
2)
10Si(OC
2H
5)
3]
2
C
6H
5-P[(CH
2)
2Si(OCH
3)
3]
2
S
4[CH
2-C
6H
4-Si(OC
3H
7)
3]
2
Si(OC
2H
5)
4，Ti(OC
3H
7)
4
In the German patent application P 39 25 356.2 on July 31st, 1989 (89 166 SO), has a functional N of tertiary amine described in the possibility about material and preparation, N '-two replaces and N, N, and N '-/N, N ', N '-trisubstituted organic oxo silyl-functional thiocarbamide.
The composition of obtainable polymer unit can be described by following formula thus:
N[(CH
2)
3SiO
3/2]
3
S[(CH
2)
3SiO
3/2]
2
HN[(CH
2)
10SiO
3/2]
2
C
6H
5-P[(CH
2)
10SiO
3/2]
2
S
4[CH
2-C
6H
4-SiO
3/2]
2
SiO
4/2，TiO
4/2
Formed copolycondensation polymer isused can be with identical chemical constitution but diverse form and as so-called random co-condensation polymer, block copolycondensation thing or also exist as so-called mixing co-condensation polymer.
According to the present invention, when the manufacturing process of carrying out about formula I, II and IV unitary of the present invention, described formed copolycondensation polymer isused can exist with one of described three kinds of forms.This means that the random distribution of component depends on the molar ratio of initial product under the pure situation that contains formula I and II unit and the unitary random co-condensation polymer of optional formula IV.Under the situation of the functional group of formula I and II unit and formula IV cross-linker groups, must consider that the silicon group of formula III exists.Under the situation of so-called block copolycondensation thing, the structural unit of structure and formula I and II and optional IV are identical.At last, so-called mixing co-condensation polymer has two kinds of structures of random co-condensation polymer and block copolycondensation thing.Therefore, the unit of formula I or II or IV can not only exist as random co-condensation polymer but also as the block copolycondensation thing.
Special advantage about raw material and quality of materials availability realizes by multipolymer, wherein, and R
1-R
3For:
Another characteristics of the present invention are to prepare above-mentioned co-condensation polymer.
The method for preparing the random organo-siloxane amine co-condensation polymer of above-mentioned shaping comprises draws together: dissolving is corresponding to uncle's amino-organosilanes of the following general formula of the required stoichiometric composition of the co-condensation polymer that will prepare in solvent:
Silane with organic functional:
That is, the selection of each silane amount should be enough to react to each other to prepare required co-condensation polymer.
In following formula, R
7-R
11Identical or different and represent the group of following formula:
R
8-Si(OR
12)
3 (VII)
R
6Have with formula (III) in identical meaning,
R
12Representative has the linearity or the branched-alkyl of 1-5 carbon atom, and
X have with formula (II) in identical meaning.
The optional linking agent that can add one or more following formulas:
M (OR)
2-4R
1 0-2Or Al (OR)
2-3R '
0-1(VIII)
Wherein, M is Siliciumatom, titanium atom, zirconium atom,
R ' for have the linearity of 1-5 carbon atom or a branched-alkyl or phenyl, and
The alkyl that the R representative has the linearity or the branching of 1-5 carbon atom.
The ratio of the atoms metal in Siliciumatom in the group of general formula (VII) and the linking agent (VIII) is 1: 0-1: 20.
Described solvent can with water base miscible, but can dissolve the silane of organic functional of the amino-organosilanes of formula V and formula (VI) and the linking agent of formula (VIII).
The water yield that under agitation adds in solution is enough to complete hydrolysis and is enough to make under the described here reaction conditions of polycondensation carry out at least.Make then reaction mixture further stir and the specified temp of room temperature to 200 ℃ under and when gelation begins or at the most after one hour with 10-2000 weight %, carry out gelation under the solvent of preferred 50-500 weight % (with respect to the total amount of the silane (VI) of amino-organosilanes (V), organic functional and the linking agent (VIII) chosen wantonly) the blended condition.Described solvent and water base unmixing, but the reaction mixture of gelation or beginning gelation can be dissolved.In addition, choose wantonly under the elevated temperature of the temperature that is higher than initial setting, at once or be at most the total amount that adds in time of 3 hours with respect to the silane (VI) of amino-organosilanes (V), organic functional and optional linking agent (VIII) in heavy-gravity homogenizing thing is 10-200 weight %, preferably the water of 50-500 weight %.The organic phase that contains siloxanes is scattered in the two-phase liquid system, and room temperature to 200 ℃ down and after being enough in reaction, to form reaction times of spherical solid siloxanes with itself and liquid phase separation.Then, optional solid product is extracted, in room temperature to 250 ℃ down and choose wantonly and carry out drying at shielding gas or under vacuum, and under 150-300 ℃ temperature tempering 1-100 hour and/or classify according to size.
The organic solvent that is suitable for hydrolysis reaction of the present invention is low-grade alkane alcohol such as independent methyl alcohol, ethanol, n-propyl alcohol and Virahol, propyl carbinol and isopropylcarbinol or Pentyl alcohol or their mixture.
Preferably, under the excessive situation of water, be hydrolyzed.
Of the present invention more specifically aspect in, in the reaction mixture of gelation or beginning gelation separately or with mixture add alcohol, toluene or the neighbour of linearity or branching with 4-12 carbon atom-,-, right-dimethylbenzene.
Usually, the halogenide or the phenoxy group compound of correspondence can also be replaced the alkoxysilyl amine compound and is used as raw material of the present invention, yet it uses does not provide any advantage, but may for example throw into question owing to discharge hydrochloric acid in hydrolysis under the muriatic situation.
The hydrolysis of raw material and optional linking agent must be can be miscible with water base but carry out in the solvent of dissolving raw material.As mentioned above, the preferred use corresponding in the monomer precursor of raw material or the alcohol of the alkoxyl group on the atoms metal of the optional linking agent that uses.Methyl alcohol, ethanol, n-propyl alcohol and Virahol, propyl carbinol and isopropylcarbinol or Pentyl alcohol are suitable especially.Also mixture that can such is pure is as the solvent of hydrolysis.Can also use with water base other miscible polar solvents to replace alcohol, yet this seems not quite reasonable that this is can hydrolysis separation processes reason with the solvent mixture of alcohol because consider.
Hydrolysis is preferably being carried out above under the excessive water of stoichiometry.The water yield that hydrolysis needs depends on the used concrete amino-organosilanes or the hydrolysis rate of linking agent, so that with the increase of rate of water added, it is faster that hydrolysis is carried out; Yet, can be by separating and forming two-phase system and capping.Basically preferably in homogeneous phase solution, be hydrolyzed.Because described two aspects, in fact add that according to organosilane the weight of linking agent uses fewer water.
Hydrolysis time changes with the hydrolysis tendency and the temperature of raw material and/or linking agent.The difficulty of hydrolysis and hydrolysis rate especially depend on the type of the alkoxyl group of silicon position or titanium, zirconium or aluminium position.Speed descends the most fast and along with the increase of alkyl chain length in the methoxyl group hydrolysis.In addition, the time of whole hydrolysis and polycondensation process is also depended on the basicity of amino-organosilanes.Known amine is used as the polycondensation accelerator by causing autocatalysis.Therefore, hydrolysis and polycondensation can be by adding alkali, preferred ammoniacal liquor or inorganic or organic acid and conventional polycondensation catalyst such as dibutyltin diacetate and quicken.
Make raw material keep being dissolved in solvent under specified temp and under further stirring and with the requirement of water blended thereby to cause polycondensation speed be the fact of complying with temperature variation, wherein said polycondensation speed shows by gelation.
On the experience, temperature used in hydrolysis or gelation stage is by situation decision separately.Therefore should note keeping and not contain the gelatinoid that solid and infiltration have liquid for the method steps of the so-called shaping stage of the next one.
There have the gelatinoid of liquid to be converted into the shaping stage (wherein condensation reaction is further carried out) of spheroidal particle separately the infiltration of viscosity to be initial with mixing of a certain amount of solvent by reaction mixture, gelation of wherein said reaction mixture or beginning gelation, the basic and water unmixing of described solvent but reaction mixture can be dissolved to enough degree.
Aromatic substance that suitable solvent for example replaces for symmetry with the linearity of 4-18 carbon atom or branching alcohol or phenol, linearity or branching or asymmetric dialkyl ether and diether or three ethers (for example glycol dimethyl ether), chloro or hydrofluoric ether, by one or more alkoxyl groups or mixture of aromatic compounds such as toluene or dimethylbenzene, substantially and immiscible symmetry of water or asymmetric ketone.
Yet, preferably will have the linearity of 4-12 carbon atom or branching alcohol, toluene or neighbour-,-, right-dimethylbenzene separately or add with form of mixtures in the reaction mixture of gelation or beginning gelation.
Described solvent be added on and the reaction mixture homogeneous phaseization after cause diluting and therefore cause the condensation reaction that viscosity increases speed obviously descend.
The required granularity that is formed with the organic siloxane amine compound is especially depended in the measurement that is used for the quantity of solvent of shaping stage.Can with as described below as the rule: coarse particles (having larger-diameter ball) should use seldom solvent and fine particle (having the ball than minor diameter) should use a large amount of solvents.
In addition, will be scattered in what shaping stage added by reaction mixture and with the thickness homogenizing thing of water base immiscible solvent composition and also influence particle as the degree in the additional water of dispersion agent.Violent stirring helps forming than fine particle usually.In order to stablize the dispersion of organic phase (not containing siloxanes) in water, can add a kind of known auxiliary dispersants with conventional concentration, for example long-chain carboxylic acid or its salt or polyalkylene glycol.
According to the flexible program of the inventive method, at hydrolysis stage and will be between the gelation elementary period or to be added afterwards add with water base immiscible part or all of amount solvent and solvent for use here.Under the situation that part is added, after beginning, gelation adds residuum.
Adding under the extreme cases of whole amounts, can be between the gelation elementary period or add dispersion agent, water afterwards.If organosilane mixture that is added and the optional linking agent mixture that is added have high hydrolysis and polycondensation tendency, then preferably use this flexible program.
The organic phase that contains siloxanes is disperseed and the preferred temperature that forms spherical solid from disperse phase is generally the reflux temperature of whole mixture at aqueous phase.Yet, can use the temperature identical basically with gelation stage.Scatter stage and post-reacted total time are generally 0.5-10 hour.
Gelation and shaping all can be carried out under normal pressure or superpressure (corresponding to the dividing potential drop sum in reaction mixture components under the used actual temp).
In the crosslinked or non-crosslinked organo-siloxane amine of producing shaping of the present invention, the one or more components that have the mixture of wanting gel have the situation of different hydrolysis properties and polycondensation characteristic (it also changes with the alkoxyl group type).At this moment, the research of the inventive method provides linking agent VIII and/or functional organic alkane VI not to carry out gelation with amino-organosilanes V, but amino-organosilanes is optional with linking agent VIII or organosilane VI gelation at first respectively, with carry out homogeneous phaseization with water base immiscible solvent, then linking agent or organosilane are added the homogenizing thing.
Yet, can also be simultaneously solvent and the component that still do not contain silane be added in the amino-organosilanes and optional linking agent or organosilane of gelation.
Spherical moist product and liquid dispersant separate can by ordinary method as topple over, filtration or centrifugal and carry out.
Yet, liquid phase can also be removed and is used the lower boiling extraction agent from reactor for this reason, preferred low-boiling point alcohol will remaining solids treatment once or several times so that carry out exchange partly at least and be easier to the material of later stage dry forming by the solvent that makes the common higher in the shaping stage and lower boiling extraction agent.
Described drying can be chosen wantonly at shielding gas or under vacuum and be carried out under room temperature to 250 ℃ basically.Exsiccant shaping solid can carry out tempering with sclerosis and stabilization under 150-300 ℃ temperature.
Drying and/or tempered product can be categorized as varigrained level part according to granularity in conventional equipment.Can be on demand and get rid of in extraction, dry, tempering and the classification processing method one or another.Liquid soaks, drying or tempered product can use routine techniques and carry out classification according to size.
Random in order to offset, as to choose the monomer component of crosslinked co-condensation polymer wantonly different hydrolysis properties and polycondensation characteristic according to production flexible program of the present invention, can make the monomer component of formula V and VI and the optional linking agent that exists at first carry out precondensation.For this reason, make the aminosilane of formula V, the monomer component of formula VI and the linking agent of formula VIII not have under the solvent or pass through to use under the solvent of solubilized monomer component, be not enough in existence under the water yield of complete hydrolysis, under room temperature to 200 ℃, carried out precondensation 5 minutes to 48 hours, wherein said solvent preferably uses has 1-5 the alcohol corresponding to alkoxyl group, and described complete hydrolysis preferably needs the amount of 1-100 mole %.In order to help this precondensation effect, except the amino-organosilanes that exists, can also add another kind of condensation catalyst, for example inorganic or organic acid or alkali or metallic condensation catalyst such as dibutyltin diacetate.The preferred ammoniacal liquor that uses in this aspect of the invention.After complete precondensation, carry out whole hydrolysis and polycondensation as mentioned above.
According to another method flexible program of the present invention, obtain so-called block copolycondensation thing, wherein formed the block of one or more unitary same units of formula I and formula II and optional formula IV.
The precondensation that carries out can quicken by adding a small amount of acidity or alkaline condensation catalyst or metallic condensation catalyst equally thus.The preferred ammoniacal liquor that uses in this flexible program of the present invention.The used water yield of precondensation depends on the low dimerization that will realize, the i.e. degree of block size.If precondensation uses more water, prepare unit bigger when using water still less naturally.The time of precondensation is by the difficulty and the temperature that depend on the monomer component hydrolysis as mentioned above usually.
According to another method flexible program of the present invention, obtain so-called mixing co-condensation polymer, wherein part has formed the block of one or more unitary same units of formula I and/or formula II and/or formula IV, yet wherein at least a monomer component does not carry out precondensation and at least a monomer component carries out precondensation.This flexible program is provided in the monomer of the general formula V, the VI that are provided and optional VIII, and at least a as mentioned above monomer or several monomer carry out precondensation independently of each other.Then they and the remaining monomer that does not carry out precondensation are merged.Subsequently, add more water and optional more solvent, finish the whole hydrolysis and the precondensation of whole mixture.Handle formed polycondensate according to described additive method subsequently.
The embodiment of a particularly important of the inventive method provide still soak solvent and water are arranged sphere material at 50-300 ℃, carry out Temperature Treatment 1 hour under preferred 100-200 ℃ to 1 week, wherein use superpressure as required.
Processing under " steam " or digestion condition is mainly used in physical strength and the porosity that improves shaped material equally.This processing can also be when the preparation method finishes in the dispersion that exists or can in water, carry out separately, wherein said dispersion contain product liquid mutually with solid product mutually.
The solid of the above-mentioned embodiment of the also undried aftertreatment that is formed with the organic siloxane co-condensation polymer by making formula spherical in shape at least a as steam or liquid water or liquid phase component in the presence of carry out Temperature Treatment and realize.Described being treated at 50-300 ℃, preferred 100-200 ℃ and choose under superpressure heating 1 hour wantonly to 1 week at the most.Therefore, the existence of acidity, alkalescence or containing metal catalyzer may be favourable.A particularly advantageous embodiment is used ammoniacal liquor.
The described novel feature that is formed with organic siloxane amine co-condensation polymer especially is quantitative hydrolysis productive rate, ultimate analysis and is determining of each functional group.Theoretically, there is not difference between the co-condensation polymer that obtains according to different preparation methods.Depend on pre-treatment, spherical formed copolycondensation polymer isused of the present invention has 0.01-3.0mm, and the particle diameter of preferred 0.05-2.0mm is at most 1000m
2/ g, preferably 700m at the most
2The specific surface area of/g, the long-pending and 50-1000g/l of the specific pore volume of 6.0ml/g, the preferably bulk density of 100-800g/l at the most.Adjustable aperture is that 0nm is extremely greater than 1000nm, promptly at the most greater than 1000nm.
The chemical stability of shaped product is not with mold compound is unsuitable, that is, depend on separately functional group they in air apparently higher than 150 ℃ and under protective atmosphere, be higher than 200 ℃.
Described formed copolycondensation polymer isused is except can be used as usually in a broad sense the active ingredient carriers, and another theme of the present invention is to incite somebody to action wherein according to static state or principle of dynamics that the X representative cooperates the co-condensation polymer of group to be used for from the purposes of the metal of liquid water or organic phase separate dissolved:
The another kind of purposes of all co-condensation polymers of the present invention is for being applied to gaseous organic compound and/or water vapor, the absorption of preferred organic solvent.Described liquid or steam need be according to the present invention this aspect and handle and contact with co-condensation polymer as described.
The deciding factor of this assimilating activity is especially long-pending for specific pore volume, aperture and surface properties.
On the one hand, these factors can be via preparation of the present invention and post-treating methods and are affected, can also be affected via chemical constitution on the other hand, wherein said chemical constitution is for example inserted in the polysiloxane skeleton by the cross-linker groups that will have hydrophobic interaction.The organic compound that is absorbed or the recovery of water can be by improving temperature and/or gasifying and be easy to carry out with adding warm air.
Embodiment
Following the present invention is further described by the embodiment of embodiment.
Embodiment 1
With 385.8g (0.906 mole) NH[(CH
2)
3Si (OC
2H
5)
3]
2And 114.2g (0.18 mole) N[(CH
2)
3Si (OC
2H
5)
3]
2Mix with 500ml ethanol.Mixture is heated to 70 ℃ with double-jacket in 3 liters reactor, and at first mixes, mix with the 150ml water that desalts then with the 1-octanol of 500ml.Mixture is cooled to 40 ℃ and under this temperature, further stir and begin stirring under (200rpms) then until gelation.After gelation begins, add the other 300ml octanol wherein dissolved the 2.5g polyoxyethylene glycol and the 800ml water that desalts, and the speed of rotation of used paddle agitator is risen to 500rpms.Under refluxing, mixture was stirred 3 hours then, cooling then, with the alcohol extraction that is total up to 1 liter, then under nitrogen gas stream under 90 ℃ only dry 4 hours, 110 ℃ dry 4 hours and 130 ℃ dry 6 hours down down.
Obtained being total up to that the polymer unit by following formula of 237.5g (theoretical yield 99.8%) forms is formed with organic siloxane amine co-condensation polymer:
N[(CH
2)
3SiO
3/2]
3.5HN[(CH
2)
3SiO
3/2]
2
It 97% has the granularity of 0.1-1.6mm.
Specific surface area: 485m
2/ g
Total specific pore volume is long-pending: 2.2ml/g
Bulk density: 346g/l
Embodiment 2
(C with 76.9g (0.18 mole)
6H
5) P[(CH
2)
2Si (OCH
3)
3]
2, 223.1g (0.35 mole) N[(CH
2)
3Si (OC
2H
5)
3]
2And the Si (OC of 73.8g (0.35 mole)
2H
5)
4Add in the 350ml ethanol.Mixture is heated to 75 ℃ with the KPG agitator of being furnished with crescent stirring piece, reflux exchanger and internal thermometer in 3 liters reactor.Described clear solution and the 130ml water that desalts is mixed under 90 ℃, under refluxing, stirred 15 minutes then and be cooled to 70 ℃.The viscous solution that this is limpid keeps down beginning until gelation in stirring (250rpms) slowly under this temperature.After gelation begins about 1 minute, add 600ml toluene, and after homogeneous phaseization is finished, under 50 ℃, add the water that desalt of 700ml temperature.At reflux temperature and under 700rpms mixture was stirred 2 hours then, cooling is transferred to complete reaction mixture in the stainless steel cauldron then then, and under internal pressure, slowly stirs 24 hours down at 150 ℃.
Filter out from liquid phase with the mixture cooling and with the shaping solid then.At N
2Under the atmosphere 90 ℃ down dry 6 hours and at 130 ℃ down after dry 12 hours, obtained the symmetrical spherical products that the polymer unit by following formula of 178g (theoretical yield 99.6%) is formed:
N[(CH
2)
3SiO
3/2]
3·0.5(C
6H
5)P[(CH
2)
2SiO
3/2]
2·SiO
4/2，
It 97% has the granularity of 0.2-1.55mm.
Specific surface area: 456m
2/ g
Total specific pore volume is long-pending: 2.6ml/g
Bulk density: 423g/l
Embodiment 3
S[(CH with 912.1g (2.06 moles)
2)
3Si (OC
2H
5)
3]
2Mix with 500ml ethanol and be heated to reflux temperature with 10 liters of quickfit devices being furnished with agitator, reflux exchanger and internal thermometer.After reaching reflux temperature, the 50ml water that desalts is added in this solution.At first under refluxing, stirred 1 hour then.Then, the N[(CH that adds 260.0g (0.41 mole)
2)
3Si (OC
2H
5)
3]
3, 429.2g (2.06 moles) Si (OC
2H
5)
4With 1200ml ethanol and other 450ml water.Mixture was stirred other 25 minutes under refluxing, be cooled to 76 ℃ of also further slow stirrings then and begin until gelation.After gelation begins, add the 1-hexanol of 2500ml, and after 10 minutes, add 3.0 liters of water that desalt that wherein dissolved the 7.5g polyvinyl alcohol.Mixture further stirred 1 hour and filters out the shaping solid under refluxing then.With this solid and 3.0 liters of 2%NH
3Solution mixes, and is transferred to then in the steel reactor and at 130 ℃ to stir 48 hours down.Then mixture cooled off, filters out solid, use the washing with alcohol that is total up to 5.0 liters, and at N
2Under the atmosphere of shielding gas 80 ℃ down dry 6 hours and 130 ℃ dry 18 hours down.Obtained being total up to the mixing co-condensation polymer of forming by unit of following formula of 692g (theoretical yield 99%):
N[(CH
2)
3SiO
3/2]
3·5S[(CH
2)
3SiO
3/2]
2·5SiO
4/2。
Spherical products above 96% exists with the granularity of 0.3-1.8mm.
Specific surface area: 636m
2/ g
Total specific pore volume is long-pending: 3.2ml/g
Bulk density: 366g/l
Embodiment 4
HN[(CH with 280.1g (0.66 mole)
2)
3Si (OC
2H
5)
3]
2, 82.9g (0.13 mole) N[(CH
2)
3Si (OC
2H
5)
3]
3, 137.1g (0.66 mole) Si (OC
2H
5) and (CH of 195.7g (1.32 moles)
3)
2Si (OC
2H
5)
2Add in the 700ml ethanol.Mixture is heated to reflux temperature in being furnished with 6 liters of Glass Containerss of agitator, condenser and dropping funnel, mixing with 200ml water then.
This solution is cooled to 50 ℃ and remain under this temperature and begin until gelation at once.After gelation begins, add the 1400ml octanol, add the 1500ml that has wherein dissolved the 2.5g polyvinyl alcohol water that desalts then.Use the mode similar to embodiment 3 further handle and aftertreatment after, obtained the polymerisate that the polymer unit by following formula of 306g (theoretical yield 98.5%) is formed:
N[(CH
2)
3SiO
3/2]
3·5HN[(CH
2)
3SiO
3/2]
2·5SiO
4/2·10(CH
3)
2SiO
2/2。
After classifying, 95% spherical products has the granularity of 0.3-1.6mm.
Specific surface area: 436m
2/ g
Total specific pore volume is long-pending: 1.6ml/g
Bulk density: 476g/l
Embodiment 5
N[(CH with 78.8g (0.125 mole)
2)
3Si (OC
2H
5)
3]
3Mix and to be incorporated in 80 ℃ and to stir 1h down with the 5ml water that desalts.Make the following formula thiourea derivative of 121.2g (0.25 mole) add 5ml water later at 80 ℃ of following precondensation 1h equally in addition simultaneously:
After this, two kinds of prepolycondensates are mixed to be incorporated in 200ml ethanol under refluxing, stirred 10 minutes after adding the extra water of 50ml, be cooled to 70 ℃ and further stir (200rpms) and begin then until gelation.After gelation begins about 30sec, add the 1-butanols of 300ml, add the 300ml water that desalts after 5 minutes.Reaction mixture is further stirred 2h under 600rpms, cooling filters out spherical solid from liquid phase then, wears out in reactor, then extraction similar to Example 3ly.At N
2In drying 8 hours under 90 ℃ and after under 140 ℃ dry 16 hours, obtained the block copolycondensation thing that 102g is made up of unit of following formula under the atmosphere of shielding gas:
N[(CH
2)
3SiO
3/2]
3·2S＝C[NH-(CH
2)
3SiO
3/2]
2。
94% shaped product has the granularity of 0.2-1.6mm.
Specific surface area: 456m
2/ g
Total specific pore volume is long-pending: 2.2ml/g
Bulk density: 446g/l
Embodiment 6
N[(CH with 78.8g (0.125 mole)
2)
3Si (OC
2H
5)
3]
3And 121.2g (0.25 mole)
Mix, and mixes with the 5ml water that desalts, and at first at 70 ℃ of stirring 6h.Add the extra water of 200ml ethanol and 30ml then and under refluxing, stirred 5 minutes, then mixture is cooled to 70 ℃ and further stir and begin until gelation.After gelation begins, add the 600ml decyl alcohol and add 400ml water subsequently at once.Reaction mixture is further stirred (crescent agitator) 1h under 600rpms, and similar to Example 3 continue to handle.After dry and classification, obtained the organo-siloxane amine co-condensation polymer that 100.5g is made up of unit of following formula:
Spherical products above 97% has the granularity of 0.2-1.2mm.
Specific surface area: 496m
2/ g
Total specific pore volume is long-pending: 2.2ml
Bulk density: 486g/l
Embodiment 7
Use diisopropyl ether to replace decyl alcohol at the N[(CH that does not have to make under the hot aftertreatment 78.8g (0.125 mole) similar to Example 6ly
2)
3Si (OC
2H
5)
3]
3And the heterogeneous mixture of the following formula of 118.7g (0.25 mole):
(CH
2)
3SiO(OC
2H
5)
3
(CH
2)
3SiO(OC
2H
5)
3
In reactor, react.Obtained the co-condensation polymer that 98.0g is made up of unit of following formula:
N[(CH
2)
3SiO
3/2]
3.2C
5H
4[(CH
2)
3SiO
3/2]
2，
Its 98% granularity with 0.3-1.8mm exists.
Specific surface area: 56m
2/ g
Total specific pore volume is long-pending: 0.5ml/g
Bulk density: 610g/l
Embodiment 8
N[(CH with 1007.6g (2.0 moles)
2)
3Si (OC
2H
5)
3]
3Be dissolved in the 500ml ethanol.With this solution and mixed the being incorporated in stirring 1h down that refluxes of 30ml water.Add 769.2g's (2.0 moles) then
Si (the OC of (528.9g 2.0 moles)
3H
7)
4Also under refluxing, stirred 5 minutes again with 700ml water, then mixture is cooled to 60 ℃ of also further slow stirrings and begins until gelation.After gelation begins, add 2.8 liters of 2-Ethylhexyl Alcohols at once, add 2.5 premium on currency then.After ground similar to Example 3 is further handled, and aging and use NH in HCl
3After the neutralization, obtained the shaped product that 1190g is made up of unit of following formula:
N[(CH
2)
3SiO
3/2]
3·O＝C[NH-(CH
2)
3-SiO
3/2]
2·SiO
2。
95% shaped product exists with the granularity of 0.1-1.2mm.
Specific surface area: 466m
2/ g
Total specific pore volume is long-pending: 1.8ml/g
Bulk density: 490g/l
Embodiment 9
N[(CH with 50.4g (0.1 mole)
2)
3Si (OCH
3)
3]
3And the HN[(CH of 107.6g (0.2 mole)
2)
10Si (OCH
3)
3]
2Mix, and after adding 5ml water, under 60 ℃ and stirring, carried out precondensation 24 hours.Then prepolycondensate and 200ml Virahol and the extra water of 40ml are mixed.Solution further stirs under refluxing and begins until gelation then.After gelation begins, add the 300ml octanol, and behind extra 30 minutes, add 300ml water.Under refluxing, this suspended substance is stirred 3h, from liquid phase, filter out solid then and use the washed with isopropyl alcohol that is total up to 1 liter.At N
2Under the atmosphere 100 ℃ dry 8 hours down, 130 ℃ dry 8 hours and down at 160 ℃ down after dry 16 o'clock, obtained the polymerisate that 106.0g is made up of the polymer unit of following formula:
N[(CH
2)
3SiO
3/2]
3·2HN[(CH
2)
10SiO
3/2]
2。
95% shaped product exists with the granularity of 0.3-2.4mm.
Specific surface area: about 1m
2/ g
Bulk density: 752g/l
Embodiment 10
With 644.1g's (1.0 moles)
(61.3g 0.1 mole)
And the Al (OC of 24.6g (0.1 mole)
4H
9)
3Stir 24h down with the 1n aqueous solution of 2ml HCl and at 80 ℃.Then, add 700ml ethanol and 200ml water and with mixture restir 10min under refluxing.
After using dimethylbenzene (cuts) to replace the method for octanol to carry out, obtained the polymerization polymers that 345g is made up of the polymer unit of following formula similar to Example 3ly:
98% shaped product exists with the granularity of 0.3-2.2mm.
Specific surface area: 398m
2/ g
Total specific pore volume is long-pending: 1.6ml/g
Bulk density: 486g/l
Embodiment 11
Make the N[(CH of 71.4g (0.1 mole) similar to Example 10ly
2)
5-Si (OC
2H
5)
3]
3, 42.9g (0.1 mole) S=C[NH-CH
2-Si (OC
2H
5)
3]
2, 21.2g (0.1 mole) (C
2H
5) Ti (OC
2H
5)
3And the Si (OC of 208.3g (1.0 moles)
2H
5)
4Carry out precondensation, and similar to Example 3 being further processed.Obtained the polymerisate that 125g is made up of unit of following formula:
N[(CH
2)
5SiO
3/2]
3·S＝C[NH-CH
2-SiO
3/2]
2·(C
2H
5)TiO
3/2·10SiO
2，
Its 99% granularity with 0.2-2.4mm exists.
Specific surface area: 296m
2/ g
Embodiment 12
N[(CH with 126.0g (0.2 mole)
2)
3Si (OC
2H
5)
3]
3And the thiocarbamide of the dimethyl aminoethyl of the following formula of 111.2g (0.2 mole) replacement:
Be dissolved in the 250ml ethanol and mix with the 80ml water that desalts.Described clear solution is heated to reflux temperature, and under refluxing, stirred 10 minutes and be cooled to 70 ℃.This solution is begun until gelation further stirring under 300rpms under this temperature.After gelation begins, at first add the 500ml octanol, add 600ml water then.Under reflux temperature mixture was further stirred 2 hours, cooling leaches solid and 500ml 2%NH then
3Aqueous solution, and as embodiment 3 handle, aftertreatment and dry.Obtained the polymerisate that 125.0g is made up of the polymer unit of following formula:
98% shaped product exists with the granularity of 0.3-1.8mm.
Specific surface area: 526m
2/ g
Total specific pore volume is long-pending: 1.86ml/g
Bulk density: 416g/l
Embodiment 13
N[(CH by 126.0g (0.2 mole)
2)
3Si (OC
2H
5)
3]
3And the thiocarbamide of the dimethyl aminoethyl of the following formula of 111.2g (0.2 mole) replacement:
Initial, obtained the polymerisate that 125.3g is made up of the polymer unit of following formula similar to Example 12ly:
97% shaped product exists with the granularity of 0.3-1.8mm.
Specific surface area: 496m
2/ g
Total specific pore volume is long-pending: 1.93ml/g
Bulk density: 401g/l
Embodiment 14
N[(CH by 630.1g (1.0 moles)
2)
3Si (OC
2H
5)
3]
3, 44.3g (1.0 moles) S[(CH
2)
3Si (OC
2H
5)
3]
2And the Zr (OC of 19.2g (0.05 mole)
4H
9)
4Initial, obtained the polymerisate that 320.0g is made up of the polymer unit of following formula similar to Example 10ly:
N[(CH
2)
3SiO
3/2]
3·0.1S[(CH
2)
3SiO
3/2]
2·0.05ZrO
4/2。
95% shaped product exists with the granularity of 0.2-2.4mm.
Specific surface area: 426m
2/ g
Total specific pore volume is long-pending: 1.75ml/g
Bulk density: 452g/l
Embodiment 15
Is that the shaping organopolysiloxane co-condensation polymer of 0.1-0.2mm is suspended in the 100ml water that has wherein dissolved 50mg Cu (I) with 5g according to the granularity of embodiment 1 preparation.Under 90 ℃, this suspended substance is stirred 3h, go out solid from liquid filtration then and also wash once more with 50ml water.The analysis of liquid phase shows that the residual volume of the dissolved Cu of institute (I) is total up to 2mg, and promptly 96% Cu (I) is combined.
Embodiment 16
Is that the co-condensation polymer that contains the sulfane base of 0.3-1.8mm becomes the what slurry with 50ml in water according to the particle diameter of embodiment 3 preparation, is transferred to then in the glass column that internal diameter is 20mm.In 1 hour, make described post load 200ml and wherein dissolved (NO as Hg
3)
2The water of 10mg mercury.After washing once more with 50ml water, the analysis of the liquid that passes through shows that the content of remaining mercury is 5 μ m.
Embodiment 17
Is that the co-condensation polymer of 0.2-0.3mm is suspended in wherein and has dissolved as PdCl with 5g according to the granularity of embodiment 2 preparation
2The water of 3mg palladium in.At room temperature this suspended substance is stirred 3h, filter out solid then and use the 30ml water washing.Analyzing the content that shows remaining palladium is 50 μ m.
Embodiment 18
Similarly 50ml has wherein been dissolved as Na with embodiment 17
2PtCl
4The ethanolic soln of 5mg platinum under reflux temperature, be that the co-condensation polymer of preparation among the embodiment 5 of 0.2-0.3mm was handled 3 hours with the 5g granularity.Analyzing the amount that shows remaining platinum is 0.1mg.
Embodiment 19
Similar to Example 18 and use the polysiloxane of preparation among the 5g embodiment 12 and use rhodium (as RhCl
33H
2O dissolving) replacing the test of platinum to cause the amount of remaining rhodium is 0.1mg.
Embodiment 20
The co-condensation polymer of preparation among the 5g embodiment 1 is placed wash bottle.With this wash bottle constant temperature to 20 ℃ and load the airflow of 100ml/h on dividing plate, it is 90% m-xylene that wherein said airflow contains saturation value.The absorption of m-xylene is by the increase of periodic monitoring polymer weight and monitor.Weight increase under the equilibrium state is determined as 65%.
Embodiment 21
The co-condensation polymer of preparation among the 5g embodiment 3 is placed wash bottle.The airflow that this wash bottle constant temperature to 20 ℃ and loading on dividing plate is contained similar to Example 20ly 90% 1.Weight increase under the equilibrium state is determined as 95%.
Embodiment 22
The polysiloxane of preparation causes weight to increase to 58% with embodiment 20 similar methods among use Virahol and the embodiment 8.
To aforesaid other variations and modify and to be significantly to those skilled in the art and to be included among the appended claims.
This with reference to and merge German priority application P 39 25 359.7.
Claims (25)
1. big ball particle that includes the organic siloxane co-condensation polymer, wherein said organo-siloxane co-condensation polymer consist of unit of following formula:
And unit of following formula:
Wherein, R
1-R
5Identical or different and represent the group of following formula:
Wherein, R
6Be directly connected in the X group that nitrogen-atoms or two key connect, and representative has the linearity of 1-10 carbon atom or the alkylidene group of branching, the cycloalkylidene with 5-8 carbon atom or the following unit of general formula:
Wherein, n is the numerical value of 1-6 and the methylene radix that expression is connected in nitrogen, and m is the numerical value of 0-6,
Wherein, be connected in Siliciumatom Sauerstoffatom free valency through type (III) other groups Siliciumatom as silicon dioxide skeleton and/or via one or more crosslinked bridging types the atoms metal in crosslinked and saturated:
M is Siliciumatom, titanium atom or zirconium atom and R ' for having linearity or the branched-alkyl or the phenyl of 1-5 carbon atom, and the Siliciumatom of the middle group of formula (III) and the ratio of the atoms metal in the bridging type crosslinked (IV) are 1: 0-1: 20, and
Wherein, R " equal H or for having linearity or the branched-alkyl or the group (CH of 1-5 carbon atom
2)
n-NR
2' ", wherein n represents the numerical value of 1-6, and R ' " have and R " identical meaning, described particulate diameter is 0.01-3.0mm, specific surface area is 1000m at the most
2/ g, specific pore volume is long-pending for 6.0ml/g and bulk density are 50-1000g/l at the most.
2. according to the organo-siloxane co-condensation polymer of claim 1, it is characterized in that formula (I) unit and the unitary ratio of formula (III) are 0.03: 99.97-99.99: 0.01.
3. according to the organo-siloxane co-condensation polymer of claim 1, it is characterized in that they are random co-condensation polymer, block copolycondensation thing or mix co-condensation polymer.
4. according to the organo-siloxane co-condensation polymer of claim 1, it is characterized in that R
1-R
5Represent the group of following formula:
5. according to the organo-siloxane co-condensation polymer of claim 1, wherein said particle have 0.05-2.0mm diameter, be at most 700m
2The ratio hole value of/g and the bulk density of 100-800g/l.
6. according to the organo-siloxane co-condensation polymer of claim 2, wherein said ratio is 5: 95-95: 5.
7. method for preparing the big spheroidal particle of random organo-siloxane amine co-condensation polymer, wherein said method are included in the solvent dissolving corresponding to uncle's amino-organosilanes of the following formula of the required stoichiometric composition of the co-condensation polymer that will prepare:
Silane with organic functional:
Wherein, R
7-R
11Identical or different and represent the group of following formula:
R
6-Si(OR
12)
3 (VII)
R
6Have identical meaning in the formula (III) with claim 1,
R
12Representative has the linearity or the branched-alkyl of 1-5 carbon atom, and
X has identical meaning in the formula (II) with claim 1,
The optional linking agent that can add one or more following formulas:
M (OR)
2-4R '
0-2Or Al (OR)
2-3R '
0-1(VIII)
Wherein, M is Siliciumatom, titanium atom, zirconium atom,
R ' for have the linearity of 1-5 carbon atom or a branched-alkyl or phenyl, and
The alkyl that the R representative has the linearity or the branching of 1-5 carbon atom, the ratio of the atoms metal in Siliciumatom in the group of general formula (VII) and the linking agent (VIII) is 1: 0-1: 20,
Described solvent can with water base miscible, but can dissolve the silane of organic functional of the amino-organosilanes of formula V and formula (VI) and the linking agent of formula (VIII),
Under agitation the water yield that adds in gained solution is enough to make silane complete hydrolysis and condensation to form reaction mixture at least, make reaction mixture further stir and the certain temperature of room temperature to 200 ℃ under gelation, make reaction mixture when gelation begins or at the most after one hour with the solvent of 10-2000 weight %, described solvent and water base unmixing, but can dissolve the reaction mixture of gelation or beginning gelation, the described gel of homogenizing, and choose wantonly under the elevated temperature of the temperature that is higher than initial setting, in formed thickness homogenizing thing, add in time of 3 hours with respect to amino-organosilanes (V) at once or being at most, the total amount of silane of organic functional (VI) and optional linking agent (VIII) is the water of 10-200 weight %;
The formed organic phase that contains siloxanes is scattered in the formed two-phase liquid system; and under room temperature to 200 ℃, be enough to form after reaction times of spherical solid itself and liquid phase separation; then; choose wantonly solid product is extracted; in room temperature to 250 ℃ down and choose wantonly and carry out drying at shielding gas or under vacuum, and under 150-300 ℃ temperature tempering 1-100 hour and/or classify according to size.
8. according to the method for claim 7, the amount that wherein is used for the solvent of gelation is 50-500%, and the water yield is 50-500%.
9. according to the method for claim 7, wherein with methyl alcohol, ethanol, n-propyl alcohol and Virahol, propyl carbinol and isopropylcarbinol or Pentyl alcohol separately or with the form of mixture as the solvent in the hydrolysis.
10. according to the method for claim 7, wherein said hydrolysis uses excessive water to carry out.
11., wherein in the reaction mixture of gelation or beginning gelation, add linearity with 4-12 carbon atom or branching alcohol, toluene or o-Xylol, m-xylene, p-Xylol separately or with the form of mixture according to the method for claim 7.
12. according to the method for claim 7, wherein when gelation begins or afterwards, except that solvent for use, also add whole amounts at hydrolysis stage with water base immiscible solvent.
13. according to the method for claim 7, wherein gelation and be formed in normal pressure or under superpressure, carry out, wherein said superpressure is corresponding to each component of reaction mixture dividing potential drop sum under used actual temp.
14. method according to claim 7, the amino-organosilanes of wherein said formula V carries out gelation separately respectively or carries out gelation with linking agent (VIII) and/or organic functional degree silane (VI), and and carry out homogeneous phaseization with water base immiscible solvent.
15. method according to claim 7, random co-condensation polymer wherein in order to obtain to be shaped, with the amino-organosilanes of formula V, the organic functional degree silane of formula VI and the linking agent of formula (VIII), optional with the solvent that is dissolved with monomer component, be not enough in existence under the water yield of complete hydrolysis and under room temperature to 200 ℃, carried out precondensation 5 minutes to 48 hours.
16. according to the method for claim 15, wherein said solvent is the alcohol that corresponding alkoxyl group has 1-5 carbon atom.
17. according to the method for claim 15, the wherein said water yield is the 1-100 mole % of hydrolysis aequum.
18., it is characterized in that precondensation carries out in the presence of acid, alkaline or metallic condensation catalyst according to the method for claim 15.
19. method for preparing the shaping block copolycondensation thing of claim 7, wherein at first be not enough under the water yield of complete hydrolysis and under room temperature to 200 ℃ in existence, make the uncle's amino-organosilanes of formula V and the organic functional degree silane of formula (VI) and the linking agent of one or more formulas (VIII) of choosing wantonly carry out precondensation independently of one another 5 minutes to 48 hours, the optional solvent that uses, merge then and add more water and optional more solvent, make the water that has the required stoichiometry of complete hydrolysis and polycondensation at least.
20. according to the method for claim 19, wherein said precondensation carries out in the presence of acid, alkaline or metallic condensation catalyst.
21. method for preparing the shaping mixing co-condensation polymer of claim 7, wherein be not enough under the water yield of complete hydrolysis and under room temperature to 200 ℃ in existence, make formula V, (VI) and at least a monomer component (VIII) carry out precondensation independently of one another 5 minutes to 48 hours, the optional solvent that uses, then with the not monomer merging of precondensation, add more water and optional more solvent, complete hydrolysis and polycondensation afterwards.
22. wherein there is component in the method for the organosilane co-condensation polymer that an aftertreatment obtains according to claim 7 under water at least in liquid phase, under 50-300 ℃ and optional superpressure, undried spherical solid is carried out Temperature Treatment 1 hour to 1 week.
23. according to the method for claim 22, wherein said aftertreatment is carried out in the presence of acid, alkaline or metallic catalyzer.
24. the method for the metal of separate dissolved from the aqueous solution or organic solution, it comprises that the organic siloxane amine co-condensation polymer of using according to claim 1 that is formed with handles described solution:
25. the method for adsorptive gaseous organic compound and/or water vapor, it comprise selection according to claim 1 be formed with organic siloxane amine co-condensation polymer, and it is contacted with described gaseous organic compound and/or water vapor.
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