TW200540191A - Use of random copolymers - Google Patents

Abstract

The invention relates to the use of random copolymers containing at least one structural unit containing hydrophobic radicals and at least one structural unit containing hydrophilic radicals as emulsifiers, in particular in the synthesis of nanoparticles, and to processes for the production of such particles in which, in a step (a), an inverse emulsion comprising one or more water-soluble precursors of the nanoparticles or a melt is prepared with the aid of a random copolymer of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals, and, in a step (b), particles are produced.

Description

200540191 IX. Description of the invention: [Technical field to which the invention belongs] ▲ The present invention relates to the use of random copolymers as emulsifiers, specifically, in the synthesis of nano particles, and the method for making the particles .

Incorporating inorganic nano particles into the human-polymer base f not only affects the matrix: mechanical properties, such as its impact strength 'can also modify its optical properties', such as wavelength-dependent transmission, color (absorption spectrum) And refractive index. In mixtures for optical applications, particle size plays an important role because the addition of a substance with a refractive index different from that of the matrix will cause irreversible scattering of light and eventually opacity. —The defined wavelength passes through the substrate—its reduced radiation intensity indicates that it is highly dependent on the diameter of the inorganic particles. The development of nanomaterials suitable for interspersing polymers requires not only controlling particle size 'but also controlling the surface properties of the particles. Simply mixing hydrophilic particles with a hydrophobic polymer matrix (such as extrusion) will cause uneven distribution of the particles throughout the polymer 'and will cause them to agglomerate. In order for the inorganic particles to be homogenously incorporated into the polymer, these surfaces must therefore be at least hydrophobically modified. In addition, in particular, 'because nanoparticulate materials show a great tendency to form agglomerates', they can also survive the subsequent surface treatment. Surprisingly, 'it has now been found' that if a specific random M is used as an emulsifier, the nano particles can be directly obtained from the emulsion by appropriate modification and contain substantially no agglomerates. The present invention therefore relates first to the use of random copolymers as emulsifiers, the copolymers comprising at least one structural unit containing a hydrophobic group 985W.doc 200540191 at least one structural saponin containing a hydrophilic group 'specifically' is For the synthesis of nano particles in emulsion. The present invention also relates to a method for manufacturing polymer-modified nano particles, which is characterized in that in step a), an inverse emulsion or one or more water-soluble precursors of nano particles are prepared with the aid of a random copolymer. A melt, the random copolymer comprises at least one monomer containing a hydrophobic group and at least one monomer containing a hydrophilic group, and in step b), granules are prepared. [Prior art] Basically, the emulsification technology for making nano particles is known, so M.P. Pileni; J. Phys. Chem. 1993, 97, 6961-6973 describe the production of semiconductor particles in an inverse emulsion, such as CdSe , CdTe, and ZnS. However, the synthesis of inorganic materials often requires precursors with high salt concentrations in the emulsion, and their concentrations will change as the reaction proceeds. Low molecular weight surfactants will react to this high salt concentration, and as a result, the stability of the emulsion will be in crisis (Paul Kent and Brian R. Saunders; Journal of Colloid and Interface Science 242, 437-442 (2001)). In particular, the particle size can only be controlled to a limited range (M.-H. Lee, C.Υ. Tai, C.Η. Lu, Korean J. Chem. Eng. 16, 1999, 818-822) . K. Landfester (Adv. Mater. 2001, 13, No. 10, 765-768) proposed the use of high molecular weight surfactants (PEO-PS block copolymers), and combined with ultrasound to manufacture from metal salts Particle size ranges from about 150 to about 300 nm. [Summary of the Invention] Random copolymers containing at least one monomer containing a hydrophobic group and at least one monomer containing a hydrophilic group of 98510.doc 200540191 are now able to provide an emulsifier 'which can promote inorganic nano Rice granules are produced in inverse emulsions to control particle size and particle size distribution. At the same time, due to the use of these new emulsifiers, nano particles can be separated from the dispersion liquid without substantial agglomerates, because individual particles will form directly as the polymer is applied. In addition, the nano particles obtained by this method can be specifically, simply and uniformly dispersed in the polymer, and in particular, it may substantially avoid undesired damage to the transparency of the polymer in visible light. In the random copolymer, the random copolymer used according to the present invention will preferably exhibit a weight ratio of structural units containing a hydrophobic group and structural units containing a hydrophilic group ranging from 1: 2 to 500 : 1, preferably in the range from 1: 1 to 10 (M, and particularly preferably in the range from 7: 3 to 10: the average molecular weight of the random copolymer is usually in the range from Mw = 1000s The preferred range is from 1500 to 100,000 g / m01 and the particularly preferred range is from 2000 to 40.000 g / cabuter. The copolymer has been found herein as shown by formula j :

Where x and Y are conventional non-ionic or ionic monomer groups, and R represents hydrogen or a hydrophobic side group, 'is preferably selected from the group consisting of a branch having at least 4 carbon atoms 985l0.doc 200540191 Unbranched alkynyl groups in which one or more (preferably all) fluorene atoms may be substituted by fluorine atoms, and R2 represents a hydrophilic side group, which preferably has a phosphonate, sulfonate , A polyhydric alcohol or a polyether group, and -X-R1 and -γ-R2 of each of which may have a plurality of different meanings in a molecule, so as to meet the requirements of a specific method according to the present invention. A particularly preferred polymer provided according to the present invention is that -Y-R2 represents a betaine structure. Next, the polymer of the formula I is particularly preferably X and γ which represent -C (= 0)-, _C (= 0) _NH_,-(CH2) n-, phenyl, naphthyl or azidinyl. Furthermore, at least one structural unit in the polymer contains at least one quaternary nitrogen atom. Its R2 preferably represents a-(CH2) m- (N + (CH3) 2MCH2) n-S03- side group or a-(CH2 ) m- (N + (CH3) 2HCH2) n_P〇32- side group, where m represents an integer 'ranging from 1 to 30, preferably ranging from 1 to 6, particularly preferably 2 and n represents an integer, range From 1 to 30, preferably in the range from 1 to 8, particularly preferably 3 in order to use the polymer advantageously and conveniently. The random copolymer used is particularly preferably prepared according to the following flow chart:

98510.doc -9- 200540191 The desired amounts of lauryl methacrylate (LMA) and dimethyl-aminoethyl methacrylate (DMAEMA) are known here The method of copolymerization is preferably performed by addition of free radicals in toluene with AIBN addition. Next, a betaine structure can be obtained by a known method by reacting an amine with 1,3-propanesultone (l, 3-pro-panesultone). Another copolymer used may include styrene, vinylpyrrolidone, vinylidene, i-styrene, or methoxystyrene, and these examples are not a limitation. In addition, an equally preferred embodiment of the present invention is the use of a polymer, which is characterized in that at least one structural unit is an oligomer or polymer, preferably a macromonomer, of which polyethers, polyolefins, and Polyacrylates are particularly preferred macromonomers. The precursors that can be used for inorganic nano particles are water-soluble metal compounds, preferably Shi Xi, decorative, starting, chromium, nickel, titanium, titanium, iron, zirconium and / or zirconium compounds. Reacts with an acid or lye to produce corresponding metal-oxide particles. The mixed oxide can be obtained here by a simple method by appropriately mixing the corresponding precursors. Those skilled in the art will have no difficulty in selecting suitable precursors; the applicable compounds are all such compounds that can precipitate the corresponding target compound from an aqueous solution. An overview of suitable precursors that can be used for oxide precipitation is described in, for example, K. Osseo-Asare " Microemulsion-mediated Synthesis of nanosize Oxide Materials "in: Kumar P., Mittal KL? (Editors), Handbook of microemulsion science and technology, New York: Marcel Dekker, Inc., pp. 559-573 in Table 6, its content is clearly disclosed in the content of this application. 98510.doc -10- 200540191 Hydrophilic smelts can also be used in the present invention as Nano-particles. The chemically-dispelled reaction used to make nano-particles is not absolutely necessary in this example. The alkali metal or soil test metal that is the precursor is Lithium sulphate, which is also sodium sulphate. React with acid or test solution to obtain stone dioxide. In the same way, in the preferred embodiment of the present invention and the diastolic body is poor, a wide variety of y-soluble compounds that can use precious metals are preferably silver acetate, and A reducing agent reaction, preferably citric acid, to obtain the metal.

In order to prepare nano metal sulfide, the same as the present invention is preferred-a soluble metal compound, preferably-a soluble, bright compound, and hydrogen sulfide to obtain the metal sulfide. In another embodiment of the present invention, a soluble metal compound 'such as preferably chlorinated per' and carbon dioxide is used to obtain metal carbonates of nano particles. The nano granules produced are particularly preferably such oxides or chlorine oxides that are essentially cut, zinc, starting, chrome-nickel, titanium, titanium, iron, period and / or wrong. Depending on the decision of dynamic light scattering or transmission electron microscope, the preferred particles have an average particle size from 3 to 3 nm, specifically from 20 to 80 micron, and very specific and preferably from 3G to nm . In particular, also in the preferred embodiment of the present invention, the particle size distribution is very narrow, that is, the variation range is lower than the average value of 1GG%, and particularly preferably the maximum value of the average value of 5 ()%. This article is used in the application of these nano particles in the compound state, especially if the nano particles have a maximum absorption range of 3⑻ ·, preferably in the range of up to 400 nm, particularly good. The rice particles can absorb radiation, in particular in the UV-A region. 98510.doc 200540191 The emulsification process can be carried out in various ways here: As mentioned before, the granules are usually prepared by cooling the melt in step b) using a reactive brake for flooding. The precursors can be reacted at this time with & ^ a test solution, a test solution, a reducing agent or an oxidant, depending on the process variables used. In order to manufacture particles of the desired size range, it would be particularly advantageous if the emulsified droplet size in the emulsification reaction ranged from 5 to 500 nm, Α to 500 nm, preferably in the range of 10 to 200 nm. The size of the emulsified droplets of the system towel can be set here by methods known to those skilled in the art, and the oil phase can be selected by those skilled in the art to match the reaction system. For example, to produce ZnO particles, toluene and ring Hexane has proven to be successful as an oil phase. In certain cases, in addition to random copolymers, the use of another co-emulsifier may be helpful, preferably a non-ionic surfactant. The preferred co-emulsifier is visible In the case of ethoxylation or propoxylation, relatively long-chain alcohols or alcohols have various degrees of ethoxylation or propoxylation (for example, from 0 to 50 m). 〇1 alkylene oxide bond). It may also be useful to use dispersing aids, preferably water-soluble, high molecular weight, organic compounds containing polar groups such as polyvinylpyrrolidone, vinyl propionate or acetic acid and Copolymers of vinylpyrrolidone, partially saponified acrylic and acrylonitrile copolymers, and polyvinyl alcohols all have various residual acetic acid inclusions, cellulose ethers, gelatin, block copolymer modified starch, low molecular weight polymers, Contains carboxyl and / or sulfopolymers, or mixtures of these. Particularly preferred protective colloids are polyvinyl alcohols, which have a residual acetate content of less than 40 mol%, specifically from 5 to 39 mol %, And / or ethylene 98510.doc -12- 200540191 enopyrrolidone-vinyl propionate copolymer, which has a vinyl ester content of less than 3 5% by weight, specifically from 5 to 30% by weight. The desired combination of properties of rice granules can be adjusted according to the given method according to the reaction conditions without such as reaction temperature, pressure and reaction time. The corresponding setting of these numbers will be absolutely no difficulty for those skilled in the art. For example, reaction It can be carried out at atmospheric pressure and room temperature for various purposes. In a preferred reaction variant, a second emulsion containing a reactant as a precursor and in an emulsified form, In step b), the precursor emulsion from step a) is mixed. The two emulsification processes give the resulting particles a particularly narrow particle size distribution. Here, it is particularly advantageous for the second emulsion to use the effect of ultrasound to make On the other hand, in the same preferred reaction variant, the precursor emulsion can be mixed with a precipitant soluble in the continuous phase of the emulsification reaction in step b). After that, it can be diffused by the sink. Precipitation reaction occurs to the microspheres containing precursors. For example, titanium dioxide particles can be obtained by diffusion of pyridine into titaniumoxy gas-containing microspheres, or silver particles can be diffused into silver nitrate using long chain aldehydes It can be obtained in microcells. In particular, nano particles according to the present invention can be used in polymers. Polymers in which nano particles can be well incorporated according to the present invention, in particular, ferric esters, polyethylene Terephthalate (PETP), polyimide (PI), ethylene (PS), polymethylmethacrylate (PMMA), or a copolymer containing at least one component of one of the polymers. Here, conventional methods for preparing polymer compositions can be used to make the combined reaction hair, for example, 'the polymer material can be mixed with the nano particles according to the present invention, 98510.doc -13-200540191, preferably in an extruder. Or mix in a batching machine. Depending on the polymer used, a batcher can also be used. A special advantage of the particles according to the present invention is that, compared to that, they only need to recognize +, ^ 0 prior art ratios are uniformly distributed. The particles in the amp & substance The polymer here can also be a polymer dispersion liquid, such as a coating ... and the occurrence thereof can be performed by a conventional mixing method. / mouth

The polymer composition containing = nanoparticle is also more suitable for surface coating. This method allows the surface or material to be protected underneath the coated surface, such as resistance to ultraviolet radiation. [Embodiment] The following examples will explain the present invention in a more detailed manner, but without limitation. Example 1. Synthesis of a macromolecular surfactant. The first step includes methyl dodecyl acrylate (methyl lauryl acrylate, · LMA) and methacrylate (DMAEMA) random copolymers. The molecular weight can be controlled by the addition of mercaptoethanol (mercaptoethanol). The copolymer obtained in this way can be modified by using 3-propane sultone to provide a saturated group. To this end, 7 g of fLMA and DMAEMA (in an amount in accordance with Table 1 below) were initially added to 12 g of toluene, and 70 under argon. At 0 o'clock, the addition reaction of 0 33 g of AIBN in 1 ml of a toluene solution was used for the initial reaction, and then a radical polymerization reaction was performed. The chain extension reaction can be controlled here by the addition of 2-mercaptoethanol (see Table 1 of 98510.doc -14- 200540191). The crude polymer is washed, freeze-dried and then reacted with 1,3-propane lutein lactone, such as V. Butun, C. E. Bennett, M. Vamvakaki, A.B. Lowe, N.C. Billingham, S. R Armes, J. Mater Chem., 1997, 7 (9), 1693-1695. The properties of the resulting polymer are described in Table 1. Table 1: Amount of monomers used and properties of the resulting polymer DMAEMA [g] DMAEMA [mol%] 1-M-based-ethanol [g] Mn [g / mol] Mw [g / mol] sugar beet in the polymer Test group [mol%] 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

Example 2: Precipitation of ZnO particles The following methods were used to precipitate ZnO particles: 1 · In each case, 0 · 4 g of Zn (Ac0) 2 * 2H20 in 1 · 1 g of water '(emulsion 1) and 0 · An inverse emulsion of 15 g of NaOH in 1.35 g of water (emulsion 2) can be prepared using ultrasound. Emulsion 1 and Emulsion 2 each contained 150 mg of a random copolymer El-E5 (Table 1). 2. Ultrasonic treatment was performed on the mixture of Emulsion 1 and Emulsion 2, followed by drying. 3. Purification of sodium acetate can use water to wash the resulting solid. 4. Dry and re-dispers the functionalized powder by emulsifying it on the surface and stirring in toluene. FT-IR spectrometer and X-ray diffraction show the formation of ZnO. Furthermore, no reflection of sodium acetate was seen in the X-ray picture. 98510.doc -15- 200540191 Therefore, a product can be obtained from Example 2 including a synthetic macromolecular surfactant and an oxide particle. Copolymer diameter [nm] (light scattering) Variation [nm] Proportion of ZnO (wt-%) E1 37 30 30.3 E2 66 53 30.5 E3 50 41 32 Comparative Example 2a: Use of Emulsifier ABIL EM 90® as described in Example 2 In this method, a commercially available emulsifier ABIL EM 90® (cetyl dimethicone copolyol, Goldschmidt) was used instead of the random copolymer of Example 1 to obtain a stable emulsion. The resulting particle diameter is between 500 and 4000 nm. Example 3: Precipitation of silica

The precipitation of Si02 particles can be carried out according to the following methods: 1. In each case, the inverse emulsion of the aqueous solution of Na2Si03 (emulsion 1) and H2S04 (emulsion 2) can be prepared by ultrasound (concentrations in accordance with Table 2). 2. Ultrasonic treatment was performed on the mixture of Emulsion 1 and Emulsion 2, followed by drying. 3. Purification of the product solids by washing with water. 4. Dry and re-spread the obtained powder. FT-IR spectrum and X-ray diffraction showed the formation of SiO2 and no sodium silicate was present. Therefore, a product can be obtained from this step, which includes a synthetic macromolecular surfactant and silica particles. Table 2: Emulsion composition and product properties 98510.doc -16- 200540191 experimental emulsion El emulsion E2 nanoparticle particle size inm] standard deviation inm] 3a 0.15 g polymer surfactant (E4); 11.7 g toluene; 1.25 g water; 1.25 g Na2Si03 0.15 g polymer surfactant (E4); ll. 7 g toluene 2.2 g water 0.3 g H2SO4 59 19 3b 0.15 g polymer surfactant (E4); ll. 7 g toluene; 1.25 g water; 1.00 g Na2Si03 0.15 g polymer surfactant (E4); 11.7 g toluene; 1.76 g water; 0.24 g H2SO4 40 15 3c 0.15 g polymer surfactant (E4); 11.7 g toluene; 0.75 g water; 0.75 g Na2Si03 0.15 g polymer surfactant (E4); 11.7 g toluene; 1.32 g water 0.18 g H2SO4 50 20 3d 0.15 g polymer surfactant (E5); 11.7 g toluene; 0.75 g water; 0.75 g Na2SiO3 0.15 g polymerization Surfactant (E5); 11.7g toluene; 1.32 g water; 0.18 g H2SO4 43 15 3e 0.15 g polymer surfactant (E5); 11.7 g toluene; 1.25 g water; 1.25 g Na2Si03 0.15 g polymer surfactant (E5); 11.7g toluene; 2.2 g water; 0.3 g H2S04 53 12 3f 0.15 g polymer interfacial activity (E5); 11.7 g toluene; 1.0 g water; 1.0 g Na2SiO3 0.15 g polymer surfactant (E5); 11.7 g toluene; 1.76 g water; 0.24 g H2S04 93 30 Example 4: Polymer composition from Example 2 The dispersion of the particles obtained in -E1 in PMMA paint can be prepared by mixing and placed on a glass substrate and dried. After drying, the ZnO content was 10% by weight. The film showed a slight blur in nature, and the impression can be confirmed by measurement with 98510.doc -17- 200540191 using a UV-VIS spectrometer. The sample shows the following absorption values, which depend on the thickness of the thin layer (showing the percentage of incident light during transmission). Thin layer thickness UV-A (350 nm) VIS (400 nm) 1 · 2 μm 3 5% 4% 1.6 μηι 40% 5% 2.2 μπι 45% 7% Compare:

(ZηΟ (Special Pure, Merck) in PMMA paint, as shown above) 2 μm 64% 46%

98510.doc 18-

Claims (1)

200540191 10. Scope of patent application: 1. The use of a random copolymer as an emulsifier. The copolymer contains at least one structural unit containing a hydrophobic group and at least one structural unit containing a hydrophilic group. 2. The use as claimed in claim 1, characterized in that the copolymer can be used as an emulsifier in synthesizing nano particles from a self-emulsifying liquid. 3. The use as claimed in claim 1 or 2, characterized in that the weight ratio of the structural unit containing a hydrophobic group and the structural unit containing a hydrophilic group in the random copolymer ranges from 1: 2 to 500 ... 1, It is preferably in a range from 1: 1 to 100: 1, and particularly preferably in a range from 7: 3 to 10: 1. 4. The use as claimed in claim 1 or 2, characterized in that the weight average molecular weight range of the random copolymer is from ^ = 1OO00 to looo'ooo g / m0. The preferred range is from 1500 to 10.00, 〇g / mol, and particularly preferably in the range from 2000 to 100 g / mo. 5. The use as claimed in claim 1 or 2, characterized in that the copolymer is as shown in formula 丨: Where X and Y are conventional nonionic or ionic monomer groups, and R1 represents hydrogen or a hydrophobic side group, preferably selected from branched or unbranched alkanes having at least 4 carbon atoms Group, in which one or more (preferably all) fluorene atoms may be substituted by fluorine atoms, and R2 represents a hydrophilic side group, which preferably has a phosphonate, sulfonate, polyalcohol or poly Ether group, 98510.doc 200540191 and its -X-R1 and -Υ-R2 can each have many different meanings in one molecule. 6. The use as claimed in claim 5, characterized in that X and γ represent _〇_, -c (K))-0-, -C (= 0) _NH_,-(CH2) n_, phenylene ( phenyiene) or sigma. 7. The use as claimed in claim 5, characterized in that at least one of the structural units contains at least one quaternary nitrogen atom, and R2 thereof preferably represents a supporter (cH2) n_s03. A side group or a · ( CfUCN ^ CHAHCmPO32-Side group, in which the table represents an integer ranging from 1 to 30, preferably ranging from 1 to 6, particularly preferably 2 and n represents an integer ranging from 1 to 30, preferably ranging from丨 to 8, particularly preferably 3. 8. The use of claim 1 or 2 is characterized in that at least one structural unit is a polymer or polymer, preferably a macromonomer, of which polyethers Polyolefins and polyacrylates are particularly good macromolecular monomers. 9. A method for manufacturing polymer-modified nano particles, characterized in that In step a), an inverse emulsion or a melt containing—or a plurality of nanoparticle water-soluble precursors—is prepared with the aid of a random copolymer comprising at least one monomer containing a hydrophobic group and At least one hydrophilic group-containing monomer 'and in step b), particles are prepared. 10. The method of claim 9, characterized in that granules are produced by reacting the precursor in step b) or by cooling the melt. 11. The method of item 10 in month a, characterized in that the precursor reacts with an acid, a test solution, a reducing agent or an oxidant. 12. The method of claim 11: reacting with an acid or lye, characterized by using sodium silicate as a precursor to obtain silicon dioxide. 98510.doc 200540191 13. The method according to claim 11, characterized by using at least one soluble compound of a precious metal, preferably silver nitrate, and reacting with a reducing agent, preferably citric acid, to obtain the metal. 14. The method according to claim 11, characterized in that a soluble metal compound is used, preferably a soluble Pb, Cd4Zn compound, and hydrogen sulfide are reacted to obtain the metal sulfide. 15. A method according to claim u, characterized in that a soluble metal compound, such as preferably calcium chloride, is reacted with carbon dioxide to obtain metal carbonates of nano particles. 16. The method according to any one of claims 9 to 5, characterized in that the emulsion droplet size in the emulsion ranges from 5 to 500 nm, preferably from 10 to 20 nm. 17. The method according to any one of claims 9 to 15, characterized in that a second emulsion containing a reactant as a precursor and in an emulsified form is mixed in step ... with the precursor emulsion from step a) . The method of claim 17 is characterized in that the two emulsions are mixed with each other by the action of ultrasound. 19. The method according to any one of claims 9 to 15, characterized in that one of the water-soluble metal compounds is preferably 'Shi Xi, Shi, Ming' Chromium, Lu, Ci, Qin, Iron, Ji or Wuji. Or more precursors' and these precursors are preferably reacted with an acid or lye. 20. The method according to any one of claims 9 to 15, characterized in that a co-emulsification can be used, and a nonionic surfactant is preferred. 98510.doc 200540191 7. Designated Representative Map: (1) The designated representative map in this case is: (none). (II) Simple explanation of the component symbols in this representative drawing. 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (none) 98510.doc