CN1906124A - Nanoparticles - Google Patents
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- CN1906124A CN1906124A CNA2004800410706A CN200480041070A CN1906124A CN 1906124 A CN1906124 A CN 1906124A CN A2004800410706 A CNA2004800410706 A CN A2004800410706A CN 200480041070 A CN200480041070 A CN 200480041070A CN 1906124 A CN1906124 A CN 1906124A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to polymer-modified nanoparticles, suitable as UV stabilisers in polymers, which may be obtained by a method with the steps a) production of an inverse emulsion containing one or several water-soluble precursors for the nanoparticles or a melt, from a statistical copolymer of one monomer with hydrophobic groups and at least one monomer with hydrophilic groups and b) the generation of particles as well as the use thereof for UV protection in polymers.
Description
The present invention relates to polymer modification nano particle, this particulate manufacture method, with and in polymkeric substance, be used for the purposes of ultraviolet protection.
Inorganic nanoparticles is added in the polymeric matrix, not only can influence the mechanical property of parent, for example, shock strength also can change its optical property, for example transparence, color (absorption spectrum) and the specific refractory power of wavelength decision.Be used for the mixture of optical applications, owing to added the specific refractory power material different with the parent specific refractory power, causing scattering of light inevitably and finally cause opaqueness, granularity has been played the part of important role.The reduction of the radiation of specific wavelength intensity by mixture the time demonstrates the high dependency to the inorganic particle diameter.
In addition, extremely a large amount of polymkeric substance means for practical application the ultraviolet radiation sensitivity, must make polymeric uv stable.Regrettably, many right and wrong of inorganic ultraviolet filtering agent that are suitable as stablizer substantially own are fast to light, therefore still need can life-time service appropriate materials.
Suitable material therefore must be at the ultra-violet region extinction, and is transparent as far as possible in the visible region, and can directly add in the polymkeric substance.Although many metal oxides absorb UV-light, for above-mentioned reasons, they are difficult to add in the polymkeric substance under the situation of machinery that does not weaken the visible region or optical property.
The nano material that exploitation is suitable for being dispersed in the polymkeric substance not only needs control size, also needs to control the particulate surface property.Hydrophilic particle with simple mixing the (for example, passing through extrusion molding) of hydrophobic polymer parent cause the uneven distribution of particle in whole polymkeric substance, cause its gathering in addition.For inorganic particle is evenly added in the polymkeric substance, its surface therefore at least must be by hydrophobic modified.In addition, this nano-particle material shows to such an extent that very easily form agglomerate especially, and they also can stand surface treatment subsequently.
Astoundingly, have been found that now nano particle can directly precipitate if use some random copolymers as emulsifying agent from emulsion, and the suitably modification of surface quilt, and generate agglomerate hardly.
Thus obtained particle sneak into aspect the hydrophobic copolymer especially favourable because particle can be evenly distributed in the whole polymkeric substance by simple method, and in the visible region absorbing radiation hardly.
Therefore the present invention at first relates to the nano particle of the polymer modification that is suitable as the ultra-violet stabilizer in the polymkeric substance, it is characterized in that, it can obtain by the following method: in step a), by means of at least a monomer of hydrophobic group and reversed-phase emulsion or the melt that at least a monomeric random copolymers preparation that contains hydrophilic radical contains one or more water-soluble precursors of this nano particle of containing, in step b), make particle.
The invention further relates to the polymer modification particulate method of making, it is characterized in that: in step a), by means of at least a monomer of hydrophobic group and reversed-phase emulsion or the melt that at least a monomeric random copolymers preparation that contains hydrophilic radical contains one or more water-soluble precursors of this nano particle of containing, in step b), make particle.
The emulsion technology that the manufacturing nano particle is used is known substantially.For example, M.P.Pileni; J.Phys.Chem.1993,97,6961-6973 has described the semiconductor grain of in reversed-phase emulsion Production Example such as CdSe, CdTe and ZnS and so on.
But, the synthetic high salt concentration that usually requires precursor material in the emulsion of inorganic materials, and this concentration can change in reaction process.Low molecular weight surfactants produces reaction to this high salt concentration, and therefore, the stability of emulsion is difficult to guarantee (Paul Kent and Brian R.Saunders; Journalof Colloid and Interface Science 242,437-442 (2001)).Especially, granularity only can be controlled in the limited scope (M.-H.Lee, C.Y.Tai, C.H.Lu, Korean J.Chem.Eng.16,1999,818-822).
K.Landfester (Adv.Mater.2001,13, No.10 765-768) proposes to use high molecular weight surface promoting agent (PEO-PS segmented copolymer) with combination of ultrasound, is about 150 nano particles to about 300 nanometers so that make size range by metallic salt.
Now, select at least a monomer and at least a monomeric random copolymers that contains hydrophilic radical that contains hydrophobic group, can provide and be beneficial to the emulsifying agent of under the situation of control size and size-grade distribution, making inorganic particle by reversed-phase emulsion.Simultaneously owing to directly formed one particle with polymeric coating, use these New-type emulsifiers can make inorganic particle under the situation that forms agglomerate hardly with separated dispersion.
In addition, can especially simply and be evenly distributed in the polymkeric substance by the nano particle that this method obtains, it especially can avoid the not desirable reduction of these polymkeric substance transparency in visible light basically.
The random copolymers that preferably uses according to the present invention has 1: 2 to 500: 1, preferred 1: 1 to 100: 1, preferred 7: 3 to 10: 1 especially structural unit that contains hydrophobic group in this random copolymers and the weight ratio that contains the structural unit of hydrophilic radical.The weight-average molecular weight of this random copolymers is generally M
w=1000 to 1,000,000 gram/mole is preferably 1500 to 100,000 gram/moles, is preferably 2000 to 40,000 gram/moles especially.
Have been found that multipolymer meets structural formula I
Wherein,
X and Y are equivalent to the conventional nonionic or the group of ion monomer, and
R
1Represent hydrogen or hydrophobicity side group, be preferably selected from the branching or the nonbranched alkyl group that contain at least 4 carbon atoms, wherein one or more, preferably all H atoms can replace by fluorine atom, and
R
2Represent the wetting ability side group, it preferably contains phosphonate radical, sulfonate radical, poly-hydroxy or polyether group,
And wherein-X-R
1With-Y-R
2Can have multiple different implication respectively, they satisfy requirement of the present invention at intramolecularly with ad hoc fashion.
According to the present invention especially preferably-Y-R
2Polymkeric substance when representing betaine (betaine) structure.
The polymkeric substance of preferred especially following structural formula I again---wherein X and Y represent independently of one another-O-,-C (=O)-O-,-C (=O)-NH-,-(CH
2)
n-, phenylene or pyridyl.In addition, can advantageously use following polymkeric substance---wherein at least a structural unit contains at least one quaternary nitrogen atoms, wherein R
2Preferred representative-(CH
2)
m-(N
+(CH
3)
2)-(CH
2)
n-SO
3 -Side group or-(CH
2)
m-(N
+(CH
3)
2)-(CH
2)
n-PO
3 2-Side group, wherein m represents 1 to 30 integer, and is preferred 1 to 6, preferred especially 2, and n represents 1 to 30 integer, and preferred 1 to 8, preferred especially 3.
Can prepare the preferred especially random copolymers that uses according to following scheme:
Lauryl methacrylate(LMA) of desired amount (LMA) and dimethylaminoethyl methacrylate (DMAEMA) at this by the currently known methods copolymerization, preferably by add AIBN in toluene by means of free-radical polymerized.Subsequently, by currently known methods, by amine and 1, the reaction of 3-N-morpholinopropanesulfonic acid lactone obtains the betaine structure.
Preferred other multipolymer that uses can contain vinylbenzene, vinyl pyrrolidone, vinyl pyridine, halogenated styrenes or methoxy styrene, and these examples are not limitations of the present invention.In the another kind of same preferred embodiment of the present invention, use has the polymkeric substance of following characteristics---and at least a structural unit is oligopolymer or polymkeric substance, be preferably macromonomer, wherein polyethers, polyolefine and polyacrylic ester are especially preferably as macromonomer.
The suitable precursor of inorganic nanoparticles is a water soluble metallic compound, is preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium compounds, wherein, these precursors preferably with acid or alkaline reaction, to make the corresponding metal oxide particle.Can obtain mixed oxide in simple mode by the corresponding precursor of suitable mixing at this.For those skilled in the art, select suitable precursor not difficult; Suitable compounds is to be fit to all that compound that from aqueous solution precipitated phase is answered target compound.For example, at K.Osseo-Asare " Microemulsion-mediated Synthesis ofnanosize Oxide Materials " in:Kumar P., Mittal KL, (editor), Handbook ofmicroemulsion science and technology, New York:Marcel Dekker, Inc., provided the summary of the precursor that is suitable for preparing oxide compound in the table 6 of 559-573 page or leaf, its content belongs to the application's disclosure clearly.
In the present invention, the wetting ability melt also can be used as the precursor of nano particle.In the case, the chemical reaction that is used to make nano particle is not to be the sin qua non.
The nano particle of preferably making is those particles of being made up of the oxide compound or the oxyhydroxide of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium substantially.
Detect by Malvern ZETASIZER (dynamic light scattering) or transmission electron microscope, these particles preferably have 3 to 200 nanometers, the particularly mean particle size of 20 to 80 nanometers, especially preferred 30 to 50 nanometers.Of the present invention concrete, equally preferred embodiment in, size-grade distribution is narrow, that is to say, mobility scale is sub-average 100%, especially preferably mostly is most 50% of mean value.
When these nano particles are used for ultraviolet protection in polymkeric substance, if nano particle has the maximum absorption that in the 300-500 nanometer range, preferably is up to 400 nanometers, this is particularly preferred, and wherein, particularly preferred nano particle is absorbed in the radiation in the UV-A zone especially.
Can carry out emulsion method with several different methods herein:
As mentioned above, usually in step b), cool off by the reaction of precursor or by melt and to make particle.According to selected different methods, precursor this can with acid, alkali lye, reductive agent or oxidant reaction.
In order to make the particle in the desired particle size range, particularly advantageous is that drop size is 5 to 500 nanometers in the emulsion, preferred 10 to 200 nanometers.Drop size in the given system is set by method known to those skilled in the art at this, and wherein, those skilled in the art can make oil phase and reaction system be complementary respectively.Make for the ZnO particulate, for example toluene and hexanaphthene are verified can successfully be used as oil phase.
In some cases, what possibility was useful is to use other co-emulsifier except that random copolymers, be preferably nonionic surface active agent.Preferred co-emulsifier is optional to be the alkanol of relative long-chain ethoxylation or propenoxylated, as to have different ethoxylation degrees or propoxylation degree or alkylphenol the adducts of 0 to 50 mol of alkylene oxide (for example with).
It also may be favourable using dispersion aids; the water-soluble polymer weight organic compounds that preferably contains polar group; Polyvinylpyrolidone (PVP) for example; propionate or vinyl-acetic ester and vinylpyrrolidone copolymers; the partly-hydrolysed multipolymer of acrylate and vinyl cyanide; polyvinyl alcohol with different residual acetate content; ether of cellulose; gelatin; segmented copolymer; treated starch contains the water-soluble low molecular weight polymkeric substance of carboxyl and/or alkylsulfonyl or the mixture of these materials.
Especially preferred protective colloid is that residual acetate content is lower than 40 moles of %, is in particular the polyvinyl alcohol of 5 to 39 moles of %, and/or vinyl ester content is lower than 35 weight %, is in particular vinyl pyrrolidone-vinyl propionate ester copolymer of 5 to 30 weight %.
Can be in mode targetedly, the reaction conditions by attemperation, pressure and duration of the reaction and so on is to set the desirable properties of combination of required nano particle.To those skilled in the art, the arrange accordingly of these parameters is had no problem fully.For example, for many purposes, can under normal atmosphere and room temperature, operate.
In the preferable methods variant, second emulsion (wherein the reactant of precursor is the emulsification form) is mixed with preceding precursor emulsion from step a) in step b).This pair of emulsion method can be made the narrow especially particle of size-grade distribution.For these two kinds of emulsions, possibility is particularly advantageous to be intermingling under the ultrasonic wave effect.
In another same preferable methods variant, with preceding precursor emulsion step b) with in emulsion external phase soluble precipitant mix.Precipitation agent is diffused in the micella that contains precursor to precipitate.For example, pyridine is diffused in the micella that contains chlorination oxygen titanium making titanium dioxide granule, or long-chain aldehyde is diffused in the micella that contains Silver Nitrate to make silver-colored particle.
Nano particle of the present invention is used in particular for the ultraviolet protection in the polymkeric substance.In this purposes, this particle or protection polymkeric substance self are not degraded by ultraviolet radiation, perhaps use with the form of for example protective membrane and contain the ultraviolet protection of the polymer composition of this nano particle as other material.Therefore the present invention further relates to the corresponding uses that nano particle of the present invention is used for the UV stable of polymkeric substance, also relates to mainly by at least a to contain the polymer composition that nano particle of the present invention is the UV stable that constitutes of the polymkeric substance of feature.The polymkeric substance that nano particle of the present invention can be sneaked into wherein well especially is polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethylmethacrylate (PMMA) or the multipolymer that contains at least a portion of one of described polymkeric substance.
Can sneak into by the traditional method of preparation polymer composition in this article.For example, polymer materials can preferably mix with nano particle of the present invention in the forcing machine or the machine that is mixed.According to used polymkeric substance, also can use a plurality of machines that are mixed.
The special advantage of particulate of the present invention is, compared with prior art, this uniform particles is distributed in only needs lower energy input in the polymkeric substance.
At this, polymkeric substance also can be the dispersion of polymkeric substance, for example, and coating.Can sneak into by traditional married operation at this.
In addition, the polymer composition of the present invention that contains this nano particle further is specially adapted to coating surface.This can make the surface or the material that is positioned under the coating is resisted for example ultraviolet radiation.
The following example will be explained the present invention and unrestricted the present invention in more detail.
Embodiment
Embodiment 1: molecules surfactant synthetic
The first step comprises synthesize methyl acrylic acid 12 carbon esters (lauryl methacrylate(LMA): LMA) and the random copolymers of dimethylaminoethyl methacrylate (DMAEMA).Can add mercaptoethanol with the control molecular weight.Can be by 1, the 3-N-morpholinopropanesulfonic acid lactone carries out modification so that saturated group to be provided to thus obtained multipolymer.
For this reason, at first the DMAEMA with 7 gram LMA and following the amount of Table 1 adds in the 12 gram toluene, and by after being added in the gram of 0.033 in 1 milliliter of toluene AIBN initiation reaction, carries out radical polymerization at 70 ℃ under argon gas.Can add 2 mercapto ethanol at this and increase (seeing Table 1) with Quality Initiative.With the washing of rough polymkeric substance, lyophilize and then with 1, the 3-N-morpholinopropanesulfonic acid lactone reaction, as V.Butun, C.E.Bennett, M.Vamvakaki, A.B.Lowe, N.C.Billingham, S.P.Armes, J.Mater.Chem., 1997,7 (9), described in the 1693-1695.
Provided the characteristic of resulting polymers in the table 1.
Table 1: the characteristic of used monomeric amount and resulting polymers
| DMAEMA [gram] | DMAEMA in the polymkeric substance [mole %] | 1-mercaptoethanol [gram] | M n[gram/mole] | M w[gram/mole] | Betaine group [mole %] | |
| E1 | 1.08 | 19 | 0.033 | 18000 | 31000 | 16 |
| E2 | 1.08 | 19 | 0.011 | 28000 | 51000 | 19 |
| E3 | 1.08 | 21 | 0.066 | 13000 | 21000 | 21 |
| E4 | 1.09 | 20 | --- | 59000 | 158000 | 14.6 |
| E5 | 0.48 | 10.7 | --- | 52000 | 162000 | 7.5 |
Embodiment 2:ZnO particulate precipitation
Precipitate the ZnO particle by following method:
1. prepare 0.4 gram Zn (AcO) respectively by means of ultrasonic wave
22H
2The reversed-phase emulsion (emulsion 2) of the reversed-phase emulsion (emulsion 1) of the aqueous solution of O in 1.1 gram water and the aqueous solution of 0.1 gram NaOH in 1.35 gram water.Emulsion 1 and emulsion 2 contain the random copolymers of the E1-E5 of 150 milligrams of tables 1 separately.
2. the mixture to emulsion 1 and emulsion 2 carries out supersound process, and dry then.
3. wash the gained solid with water with purifying acetic acid sodium.
4. dry, and will functionalized from the teeth outwards polymkeric substance redispersion by emulsifying agent in the toluene by stirring into.
FT-IR spectrum and X-ray diffraction show formation ZnO.In addition, in the X ray collection of illustrative plates, can't see the reflection of sodium acetate.
Therefore, embodiment 2 has obtained the product that is made of synthetic molecules surfactant and Zinc oxide particles.
| Multipolymer | Diameter [nanometer] (scattering of light) | Change [nanometer] | The ratio of ZnO (weight %) |
| E1 | 37 | 30 | 30.3 |
| E2 | 66 | 53 | 30.5 |
| E3 | 50 | 41 | 32 |
Comparative example 2a: use emulsifying agent ABIL EM 90
According to the program described in the embodiment 2, use commercial emulsifier ABIL EM 90
(hexadecyl dimethione copolyol, Goldschmidt) random copolymers among the replacement embodiment 1 can not obtain stable emulsion.Thus obtained particle diameter is between 500 to 4000 nanometers.
Embodiment 3: polymer composition
The dispersion of particle in the PMMA lacquer by being mixed with embodiment 2-E1 is administered on the glass substrate it and drying.Dried ZnO content is 10 weight %.This film shows almost imperceptible muddiness.Use the UV-VIS spectrometer, measure, confirmed this impression.According to bed thickness, sample presents following absorption value (per-cent that has shown incident light loss in transmission process).
Bed thickness UV-A (350 nanometer) VIS (400 nanometer)
1.2 micron 35% 4%
1.6 micron 40% 5%
2.2 micron 45% 7%
Contrast:
(ZnO (ultrapure, Merck) in PMMA lacquer as above)
2 microns 64% 46%
Claims (21)
1. the nano particle of polymer modification, it is suitable as the ultra-violet stabilizer in the polymkeric substance, it is characterized in that, it can obtain by the following method: in step a), by means of at least a monomer of hydrophobic group and reversed-phase emulsion or the melt that at least a monomeric random copolymers preparation that contains hydrophilic radical contains one or more water-soluble precursors of this nano particle of containing, with in step b), make particle.
2. according to the nano particle of claim 1, it is characterized in that this particle is made up of the oxide compound or the oxyhydroxide of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium substantially.
3. according to the nano particle of at least one of aforementioned claim, it is characterized in that detecting by dynamic light scattering or transmission electron microscope, this particle has the mean particle size of 3 to 200 nanometers, preferred 20 to 80 nanometers, preferred especially 30 to 50 nanometers, and its size-grade distribution is preferably narrow.
4. according to the nano particle of at least one of aforementioned claim, it is characterized in that its maximum absorption in the scope of 300-500 nanometer, preferably in the scope that is up to 400 nanometers.
5. make the method for polymer modification nano particle, it is characterized in that, in step a), by means of at least a monomer of hydrophobic group and reversed-phase emulsion or the melt that at least a monomeric random copolymers preparation that contains hydrophilic radical contains one or more water-soluble precursors of this nano particle of containing, with in step b), make particle.
6. according to the method for claim 5, it is characterized in that in step b), make particle by the reaction of precursor or by the cooling of melt.
7. according to the method for claim 6, it is characterized in that this precursor and acid, alkali, reductive agent or oxidant reaction.
8. according to the method for at least one of aforementioned claim, it is characterized in that drop size is 5 to 500 nanometers in the emulsion, preferred 10 to 200 nanometers.
9. according to the method for at least one of aforementioned claim, it is characterized in that in step b) second emulsion is mixed with preceding precursor emulsion from step a), in second emulsion, the reactant of precursor is the emulsification form.
10. according to the method for claim 9, it is characterized in that by action of ultrasonic waves described two kinds of emulsion intermingling.
11. method according at least one of aforementioned claim, it is characterized in that described one or more precursors are selected from water soluble metallic compound, be preferably the compound of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium or zirconium, and these precursors preferably with acid or alkaline reaction.
12. according to the method for at least one of aforementioned claim, it is characterized in that using co-emulsifier, preferred nonionic surface active agent.
13. method according at least one of aforementioned claim, it is characterized in that the weight ratio that contains the structural unit of hydrophobic group and contain the structural unit of hydrophilic radical in described random copolymers is 1: 2 to 500: 1, preferred 1: 1 to 100: 1, preferred especially 7: 3 to 10: 1, and the weight-average molecular weight of this random copolymers is M
W=1000 to 1,000,000 gram/mole is preferably 1500 to 100,000 gram/moles, is preferably 2000 to 40,000 gram/moles especially.
14., it is characterized in that described multipolymer meets structural formula I according to the method for at least one of aforementioned claim
Wherein,
X and Y be corresponding to the nonionic of routine or the group of ion monomer, and
R
1Represent hydrogen or hydrophobicity side group, be preferably selected from the branching or the nonbranched alkyl group that contain at least 4 carbon atoms, wherein one or more, preferably all H atoms can be replaced by fluorine atom, and
R
2Represent the wetting ability side group, it preferably contains phosphonate radical, sulfonate radical, poly-hydroxy or polyether group,
And wherein-X-R
1With-Y-R
2In molecule, can have multiple different implication separately.
15. the method according to claim 14 is characterized in that, X and Y represent independently of one another-O-,-C (=O)-O-,-C (=O)-NH-,-(CH
2)
n-, phenylene or pyridyl.
16., it is characterized in that at least a structural unit contains at least one quaternary nitrogen atoms, wherein R according to the method for at least one of aforementioned claim
2Preferred representative-(CH
2)
m-(N
+(CH
3)
2)-(CH
2)
n-SO
3 -Side group or-(CH
2)
m-(N
+(CH
3)
2)-(CH
2)
n-PO
3 2-Side group, wherein m represents 1 to 30 integer, and is preferred 1 to 6, especially preferred 2, and n represents 1 to 30 integer, and preferred 1 to 8, especially preferred 3.
17., it is characterized in that at least a structural unit is oligopolymer or polymkeric substance according to the method for at least one of aforementioned claim, be preferably macromonomer, wherein polyethers, polyolefine and polyacrylic ester are especially preferably as macromonomer.
18., be used for the UV stable of polymkeric substance according to the purposes of the nano particle of at least one of claim 1 to 4.
19. substantially the polymer composition of the UV stable of being made up of at least a polymkeric substance is characterized in that this polymkeric substance contains the nano particle according at least one of claim 1 to 4.
20., it is characterized in that this polymkeric substance is polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethylmethacrylate (PMMA) or the multipolymer that contains at least a portion of one of described polymkeric substance according to the polymkeric substance of claim 19.
21. the method for polymer composition of preparation UV stable is characterized in that, polymer materials is mixed with nano particle according at least one of claim 1 to 4, preferably mixes in extruding machine or compounding machine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004004210.1 | 2004-01-27 | ||
| DE200410004210 DE102004004210A1 (en) | 2004-01-27 | 2004-01-27 | Producing polymer-modified nanoparticles useful as ultraviolet stabilizers in polymers comprises preparing an inverse emulsion comprising nanoparticle precursors or a melt using an amphiphilic copolymer |
| EP04023003.9 | 2004-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1906124A true CN1906124A (en) | 2007-01-31 |
Family
ID=34801117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800410706A Pending CN1906124A (en) | 2004-01-27 | 2004-12-15 | Nanoparticles |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1906124A (en) |
| DE (1) | DE102004004210A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422621B (en) * | 2007-10-31 | 2011-08-10 | 韩国科学技术研究院 | Method for the production of bio-imaging nanoparticles with high yield by early introduction of irregular structure |
| WO2016000252A1 (en) * | 2014-07-04 | 2016-01-07 | Dow Global Technologies Llc | Inorganic particles with improved flowability |
| CN105504879A (en) * | 2016-01-19 | 2016-04-20 | 王虹 | Method for preparing core-shell type silicon dioxide coated ammonium phosphate based on reversed-phase micro-emulsion method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1203118A1 (en) * | 1999-07-19 | 2002-05-08 | Nano-Tex LLC | Nanoparticle-based permanent treatments for textiles |
| US7138468B2 (en) * | 2002-03-27 | 2006-11-21 | University Of Southern Mississippi | Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT |
-
2004
- 2004-01-27 DE DE200410004210 patent/DE102004004210A1/en not_active Withdrawn
- 2004-12-15 CN CNA2004800410706A patent/CN1906124A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422621B (en) * | 2007-10-31 | 2011-08-10 | 韩国科学技术研究院 | Method for the production of bio-imaging nanoparticles with high yield by early introduction of irregular structure |
| WO2016000252A1 (en) * | 2014-07-04 | 2016-01-07 | Dow Global Technologies Llc | Inorganic particles with improved flowability |
| CN105504879A (en) * | 2016-01-19 | 2016-04-20 | 王虹 | Method for preparing core-shell type silicon dioxide coated ammonium phosphate based on reversed-phase micro-emulsion method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004004210A1 (en) | 2005-08-18 |
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