CN1247639C - Composite microparticles of molecular sieve-polymer and preparation process thereof - Google Patents
Composite microparticles of molecular sieve-polymer and preparation process thereof Download PDFInfo
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- CN1247639C CN1247639C CN 200410012147 CN200410012147A CN1247639C CN 1247639 C CN1247639 C CN 1247639C CN 200410012147 CN200410012147 CN 200410012147 CN 200410012147 A CN200410012147 A CN 200410012147A CN 1247639 C CN1247639 C CN 1247639C
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Abstract
The present invention relates to a molecular sieve-polymer compound particulate and a preparation method thereof, which belongs to the field of high molecular materials, more specifically a nuclear-shell structure composite particle and a preparation method thereof. The present invention is characterized in that the compound particulate structure is composed of the following three parts: (A), a molecular sieve particulate is taken as a core; (B), several kinds of monomers form a rubber layer with certain cross linking density and certain thickness as a middle layer by being copolymerized in the holes and on the external surface of the molecular sieve particulate; (C), several kinds of monomers carry out grafting and cross linking in a copolymerization mode for forming a polymer with high glass temperature as a shell layer. The shock resisting modifying agent has the design characteristics that a superfine particle of a molecular sieve is taken as the core; organic monomers enter holes for carrying out polymerization; thereby, the core particle and the rubber layer can be firmly connected; the graft polymerization of the shell layer and the rubber layer forms a polymer with high glass temperature for forming the shell layer; different functional groups can be designed according to different purposes. Because the shock resisting modifying agent comprises inorganic particles, the shock resisting modifying agent not only has improved shock resistance, but also can keep elastic modulus and tensile strength without change.
Description
Technical field
A kind of molecular sieve of the present invention-polymkeric substance composite particles and preparation method belong to polymeric material field, particularly are a kind of nucleocapsid structure composite particless and preparation method thereof.
Technical background
It is present the most frequently used a kind of method of modifying to improve resistance to impact shock that thermoplastic polymer carries out blending and modifying with anti-impact modifier, and the commercialization anti-impact modifier product esters of acrylic acid nucleocapsid structure anti-impact modifier (ACR) of Shi Yonging all has good impact-resistant modified effect to polyvinyl chloride in a large number.
Therefore polypropylene, changes polyacrylic crystalline structure with nucleator and improves polyacrylic shock resistance because crystallinity is good, as: the beta-crystal nucleator is widely studied owing to bringing out beta-crystal; Another kind is to add various nanoparticles to be used to strengthen Research on Toughening existing a large amount of related articles and patent report, especially CaCO
3And SiO
2Correlative study.
The micropore that utilizes the nanoporous inorganic particulate to be had, the molten resin pressurization is entered in the micropore, make resin and inorganic materials mortise, be used to strengthen, Research on Toughening obtained good result, do not possess ubiquity but this preparation method is used for the study on the modification of material.
Existing patent or article report are to nanometer SiO
2Surface graft modification coats the research that methyl methacrylate is used for erosion-resisting characteristics on its surface then.To nanometer CaCO
3Surface grafting acrylate or other have polymkeric substance to be used to change the research of polypropylene crystal formation, and report is also arranged.
Molecular sieve is representative porous crystal of a class or unbodied porous material, the micropore internal adsorption organic monomer of molecular sieve then initiated polymerization prepare composite study relevant report also arranged, but this composite study mainly is monomer confinement polymerization in the micropore of molecular sieve, is used to prepare nano material.
On the basis of the above, this patent has been invented a kind of method for preparing molecular sieve-polymkeric substance nucleocapsid structure composite particles.Select promptly that to have porous molecular sieve particulate be core particle for use, by organic monomer in the hole of its particle and surface aggregate, make polymkeric substance and inorganic particulate mortise, the middle layer of this composite particles is a rubber elastic layer, shell be with the rubber layer graft polymerization have a higher resin layer of second-order transition temperature.Difference according to the use object of anti-impact modifier, can be designed to different chain structures and have different functional groups at its shell, be used to regulate the consistency of composite particles and matrix resin, the shock resistance research that is used for various types of resins with the composite particles of this design philosophy preparation has ubiquity, as: the design of the composition of rubber layer and shell, multipolymer proportioning, functional groups has handiness.And, utilize porous inorganic particle for core particle can with the rubber layer mortise, can increase tensile strength and thermotolerance again.
Summary of the invention
A kind of molecular sieve of the present invention-polymkeric substance composite particles and preparation method, its purpose are to disclose the technical scheme of a kind of molecular sieve-polymkeric substance nucleocapsid structure composite particles and preparation method thereof.
A kind of molecular sieve of the present invention-polymkeric substance composite particles is characterized in that it is that a kind of particulate with molecular sieve is that core particle and certain thickness rubber layer are the composite particles of the nucleocapsid structure of middle layer and the composition of the polymkeric substance shell with high glass transition temperature.
The preparation method of above-mentioned a kind of molecular sieve-polymkeric substance composite particles is characterized in that:
I. at first choosing the molecular sieve particulate is core particle;
II. coat the polymeric elastic middle layer: choose monomer,, in above-mentioned selected molecular sieve microparticle pores, reach outer surface formation and have certain cross-linking density and certain thickness rubber middle layer by the copolymerization mode;
III. the formation of shell: choose the monomer identical or different, form polymkeric substance shell with high glass transition temperature by graft polymerization and rubber middle layer with Step II;
IV. the weight ratio of core particle, rubber middle layer, shell is 100: 30～200: 10～80; Being used for selected diene base monomer of rubber middle layer polymerization and the monomeric weight ratio of mono alkenyl is 0.1～5.0: 99.9～95.
The preparation method of above-mentioned a kind of molecular sieve-polymkeric substance composite particles, it is characterized in that, its described core particle comprises 5A, ZSM-5,10X, 13X, mordenite, NaY type zeolite molecular sieve, MCM-41, SBA-15 type mesoporous molecular sieve, its pore diameter range is 0.5～50nm, its particle diameter is 0.01～5.0 μ m, and its ideal particle diameter is 0.01～0.5 μ m.
The preparation method of above-mentioned a kind of molecular sieve-polymkeric substance composite particles, it is characterized in that, the monomer that described rubber middle layer is selected for use comprises mono alkenyl monomer and diene base monomer, and the mono alkenyl monomer is vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, propenoic acid beta-hydroxy ethyl ester, vinylformic acid γ-hydroxypropyl acrylate, vinylbenzene; Diene base monomer is two vinylformic acid glycol esters, two vinylformic acid propylene glycol ester, two vinylformic acid butanediol ester, two vinylformic acid hexylene glycol ester, Vinylstyrene, divinyl.
The preparation method of above-mentioned a kind of molecular sieve-polymkeric substance composite particles, it is characterized in that the monomer that described shell is selected for use comprises: methyl methacrylate, methacrylic acid, propenoic acid beta-hydroxy ethyl ester, vinylformic acid γ-hydroxypropyl acrylate, vinylbenzene, vinylchlorid, two vinylformic acid glycol ester, Vinylstyrene, maleic anhydride.
The invention has the advantages that, be core with the porous inorganic particle, and rubber layer is combined closely by the polymerization and the inorganic particulate of monomer in the hole, and shell and rubber layer form the polymkeric substance that has than high glass transition temperature by graft polymerization.General and the rubber elastic layer of the selected monomer of shell polymerization can graft polymerization, has good consistency with matrix resin on the other hand.This anti-impact modifier has not only improved erosion-resisting characteristics, and Young's modulus and tensile strength still can remain unchanged.This anti-impact modifier not only can be used for polypropylene modification, also can be used to improve the shock resistance of polyvinyl chloride.
The present invention further describes with the following examples, but is not limited in this.
Embodiment
Embodiment 1
In the four-hole bottle of 1000ml, adding median size is 2.91 μ m, 13X molecular sieve 100 grams of surface modification treatment had been carried out with 2.5% titanate coupling agent, put into baking oven for heating to 150 ℃, kept 4 hours, after the baking oven taking-up, load onto stirring rapidly, thermometer, condenser and dropping funnel, vacuumized 1～2 hour, when treating that temperature reaches 50～60 ℃, break away from vacuum, keep negative pressure, add mix monomer 20 grams that prepare in advance, adsorbed 1 hour, afterwards, add the deionized water 500ml that has been dissolved with sodium lauryl sulphate 2.0 grams, mix, when being heated to 65～70 ℃, add 0.5% potassium persulfate solution 10ml, keep and be added dropwise to 0.5% potassium persulfate solution 10ml, kept 1 hour at 70 ℃, begin to drip all the other mix monomer 20 grams, at the uniform velocity dripped about 2 hours, drip shell component mix monomer 20 grams then, dripped 1 hour, and after adding, dripped 0.5% Potassium Persulphate 20ml, dripped 1 hour, be warming up to 90 ℃ and wore out 0.5 hour, be cooled to below 50 ℃, add 10%NaCl solution breakdown of emulsion, filter, washing, dry.
The elastic layer mix monomer is formed (weight): butyl acrylate 92%, methyl methacrylate 5%, methacrylic acid 0.5%, hydroxyethyl methylacrylate 1.5%, two vinylformic acid butanediol esters 1%.
The shell mix monomer is formed (weight): methyl methacrylate 95%, methacrylic acid 0.5%, hydroxyethyl methylacrylate 0.5%, two vinylformic acid butanediol esters 1%, maleic anhydride 2%.
Application result is as follows in polypropylene:
| Addition | Breach shock strength/KJ/m 2 | Tensile strength/Mpa |
| 0 | 32.03 | 27.63 |
| 3％ | 69.4 | 27.52 |
Annotate: polypropylene model EPS-30R, ethylene plant, huge port, Tianjin produces:
Embodiment 2
Choosing median size is the 5A type molecular sieve of 2.6 μ m, and with the titanate coupling agent modification that accounts for molecular sieve 2.5%, preparation process is identical with embodiment 1.
The elastic layer mix monomer is formed: butyl acrylate 92%, methyl methacrylate 5%, methacrylic acid 1%, hydroxyethyl methylacrylate 1%, two vinylformic acid butanediol esters 1%.
The shell mix monomer is formed: vinylbenzene 40%, methyl methacrylate 58%, methacrylic acid 1%, hydroxyethyl methylacrylate 0.5%, two vinylformic acid hexylene glycol esters 0.5%.
Application result is as follows in polypropylene:
| Addition | Breach shock strength/KJ/m 2 | Tensile strength/Mpa |
| 0 | 32.03 | 27.63 |
| 9％ | 95.35 | 26.50 |
Annotate; Polypropylene model EPS-30R, ethylene plant, huge port, Tianjin produces.
Claims (6)
1. molecular sieve-polymkeric substance composite particles, it is characterized in that it is that a kind of particulate with molecular sieve is a core particle, rubber layer with diene base monomer and mono alkenyl monomer copolymerization is the middle layer, is the nucleocapsid structure composite particles that shell is formed with the polymer layer with high glass transition temperature of diene base monomer and mono alkenyl monomer copolymerization.
2. the preparation method of the described a kind of molecular sieve of claim 1-polymkeric substance composite particles is characterized in that:
I. core particle: with coupling agent treatment excessively the particulate of the molecular sieve on surface be core particle;
II. coat the polyrubber middle layer: choose monomer, by the copolymerization mode, in the hole of above-mentioned selected molecular sieve particulate and outer surface form and have certain cross-linking density and certain thickness rubber middle layer;
III. the formation of shell: choose several monomers, outside rubber middle layer, form polymkeric substance shell by graft polymerization with high glass transition temperature;
IV. core particle: rubber middle layer: the weight ratio of shell is 100: 30～200: 10～80; Being used for the selected diene base monomer of rubber elastic layer and having the monomeric weight ratio of mono alkenyl is 0.1～5.0: 95～99.9.
3. the preparation method of a kind of molecular sieve according to claim 2-polymkeric substance composite particles, it is characterized in that being used for molecular sieve surface-treated coupling agent is titanate coupling agent, its consumption is 2.5% of a molecular sieve weight.
4. the preparation method of a kind of molecular sieve according to claim 2-polymkeric substance composite particles, it is characterized in that core particle selects for use the molecular sieve particulate with micropore mainly to comprise 5A, ZSM-5,10X, 13X, mordenite, NaY type zeolite molecular sieve, MCM-41, SBA-15 type mesoporous molecular sieve, its pore diameter range is 0.5～50nm, and its particle diameter is 0.01～5.0 μ m.
5. the preparation method of a kind of molecular sieve according to claim 2-polymkeric substance composite particles, it is characterized in that, described rubber middle layer selects for use monomer to comprise mono alkenyl monomer and diene base monomer, and the mono alkenyl monomer mainly comprises vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, propenoic acid beta-hydroxy ethyl ester, vinylformic acid γ-hydroxypropyl acrylate, vinylbenzene.Diene base monomer mainly comprises: two vinylformic acid glycol esters, two vinylformic acid propylene glycol ester, two vinylformic acid butanediol ester, two vinylformic acid hexylene glycol ester, Vinylstyrene, divinyl.
6. the preparation method of a kind of molecular sieve according to claim 2-polymkeric substance composite particles is characterized in that the monomer that shell is selected for use comprises: methyl methacrylate, methacrylic acid, propenoic acid beta-hydroxy ethyl ester, vinylformic acid γ-hydroxypropyl acrylate, vinylbenzene, vinylchlorid, two vinylformic acid glycol ester, Vinylstyrene, maleic anhydride.
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| CN1247639C true CN1247639C (en) | 2006-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9577289B2 (en) | 2012-12-17 | 2017-02-21 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
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| CN102005609B (en) * | 2010-10-20 | 2013-01-16 | 浙江工业大学 | Composite gel polymer electrolyte membrane and application thereof |
| CN101967237B (en) * | 2010-10-28 | 2012-07-25 | 沈阳化工大学 | Preparation method of rubber/mesoporous molecular sieve nanocomposite |
| TW201522475A (en) * | 2013-12-11 | 2015-06-16 | Ind Tech Res Inst | Thermo-responsive composite material and use thereof, and refrigerating device using same |
| CN105169845A (en) * | 2015-08-11 | 2015-12-23 | 无锡桥阳机械制造有限公司 | Composite filter |
| CN105367985A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and high toughness EVA product prepared from TPE composition |
| CN110627958B (en) * | 2019-10-16 | 2021-11-16 | 山东省科学院能源研究所 | Polyethylene composition, method for improving grafting efficiency of polyethylene and application of polyethylene composition |
| CN112940417B (en) * | 2020-12-28 | 2022-03-08 | 江苏集萃先进高分子材料研究所有限公司 | High-wave-transmittance tetrafluoroethylene copolymer plastic microporous foam material in wide frequency band and green preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9577289B2 (en) | 2012-12-17 | 2017-02-21 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
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