CN109422841B - Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material and preparation method thereof - Google Patents

Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material and preparation method thereof Download PDF

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CN109422841B
CN109422841B CN201710764723.2A CN201710764723A CN109422841B CN 109422841 B CN109422841 B CN 109422841B CN 201710764723 A CN201710764723 A CN 201710764723A CN 109422841 B CN109422841 B CN 109422841B
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郑俊萍
陈雨
丁永
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Tianjin University
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract

The invention discloses a polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, St and VDAC are used as comonomers, an initiator is added to prepare a pre-emulsion, wherein the initiator and water form a water phase, and the VDAC and St are used as oil phases; step 2, taking VDAC as a dispersing agent, and adding nano BaTiO3Pre-dispersed in an aqueous solution to obtain BaTiO3Adding VDAC and initiator into the nano-ion dispersion solution to form an emulsion polymerization system, wherein the initiator and the nano-BaTiO3And water to form an aqueous phase, VDAC, St as an oil phase; step 3, heating the emulsion polymerization system to the initiation temperature, dropwise adding the pre-emulsion into the emulsion polymerization system, stirring, and carrying out emulsion polymerization to obtain P (St-co-VDAC)/BaTiO3A copolymer emulsion. In the copolymer emulsion and the copolymer microsphere powder, the nano barium titanate is dispersed in a nano level, the dispersion state is uniform and stable, and the problem of serious agglomeration of nano particles in the polystyrene-barium titanate composite material is solved.

Description

Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a Polystyrene (PS) composite material, which particularly takes PS as a matrix and uses cationic monomers of vinyl benzyl dimethyl dodecyl ammonium chloride (VDAC) and nano barium titanate (BaTiO)3) Electrostatic interaction and steric hindrance interaction are generated between the nano barium titanate particles and the nano barium titanate particles, so that the dispersion of the nano barium titanate is promoted, and the PS-based nano composite material is prepared.
Background
The polymer-based nano composite material is a composite material which takes a polymer as a matrix and has the size of a disperse phase smaller than 100nm in at least one dimension. The polymer-based nano composite material integrates the advantages of the polymer and the nano material, realizes the optimization and complementation of the performance, and has wide research and application prospects. However, the nanoparticles have small particle size, large specific surface area, large surface energy and strong surface effect, so that the nanoparticles are easy to agglomerate and have poor dispersibility. Most of the reported methods for modifying the surface of the nano particle have complex operation and complicated steps, and bring inconvenience to the preparation of the polymer-based nano composite material.
Disclosure of Invention
The invention aims to solve the technical defects in the prior art, uses Polystyrene (PS) as a base material, adopts an emulsion polymerization method to prepare a PS-based nano composite material, and aims to use a simple, efficient and environment-friendly method to prepare BaTiO3The nano particles are dispersed in the polymer matrix to prepare the high-dispersion nano composite material. The invention synthesizes styrene type cationic monomer vinyl benzyl dimethyl dodecyl ammonium chloride (VDAC) through quaternization. The cationic monomer can be used as a dispersing agent to realize uniform dispersion of nanoparticles in a water phase and a polymer phase, and can also be used as a polymerizable emulsifier to participate in an emulsion polymerization process. On one hand, the cationic monomer disperses and stabilizes the nano particles through electrostatic interaction and steric hindrance interaction, the dispersion process is carried out in water, the operation is simple, and the nano-level dispersion effect can be realized without carrying out complicated and lengthy grafting modification on the nano particles; on the other hand, the cationic monomer is used as a polymerizable emulsifier, can participate in the reaction at the later stage of the polymerization reaction, avoids introducing new components into the system, can obtain stable polymeric microsphere emulsion without demulsification after the emulsion reaction, and is a novel green and environment-friendly emulsifier. The method can be used for preparing high-dispersion P (St-co-VDAC)/BaTiO3A nanocomposite material.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the preparation method of the polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material comprises the following steps:
step 1, St and VDAC are used as comonomers, an initiator is added to prepare a pre-emulsion, wherein the initiator and water form a water phase, and the VDAC and St are used as oil phases;
step 2, taking VDAC as a dispersing agent, and adding nano BaTiO3Pre-dispersed in an aqueous solution to obtain BaTiO3Adding St and initiator into the nano-ion dispersion liquid to form an emulsion polymerization system, wherein the initiator and the nano-BaTiO3And water to form an aqueous phase, VDAC, St as an oil phase;
step 3, heating the emulsion polymerization system to the initiation temperature, dropwise adding the pre-emulsion into the emulsion polymerization system, stirring, and carrying out emulsion polymerization to obtain P (St-co-VDAC)/BaTiO3A copolymer emulsion; wherein:
the mass ratio of the water phase to the oil phase in the step 1 is (4-8): 1, preferably 5:1, the amount of St monomer is 90.0-99.9 wt%, preferably 92-95 wt%, and the amount of VDAC is 0.1-10.0 wt%, preferably 5-8 wt%, of the mass of the oil phase; wherein the amount of initiator is 0.1-1.0 wt.%, preferably 0.2-0.5 wt.%, based on the sum of the two monomers.
The mass ratio of the water phase to the oil phase in the step 2 is (4-8): 1, preferably 5:1, the St monomer is used in an amount of 90.0-99.9 wt%, preferably 92-95 wt%, and the VDAC is used in an amount of 0.1-10.0 wt%, preferably 5-8 wt%, based on the mass of the oil phase; nano BaTiO3Is 0.1-5.0 wt%, preferably 2-3 wt% of the oil phase, and the amount of the initiator is 0.1-1.0 wt%, preferably 0.2-0.5 wt% of the sum of the two monomers;
the mass ratio of St in the step 1 to St in the step 2 is (40-50): (50-60), wherein the mass ratio of the VDAC in the step 1 to the VDAC in the step 2 is (40-50): (50-60);
wherein: st is styrene, VDAC vinylbenzyldimethyldodecylammonium chloride, P (St-co-VDAC)/BaTiO3Is a polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material.
Preferably, the mass ratio of St in the step 1 to the step 2 is 1:1, the mass ratio of VDAC in the step 1 to the step 2 is 1:1, the dropping time of the pre-emulsion in the step 3 is 1 to 1.5 hours, and the emulsion polymerization time in the step 3 is 3 to 3.5 hours.
Preferably, the P (St-co-VDAC)/BaTiO obtained in the step 33Copolymer emulsionFiltering, washing and drying to obtain copolymer powder.
Preferably, in the step 1, the VDAC and the initiator are dissolved in deionized water, and then monomer styrene is added to prepare a pre-emulsion, wherein the mass volume ratio of the VDAC to the deionized water is (10-14) g: 1L, in the step 2, firstly, BaTiO3Dispersing nano particles and a cationic monomer VDAC in deionized water, and performing ultrasonic dispersion by using an ultrasonic cell crusher to obtain an ultrasonic dispersion liquid, wherein the mass volume ratio of the VDAC to the deionized water is (10-14) g: 1L of the compound.
Preferably, the mass-to-volume ratio of VDAC to deionized water in step 1 and step 2 is 12 g: 1L of the compound.
Preferably, the initiator is Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), Benzoyl Peroxide (BPO) or potassium persulfate (KPS).
In another aspect of the invention, the invention also comprises P (St-co-VDAC)/BaTiO obtained by the preparation method3A copolymer emulsion.
Preferably, the P (St-co-VDAC)/BaTiO3BaTiO in copolymer emulsion3Uniformly dispersing, the particle diameter of the emulsified micelle is 95-105nm, the particle size distribution index is 0.27-0.28, and BaTiO3The average grain diameter can reach 4-6 nm.
In another aspect of the invention, the invention also comprises P (St-co-VDAC)/BaTiO obtained by the preparation method3A copolymer powder.
Preferably, the P (St-co-VDAC)/BaTiO3BaTiO in copolymer powder3Homogeneously dispersed, BaTiO3The average grain diameter can reach 4-6 nm.
In another aspect of the present invention, VDAC is used to uniformly disperse BaTiO in styrene-based polymer3The use of (1).
Preferably, VDAC is copolymerized with styrene as a comonomer and an emulsifier, while VDAC is dispersed and stabilized barium titanate nanoparticles as a cationic monomer through electrostatic interaction and steric hindrance interaction.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention is to synthesize a cationic monomer vinyl benzyl dimethyl dodecyl ammonium chloride with positive charges and alkyl long chains, firstly, the cationic monomer is used as a dispersing agent to realize uniform dispersion of nano barium titanate, then, the cationic monomer is used as an emulsifying agent to realize emulsion polymerization, and the cationic monomer and styrene are copolymerized at the later stage of polymerization to obtain stable copolymer composite emulsion. The copolymer emulsion prepared by emulsion polymerization in the technical scheme of the invention meets the basic requirements of high dielectric coatings, and the dried copolymer powder basically meets the requirements of insulating films and electronic devices. In the copolymer emulsion and the copolymer microsphere powder, the nano barium titanate is dispersed in a nano level, the dispersion state is uniform and stable, and the problem of serious agglomeration of nano particles in the polystyrene-barium titanate composite material is solved.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum of cationic monomer VDAC.
FIG. 2 shows cationic monomer VDAC dispersed BaTiO3Dynamic Light Scattering (DLS) test chart of nano particles, the ordinate is hydrated barium titanate particle size (namely, Hydrodynamic size of BaTiO)3)。
Fig. 3 is a TEM photograph of the polystyrene-barium titanate composite.
Wherein: (a) p (St-SDS)/BaTiO3Emulsion, (b) P (St-SDS)/BaTiO3And (6) ultrathin slicing.
(c)P(St-co-VDAC)/BaTiO3Emulsion, (d) P (St-co-VDAC)/BaTiO3And (6) ultrathin slicing.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The raw materials and equipment used in the invention are shown in the following table:
table 1 main raw materials
Figure BDA0001393868630000031
Figure BDA0001393868630000041
TABLE 2 Main instrumentation
Figure BDA0001393868630000042
Procedure for preparation of VDAC:
26.22g of dodecyl dimethyl tertiary amine and 12.5g of 4-chloromethyl styrene are added into a 100mL single-neck round-bottom flask, and then a proper amount of diethyl ether is added as a solvent, and the mixture is stirred and reacted for 72 hours at normal temperature. The product was filtered and washed with ether until a white solid was obtained. Vacuum drying to obtain white powder product, namely cationic monomer VDAC.
To characterize the structure of the cationic monomer VDAC synthesized, approximately 15mg of cationic monomer VDAC was weighed out and dissolved in deuterated chloroform (CDCl)3) And placing the reagent in a nuclear magnetic tube for sample preparation, wherein the liquid level of the solvent is not lower than 4cm, and the nuclear magnetic hydrogen spectrum detection is facilitated. The nuclear magnetic hydrogen spectrum of the cationic monomer is shown in FIG. 1.
1H-NMR(CDCl3) 5.38(d,1H), ═ 5.84(d,1H), ═ 6.70(m,1H),. 7.59(d,1H),. 7.46(d,1H),. 5.01(s,2H),. 3.30(s,1H),. 3.45(m,2H),. 1.70(s,2H),. 1.25(m,2H),. 0.89(t, 3H). From the 1H-NMR nuclear magnetic spectrum of VDAC, it can be seen that: absorption peak of chemical shift 7.265 is CDCl3Internal standard peak of (4); the absorption peaks at chemical shifts 5.38 and 5.84 correspond to the two hydrogens on the outer side of the C ═ C double bond on the left side of the phenyl ring; the absorption peak of 6.70 corresponds to hydrogen between the C ═ C double bond and the benzene ring; the two absorption peaks of 7.59 and 7.46 correspond to the two hydrogens at the two positions on the phenyl ring; 5.01 absorption peaks correspond to two hydrogens on methylene between the benzene ring and the nitrogen atom; 3.30 corresponds to two hydrogens on the methylene group of the long chain alkyl group directly attached to the nitrogen atom; the absorption peaks of 3.45 and 1.70 correspond to four hydrogens on the second and third methylene groups on the side of the long chain alkyl group close to the nitrogen atom; the 0.89 absorption peak corresponds to three hydrogens on the methyl group at the end of the long chain alkyl group. The peak area on the nuclear magnetic map can be known by analysisIs in direct proportion to the number of protons in the molecule, and proves that the target product VDAC is successfully synthesized and the product is pure.
Initial styrene type cationic monomer VDAC dispersed BaTiO3The Dynamic Light Scattering (DLS) test pattern of the nanoparticles is shown in FIG. 2, the test result table is shown in Table 1, and the experimental test result reflects BaTiO with the increase of the VDAC concentration of the cationic monomer3Variation in particle size and polydispersity of the nanoparticles. When nanoparticles are used as a filler, the dispersion state of the nanoparticles determines the performance of the composite material, and therefore, it is particularly important to study the particle size of nanoparticle agglomerates. The critical micelle concentration (cmc) of VDAC was 3.7mmol/L, i.e., 1.35g/L, indicating that micelle formation began at a VDAC concentration of 1.35g/L in water. The cationic monomer is positively charged in water, and BaTiO3The nano particles are ionized in water, the surface of the nano particles is negatively charged, and the nano particles are subjected to VDAC and BaTiO3Electrostatic interaction between nano particles and steric hindrance interaction of VDAC long-chain alkyl to make BaTiO3The nano particles are uniformly dispersed. DLS test results show that the BaTiO without VDAC addition3The surface effect and the existence of surface hydroxyl group lead the surface of the material to have strong action, the agglomeration phenomenon occurs, and the grain diameter is larger. In addition, the PDI (polydispersity index) can reflect the degree of uniformity of the particle size, and is between 0 and 1, with smaller values indicating better monodispersity of the particles and narrower particle size distributions, and vice versa. BaTiO without VDAC addition3The particle size distribution index is large, the monodispersity is poor, and the particle size is not uniform. Addition of cationic monomer VDAC to BaTiO3The nano particles are better dispersed in water, the particle size is obviously reduced, and the polydispersity is also obviously reduced. BaTiO when the concentration of VDAC is 12g/L3The particle size of the nanoparticles reached a minimum of 18.1 nm. Comprehensively considering the factors such as the adding amount, the particle size, the polydispersity and the like of the cationic monomer VDAC, and finally determining that when the concentration of the VDAC is 12g/L, the BaTiO is dispersed3The optimum value of the nanoparticles.
TABLE 1 cationic monomer VDAC dispersed BaTiO3DLS test result table of nanoparticles
Figure BDA0001393868630000051
Figure BDA0001393868630000061
Example 1
(1) Weighing 0.4g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h to obtain pre-emulsion, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) 0.5g of BaTiO3Dispersing nano particles and 0.6g of cationic monomer VDAC in 50mL of deionized water, and ultrasonically dispersing by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: performing ultrasonic treatment for 30min in an ice bath environment with the power of 600W, the working time of 3s and the intermittent time of 2s to obtain ultrasonic dispersion liquid, and adding the ultrasonic dispersion liquid into a 250mL four-neck flask;
(3) then 10g of styrene is added into the ultrasonic dispersion liquid in a 250mL four-neck flask, emulsification is carried out for 0.5h in a normal-temperature water bath, the stirring speed is set to be 700rpm, and after 0.5h, temperature rise is started; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, after the reaction is carried out for 0.5h under the condition of heat preservation, the pre-emulsion prepared in the step (1) is dripped into a four-neck flask, and the reaction is continued for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。
(4)P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Example 2
(2) Preparing polystyrene-barium titanate nano composite emulsion taking cationic monomer VDAC as emulsifier: weighing 0.5g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing nano particles and 0.5g of cationic monomer VDAC in 50mL of deionized water, and ultrasonically dispersing by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 10g of styrene, adding the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Example 3
(2) Preparing polystyrene-barium titanate nano composite emulsion taking cationic monomer VDAC as emulsifier: weighing 0.6g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant-pressure dropping funnel for later use; 0.5g of BaTiO is added3Nanoparticles and 0.4g cationic monomer VDAC dispersed in 50mL deionized water with JY92-II NThe ultrasonic dispersion of the ultrasonic cell crusher is characterized in that the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 10g of styrene, adding the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Example 4
Preparing polystyrene-barium titanate nano composite emulsion taking cationic monomer VDAC as emulsifier: weighing 0.4g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing nano particles and 0.6g of cationic monomer VDAC in 50mL of deionized water, and ultrasonically dispersing by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 15g of styrene, adding the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; temperature ofWhen the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Example 5
Preparing polystyrene-barium titanate nano composite emulsion taking cationic monomer VDAC as emulsifier: weighing 0.4g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 15g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant-pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing nano particles and 0.6g of cationic monomer VDAC in 50mL of deionized water, and ultrasonically dispersing by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of styrene, adding the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Example 6
) Preparing polystyrene-barium titanate nano composite emulsion taking cationic monomer VDAC as emulsifier: weighing 0.4g of VDAC and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant-pressure dropping funnel for later use; then, 1.0g of BaTiO was added3Dispersing nano particles and 0.6g of cationic monomer VDAC in 50mL of deionized water, and ultrasonically dispersing by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 10g of styrene, adding the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-co-VDAC)/BaTiO3。P(St-co-VDAC)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-co-VDAC)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Comparative example 1
Preparing polystyrene-barium titanate nano composite emulsion taking traditional Sodium Dodecyl Sulfate (SDS) as an emulsifier: 0.6g SDS and 0.057g initiator KPS were weighed and dissolved inWeighing 10g of monomer styrene St in 50mL of deionized water, adding the weighed monomer styrene St into a 250mL four-neck flask, stirring and pre-emulsifying at the rotating speed of 700rpm for 2 hours, and adding the pre-emulsion into a constant-pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing the nano particles in 50mL of deionized water, and ultrasonically dispersing the nano particles by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 0.4g of SDS and 10g of styrene, adding the SDS and the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-SDS)/BaTiO3。P(St-SDS)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-SDS)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Comparative example 2
Preparing polystyrene-barium titanate nano composite emulsion taking traditional Sodium Dodecyl Sulfate (SDS) as an emulsifier: weighing 0.5g of SDS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene St, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing the nano particles in 50mL of deionized water, and ultrasonically dispersing the nano particles by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; then 0 is weighed.Adding 5g of SDS and 10g of styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a water bath at normal temperature, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-SDS)/BaTiO3。P(St-SDS)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-SDS)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
Comparative example 3
(1) Preparing polystyrene-barium titanate nano composite emulsion taking traditional Sodium Dodecyl Sulfate (SDS) as an emulsifier: weighing 0.4g of SDS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 10g of monomer styrene St, adding into a 250mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use; 0.5g of BaTiO is added3Dispersing the nano particles in 50mL of deionized water, and ultrasonically dispersing the nano particles by using a JY92-II N type ultrasonic cell crusher, wherein the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 0.6g of SDS and 10g of styrene, adding the SDS and the styrene into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation;after 2h, stopping heating, stirring, and cooling to room temperature; discharging, filtering with 300 mesh nylon filter screen, and adjusting pH to 7-8 with ammonia water to obtain polymer-based nano composite emulsion, which is marked as P (St-SDS)/BaTiO3。P(St-SDS)/BaTiO3Vacuum drying the composite emulsion at 60 ℃ to constant weight to obtain nano composite powder; p (St-SDS)/BaTiO3The powder is hot-pressed and formed by a hot-press forming machine. The hot pressing conditions are as follows: the pressure is 10MPa, the temperature is 190 ℃, and the time is 5 min.
For P (St-co-VDAC)/BaTiO3，P(St-SDS)/BaTiO3And pure PS emulsion DLS test results are shown in table 2. As can be seen from the results in the table, the particle size of the polymer-based nanocomposite emulsion added with the nanoparticles is increased to some extent compared with the pure PS emulsion, because the nanoparticles themselves have a particle size of tens of nanometers to tens of nanometers, and the particle size of the polymer-based nanocomposite microspheres is increased by a small amount after being compounded with the polymer matrix. Although the particle size is slightly increased, it is still on the nanometer scale. Comparing the particle size of the polymer-based nano-composite emulsion synthesized by using SDS as an emulsifier with the particle size of the polymer-based nano-composite emulsion synthesized by using VDAC as a polymerizable emulsifier, it can be found that the change of the particle size of the microspheres in the emulsion is not large. The analysis reason may be that the particle size of the nanoparticles is much smaller than that of the polymer microspheres, and the influence on the particle size of the microspheres is small, so that the particle size of the microspheres cannot be greatly changed. Meanwhile, the result shows that the influence of the types of the emulsifiers on the particle size is not obvious, and that compared with the traditional emulsifier SDS, the novel polymerizable emulsifier VDAC synthesized in the experiment can play a good emulsifying effect, so that the nano-scale polymer-based nano-composite emulsion is prepared, and is an emulsifier with excellent performance.
TABLE 2 DLS test results for Polymer-based nanocomposite emulsions
Figure BDA0001393868630000101
For P (St-SDS)/BaTiO3、P(St-co-VDAC)/BaTiO3To perform permeationAs shown in FIG. 3, in the TEM photograph, the contrast is small and the particle size is large PS, and the contrast is large and the particle size is small BaTiO3Nano particle, polymer micro ball grain diameter about 50nm, well dispersed BaTiO3The average grain diameter can reach about 4-6nm, and the agglomerated BaTiO3The particle size is about 50 nm. From the TEM photographs, it can be seen that the polymer-based nanocomposite emulsion, BaTiO, prepared using SDS as an emulsifier3The nano particles are not successfully compounded with the polymer matrix and have obvious agglomeration phenomenon; polymer-based nanocomposite emulsions, BaTiO, prepared using VDAC as polymerizable emulsifier3The nano particles and the polymer matrix are successfully compounded, and meanwhile, BaTiO3The nano particles are well dispersed and do not agglomerate. Due to agglomerated BaTiO3Most of them were removed by high-speed centrifugation, so that BaTiO could not be observed in TEM photograph3Nanoparticles, with few larger aggregates not removed, could be observed in TEM photographs, thus explaining the use of SDS as an emulsifier, BaTiO3The compounding of the nano particles and the polymer matrix is unsuccessful and the agglomeration phenomenon is serious; and the polymer-based nano composite emulsion particles prepared by using VDAC as a polymerizable emulsifier are successfully compounded with a matrix without the agglomeration of nano particles. After hot press forming, P (St-co-VDAC)/BaTiO3TEM of ultrathin section showed that the dispersion state of barium titanate was well maintained, and BaTiO with good dispersion3The average grain diameter can reach about 4-6 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material is characterized by comprising the following steps:
step 1, St and VDAC are used as comonomers, an initiator is added to prepare a pre-emulsion, wherein the initiator and water form a water phase, and the VDAC and St are used as oil phases;
step 2, taking VDAC as a dispersing agent, and adding nano BaTiO3Pre-dispersed in an aqueous solution to obtain BaTiO3Adding St and initiator into the nano particle dispersion liquid to form an emulsion polymerization system, wherein the initiator and the nano BaTiO3And water to form an aqueous phase, VDAC, St as an oil phase;
step 3, heating the emulsion polymerization system to the initiation temperature, dropwise adding the pre-emulsion into the emulsion polymerization system, stirring, and carrying out emulsion polymerization to obtain P (St-co-VDAC)/BaTiO3A copolymer emulsion; wherein:
the mass ratio of the water phase to the oil phase in the step 1 is (4-8): 1, the dosage of St monomer is 90.0-99.9 wt% of the oil phase, and the dosage of VDAC is 0.1-10.0 wt% of the oil phase; wherein the dosage of the initiator is 0.1 to 1.0 weight percent of the sum of the two monomers;
the mass ratio of the water phase to the oil phase in the step 2 is (4-8): 1, the dosage of St monomer is 90.0-99.9 wt% of the oil phase, and the dosage of VDAC is 0.1-10.0 wt% of the oil phase; nano BaTiO3Is 0.1 to 5.0 weight percent of the oil phase, and the dosage of the initiator is 0.1 to 1.0 weight percent of the sum of the two monomers;
the mass ratio of St in the step 1 to St in the step 2 is (40-50): (50-60), wherein the mass ratio of the VDAC in the step 1 to the VDAC in the step 2 is (40-50): (50-60);
wherein: st is styrene, VDAC is vinylbenzyldimethyldodecylammonium chloride, P (St-co-VDAC)/BaTiO3Is a polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material.
2. The method for preparing the polystyrene-vinylbenzyldimethyldodecylammonium chloride-barium titanate composite material according to claim 1, wherein the St mass ratio in the step 1 to the step 2 is 1:1, the VDAC mass ratio in the step 1 to the step 2 is 1:1, the dropping time of the pre-emulsion in the step 3 is 1-1.5h, and the emulsion polymerization time in the step 3 is 3-3.5 h.
3. The method for preparing a polystyrene-vinylbenzyldimethyldodecylammonium chloride-barium titanate composite material according to claim 1, wherein the P (St-co-VDAC)/BaTiO obtained in the step 3 is3And filtering, washing and drying the copolymer emulsion to obtain copolymer powder.
4. The method for preparing polystyrene-vinylbenzyl dimethyldodecylammonium chloride-barium titanate composite material according to claim 1, wherein in the step 1, VDAC and an initiator are dissolved in deionized water, and then monomer styrene is added to prepare a pre-emulsion, wherein the mass-volume ratio of VDAC to deionized water is (10-14): 1, in the step 2, firstly, BaTiO3Dispersing nano particles and a cationic monomer VDAC in deionized water, and ultrasonically dispersing by using an ultrasonic cell crusher to obtain an ultrasonic dispersion liquid, wherein the mass volume ratio of the VDAC to the deionized water is (10-14): 1.
5. the method of preparing a polystyrene-vinylbenzyldimethyldodecylammonium chloride-barium titanate composite material according to claim 1, wherein the initiator is azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide or potassium persulfate.
6. The method for preparing a polystyrene-vinylbenzyldimethyldodecylammonium chloride-barium titanate composite material according to claim 1, wherein the mass ratio of the water phase to the oil phase in step 1 is 5:1, the St monomer is used in an amount of 92 to 95 wt% of the mass of the oil phase, the VDAC is used in an amount of 5 to 8 wt% of the mass of the oil phase, and the initiator is used in an amount of 0.2 to 0.5 wt% of the sum of the two monomers;
the mass ratio of the water phase to the oil phase in the step 2 is 5:1, the dosage of St monomer is 92-95 wt% of the oil phase, the dosage of VDAC is 5-8 wt% of the oil phase, and nano BaTiO32-3 wt% of the oil phase, and the amount of the initiator is 0.2-0.5 wt% of the sum of the two monomers.
7. P (St-co-VDAC)/BaTiO obtained by the production method according to any one of claims 1 to 63A copolymer emulsion.
8. P (St-co-VDAC)/BaTiO as claimed in claim 73A copolymer emulsion characterized by: the P (St-co-VDAC)/BaTiO3BaTiO in copolymer emulsion3Uniformly dispersing, the particle diameter of the emulsified micelle is 95-105nm, the particle size distribution index is 0.27-0.28, and BaTiO3The average particle size is 4-6 nm.
9. P (St-co-VDAC)/BaTiO obtained by the production method according to claim 33Copolymer powder, characterized in that said P (St-co-VDAC)/BaTiO3BaTiO in copolymer powder3Homogeneously dispersed, BaTiO3The average particle size is 4-6 nm.
VDAC Uniform dispersion of BaTiO in styrene-based polymers3The method is characterized in that VDAC is vinylbenzyl dimethyldodecyl ammonium chloride, VDAC is used as a comonomer and an emulsifier to be copolymerized with styrene, and simultaneously VDAC is used as a cationic monomer to disperse and stabilize barium titanate nanoparticles through electrostatic interaction and steric hindrance interaction.
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