CN101522821B - Surface-modified particles and production method - Google Patents
Surface-modified particles and production method Download PDFInfo
- Publication number
- CN101522821B CN101522821B CN200780037490.0A CN200780037490A CN101522821B CN 101522821 B CN101522821 B CN 101522821B CN 200780037490 A CN200780037490 A CN 200780037490A CN 101522821 B CN101522821 B CN 101522821B
- Authority
- CN
- China
- Prior art keywords
- group
- particle
- surface modification
- inorganic type
- type particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to surface-modified particles, more particularly inorganic-based particles having reactive surfaces, more particularly surfaces containing silane-reactive and/or siloxane-reactive groups, preferably hydroxyl-containing surfaces and/or particles comprising or consisting of metal and/or semi-metal oxides and/or hydroxides, preferably nanoparticles, which on their surface have apolysiloxane-based modifier, having more particularly been reacted on their surface with a polysiloxane-based modifier, preferably with the formation of chemical bonds, more particularly covalent bon ds, and also to a method of producing these surface-modified particles. The particles surface-modified in this way are suitable more particularly for use as fillers and/or for use in any of a very wide variety of systems, more particularly in dispersion systems, such as coating materials, for instance paints, inks and the like, and in dispersions of all kinds, in plastics, in foams, in cosmetics, such as in nail varnishes, for example, in adhesives, in sealants, etc.
Description
The present invention relates to have reactive surfaces, especially silane reaction or siloxane reactions surface, especially the surface modified granules on the surface of hydroxyl, especially inorganic type particle, and/or relate to the particle of forming or comprise metal or half-metal oxide and/or oxyhydroxide by metal or half-metal oxide and/or oxyhydroxide, preferred nano particle, these particles have polysiloxane group properties-correcting agent on their surface, especially on their surface, react with polysiloxane group properties-correcting agent, be preferably formed chemical bond, especially covalent linkage, and relate to the correlation method of producing these surface modified granules.
The present invention relates to the purposes of these surface modified granules in addition, especially be used in coating and coating system, especially in lacquer, tinting material and the analogue, be used in the dispersion of all types, be used in the plastics, be used in the foams, be used in the makeup (especially nail varnish), be used in the tackiness agent, be used in the sealing agent, etc. purposes.In addition, the present invention relates to these surface modified granules as the purposes of filler, especially in above-mentioned system.
The present invention similarly relates to the system that contains these surface modified granules in addition, especially coating and coating system (especially lacquer, tinting material and analogue), plastics, foams and makeup, especially nail varnish.At last, theme of the present invention also has novel dispersion, and it contains these surface modified granules in carrier or dispersion medium.
Particle, especially nano particle, using priciple in coating and dispersion system is the known to the skilled of prior art field: therefore, nano particle then provides an advantage as the use of the filler of coating system, be the performance (for example anti-zoned property of Zeng Daing) that coating obtains expection, but need not to consider simultaneously disadvantageous side effect (for example poor transparency).
Well-known is that the introducing of nano particle in coating system for example can cause the improvement on the mechanical property of coating system (for example in the coating system of UV-curable).
Therefore, for example, be described among EP 1 236 765 A1 with the method for alkoxysilane-modified nano-scale silica granule, this particle is provided at the improvement on the mechanical property after in being incorporated into the coating system of corresponding UV-curable.In other senior cross-linking system, for example in Resins, epoxy, also have been found that positive effect.But the improvement on the mechanical property basically attribution be that nano particle utilizes chemical bond in conjunction with on matrix on every side.Owing to the chemical bonding of particle and organic substrate is observed the fragility of increase, this depends on the compactedness of the coating that contains this nano particle, and depends on Application Areas and harmful to coating.As long as known silica-based nano-grade size filler is not incorporated into organic substrate, then the expection improvement effect on mechanical property UV-curable or the epoxide based coating systems is very different.
Except the silica nano particle, the nano particle of other type also can be incorporated in the coating, in order to optimize their mechanical property.For example, by in the coating system of UV-curable, adding nano-grade size aluminum oxide (for example the BYK-Chemie GmbH of German Wesel be purchased product NANOBYK-3600 and NANOBYK-3601), realize the obvious improvement of wear resistance, but do not influenced the flexibility of this system.This aluminum oxide debond is in the organic substrate of coating system in this case.The stabilization of nano particle is to carry out with the wetting and dispersing additive that is purchased in lacquer matrix.
Do not belong to UV-curable or with the epoxide system be the based coating system can be similarly interpolation by nano particle be optimized at anti-zoned property.
Therefore describe a kind of method in US 6 593 417A, wherein silica granule combines for bicomponent polyurethane paint with polysiloxane.This polysiloxane has reaction active groups, and the latter can be combined with lacquer matrix by the covalency group.The keyed jointing of polysiloxane and nano particle is only undertaken by the interaction of coordination.The particular combination of nano particle and polysiloxane causes nano particle to coating/air interface orientation and causes mechanical enhancement there, and this can show by the anti-zoned property that increases.Nano particle is disadvantageous to the orientation of coating/air interface because the stress by on coating, by weathering and effect of attrition, the superiors at first be removed and therefore effect descend in time.
US 5 853 809 A instruction, the improvement on the anti-zoned property of the coating system that for example is used for automotive paints can realize by introducing modified nanoparticles.The modification of this nano particle is carried out so that polymkeric substance and this nano grain surface form the mode of covalent linkage for example by functionalized urethane.In addition, the polymer shell of the nano particle of modification in this way can participate in and the binder system of coating between the covalency keyed jointing.But the fragility for the lacquer system especially under high nano-particle content, does not describe.
Though improved the anti-zoned property of the lacquer that uses this nano particle by the known modified nanoparticles of prior art; But especially for non-radiative curing, the crosslinked system of UV especially, the way that nano particle utilizes modification to be bonded on the lacquer matrix is on the pan especially: be bonded on the lacquer matrix by nano particle, the network density of cured paint film increases, and this causes the increase fragility of this paint film.
The nano-sized filler particle that is dispersed in the polymeric matrix can be known from DE195 40 623 A1.Silane, particularly the organic radical organoalkoxysilane is described as surface-modifying agent.Surface-modifying agent is that molecular weight is not more than 500 daltonian low-molecular weight compounds.The surface group of nano-scale particle and the interaction between desirable and the matrix are depended in the functional group that this compounds must carry.Therefore modified particles demonstrates the affinity to this matrix.
Therefore the present invention based on target provide surface modified granules, especially nano-scale surface modified granules, these particles especially are suitable in the above-mentioned system and avoid at least basically or alleviate the shortcoming relevant with conventional particles at least, and the corresponding production method that this type of particle is provided.
Another object of the present invention is to be provided at new, the effective surface modification of the particle (especially nano particle) of that type of mentioning at the beginning.
In addition, the present invention based on target provide particle (especially nano particle) as the stabilising dispersions form in suitable dispersion agent or mounting medium (solvent for example, water, etc.), the form when for example in paint vehicle industry, using.The dispersion that these are new even under high granule content situation, should have high package stability.These particle dispersions, nanoparticle dispersion especially, the trend that sedimentation or gel formation take place should advantageously be excluded.In addition, this dispersion when especially if they are used for the preparation of coating, should advantageously also cause the raising of the anti-zoned property of solidified coating especially.New surface modified granules, nano particle especially, for the system of using them, especially any reactivity for the binder component in the used lacquer system should minimize as far as possible, preferably avoids the trend of cured paint film embrittlement.Especially, this surface modification is for the system of the particle that uses surface modification, for example for paint matrix, be as far as possible inertia or low reactivity as far as possible.
At last, another object of the present invention provides new surface modified granules, the preparation method of nano particle especially, this method can be carried out and can wide region changes with plain mode, especially for the new surface modified granules of custom-made is provided at the different application purpose by this way, the dispersion of especially nano particle, and these particles.
The applicant now finds amazedly, if have reaction active groups (preferred silane or siloxane reactions active group on the surface of particle, hydroxyl particularly) particle (especially inorganic type particle), and/or by metal and/or half-metal oxide, that oxyhydroxide and/or oxide hydroxide constitute or comprise these metals and/or half-metal oxide, the particle of oxyhydroxide and/or oxide hydroxide (preferred nano particle), react with polysiloxane group properties-correcting agent, be preferably formed chemical bond (especially covalent linkage), this properties-correcting agent has higher molecular weight, preferred structurally is linear, not with substrate reaction on every side with have modification with group (especially polar group), then above-mentioned target can realize with efficient manner.In this way, the dispersiveness of particle is improved in surprising mode, be improved with known system is mutually surface improved, and polarity is controlled better.
In order to address the above problem, the present invention has advised the surface modified granules according to claim 1.Other favourable performance is the theme of relevant dependent claims 2-11.
Other themes of the present invention are the preparation methods according to the surface modified granules of the present invention of claim 13.Other favourable character is the theme of subordinate claim to a method.
Again, another theme of the present invention is according to the surface modified granules of the present invention of claim 18 purposes as filler.
Another theme of the present invention is at coating and coating system (lacquer especially according to the surface modified granules of the present invention of claim 19, tinting material and analogue) in, in all types of dispersions, in plastics, in foam materials, in makeup (especially nail varnish), the purposes in tackiness agent and in sealing agent.
In addition, theme of the present invention is the dispersion according to claim 20 equally, and it contains the surface modified granules of the present invention in carrier or dispersion medium.
At last, another theme of the present invention is the coating that contains surface modified granules of the present invention and the coating system according to claim 21, especially lacquer, tinting material and analogue, plastics, foam materials, makeup (especially nail varnish), tackiness agent and sealing agent.
According to surface modified granules of the present invention, especially nano particle describes the present invention below.Therefore those embodiments for this purpose are applicable to other side of the present invention and theme-preparation method of the present invention, purposes of the present invention, dispersion of the present invention, etc.-in order to avoid also unnecessary mentioning repeatedly for other side of the present invention and theme.
Theme of the present invention-be to have reaction active groups (preferred silane reactive behavior or siloxane reactions active group at particle surface according to a first aspect of the invention-therefore, hydroxyl particularly) surface modified granules, especially inorganic type particle, and/or by metal and/or half-metal oxide, that oxyhydroxide and/or oxide hydroxide are formed or comprise metal and/or half-metal oxide, the particle of oxyhydroxide and/or oxide hydroxide, preferred nano particle, wherein this particle has polysiloxane group properties-correcting agent on their surface, especially on their surface, react with polysiloxane group properties-correcting agent, be preferably formed chemical bond, especially covalent linkage, wherein said surface modified granules is characterised in that this properties-correcting agent is the polysiloxane with following general formula
(R
1 xR
2 3-xSiR
3)
yR
4
Wherein in general formula:
X=0-2 (comprising end value), especially x=0;
Y=1-10 (comprising end value), especially y=2-5;
R
1=any monovalent organic radical group preferably has 1-18 carbon atom, especially 1-10 carbon atom, especially 1-3 carbon atom;
R
2=OH group or comprise following group or the hydrolysable group of being formed by following group:
-have a 1-6 carbon atom, the alkoxyl group of especially linearity of 1-2 carbon atom or branching or ring-type,
-halogen atom, especially the chlorine atom or
-have 1-4 carbon atom, especially a hydroxy-acid group of 2 carbon atoms;
R
3=oxygen or the divalent organic group at least that comprises following group or formed by following group:
-linearity or branching, preferred linear alkylidene group has 1-8 carbon atom especially,
-alkylene ether,
-alkylidene group thioether,
-alkylidene group polyethers, preferably with oxyethane, propylene oxide, butylene oxide ring or Styrene oxide 98min. or these hopcalites are the basis, or based on statistics or block polyether,
-arylidene polyethers,
-alkylidene group polyester or
-organic aliphatic series or aromatics or araliphatic group, especially wherein this group also contains urea alkane and/or urea groups except containing ester and/or ether group;
R
4=comprise having 4-200 Si unit and have C at Siliciumatom
1-C
18The polydialkysiloxane of alkyl or one or the multivalence group formed by this polydialkysiloxane, wherein this C
1-C
18Moieties ground and under each situation independently of one another selected leisure (i) listed following modification in (iv) substitute with group (G) with one or more the following modifications in the group (G1) to (G4) or replace, be preferably the modification of polarity with group (G) (namely, in other words exchanged by these groups, especially by grafting):
(i) group (G1) that contains (gathering) ether group, especially based at least a alkylene oxide,
The group (G2) that (ii) contains the polyester group,
The group (G3) that (iii) contains aromatic yl alkyl group,
The group (G4) that (iv) contains perfluorinated alkyl.
Favourable embodiment of the present invention is to list in the dependent claims.
Conclusive feature of the present invention must be radicals R
4Preferably polar-modified: as previously described, the alkyl of polydialkysiloxane group (i.e. C on Siliciumatom
1-C
18Alkyl) partly and independently of one another be modified group (G) exchange usefulness, preferred polarity or substitute (for example by grafting).Surprisingly, in this way, improved the dispersiveness of particle of the present invention on the one hand.On the other hand, this polarity can on purpose be controlled by this way, thereby makes that in this way those application performances also can custom-made.At last, make surface modification significantly to improve by this way, especially for required application performance (for example Qi anti-zoned property, etc.).Radicals R
4Modification therefore select in the following manner with group (G), namely at application system or application matrix and their inclusion (for example paint matrix), require them advantageously compatible, especially inertia or be weak reactive behavior in all cases as far as possible.The modification of preferred polarity group (G), for example, the starting raw material by from being purchased is grafted to radicals R
4Going up (for example by hydrosilylation or addition reaction or by condensation reaction) is introduced; This is that those skilled in the art know and also describes in more detail hereinafter.
Especially, be the theme of claim 2-5 with regard to the preferred embodiment of modification with regard to the selection of group (G).
The particular embodiments of surface modified granules of the present invention is the theme of claim 6.
Improve in the property of particle of the present invention that the additional surface modification of implementing with silane that is according to the theme of claim 11 and/or 12 realizes.
Particle of the present invention, nano particle especially, granularity be in the 0.1-1000nm scope, especially in the 0.5-500nm scope, in the preferred 1-350nm scope, more preferably in the 2-200nm scope, especially preferably be lower than 100nm, most preferably be lower than 50nm.This granularity can be measured by the transmission electron microscope art according to the present invention.
According to the present invention, have in above-mentioned size range (namely in the 0.1-1000nm scope, especially in the 0.5-500nm scope, in the preferred 1-350nm scope, more preferably in the 2-200nm scope, especially preferably be lower than 100nm, most preferably be lower than 50nm) the subdivided solids of granularity be called as nano particle.As mentioned before, the mensuration of granularity can especially be undertaken by transmission electron microscope art (TEM) in the context of the present invention.Can carry out the granularity that TEM studies to measure particle of the present invention or nano particle: corresponding nanoparticle dispersion is diluted usually for this purpose, transfers to carbon sieve (especially 600 sieve mesh carbon films) and goes up also dry; Under each situation, analyze with for example LEO 912 transmission electron microscopes then.The evaluation Example of TEM image is carried out with digital form as the software with analySISSoft Imaging System GmbH company.Particle diameter generally calculates at least 1000 particles under each situation, and wherein the measured area of particle or nano particle is related with circle of the same area.Obtain mean value from measured result subsequently.
Particle required for protection, especially nano particle, it generally is inorganic particle, the group of reactive behavior, the group preferred silane reactive behavior or the siloxane reactions activity, especially hydroxyl is positioned at or is arranged on the surface of this particle, and these groups are that chemical bond (preferably covalently key) keyed jointing of properties-correcting agent is needed; That is, the lip-deep reaction active groups that is positioned at the particle of the modification of wanting must react with properties-correcting agent.Except being the preferred hydroxyl according to the present invention, also can consider the group with other silane and/or siloxane reactions activity, halogen (for example fluorine or chlorine) or contain the group of halogen atom for example, etc.
Especially, can consider by at least a metal and/or half-metal oxide, oxide hydroxide and/or oxyhydroxide; The mixture of different metals and/or half-metal oxide, oxide hydroxide and/or oxyhydroxide or binding substances those particles that form or that comprise these components (for example being formed the particle that oxide hydroxide or oxyhydroxide are formed by hybrid metal and/or half-metal oxide).For example, the oxide compound of aluminium, silicon, zinc and/or titanium etc., oxyhydroxide and/or oxide hydroxide can be used for preparing modified particles or nano particle.In addition, oxide hydroxide, for example aluminum oxide oxyhydroxide also can come modification according to described method.Same suitable be optional and above-mentioned metal and/or half-metal oxide, other inorganic materials of oxide hydroxide and/or oxyhydroxide blending, especially inorganic salt such as phosphoric acid salt, vitriol, halogenide, carbonate, etc.Yet, according to the present invention, the metal of the above-mentioned type and/or half-metal oxide, oxide hydroxide and/or oxyhydroxide are preferred.
Particle used according to the invention, especially oxide compound, oxyhydroxide or oxide hydroxide particle, especially nano particle, the preparation method can carry out ion-exchange techniques for example, plasma method by various methods, the sol/gel method, the precipitator method, crush method (for example by levigate) or flame hydrolysis, etc.; According to the present invention, production method and the present invention of oxide compound or hydroxide particles are uncorrelated, and namely according to the present invention, the particle of the above-mentioned type of producing can be carried out surface modification arbitrarily.
In the context of the present invention, surface modified granules that find, innovation, especially nano particle also is called particle of the present invention or nano particle of the present invention respectively.In the context of the present invention, the new dispersion of particle of the present invention or nano particle also is known as dispersion of the present invention.
In view of prior art, fully surprising and unpredictalbely be for those skilled in the art, the above-mentioned purpose that constitutes basis of the present invention can be passed through particle of the present invention, by preparation method of the present invention, realizes by dispersion of the present invention and aforesaid all the other themes of the present invention.
The preparation of particle of the present invention and dispersion of the present invention can be carried out according to plain mode, need not complicated method or process.
Nano particle of the present invention for example is applicable to preparation example such as heat-setting, coating system radiation curing or two-pack, and thermoplastics, foams, etc.
By dispersion of the present invention is provided, the particle enriched material (especially nano particle enriched material) of easy disposal successfully is provided, it for example can be metered in the various coating systems simply in order to realize required effect, for example improved mechanical stability, for example anti-zoned property.
In addition, except simply being metered into of dispersion of the present invention, also find the good stability of dispersion for sedimentation and gel formation, even especially under high solid content situation.
Particle of the present invention, especially nano particle, advantageously being modified in the following manner covers with group, that is, the functionalization active group crested that may be still exists at particle surface is to because sterically hindered former thereby degree that no longer react with other functional group.
Particle of the present invention, nano particle especially, the surface covered with group by the modification of at least a type.Modification illustrates below with the structure of group:
Modification, preferably in covalent linkage keyed jointing mode, is incorporated on the particle surface with chemical bonding with group.Modification has different structural units with group, they can and particle surface between form chemical bond at least respectively, covalent linkage especially.In addition, this modification is made up of part at interval with group, and the latter can not any reaction be taken place and similarly show inertia basically for matrix (for example other coating composition, plastic components etc.) with particle surface.Modification with group compartment can for example the polymkeric substance of the number-average molecular weight in 300-5000 dalton scope constitutes by for example having.The structure optimization of spacer groups is linear.
This means that properties-correcting agent is by at least a or multiple anchoring group that particle surface is shown reactive behavior and polydialkysiloxane (radicals R that=front defines
4Component) constitute.Anchoring group with syndeton can either be connected in the end of polydialkysiloxane, and the side group that also can be used as on polydialkysiloxane exists.
The structure of properties-correcting agent used according to the invention can illustrate with illustration by following example, wherein in the example of giving an example for the diagram in radicals R
4(=polydialkysiloxane) selects three kinds of dissimilar polarity substituting groups or modification with group (G) (can be referring to above explanation with referring to Patent right requirement for substituent meaning):
Index a describes the quantity of anchoring group, index b, and c, d... are described in polydialkysiloxane (R
4) side group on preferred polar substituent or modification with the quantity of group (G), wherein:
a≥1
b+c+d+...≥1。
In addition, as previously described, the surface modification of particle can be carried out with silane according to claim 11 and/or 12, and described silane generally similarly is bonded on the particle surface by at least one chemical bond (especially covalent linkage) and advantageously has one or more compartments.Relevant details can be referring to claim.
The preparation of nano particle of the present invention can be by simply mixing properties-correcting agent to carry out with particulate state (especially Nanoparticulate) powder.Must guarantee preferably to take place chemical bond (especially covalent linkage) keyed jointing between properties-correcting agent and the nano grain surface.Its condition depends on the reactivity of the functional group of reacting each other and can easily be determined by those of skill in the art.If at room temperature namely do not react, then the chemical bond of properties-correcting agent (especially covalent linkage) keyed jointing for example can heat about 1 hour time and realizes under about 80 ℃ temperature by the mixture with nano particle sprills and properties-correcting agent.
The preparation of properties-correcting agent used according to the invention is that those skilled in the art are known and can for example realize in the following manner:
From the open chain that is purchased and polydimethylsiloxane and the functionalized polydimethylsiloxane of Si-H of ring-type, the functionalized polydimethylsiloxane of Si-H can be in balanced reaction (for example according at Noll, " Chemie und Technologie der Silicone ", described in the Wiley/VCHWeinheim 1984) middle preparation, it can be converted to according to properties-correcting agent reagent used in the present invention in additional step.Within the scope of the invention, the quantity of Si-H group must be at least two and (needs at least one to be used for anchoring group (R in the functionalized polydimethylsiloxane of Si-H
1 xR
2 3-xSiR
3)
yThe Si-H group of connection be used for the polar-modified Si-H group that is connected with at least one).
Unsaturated compound, 1-octene for example, 1-decene, 1-dodecylene, cetene and 1-vaccenic acid, can pass through currently known methods, use appropriate catalyst, chloroplatinic acid for example, Si Paier (Speyers) catalyzer, platinum divinyl tetramethyl disiloxane title complex or be attached to platinic compound on the solid support material in the presence of, added on the polysiloxane with Si-H group; The hydrosilylation condition generally is known, and this hydrosilylation temperature preferably between room temperature and 200 ℃, preferably between 50 ℃ and 150 ℃, depends on employed catalyzer.
Similar with the addition of alkene, other compound with unsaturated group also can be in addition added on the Si-H group at the category of hydrosilylation.For example, polyalkylene glycol allyl group alkyl oxide (for example polyglycol AM type, Clariant GmbH) or tri-alkoxy vinyl silanes (for example Dynasylan VTMO or Dynasylan VTEO, Degussa AG) can be added on the Si-H group.
In addition, lactone, for example 6-caprolactone and/or δ-Wu Neizhi, at the unsaturated alcohols of olefinic, vinyl carbinol for example, hexenol, allyl group glycol or vinyl hydroxyl butyl ether, on addition compound can be added on the Si-H group.For example, these compounds can be by alkylation or acidylate.
Except alefinically unsaturated compounds the possibility of addition on the Si-H group, also having possibility is to allow the compound of hydroxy-functional be coupled on the functionalized polydimethylsiloxane of Si-H through condensation reaction.For example, pol yalkylene glycol monoalkyl ether (for example butyl polyoxyethylene glycol) can pass through this known procedures and the condensation of Si-H group, divides releasing hydrogen gas simultaneously.For example, acetopyruvic acid zinc can be as the catalyzer in this reaction.By similar mode, other substituting group, the group that for example has ester group also can be inserted in the polydimethylsiloxane.
Also can carry out hydrosilylation and condensation reaction with modification Si-H functionalized poly dimethyl siloxane.Can use the method for combination to prepare properties-correcting agent equally.
Opposite with hydrosilylation (formation of Si-C key), in condensation reaction, form the Si-O key.
In this way, radicals R
4Can be by for example coming modification at (i) of claim 1 listed polar group (G) in (iv).
Particle of the present invention, especially nano particle can for example be directly used in coating and plastics.Particle of the present invention, nano particle especially, however for example be particularly suitable at water solvent, softening agent, wax, mineral oil and reactive diluent and in being generally used for other mounting medium of coating and plastics industry, prepare dispersion.
The preparation of dispersion of the present invention is to be undertaken by using conventional dispersing apparatus as tooth-like colloidal mill, dissolver, ultrasonic disperser etc. corresponding modified particles to be incorporated in required dispersion medium or mounting medium or the dispersion agent.
By properties-correcting agent being added in the particle dispersion (especially nanoparticle dispersion), obtain dispersion of the present invention.In this method, must guarantee to take place chemical mode (especially covalent linkage) coupling between properties-correcting agent and the particle surface (especially nano grain surface) equally.Dispersion of the present invention is for example transferred to the another kind of dispersion medium by distilling from a kind of dispersion medium and is realized.These methods are optimized easily by using suitable entrainment agent, and this entrainment agent forms lower boiling azeotrope with the dispersant media that will remove.
The granule content of dispersion of the present invention (measuring as ignited residue) can in this way be increased to and be higher than 40% and do not have gel formation or a significant sedimentation.
Dispersion of the present invention can comprise at least a additional substances that comes from typical paint additive, binding agent or the linking agent scope.What for example can mention here is wetting with dispersing additive with for the additive of controlling rheological property, also has defoamer, photostabilizer and catalyzer.
Particle of the present invention, especially nano particle and dispersion of the present invention can obtain utilizing extremely widely.The double especially good activity of the wide suitability of particle of the present invention (especially nano particle) and dispersion of the present invention has surmounted particle (especially nano particle) and the dispersion of prior art far away.
Particle of the present invention (especially nano particle) and dispersion are used the latter for example to be further processed to be coating, tackiness agent, plastics etc. by adding in the existing system.Even the interpolation of a spot of particle of the present invention (especially nano particle) and dispersion of the present invention namely produced the mechanical stability that especially improves, also has the resistivity to the raising of the chemical affect effect of the coating of final acquisition and moulded work simultaneously.
It is shocking that coating and processing of plastic performance are subjected to inappreciable influence, therefore for these are used, needn't carry out the optimization again of external parameter.
Particle of the present invention (especially nano particle) and their dispersion are particularly suitable for coating, plastics, and tackiness agent, sealing agent, etc.
Other embodiment of the present invention, modification and variation are that the narration of those skilled in the art on read recognized afterwards easily and are attainable, need not it and depart from the scope of the present invention.
The present invention illustrates by following embodiment, but these embodiment in no case limit the present invention.
Embodiment
1. the preparation of properties-correcting agent (" properties-correcting agent 1-11 ")
| 1 | 2 | 3 | 4 | 5 | 6 | |||
| Raw material | Manufacturers | |||||||
| A | Baysilone-Oel MH 15 | GEBayer | 24.71 | 24.71 | 24.71 | 25.50 | 26.93 | 22.82 |
| B | Dynasylan VTMO | Degussa | 16.73 | 16.73 | 16.73 | 17.26 | 18.23 | 15.45 |
| C | Uniox MUS 15 | NOF Europe | 24.71 | 22.32 | ||||
| C | Unilube MB 40 S | NOF Europe | 24.71 | 17.97 | ||||
| C | Unilube MA 170T | NOF Europe | 24.71 | 30.46 | ||||
| D | The 1-octene | 33.76 | 33.76 | 33.76 | 34.84 | 36.79 | 31.18 | |
| E | Karstedt-Kat 0.2％ | W.C.Heraeus | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| 7 | 8 | 9 | 10 | 11 | |||
| Raw material | Manufacturers | ||||||
| A | MDH29D86M | See note | 40.21 | 40.21 | 40.20 | 44.52 | 33.26 |
| B | Dynasylan VTMO | Degussa | 6.46 | 6.46 | 6.46 | 7.15 | 5.34 |
| C | Uniox MUS 15 | NOF Europe | 40.21 | ||||
| C | Unilube MB 40S | NOF Europe | 40.21 | 33.82 | |||
| C | Unilube MA 170T | NOF Europe | 40.24 | 50.54 | |||
| D | The 1-octene | 13.03 | 13.03 | 13.03 | 14.43 | 10.78 | |
| E | Karstedt-Kat 0.2％ | W.C.Heraeus | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
General preparation procedure:
(A) joined in the 250ml four neck flasks that agitator, thermometer, reflux exchanger and protection gas pipe connecting are housed, under nitrogen, be heated to 80 ℃, add then (E).Then (B) dripped in 40 minutes.Reaction mixture stirred 30 minutes down at 120 ℃ subsequently, (C) was dripped into through time of 20 minutes then.Reaction mixture stirred other 30 minutes down at 120 ℃ after adding end.(D) dripped into through time of 150 minutes subsequently, stirred subsequently 60 minutes.
Note:
Polysiloxane MDH29D86M (referring to diagram) passes through Noll simply, and " Chemie undTechnologie der Silicone ", Wiley/VCH Weinheim prepares in the balanced reaction described in 1984.
2.
The preparation of nano particle enriched material (" nano particle enriched material 1-11 ")
General preparation procedure
In the 250ml four neck flasks that agitator, thermometer and reflux exchanger are housed, drop into (A) and sneak into (B).Be heated to 70 ℃ and interpolation (C) then.After 90 minutes reaction times, add (D).After applying vacuum, under 70 ℃ temperature, remove the solvent mixture of 100g.(E) and (F) successively add now, stirred 120 minutes down at 70 ℃.Add subsequently (G).By under vacuum, isolating the 60g solvent mixture, reach 21.7% nano-particle content.
3.
Application Example (" Application Example 1-11 ")
Bicomponent automobile is repaired system
| Component 1 | Comparative sample | Application Example 1-11 |
| Macrynal SM515/70BAC | 46.7 | 46.7 |
| Acetic acid methoxyl group propyl ester | 8.3 | 8.3 |
| The acetic acid butanediol ester | 1.3 | 1.3 |
| TinStab BL277 (1% solution in butylacetate) | 0.2 | 0.2 |
| Butylacetate | 10.1 | 10.1 |
| Nano particle enriched material 1-11 | --- | 5.3 |
| Component 2 | Comparative sample | Application Example 1-11 |
| Desmodur N 3390 | 26.5 | 26.5 |
| Butylacetate | 6.9 | 6.9 |
Macrynal SM 515/70BAC (polyacrylic ester of hydroxy-functional): UCB
TinStab BL277 (dibutyl tin dilaurate): Akcros Chemicals
Desmodur N 3390 (aliphatic polyisocyanate): Bayer AG
The composition of each component is thoroughly mixed.And then this two-pack 1 and 2 is mixed before applying.The applying of coating system used and to be sprayed onto the PMMA plate by spraying method and (to carry out on the 200mm * 400mm).After at room temperature one hour seasoning time, 12 hours time is carried out in the forced drying under 60 ℃.The layer thickness of the coating that obtains is about 45 μ m.
(Type C M-5 AT-LAS) tests anti-zoned property with the fastness to rubbing tester.For this purpose, cated plate polishing cloth (3M polishing paper, the grade of 3M company; 9mic) reproducibly wearing and tearing (compelling force: 9N).The evaluation of scratch-proofness is by measuring the gloss of abrading section, with the gloss of non-abrading section on this test film to recently carrying out.The result is reported to residual gloss degree percentage ratio (%).Glossiness is measured with the micro-TRI-Gloss device of BYK-GARDNER company.Viewing angle is set in 85 °.
The quality of coatingsurface, especially the flowability of coating is estimated with optical means by the scale of using 1-5.1 value is corresponding to the extraordinary flowability of coating, and 5 value is corresponding to the coating flowability of difference, and itself shows as orange skin shape surface.
| Residual gloss, % | Mobile | |
| The comparative example | 10 | 5 |
| Application Example 1 | 81 | 4 |
| Application Example 2 | 86 | 2 |
| Application Example 3 | 84 | 4 |
| Application Example 4 | 75 | 4 |
| Application Example 5 | 83 | 2 |
| Application Example 6 | 69 | 2 |
| Application Example 7 | 80 | 4 |
| Application Example 8 | 68 | 4 |
| Application Example 9 | 85 | 2 |
| Application Example 10 | 67 | 2 |
| Application Example 11 | 53 | 2 |
4.
The preparation of properties-correcting agent (" properties-correcting agent 12 ")
The Si-H functional polysiloxanes that 100g is had following average structure joins in the 250mL four neck flasks that well heater, internal thermometer, agitator, reflux exchanger and shielding gas pipe connecting are housed:
This polysiloxane is easily at Noll, and " Chemie und Technologie derSilicone ", Wiley/VCH Weinheim prepares in the balanced reaction described in 1984.
This polysiloxane is heated to 70 ℃ in nitrogen atmosphere, add the 10ppm chloroplatinic acid then.Add poly-(ethylene oxide) glycol-a-methyl-o-allyl ethers (UnioxPKA-5009, NOF Europe) of 251g then, make temperature of reaction be no more than 80 ℃.Add 73g vinyltrimethoxy silane (for example Geniosil XL10, Wacker Chemie GmbH) then.Must the careful attention temperature of reaction be no more than 80 ℃.Reaction mixture stirred one hour down at 80 ℃ after adding.Apply vacuum then, the volatile component of the unreacted vinyltrimethoxy silane of about 2g and polysiloxane is distilled separation.Product is low viscosity and has slight amber shape color.
5.
Nano particle enriched material (" nano particle enriched material 12 ") and the corresponding relatively preparation of thing
40g nano particle size aluminum oxide be preset in the kitchen mixers and mix with 4g from the modifying agent among the last preparation embodiment (" properties-correcting agent 12 ").Mixture homogenized 1 minute then.The powder that scribbles modifying agent heated one hour down at 80 ℃.This modified nanoparticles of 40g is stirred in the solution of 56.8g acetic acid methoxyl group propyl ester and 3.2g wetting agent and dispersing auxiliary (BYK-9077, BYK-Chemie GmbH), disperses with ultrasonic wave then.The dispersion that obtains has low viscosity and do not demonstrate the trend of gel formation or sedimentation after storing in 28 days.
6.
Application Example
The UV transparent varnish
| Component | Nulling sample | Compare thing | Application Example 12 |
| Sartomer SR-368 1(isocyanuric acid ester triacrylate) | 27g | 27g | 27g |
| Sartomer SR-494 1(ethoxylation tetramethylol methane tetraacrylate) | 9g | 9g | 9g |
| Sartomer CD-501 1(Viscoat 295) | 27g | 27g | 27g |
| Sartomer SR-238 1(1,6 hexanediol diacrylate) | 27g | 27g | 27g |
| Esacure KB1 2 | 5g | 5g | 5g |
| Benzophenone | 5g | 5g | 5g |
| Nanoparticle dispersion 12 | 0g | 0g | 2.5g |
| Properties-correcting agent 12 | 0g | 0.1 | 0g |
1：Sartomer Company，Inc
2：LAMBERTI S.p.A.chemical specialties
Each component of transparent varnish is mixed for some time of also at room temperature in the dark storing at least 12 hours up hill and dale mutually.
This varnish is with on the 25 μ m volution scraper paint polyvinyl chloride panels, and seasoning is 15 minutes then.Being solidificated in the UV equipment of coating carried out.This coating is handled twice altogether with the yield of radiation of 120W/cm under the belt speed of 5.0m/min.
After three days period of storage, stain cated polyvinyl chloride panel with KIWI board (KIWI is brown) shoe polish.This shoe polish is removed with dried cloth is manual after 30 and 60 minutes and after 24 hours, and the test position is with the optical means evaluation.
| Duration of test runs | Nulling sample | Compare thing (only being polysiloxane) | Application Example 12 |
| 30 minutes | Stain slightly | Highly stain | Do not stain |
| 60 minutes | Highly stain, varnish weathers | Highly stain | Do not stain |
| 24 hours | Very highly stain, varnish partly dissolves away | Very highly stain, varnish weathers | Do not stain |
Claims (17)
1. the inorganic type particle of surface modification, this particle is included in their lip-deep reaction active groups, and wherein this particle reacts with polysiloxane group properties-correcting agent on their surface,
Wherein:
Described properties-correcting agent is the polysiloxane with following general formula
(R
1 x R
2 3-x Si R
3)
y R
4
Wherein in this general formula:
● x=0-2 comprises end value;
● y=1-10 comprises end value;
● R
1=have an any monovalent organic radical group of 1-18 carbon atom;
● R
2=OH group or the hydrolysable group that comprises following group or formed by following group:
-have linearity or alkoxyl group branching or ring-type of 1-6 carbon atom,
-halogen atom, or
-have a hydroxy-acid group of 1-4 carbon atom;
● R
3=oxygen or the divalent organic group at least that comprises following group or formed by following group:
-have an alkylidene group of linearity or the branching of 1-8 carbon atom,
-alkylene ether,
-alkylidene group thioether,
-with oxyethane, propylene oxide, butylene oxide ring or Styrene oxide 98min. or these hopcalites are the basis, or based on statistics or the alkylidene group polyethers of block polyether,
-arylidene polyethers,
-alkylidene group polyester, or
-organic aliphatic series or aromatics or aryl aliphatic group;
● R
4=comprise and have 4-200 Si unit and have C at Siliciumatom
1-C
18The polydialkysiloxane of alkyl or unit price or the multivalence group formed by this polydialkysiloxane, wherein this C
1-C
18Moieties ground and under each situation independently of one another selected leisure (i) listed following modification in (iv) substitute with group G with one or more the following modifications in the group G 1 to G4 or replace:
(i) contain the group G 1 of ether or polyether group,
The group G 2 that (ii) contains the polyester group,
The group G 3 that (iii) contains aromatic yl alkyl group,
The group G 4 that (iv) contains perfluorinated alkyl.
2. according to the inorganic type particle of the surface modification of claim 1, wherein this particle is nano particle.
3. according to the inorganic type particle of the surface modification of claim 1, wherein
● the group G 1 that contains ether or polyether group is based at least a alkylene oxide of following general formula
Radicals R wherein ' the expression hydrogen atom, phenyl or alkyl; With
● the group G 1 that contains ether or polyether group has the molecular weight in 116-15000 dalton scope; With
● polydialkysiloxane and modification are 12 with the mass ratio of group G 1: 1-0.07: in 1 scope.
4. according to the inorganic type particle of the surface modification of claim 1, wherein
● the group G 2 that contains the polyester group is aliphatic and/or alicyclic and/or aromatic polyester group or contain one group in the middle of these groups; With
● the group G 2 that contains the polyester group contains at least three groups
● the group G 2 that contains the polyester group has the molecular weight in 344-4000 dalton scope; With
● polydialkysiloxane and modification are 1 with the mass ratio of group G 2: 5-1: in 0.05 scope.
5. according to the inorganic type particle of the surface modification of claim 1, the group G 3 that wherein contains arylalkyl is phenyl propyl group or the group that contains this group.
6. according to the inorganic type particle of the surface modification of claim 1, wherein this particle reacts with polysiloxane group properties-correcting agent on their surface, has formed covalent chemical bond.
7. according to the inorganic type particle of the surface modification of claim 1, wherein the mark of properties-correcting agent is the 0.01-50 weight % with respect to the gross weight of surface modified granules.
8. be included in the dispersion according to the inorganic type particle of the surface modification of claim 1 in carrier or the dispersant media.
9. according to the purposes of inorganic type particle in coating, plastics, foams, makeup, tackiness agent or sealing agent of the surface modification of claim 1.
10. according to the purposes of claim 9, wherein said coating is selected from lacquer and tinting material.
11. coating, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
12. according to the coating of claim 11, wherein this coating system is selected from lacquer and tinting material.
13. plastics, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
14. foams, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
15. makeup, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
16. tackiness agent, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
17. sealing agent, it comprises the inorganic type particle according to the surface modification of claim 1 as filler.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006036950.5 | 2006-08-06 | ||
| DE102006036950 | 2006-08-06 | ||
| DE102006037106.2 | 2006-08-07 | ||
| DE102006037106 | 2006-08-07 | ||
| DE102006037596.3 | 2006-08-10 | ||
| DE102006037596 | 2006-08-10 | ||
| PCT/EP2007/006273 WO2008017364A2 (en) | 2006-08-06 | 2007-07-16 | Particles surface-modified with polysiloxane and production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101522821A CN101522821A (en) | 2009-09-02 |
| CN101522821B true CN101522821B (en) | 2013-07-03 |
Family
ID=41082410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780037490.0A Expired - Fee Related CN101522821B (en) | 2006-08-06 | 2007-07-16 | Surface-modified particles and production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101522821B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2688835B1 (en) * | 2011-03-22 | 2016-06-29 | Cornell University | Nanoscale ionic material (nim) compositions via acid/base reaction |
| KR102543599B1 (en) * | 2015-05-27 | 2023-06-13 | 니폰 제온 가부시키가이샤 | Carbon film and manufacturing method thereof, and fibrous carbon nanostructure dispersion liquid and manufacturing method thereof |
| JP6524901B2 (en) * | 2015-12-08 | 2019-06-05 | 信越化学工業株式会社 | Silicone rubber composition and cured product thereof |
| CN110028312B (en) * | 2019-04-28 | 2022-04-05 | 国装新材料技术(江苏)有限公司 | High-temperature-resistant ceramic precursor slurry and preparation method thereof |
| CN113909443A (en) * | 2021-10-29 | 2022-01-11 | 江苏智疆航空科技发展有限公司 | Ceramic core for aircraft engine and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121044A (en) * | 1994-06-01 | 1996-04-24 | 瓦克化学有限公司 | Process for the silylation of inorganic oxides |
| CN1718613A (en) * | 2004-07-08 | 2006-01-11 | 比克化学股份有限公司 | Polyester-modified polysiloxanes and their use as additives for thermoplastics, moulding compounds and coating materials |
-
2007
- 2007-07-16 CN CN200780037490.0A patent/CN101522821B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121044A (en) * | 1994-06-01 | 1996-04-24 | 瓦克化学有限公司 | Process for the silylation of inorganic oxides |
| CN1718613A (en) * | 2004-07-08 | 2006-01-11 | 比克化学股份有限公司 | Polyester-modified polysiloxanes and their use as additives for thermoplastics, moulding compounds and coating materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101522821A (en) | 2009-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2536441C (en) | Surface-modified nanoparticles, their preparation and use | |
| KR101139299B1 (en) | Surface-modified particles and production method | |
| CN101233182B (en) | Stabilized HDK suspensions for reinforcement of reactive resins | |
| CN101166795B (en) | Coated particles and coating compositions comprising coated particles | |
| KR101249949B1 (en) | Organosilane-modified polysiloxanes and their use for surface modification | |
| Bauer et al. | UV curable acrylate nanocomposites: properties and applications | |
| CN101198650B (en) | Process for modifying inorganic oxygen-containing particulate material, product obtained therefrom, and use thereof | |
| CN101522821B (en) | Surface-modified particles and production method | |
| US20150252166A1 (en) | Black ceramic additives, pigments, and formulations | |
| JP2007536418A (en) | Moisture crosslinkable composition containing alkoxysilyl functional particles | |
| CN101568603B (en) | Organofunctional silicone resin layers on metal oxides | |
| TWI501808B (en) | Use of dispersion agent for inorgainc micro particle, inorganic micro particle dispersion liquid, and inorganic micro particle dispersion using dispersion agent for inorganic micro particle, paint and cured article | |
| JP2009505934A (en) | Modified nanoparticles | |
| CN101495558A (en) | Nanopartikel | |
| KR100926813B1 (en) | Varnish containing particles with protected isocyanate groups | |
| CN101522777A (en) | Compositions containing phosphonate-functional particles | |
| EP1924655A2 (en) | Process for the production of a scratch resistant vehicle coating | |
| Musante et al. | Synthesis and Characterization of New Organic–Inorganic Hybrid Nanosilica Fillers Prepared by Sol–Gel Reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130703 Termination date: 20210716 |