TWI361196B - Preparations of polymeric microspheres with multiple functional groups and with metallic nanoparticles deposited thereon - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for preparing a plurality of functional group-based polymer microspheres, and particularly to a method for preparing polymer microspheres having both an anionic group and a cationic group. . The present invention also provides a method for producing a polymer microsphere to which metal nanoparticles are attached. The prior art nano composite materials have a wide range of aspects, and the preparation methods thereof are also diverse, and can be roughly classified into four categories: metal nanoparticles and macromolecules are directly blended; 1i polymer nano-particles are formed in the polymer matrix; The monomer is polymerized into a polymer in the presence of metal nanoparticles; and the metal nanoparticles are produced together with the polymer. The most important method for preparing nanocomposite materials is to effectively control the size of the metal nanoparticle itself to ensure that at least one dimension of the composite phase in the composite is within the nanometer size, and then consider controlling the rice. The case of particle aggregation. When preparing nanoparticles by chemical reduction, it is usually used as an interfacial activity agent, a metal salt, a reducing agent, and a reducing agent. There are many types such as hydrazine, sodium borohydride, hydrogen, etc. The surfactant is first dissolved in the liquid phase, the metal ions are added to the stirring, and finally the reducing agent is added to reduce the metal ions to the nanoparticles. U.S. Patent No. 6,737,486 discloses a polymerization process which involves the use of an organohalide compound as a starter in a reactive ice-cold (Ilving p〇lymerizati〇n) system to effect methylation of methyl methacrylate. It can clearly control the structure and molecular weight of the polymer. Adding organic halogen as a starter in the poly 5 1361196 system, it requires more steps for purification due to its toxicity, and it is limited in the application of biomedicine. U.S. Patent No. 7,112,369 discloses the use of styrene as a monomer, the addition of divinyl benzene for polymerization, and the use of maleic anhydride and diisopropyl azocarboxylate. The surface modification is carried out to form a polymer microsphere having a vinyl group on the surface, and a metal carboxylate is further added to prepare a metal-polymer composite. In this patented method, since there is no emulsifier in the polymerization process, it is necessary to use two or even three steps to reach the polymer microparticle having a vinyl surface.

Chungui Tian, Enbo Wang, Lei Gao, Zhenhui Kang Chao Zhang, Chunlei Wang, and Yang Lan S£A Precursor

Route for the Preparation of Metal

Large Scale, ', Chemistry Letters Vol. 35, No. 7 (2〇〇6), published a polystyrene microsphere as a seed, modified by polyethyleneimine surface as a ruthenium drive, reacted with silver nitrate solution , after heating to i 〇〇 it, you can get

Ag^PS composite microspheres. The method of this paper requires a higher reaction temperature to synthesize ruthenium/metal composite microspheres. The application discloses a method for the H-composite material, which may be a benzene-ethylation--polymer, and may also be incorporated into the surface of the patent of the applicant's patent application No. 2〇〇8〇丨〇5〇. Polystyrene complex with nano metal particles

6 The internal order is incorporated into the present specification by reference. SUMMARY OF THE INVENTION The main object of the present invention is to synthesize a colloidal particle having two or more functional groups, and further modify the surface of the particle with a metal to make it have various special functions such as chemical reaction catalytic activity, and biomolecule binding f- Photopolymer colloidal particles with optical response to optical absorption characteristics. In the emulsion-free emulsion polymerization method (Emuisifier_free p〇lymerizati〇n) system, polymer colloidal particles with two or more different functional groups on the surface are prepared, which can be stably suspended in an aqueous solution. The metal nanoparticles are precipitated under the conditions of adding a reducing agent, and a good dispersion effect is achieved. The present invention includes, but is not limited to, the following preferred embodiments: L. A method for preparing a complex number of functional polymer microspheres comprising an initiator having an anionic group and a starting group having a cationic group Free radically polymerizing an unsaturated vinyl monomer and a selective unsaturated vinyl copolymerizable monomer in the presence of an agent, characterized by copolymerizing the unsaturated vinyl monomer and optionally the unsaturated vinyl group The monomer is mixed in a bath to dissolve the initiator having an anionic group and an initiator having a cationic group or an aqueous solution having an anion and a cationic group as an initiator, and The radical polymerization of the obtained mixture is carried out by adding an emulsifier to obtain a colloidal dispersion of polymer microspheres having both the anionic group and the cationic group. 2. The method according to the above item 1, wherein the method does not use the copolymerized monomer, and then the radical polymerization forms a homopolymer 1361196 of the unsaturated vinyl monomer. 3. The method of item 2 above, wherein the unsaturated vinyl monomer is a stupid ethylene monomer, and the free radical polymerization then forms a styrene homopolymer. 4. The method according to the above item 1, wherein the method uses the copolymerized monomer, and then the radical polymerization forms a copolymer of the unsaturated vinyl carbody and the unsaturated vinyl copolymerizable monomer, wherein The copolymerized monomer is acrylic acid, methacrylic acid, decyl acrylate or decyl methacrylate monomer. The method according to the above item 1, wherein the initiator having an anionic group is the persulfate initiator. 6. The method of the above 5, wherein the persulfate initiator is an alkali metal persulfate. 7. The method according to the above item 1 or 3, wherein the cationic group-containing initiator is an azo compound initiator. 8. The method of item 7, wherein the azo compound initiator has the following chemical formula:

® XC-CRiR2-N=N-CR, R2-CX The center and the ruler 2 are independently C1_C3 alkyl; and X is ξΝ, =ΝΗΝΗ2 =NHNH(CH2)nC〇〇H, =ONHC(CH2OH)3 , =〇NH(CH2)n〇Hj =NHNC4H8, where n is an integer from 1-3. 9. The method according to the above item 8, wherein the azo compound initiator is 2,2,-azobis(2-mercaptopropene) dihydrochloride, 2,2,-azobis[ν_( 2 carboxyethyl)-2-mercaptopropane hydrate, < 2,2,-azobis(1iminopyridinium-2-ethylpropane) dihydrochloride. The method of the above item 1, wherein the azo compound initiator is 2,2,-azobis(2-p-propionamidine) dihydrochloride. 11. The method according to the above item 1, wherein the volume ratio of all monomers to the aqueous solution is 1:5 to 1:19 and the unsaturated vinyl monomer = and the selectivity of the unsaturated ethyl group under stirring The dilute-copolymerized monomer is mixed in the aqueous solution in which the initiator having an anionic group and the initiator having a cationic group are dissolved. Wherein the aqueous solution has the initiator having an anionic group having a cationic group

12. The method of the above item u, wherein the initiator of the subtype group has a ratio of 1:5 to 5:1 to the ear. 13. The method of item U above, wherein a temperature of from 40 to 80 ° C is carried out. 14. The method according to the above item u, i 〆, an average particle diameter of 200 to 1500 nm. The radical polymerization reaction obtained in the middle of the molecular microspheres has a method of the above-mentioned 11th § & s, soil term, wherein the obtained polymer microspheres have

-Zeta surface potential of -50 to 50 mV. A method for preparing a polymer microsphere to which a surface of a nano metal particle is attached, comprising a colloidal dispersion of a polymer microsphere prepared by the method according to any one of the preceding claims 1 to 14 The water solution containing the noble metal ions is contacted, and the metal ions are reduced to an elemental state and attached to the surface of the polymer microspheres. 17: The method of claim 16, wherein the aqueous solution containing the noble metal ion is an aqueous solution containing gold (AU), silver (AS), palladium (Pd), platinum (Pt) or ruthenium (RU) ions. 9 As in the method of item 17 above, the aqueous solution containing noble metal ions is an aqueous solution containing gold ions or ions. Ϊ9. According to the above item 16, the itch ★ 'method', the contact system is carried out at 50-I001C; m degrees. The advantages of the invention are as follows: the same (official) 1 step can be used to synthesize the average particle size And the surface has a variety of non-two-energy polymer steroid particles, simplifying the synthesis of tedious steps. Zi, Tong Yucheng's S-energy colloidal particles are amphoteric polymer colloidal particles I 3 have cationic and anionic functions The end group is obtained, and the surface potential of the surface functional groups of the microspheres and the average particle diameter of the spheres can be controlled to achieve special applications by using a ratio of the initiator, when 庠π _ ^ value Μ n Requirements: surface potential and particle size of the microspheres, in the k () door knife colloidal particles by surface functional groups, can be stably dispersed in aqueous solution 'has a good dispersion effect. (d) with no emulsifier 澍 human molecular colloid Pull 7 'mouth to I to prepare two different functional groups can avoid the trouble of the original surfactant removal, tin is in the (four) particle table U from the field containing metal. The earth group does not add a reducing agent to sink Analysis of the (5) functional machine group can be used for me, Rota, work "^ with It belongs to the smashing rice... Η group, which can be reduced separately on the microspheres, forming multi-metal particles composite two: the amount of sputum group can be regulated' Therefore, the proportion of all kinds of reduced water particles can be reduced Regulation: m such as s 2) can be: a reducing group, producing nanoparticulates, 4 using another group such as marriage 2 or -COOH and metal nanometer 1361196 grain coordination to strengthen nanoparticle in micro Adhesiveness of the surface of the sphere. Embodiments The present invention discloses a method for preparing a plurality of initiators for preparing a polymer to prepare a seed=ball. In particular, it relates to amphoteric molecule having two or more functional groups on the surface. The method of microspheres, — more specifically, the surface of the molecular microspheres, which is used to reduce metal ions, so that the surface of the microspheres has metal

particle. The microspheres prepared by the method of the invention are formed by a surfactant-free emulsion polymerization, in which a plurality of initiators are involved in the reaction, and a two-step high-knife is obtained, which has both anionic and cationic functional groups. In the case of I and the core, it is not necessary to add a surfactant, and the function of the basic body charge can be utilized, so that the polymer microspheres have good dispersibility and form a colloidal dispersion. And the group can play the role of a reducing agent, so that the metal ions can be mineralized on the surface of the microspheres by the size of the nanoparticles. The invention is an emulsifier-free emulsion polymerization method, and styrene, acrylic acid, methacrylic acid a monomer of methyl acrylate, decyl methacrylate or acrylonitrile is added to a water-soluble anionic initiator such as ammonium persulfate (APS) or potassium persulfate (p〇) which simultaneously dissolves the group hydrazine. Tassium persulfate; KPS) or sodium persulfate (SPS) and group 2 of water-soluble cationic azo-type initiator in aqueous solution, free radical polymerization under stirring, to prepare a surface with complex functions Amphoteric polymer microsphere particles. The cationic azo type initiator is, for example, manufactured by Nippon Shokuhin Co., Ltd.: 1361196 2,2·-azobis(2-mercaptopropene) dihydrochloride (V-50) (2,2'- Azobis(2-methylpropionamidine)dihydrochloride (V-50))

HN CH3 CH3 NH

^C—G—N=N—C—C( 2HCI H2n CH3 CH3 NH2 2,2·-azobis[N-(2-carboxyethyl)-2-mercaptopropene hydrate (VA-057) (2,2'-Azobis[N-(2-carboxyethyl)-2-methy lpropionamidine]hydrate (VA-05 7))

NH CH3 CH3NH 4H20 ^C—C—N=N—C—HOOCH2CH2CHN CH3 ch3 nhch2ch2cooh 2,2′-azobis(1-imino-1-pyrrolidinyl-2-ethylpropane) dihydrochloride ( VA-067) (2,2'-Azobis(l-imino-l-pynOlidino-2-ethylpropane)dihydrochloride (VA-067))

The method of the invention eliminates the trouble of removing the surfactant from the general emulsion polymerization, and is also reactive on the surface such as sulfate group (-S04), amine group (-NH), imine (=NH), cyanide. Base (-CN), imidazole, acid-lowering group (COOH) or hydroxyl (one OH), etc., in addition to stable dispersion of micro 12 1361196 balls, can further reduce metal ions, so that micro The further metallization of the ball makes the application more extensive. More particularly, a plurality of initiator systems have a plurality of functional groups on the surface of the microspheres, which can be controlled by the ratio of the starting dose to the type 'altering the ratio of functional groups on the surface of the microspheres, surface potential and average particle size, etc. Therefore, 'the metal nanoparticles reduced on the surface of the microspheres can be two or more' forming a multi-metal or alloy structure and the ratio can be regulated. The invention may be further understood by the following examples, which are intended to be illustrative only and not to limit the scope of the invention. Comparative Example 1 5 ml of styrene monomer was mixed with 54 ml of a 3.4 χ10·3 Μper potassium persulfate (kps) aqueous solution, and the obtained mixture was placed at 75. The oil of hydrazine was reacted under stirring for 24 hours, thereby forming a dispersion of polystyrene microspheres. Take 2 ml of the dispersion of the above-mentioned prepared polystyrene microspheres, and 20 ml of HAuCl 4 aqueous solution (gold ion concentration 10000 PPM), respectively, and heat them to 80 C ', and mix the two (rotation speed 3 〇〇rPIV1) for 5 minutes. . After the reaction, the polystyrene microspheres are separated by filtration and washed with deionized water, and then dried at a temperature of 冋 to obtain a polystyrene composite material having metal nanoparticles adhered on the surface thereof, and an anion-ionic initiator is simply used. The particle I of the synthesized polymer microspheres is 'but after reacting with the metal salt aqueous solution, the metal particles precipitated on the surface have agglomerated and become large, and are easily peeled off as shown in Fig. 1a. 13 1361196 Comparative Example 2 In addition to the temperature of the dispersion of the anionic initiator and the polystyrene microspheres substituted with the cationic initiator V-500 and the temperature of the aqueous solution of H AuC14 were respectively heated to 80 ° C, 'repeated' The procedure of Comparative Example 1. The single-use cationic initiator has a uniform particle size of the polymer microspheres, and a high reaction temperature is required to mix with the metal salt aqueous solution, and the particle size of the metal particles precipitated on the surface is not uniform, as shown in FIG. b is shown.

Example 1 5 ml of stupid ethylene monomer was mixed with 54 ml of an aqueous solution of a starting agent having a total concentration of 3 · 4 χ 1 〇 - 3 M, and the obtained mixture was placed in a 75 C oil bath for stirring. The reaction was carried out for 24 hours, thereby forming a dispersion of polystyrene microspheres. Table 1 lists the molar ratios of the cationic initiator (V-50) and the anionic initiator (Kps) used in the examples, and the average of the styrene microspheres obtained by changing the molar ratio. Diameter and Zeta surface potential. Table 1 V-50: KPS (M) Average particle size (nrn) Zeta surface potential (mv) 0:1 230 -48 1:2 1105 -35 1:3 1180 -32 1:1 —— 867 5-— 3 :1 1138 34 2:1 1231 15 1:0 1000 53 14 1361196 The average particle diameter and the Zeta surface potential in Table 1 were measured by interface potential analysis. It can be seen from the different initiator ratios that different = stupid ethylene microspheres particle size and surface potential can be obtained. As the ratio of anionic initiators increases, the negative charge on the surface of the styrene microspheres will follow. Increase: Conversely 'increasing the proportion of cationic initiators, the positive charge on the surface of % polystyrene microspheres will increase.

The surface functional groups of the polystyrene microspheres were identified by infrared spectrometer (IR). The surface of the polystyrene ethylene microspheres was confirmed by IR to have sulfate and amine functional groups. As shown in Fig. 2, the absorption peak of polystyrene is 3〇4〇_2_cm, and there are =CH, 1625_1575, 1525_1475(10) on the benzene ring, which is the characteristic absorption peak of the stupid ring '900-700 cm-i. Single substitution on the benzene ring, bribe -137 (10)-丨 is the s=〇 symmetric extension absorption peak, 69〇επΓΐ&s_〇 characteristic extension absorption peak, 3400-350. Cm丨 is an amine-based characteristic absorption peak, and 164〇_156〇--1 is a N H characteristic extension absorption peak. The above characteristic absorption peaks are the same as those in the general literature. This proves that the microsphere surface does have a plurality of functional groups. Example 2 The granules of the polystyrene U spheres having the average particle diameter of 丨138 nm prepared in the above Example 1 were 20 liters and the aqueous solution of HAuCl 4 (gold ionicity 1 〇〇〇〇 PPM) 20 ml was heated separately. To 80 C 'Add the two to the mixed (10) speed 3 〇〇 RPM) reaction 5 minutes ^ After the reaction, the polystyrene microspheres are separated and washed with deionized water, then dried at high temperature. A polystyrene composite having metal nanoparticles attached to the surface. Polystyrene with a bifunctional group on the surface 15 1361196 Polymer microspheres reacted with aqueous HAuCU solution to obtain uniform precipitation of gold nanoparticles on the surface of the microspheres, as shown in Figures 3a and 3b and particles of gold nanoparticles. The diameter is less than 10 nm. Example 3 The procedure of Comparative Example 2 was repeated except that the aqueous solution of HAuCi4 was replaced with an aqueous solution of PdCh (800 Ppm). After the polyfunctional ethylene polymer microspheres having a bifunctional group are reacted with an aqueous solution of PdC12, the palladium nanoparticles can be uniformly precipitated on the surface of the microspheres as shown in Figs. 4a and 4b. BRIEF DESCRIPTION OF THE DRAWINGS Figure U shows a TEM photograph of polystyrene microspheres to which gold nanoparticles are attached to the surface prepared by the control. Fig. 1b shows a TEM photograph of the polystyrene microspheres to which the gold nanoparticles are adhered on the surface prepared in Comparative Example 2. Figure 2 shows an embodiment of the invention! #FT-IR spectrum of the prepared polystyrene microspheres. Fig. 3J3b shows a TEM photograph of a polystyrene microsphere having a gold nanoparticle adhered to the surface prepared in Example 2 of the present invention, wherein Fig. 33 is magnified 30,000 times and Fig. 3b is enlarged 60,000 times. 4a and 4b show TEM photographs of polystyrene microspheres to which nanoparticle particles are attached, which are prepared in Example 3 of the present invention, wherein the figure is 30,000 times magnification and Fig. 4b is 60,000 times magnification.

Claims (1)

1361196 X. Patent application scope: 1. A method for preparing a plurality of functional group-based polymer microspheres, comprising: in the presence of an initiator having a ionic group and a starter having a cationic group, free Polymerized unsaturated vinyl monomer and a selective unsaturated vinyl copolymerizable monomer, characterized by mixing the unsaturated vinyl monomer and optionally the unsaturated vinyl copolymer monomer in a solution An aqueous solution having an anionic group-containing initiator and a cationic group-containing initiator or an initiator having both an anionic group and a cationic group, and obtained by adding an emulsifier The mixture is subjected to a radical polymerization to obtain a colloidal dispersion of polymer microspheres having both the anionic group and the cationic group. 2. The method of claim 1, wherein the method does not use the conjugate κ. The monomer, then the free radical polymerization forms a homopolymer of the unsaturated vinyl monomer. 3. The method of claim 2, wherein the unsaturated vinyl monomer is a stupid ethylene monomer, and the free radical polymerization forms a stupid ethylene homopolymer. 4. The method of claim 2, wherein the method uses the copolymerized monomer, and the radical polymerization forms a copolymer of the unsaturated vinyl monomer and the unsaturated vinyl copolymerizable monomer, Wherein the copolymerized monomer is acrylic acid, methacrylic acid, decyl acrylate or methyl methacrylate monomer. 5. The method of claim 1 or 3, wherein the initiator having an anionic group is the persulfate initiator. 17 1361196 6. The method of claim 5, wherein the persulfate initiator is a persulfate metal salt. 7. The method of claim 3, wherein the initiator having a cationic group is an azo compound initiator. 8. The method of claim 7, wherein the azo compound initiator has the following chemical formula: ° XC-CRiR2-N=N-CR|R2-CX wherein 1 and 1 are independently (:^(b) Alkyl; and =NHNH(CH2)nC〇OH, =〇NHC(CH2OH)3, =〇NH(CH2)n〇H -NHNC4H8 ' wherein η is an integer of ι_3. 9. The method of claim 8, wherein the azo compound initiator is 2, and polyazobis(2-methylpropane) diterpene [N-(2-retinoethyl)·2 _Methylpropionate hydrate, or 2,2,-azobis(1 -imino-1pyrrolidinyl-2-ethylpropane) dihydrochloride. The method of claim Μ, wherein the azo compound initiator is 2,2'-azobis(2-methylpropanol) dihydrochloride. 11·If you apply for a patent scope帛! The method of the invention wherein the ratio of all the single liquids is 1:5 to 1:19 and the unsaturated vinyl monomer and the optional non-tetravinyl copolymerized monomer are mixed in the case of mixing The aqueous solution of the initiator having an anionic group and an initiator having a cationic group is dissolved. Wherein the aqueous solution has the group having a % ionic group as described in the method of claim 11 of the invention, wherein the initiator having an anionic group has a molar ratio of the initiator to the starting agent of 1. 5 to 5:1. 18 1361196 13 · The method of the nth item of the patent scope of the application, the radical polymerization in the deer + human body is "at 40-80. (: a temperature is carried out. 14) as claimed in the nth item The method, throwing a gentleman w, the obtained polymer microspheres have an average particle diameter of 200-1500 nm. 15. As claimed in the nth item of the patent range ^ + β wherein the obtained polymer microspheres have - Zeta surface potential of 50 to 50 mV. - A method for preparing a polymer microsphere to which a surface of a nano metal particle is attached, comprising a colloidal dispersion of the polymer microsphere prepared by the method according to any one of the preceding claims 1 to 5 The aqueous solution containing the noble metal ions is contacted, and then the ions of the genus I. are immersed in the elemental state and attached to the surface of the polymer microsphere. 17. The method of claim 16, wherein the aqueous solution containing the noble metal ion is an aqueous solution containing gold (Au), silver (Ag), palladium (Pd), platinum (Pt) or (Ru) ions. The method of claim 17, wherein the aqueous solution containing the noble metal ion is an aqueous solution containing gold ions or palladium ions. 19. The method of claim 16, wherein the contact is at 5 〇, w. A temperature of 〇 is carried out. 0