阅读说明：本技术 一种高聚物复合纳米粒子相容剂的制备方法 (preparation method of high polymer composite nanoparticle compatilizer ) 是由 王月欣 陈乙刚 张倩 于 2019-10-14 设计创作，主要内容包括：本发明为一种高聚物复合纳米粒子相容剂的制备方法。该方法包括如下步骤：(1)将纳米粒子水溶液滴加到含有聚乙烯亚胺溶液中反应,最后得到中间体1；(2)将中间体1溶液和非极性高聚物接枝物溶液搅拌反应,得到纳米粒子相容剂。本发明得到的相容剂的极性部分是聚乙烯亚胺,不仅含有仲胺、叔胺,还含有伯胺,容易接枝在纳米粒子上,使得非极性聚烯烃接枝物在纳米粒子上的接枝率提高,并且制备工艺简单,处理方便。(The invention relates to a preparation method of a high polymer composite nanoparticle compatilizer. The method comprises the following steps: (1) dripping the nano particle aqueous solution into a solution containing polyethyleneimine for reaction to obtain an intermediate 1; (2) and stirring the intermediate 1 solution and the nonpolar high polymer graft solution for reaction to obtain the nanoparticle compatilizer. The polar part of the compatilizer obtained by the invention is polyethyleneimine, not only contains secondary amine, tertiary amine, but also contains primary amine, and is easy to graft on the nano particles, so that the grafting rate of the non-polar polyolefin graft on the nano particles is improved, and the compatilizer has the advantages of simple preparation process and convenient treatment.)

1. A preparation method of a high polymer composite nanoparticle compatilizer is characterized by comprising the following steps:

(1) Carrying out ultrasonic treatment on a nanoparticle aqueous solution for 5-20 minutes, dropwise adding the nanoparticle aqueous solution into a solution containing polyethyleneimine within 10 ~ 15 minutes, continuously stirring and reacting at the temperature of 50 ℃ of ~ 100 ℃ for 6 ~ 9 hours, centrifuging the modified nanoparticles, washing with deionized water to remove residual polyethyleneimine, and finally, freeze-drying to obtain modified nanoparticle powder, namely an intermediate 1;

The concentration of the nanoparticle water solution is 0.5g/L ~ 2g/L, the concentration of the polyethyleneimine solution is 0.5 g/L-2 g/L, and the mass ratio of the nanoparticles to the polyethyleneimine is =1: 1-1: 2;

(2) Dispersing the intermediate 1 in a first solvent and carrying out ultrasonic treatment for 10-25 minutes to obtain a suspension, namely a solution M; at the same time, dissolving the non-polar high polymer graft in a second solvent at 70-100 ℃, wherein the solution is expressed as solution N; then, mechanically stirring the solution M and the solution N at the temperature of 100-140 ℃ for reaction for 5-10 h; finally, centrifugally separating the mixture, washing with a third solvent and drying to obtain the nanoparticle compatilizer;

Wherein the mass ratio of the intermediate 1: the nonpolar high polymer =1: 1-3: 1; adding 0.01-0.2 g of the intermediate 1 into every 50-100 mL of the first solvent, and adding 0.01-0.2 g of the non-polar high polymer graft into every 50-100 mL of the second solvent;

The nano particles are one or a mixture of two of graphene oxide and carbon nano tubes.

2. The method for preparing the polymer composite nanoparticle compatilizer according to claim 1, wherein the polyethyleneimine is one or a mixture of linear and branched polyethyleneimine.

3. the method of claim 1, wherein the non-polar polymer is one of maleic anhydride grafted with substance A, glycidyl methacrylate grafted with substance A, or acrylic acid grafted with substance A; the substance A is polypropylene, low-density polyethylene, high-density polyethylene, ultrahigh molecular weight polyethylene, random copolymerization polypropylene, ethylene-propylene copolymer, ethylene-propylene-cyclopentadiene terpolymer, polystyrene, ethylene-octene copolymer, ethylene-butene copolymer, styrene-butadiene copolymer or ethylene-vinyl acetate copolymer.

4. the method for preparing the polymer composite nanoparticle compatilizer according to claim 1, wherein the first solvent and the second solvent in the step (2) are the same or different and are one or a mixture of several of benzene, toluene, m-xylene, o-xylene and p-xylene.

5. The method for preparing the high polymer composite nanoparticle compatilizer according to claim 1, wherein the third solvent in the step (2) is one or more of benzene, toluene, xylene, dichloroethane, carbon tetrachloride and absolute ethyl alcohol.

Technical Field

The invention belongs to the technical field of compatilizers, and aims at a typical incompatible high polymer blending system to prepare a novel nano particle compatilizer containing multiple active functional groups, play a good compatibilization role in the blending system and comprehensively improve the performance of a blending material.

Background

With the increasingly wide application of polymer materials, single polymer materials cannot meet the requirements of people on the comprehensive properties of the materials, so that blended materials are produced at the same time. The macromolecular blend system is a multi-component system composed of two or more polymers, but the compatibility, the interface energy and the interface cohesiveness of most blended macromolecular materials are poor due to large polarity difference among the components, so that the phase separation of the blend is generated, and the performance of the blend material is poor and even lower than that of a single-component material. Therefore, to obtain a blend material with good properties, it has become a common technique to add a third component, i.e., a compatibilizer, to the system. The improvement in compatibility depends to a large extent on the structure, molecular weight and concentration of the compatibilizing agent or, in the case of reactive compatibilization, the extent of the interfacial reaction. Although the phase separation problem of the polymer can be solved to a certain extent by the compatilizer in the prior art, the effect of the compatilizer on a system with large polarity difference and high relative molecular mass of each component of the blend is still poor.

The current industrial commonly used compatibilizers are mainly: maleic anhydride graft polymers and block copolymers. The maleic anhydride grafted polymer belongs to a reactive compatilizer, maleic anhydride is grafted to a main chain of polyolefin, the grafting rate is low, only one anhydride group is used as an active functional group, the structure is single, and the application range is narrow. The block copolymer has simple operation in the compatibilization process and low requirements on processing equipment, but when the critical micelle concentration is higher, the molecules of the copolymer compatibilizer are easy to form a supermolecule aggregate in the blend, so that the utilization rate of the compatibilizer is reduced.

With the development of blending technology, the development and development of new compatilizers are urgently required. In recent years, inorganic nanoparticles have also been used as compatibilizers because of their tendency to bridge immiscible polymers and provide their inherent function, improving the physical, chemical, mechanical, thermal and other important properties of immiscible polymer blends. Elias et al investigated the effect of silica nanoparticles on immiscible polypropylene/polyethylene co-vinyl acetate blends and found that when the silica nanoparticles are located at the interface of the two phases, both the phase size and the interfacial tension decrease. In addition, the migration of silica between the two phases can be controlled by changing the mixing sequence. (Elias L, Fenouillot F, Majeste J C, et al, interferometric polymeric compositions stabilized with nano-silica particles: Rheology and effective interfacial tension [ J ]. Polymer,2008,49(20): 4378-. Hong et al studied the distribution of carbon black in immiscible blends controlled by thermodynamic and kinetic factors and found that when carbon black is located at the interface of the blend, re-aggregation of the dispersed phase is sufficiently inhibited and the compatibility of the blend is improved. (Hong J S, Namkung H, Ahn K H, et al. the roll of organic modified layered silicate in the break up and the catalysis of the droplets in PBT/PE blends [ J ]. Polymer,2006,47(11): 3967-. Feng et al compatibilize immiscible polyamide/polyphenylene ether blends with the amphiphilic structure of graphene oxide sheets, the compatibility of graphene oxide due to strong interactions between graphene oxide and polyamide and polyphenylene ether phases minimizing their interfacial tension, and found that the mechanical properties and thermal stability of graphene oxide compatibilized blends are greatly improved. (Cao Y, Zhang J, Feng J, et al. compatibility of immiscible polymer blends using graphene oxide sheets [ J ]. Acs Nano,2011,5(7): 5920-.

The nano particles can be effectively compatibilized by modifying, the surface modification technology of the nano particles is a new science, and the following four purposes can be achieved by modifying the surfaces of the nano particles: improving or changing the dispersibility of the nano particles and preventing the agglomeration of the nano particles; improving the compatibility between the nano particles and other substances; improving the surface activity of the nano particles; fourthly, the particle surface generates new physical, chemical and mechanical properties and new functions.

Currently, surface-modified hybrid nanoparticles have been tried as potential thermodynamic compatibilizers for immiscible blends. The appropriate modification method is chosen to interact with the blend components, enhancing the positioning of the hybrid nanoparticles at the interface, ensuring their effective compatibilization of the blend. Ray et al found that in PS/PP blends, the interfacial tension was reduced due to the enhanced interaction between the organically modified montmorillonite and the polymer, resulting in finer domain sizes of the dispersed phase. (Ray S S, Pouliott S, Bousmina M, et al, roll of organic modified layered silicate as an active interfacial modifier in an amorphous polystyrene/polypropylene blends [ J ]. Polymer,2004,45(25): 8403-8413.). Wu et al use functionalized multi-walled carbon nanotubes to control the morphology of immiscible polycaprolactone/polylactide blends, by adding multi-walled carbon nanotubes, the size of the polylactide phase is significantly reduced due to the selective positioning of the multi-walled carbon nanotubes in the blend; the multi-walled carbon nanotubes containing carboxyl are selectively positioned at the interface of the matrix polycaprolactone phase and the phase, and the non-functionalized multi-walled carbon nanotubes are only dispersed in the matrix polycaprolactone phase. (Wu D, Zhang Y, Zhang M, et al.Selective localization of multiwalled carbon nanotubesin poly (. epsilon. -capralactone)/polylactade blend [ J. Biomacromolecules,2009,10(2): 417-. Huang et al, directed to a polymethylmethacrylate/polystyrene-acrylonitrile blend system, controlled the selective positioning of silica nanoparticles at the interface of two phases or in a region rich in polymethylmethacrylate by grafting polystyrene chains onto the surface of the silica nanoparticles. (Huang C, Gao J, Yu W, et al. phase separation of poly (methyl methacrylate)/poly (styrene-co-acrylic nitrile) blends with controlled polymerization of silicon nanoparticles [ J ]. Macromolecules,2012,45(20): 8420-8429.).

the subject group disclosed a preparation method of CN104962026A a novel composite compatilizer, which comprises a polar part, nonpolar polyolefin and nanoparticles, wherein the compatilizer is prepared from polyethylene polyamine and formaldehyde through nucleophilic addition-elimination reaction in the preparation process. The subject group disclosed the preparation of CN106046647A a multifunctional group-containing polar-controllable compatibilizer, which comprises polar glycidylamine, nonpolar polyolefin and nanoparticles, and the compatibilizer is prepared from polyethylene polyamine and epichlorohydrin through condensation reaction during the preparation process. However, the above two compatibilizers also have disadvantages: (1) the preparation process of the polar parts of the two compatilizers is complex and inconvenient to process; (2) the formaldehyde and the epichlorohydrin used in the preparation process of the two compatilizers have high toxicity and are not environment-friendly.

Disclosure of Invention

The invention aims to provide a preparation method of a high polymer composite nanoparticle compatilizer aiming at the defects in the prior art. The invention adopts the polyethyleneimine as a polar part, the obtained compatilizer has a structure consisting of three parts of nonpolar polyolefin-polar imine-nano particles, the polyethyleneimine of the polar part not only contains secondary amine and tertiary amine, but also contains primary amine and is easy to graft on the nano particles, so the compatilizer has rich amino functional groups, and the existence of the functional groups improves the grafting rate of a nonpolar polyolefin graft on the nano particles; and the polar part of the compatilizer is polyethyleneimine, the preparation process is simple, and the compatilizer has a good compatibility effect when added into a blending system.

The technical scheme of the invention is as follows:

A preparation method of a high polymer composite nanoparticle compatilizer comprises the following steps:

(1) Carrying out ultrasonic treatment on the nanoparticle aqueous solution for 5-20 minutes, then dropwise adding the nanoparticle aqueous solution into a solution containing polyethyleneimine within 10-15 minutes, and continuously stirring and reacting for 6-9 hours at 50-100 ℃; then, centrifuging the modified nanoparticles and washing with deionized water to remove residual polyethyleneimine; finally, modified nanoparticle powder, namely an intermediate 1, is obtained by freeze drying;

Wherein, the concentration of the nano particle water solution is 0.5 g/L-2 g/L, and the concentration of the polyethyleneimine solution is 0.5 g/L-2 g/L; the mass ratio of the nano particles is as follows: polyethyleneimine is 1: 1-1: 2;

(2) Dispersing the intermediate 1 in a first solvent and carrying out ultrasonic treatment for 10-25 minutes to obtain a suspension, namely a solution M; at the same time, dissolving the non-polar high polymer graft in a second solvent at 70-100 ℃, wherein the solution is expressed as solution N; then, mechanically stirring the solution M and the solution N at the temperature of 100-140 ℃ for reaction for 5-10 h; finally, centrifugally separating the mixture, washing with a third solvent and drying to obtain the nanoparticle compatilizer;

Wherein the mass ratio of the intermediate 1: the nonpolar high polymer is 1: 1-3: 1; adding 0.01-0.2 g of the intermediate 1 into every 50-100 mL of the first solvent, and adding 0.01-0.2 g of the non-polar high polymer graft into every 50-100 mL of the second solvent;

the nano particles are one or a mixture of two of graphene oxide and carbon nano tubes.

the polyethyleneimine is linear or branched or a mixture of the two.

The grafted nonpolar high polymer is one of substance A grafted maleic anhydride, substance A grafted glycidyl methacrylate or substance A grafted acrylic acid;

the substance A is polypropylene, low-density polyethylene, high-density polyethylene, ultrahigh molecular weight polyethylene, random copolymerization polypropylene, ethylene-propylene copolymer, ethylene-propylene-cyclopentadiene terpolymer, polystyrene, ethylene-octene copolymer, ethylene-butene copolymer, styrene-butadiene copolymer or ethylene-vinyl acetate copolymer;

The first solvent and the second solvent in the step (2) are the same or different and are one or a mixture of more of benzene, toluene, m-xylene, o-xylene and p-xylene.

The third solvent in the step (2) is one or a mixture of more of benzene, toluene, xylene, dichloroethane, carbon tetrachloride and absolute ethyl alcohol.

the invention has the substantive characteristics that:

In two patents previously disclosed in this group, the polar moieties of the compatibilizer were (1) prepared by nucleophilic addition-elimination reaction of polyethylene polyamine and formaldehyde, respectively; (2) preparing a polar part by using polyethylene polyamine and epoxy chloropropane through a condensation reaction; the invention adopts the polyethyleneimine as the raw material, and the polar part of the obtained compatilizer is the polyethyleneimine, not only contains secondary amine, tertiary amine, but also contains primary amine, and is easy to graft on the nano particles, so the compatilizer has abundant amino functional groups, and the existence of the functional groups improves the grafting rate of the non-polar polyolefin graft on the nano particles.

In the preparation steps, the polar parts in the two previous patents are prepared by two reactants through intermediate reaction and multi-step treatment, and the polyethylene imine is directly adopted as the polar part on the basis of the compatilizer, so that the intermediate reaction step is omitted, the preparation process is simple, and the treatment is convenient.

The invention has the beneficial effects that:

The invention provides the high polymer composite nanoparticle compatilizer and the preparation method thereof, and the high polymer composite nanoparticle compatilizer plays a good role in practical application. The compatilizer consists of three parts of non-polar polyolefin-polar imine-nano particles, and the innovation of the compatilizer is as follows: (1) the invention provides a new idea on the basis of more than CN106046647A, polyethyleneimine is used for replacing epoxy chloropropane with high toxicity in CN106046647A and is used as a polar part of the nanoparticle compatilizer, and the preparation process is simple; in addition, the polarity of the compatilizer is adjusted by adjusting the amount of polyethyleneimine, so that a proper compatilizer is provided for a blending system with different polarities; (2) compared with the traditional high polymer grafted maleic anhydride compatilizer and the compatilizer in CN106046647A, the polyethylene imine not only contains secondary amine, tertiary amine and primary amine, and is easy to be grafted on the nano particles, so that the grafting rate of a non-polar polymer graft on the nano particles is improved, and the compatilizer has higher grafting rate; (3) the compatilizer not only can exert the characteristics of each component, but also can fully exert the synergistic effect among the components, and well promotes the compatibility of a polar and non-polar polymer blending system; (4) the compatibilizer has the characteristics of more nano particle surface atoms, large specific surface area and the like, and can play an obvious compatibilization effect by adding a small amount compared with the traditional polymer compatibilizer; (5) the compatilizer can be selectively positioned at the interface of two phases, so that the surface tension of the two phases is greatly reduced, and the two phases are better compatible; (6) the invention has simple preparation process and convenient treatment. In conclusion, the compatibilizer can satisfy more blending systems.

The specific implementation mode is as follows:

the graphene oxide is a known material, is purchased from the market, and has a lamella thickness of 0.5-1.2 nm and a lamella diameter of 1-25 mu m.

the non-polar polymer graft related to the present invention is a known material, for example, polypropylene grafted maleic anhydride, high density polyethylene grafted maleic anhydride, low density polyethylene grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride, polyisobutylene grafted maleic anhydride can be obtained commercially; ultra-high molecular weight polyethylene grafted maleic anhydride can be made according to the reference (von shaohawa, zuo jiandong, yellow mega ge, et al. UHMWPE mixed grafted maleic anhydride research [ J ]. modern plastics processing applications, 2004,03: 13-16.).