CN1143868C - In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material - Google Patents
In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material Download PDFInfo
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- CN1143868C CN1143868C CNB011333472A CN01133347A CN1143868C CN 1143868 C CN1143868 C CN 1143868C CN B011333472 A CNB011333472 A CN B011333472A CN 01133347 A CN01133347 A CN 01133347A CN 1143868 C CN1143868 C CN 1143868C
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Abstract
The present invention relates to a method for preparing polyacrylic ester / clay nanometer composite material by in-situ polymerization. The method of the present invention uses the characteristic that most of polyacrylic ester can be prepared by an emulsion polymerization method, clay which is easily dissolved in water is selected as an inorganic component, the emulsion polymerization of acrylic ester is carried out in a micro suspension solution containing a certain quantity of clay so that the polyacrylic ester / clay nanometer composite material is obtained. The present invention uses water as a polymerization medium so as to have the advantages of no pollution, simple operation and easy industrial production.
Description
Technical field: the present invention relates to a kind of preparation method of polyacrylic ester based nano composite material, specially refer to the nano composite material preparation method that polyacrylic ester and clay are formed.
Background technology: since J.Mater. Res.1993,8,1185 over-all propertieies of having reported nylon/phyllosilicate nano intercalated compound obviously than nylon well after, the nano intercalated composite study of polymkeric substance-inorganic component becomes studies focus in the Materials science.Adopt the layered inorganic component modification polymkeric substance of a small amount of 1-dimention nano size, rigidity, the intensity of polymkeric substance are obviously improved, and the material proportion and the transparency are more constant than substantially with polymer phase, also can improve thermostability, flame retardant resistance and the barrier of polymkeric substance simultaneously.
Along with going deep into of research, various polymkeric substance and laminated nm-silicate composite material have appearred.The resene polymkeric substance has: nylon 6, Resins, epoxy, polystyrene, polyester, polyethylene oxide, polypropylene etc.; Rubber polymer has: paracril, styrene-butadiene rubber(SBR), silicon rubber etc.The preparation method who is adopted has melting mixing method, solution mixing method and situ aggregation method.
Most clay/polymer based nanocomposites are by the method preparation of in-situ polymerization.The method of in-situ polymerization is meant, obtains external phase and nano grade discontinuous phase in the process of chemical reaction simultaneously, specifically can be divided into original position mass polymerization, in-situ solution polymerization, in-situ suspension polymerization, in-situ emulsion polymerization and original position slurry polymerization.Adopt in-situ polymerization can solve owing to the chemical structure between inorganic component and polymkeric substance and physical condition differ greatly cause be difficult to the dispersive problem.China applies for a patent 96105362 and 97103917 and has reported respectively and utilize the original position bulk polymerization successfully to prepare clay scattered nano combined material in polymeric substrates such as nylon, silicon rubber.J.Mater. Res., 1993,8,1179 announcements utilize α, the positively charged ion of omega-amino acid embeds between the clay crystal layer and obtains organic clay, causing the monomer caprolactam polymerization that is penetrated between clay seam between the crystal layer, has successfully made clay/nylon 6 nano-composite then.Yet, can not find as a rule to resemble the easy monomer that carries out in-situ polymerization between clay seam that enters the hexanolactam, form nano composite material.Therefore this preparation method has certain limitation on applicable surface, and this method cost height, and the complex process instability is difficult to realize suitability for industrialized production.
China applies for a patent 98103038.6 reports and adopts the in-situ emulsion polymerization method can prepare polystyrene/clay nano composite material.Because in-situ emulsion polymerization adopts dispersion medium to be water, and is environmentally friendly, receives much concern in recent years.But the subject matter of above-mentioned work is clay must carry out organic modification, just can be used to prepare composite nano polymer/clay material, complex process, cost height.
Summary of the invention: the objective of the invention is to propose the method that a kind of in-situ emulsion polymerization prepares polyacrylic ester/clay nanocomposites.Wherein used clay has easily by the water-soluble characteristics that rise, and does not need the processing that organises.
Method of the present invention is based on the characteristics of all available emulsion polymerization way preparation of acrylic ester monomer, aqeous suspension at clay carries out in-situ emulsion polymerization, final emulsion directly film forming is used, or the adding flocculation agent condenses, slough moisture, thereby obtain polyacrylic ester/clay nanocomposites.The unit cell of used clay is made up of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connects by public Sauerstoffatom between the two, and montmorillonitic clay layer internal surface has negative charge.Therefore, generally adsorbing positively charged ion between the clay crystal layer, this structure makes water and other polar molecule can enter between the clay crystal layer, and the exchange interaction between extraneous positively charged ion and inner positively charged ion can take place.Clay and water are mixed, just can form a stable clay water suspensoid, clay crystal layer wherein is under the hydration of interlayer cation, and is separated from one another.Formed nano composite material has excellent mechanical property, heat-resisting and flame retardant properties, to the barrier property and the wear resisting property of gas and liquid.
Polyacrylic ester of the present invention/clay nanocomposites in-situ emulsion polymerization preparation method follows these steps to implement: 3-13 part clay is joined in 600-1000 part water, under agitation form the microemulsion of clay, left standstill after being uniformly dispersed 12 hours; Before carrying out letex polymerization, above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour with ultrasonic wave; 100 parts of acrylate monomers and 1-3 part emulsifying agent are dissolved in the above-mentioned microemulsion of 600-1000 part, or to add 2 parts of polyvinyl alcohol simultaneously be stablizer, under brute force stirs, form stable emulsion; System vacuumizes, inflated with nitrogen three times respectively, last nitrogen protection; Under agitation as appropriate speed, system is warmed up to 70-80 ℃, 0.5-2.5 part initiator and 0.1-0.5 part Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 4-6 hour; With gained emulsion direct pouring film forming, or after breakdown of emulsion, washing, drying, obtain the nano composite material of emulsion polymerization prepared.
The used acrylate monomer raw material of the present invention comprises methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, and any two kinds, any three kinds of monomeric mixtures in the above-mentioned monomer.Used clay mainly contains bentonite, polynite, halloysite for easily by the water-soluble kind that rises, wherein the present invention preferably interlayer cation be the clay of sodium ion, as sodium base bentonite, the sodium ion exchange capacity is 100meq/100g.The used clay of the present invention does not need to handle through intercalator, and its particle size generally should be at 1-50 μ m, and interfloor distance is 0.2-0.5nm.The initiator that adopts is Potassium Persulphate or ammonium persulphate; Emulsifying agent is dodecylbenzene sodium sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, polyoxyethylene nonylphenol ether, can use separately, also can two or more mixing use; Molecular weight regulator is a Dodecyl Mercaptan; Stablizer is a polyvinyl alcohol.The dispersion medium of in-situ polymerization is a water, and its effect is to promote the dispersion of clay in acrylate monomer.
Compare with other method of preparation polymer nanocomposites above-mentioned, technical solution of the present invention technology is simple, environment is not polluted, and to monomeric wide accommodation, the performance height of gained nano composite material, and preparation cost is lower.
Further specify the present invention below by experiment embodiment.But the present invention is not limited to this.
Embodiment:
Embodiment 1
3 gram sodium base bentonites are added in stirred in 600 ml waters 4 hours, be dispersed to microemulsion, left standstill after mixing 12 hours, above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour with ultrasonic wave.Adding 100 gram ethyl propenoate monomers and 1 gram dodecylbenzene sodium sulfonate emulsifying agent are dissolved in the above-mentioned microemulsion, add 2 gram polyvinyl alcohol again as stablizer, the stable emulsion of formation under brute force stirs.Find time inflated with nitrogen three times of system, last nitrogen protection.Under agitation system is warmed up to 80 ℃, 0.5 gram Potassium Persulphate and 0.2 gram Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 4 hours.After reaction finishes,, get nano composite material after the drying directly with emulsion film forming.
Embodiment 2
Emulsion preparation argillaceous is with example 1.With the gained emulsion breaking, wash after reaction finishes, obtain the nano composite material of emulsion polymerization prepared after the drying.
Embodiment 3
5 gram sodium base bentonites are added in stirred in 700 ml waters 4 hours, be dispersed to microemulsion, left standstill after mixing 12 hours, above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour with ultrasonic wave.Adding 100 gram ethyl propenoates and methyl methacrylate (50: 50 weight ratios) mix monomer and 1.5 gram sodium lauryl sulphate emulsifying agents are dissolved in the above-mentioned microemulsion, form stable emulsion under brute force stirs.Find time inflated with nitrogen three times of system, last nitrogen protection.Under agitation system is warmed up to 70 ℃, 1 gram Potassium Persulphate and 0.1 gram Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 5 hours.After reaction finishes,, get nano composite material after the drying directly with emulsion film forming.
Embodiment 4
Emulsion preparation argillaceous is with example 3.With the gained emulsion breaking, wash after reaction finishes, obtain the nano composite material of emulsion polymerization prepared.
Embodiment 5
7 gram sodium-based montmorillonites are added in and carry out dispersed with stirring in 800 ml waters to microemulsion, and the time is 4 hours, leaves standstill after mixing 12 hours; Before adding acrylate monomer, with ultrasonic wave above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour, restrain butyl acrylates and methyl methacrylate (50: 50 weight ratios) mix monomer and 2 gram Sodium dodecylbenzene sulfonate emulsifying agents with 100 and be dissolved in the above-mentioned microemulsion, under brute force stirs, form stable emulsion.Find time inflated with nitrogen three times of system, last nitrogen protection.Under agitation as appropriate speed, system is warmed up to 80 ℃, 2.5 gram ammonium persulphates and 0.3 gram Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 4 hours.After reaction finishes,, get nano composite material after the drying directly with emulsion film forming.
Embodiment 6
Emulsion preparation argillaceous is with example 5.With the gained emulsion breaking, wash after reaction finishes, obtain the nano composite material of emulsion polymerization prepared after the drying.
Embodiment 7
13 gram sodium base bentonites are added in stirred in 1000 ml waters 4 hours, be dispersed to microemulsion, left standstill after mixing 12 hours, above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour with ultrasonic wave.100 gram butyl acrylates, ethyl propenoate and methyl methacrylate (30: 20: 50 weight ratios) mix monomer and 3 gram sodium laurylsulfonate emulsifying agents are dissolved in the above-mentioned microemulsion, under brute force stirs, form stable emulsion.Find time inflated with nitrogen three times of system, last nitrogen protection.Under agitation as appropriate speed, system is warmed up to 80 ℃, 1.5 gram ammonium persulphates and 0.3 gram Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 5 hours.After reaction finishes,, get nano composite material after the drying directly with emulsion film forming.
Embodiment 8
Emulsion preparation argillaceous is with example 7.With the gained emulsion breaking, wash after reaction finishes, obtain the nano composite material of emulsion polymerization prepared after the drying.
Embodiment 9
10 gram halloysites are added in and stirred in 900 ml waters 4 hours, be dispersed to microemulsion, left standstill after mixing 12 hours, above-mentioned microemulsion was carried out ultra-sonic dispersion 1 hour with ultrasonic wave.Restrain Isooctyl acrylate monomers, ethyl propenoate and methyl methacrylate (10: 40: 50 weight ratios) mix monomer and 1.5 gram Sodium dodecylbenzene sulfonatees and 1 gram polyoxyethylene nonylphenol ether blending emulsifiers with 100 and be dissolved in the above-mentioned microemulsion, under brute force stirs, form stable emulsion.Find time inflated with nitrogen three times of system, last nitrogen protection.Under agitation as appropriate speed, system is warmed up to 80 ℃, 1.5 gram ammonium persulphates and 0.5 gram Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 5 hours.After reaction finishes,, get nano composite material after the drying directly with emulsion film forming.
Embodiment 10
Emulsion preparation argillaceous is with example 9.With the gained emulsion breaking, wash after reaction finishes, obtain the nano composite material of emulsion polymerization prepared after the drying.
Claims (4)
1. an in-situ emulsion polymerization prepares the method for polyacrylic ester/clay nanocomposites, it is characterized in that following these steps to implementing: 3-13 part clay is joined in 600-1000 part water, under agitation form the microemulsion of clay, leave standstill after being uniformly dispersed; Before carrying out letex polymerization, above-mentioned microemulsion is carried out ultra-sonic dispersion with ultrasonic wave; 100 parts of acrylate monomers and 1-3 part emulsifying agent are dissolved in the above-mentioned microemulsion of 600-1000 part, or add 2 parts of stablizer polyvinyl alcohol simultaneously, under brute force stirs, form stable emulsion; System vacuumizes, inflated with nitrogen three times respectively, last nitrogen protection; Stir, system is warmed up to 70-80 ℃, 0.5-2.5 part initiator and 0.1-0.5 part molecular weight regulator Dodecyl Mercaptan are added drop-wise in the emulsion polyreaction 4-6 hour; With gained emulsion direct pouring film forming, or after breakdown of emulsion, washing, drying, obtain the nano composite material of emulsion polymerization prepared.
2. in-situ emulsion polymerization according to claim 1 prepares the method for polyacrylic ester/clay nanocomposites, it is characterized in that used clay is bentonite, polynite, halloysite, does not need the processing that organises of quaternary ammonium salt.
3. in-situ emulsion polymerization according to claim 1 prepares the method for polyacrylic ester/clay nanocomposites, it is characterized in that described acrylate monomer is methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer, and wherein any two kinds or three kinds of monomeric mixtures.
4. in-situ emulsion polymerization according to claim 1 prepares the method for polyacrylic ester/clay nanocomposites, it is characterized in that described initiator is Potassium Persulphate or ammonium persulphate.
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| CNB011333472A CN1143868C (en) | 2001-10-26 | 2001-10-26 | In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material |
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| CNB011333472A CN1143868C (en) | 2001-10-26 | 2001-10-26 | In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material |
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| CN1143868C true CN1143868C (en) | 2004-03-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339533C (en) * | 2005-07-29 | 2007-09-26 | 四川大学 | Montmorillonite-acrylic acid series nanometer textile glue size and its preparation method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10237259A1 (en) | 2002-08-14 | 2004-02-26 | Basf Ag | Clay mineral giving specified particle size on stirring in water is used as a leather tanning agent, especially in combination with an organic tanning agent |
| DE10255095A1 (en) * | 2002-11-26 | 2004-06-03 | Basf Ag | Process for the manufacture of a semi-finished leather product |
| CN100368457C (en) * | 2005-06-09 | 2008-02-13 | 中国科学院化学研究所 | Method for preparing polyphenylene ethenylene clay nanometer composite |
| CN100365082C (en) * | 2005-06-30 | 2008-01-30 | 同济大学 | Clay acrylic surface decorating material and its preparing method |
| CN100348622C (en) * | 2006-01-12 | 2007-11-14 | 上海交通大学 | Polymerization method for preparing monodispersal organic/inorganic composite nano-microsphere |
| CN101864023B (en) * | 2010-05-25 | 2011-10-19 | 武汉理工大学 | Preparation process of poly-fluorine-containing acrylic ester/ montmorillonite composite emulsion |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339533C (en) * | 2005-07-29 | 2007-09-26 | 四川大学 | Montmorillonite-acrylic acid series nanometer textile glue size and its preparation method |
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Granted publication date: 20040331 Termination date: 20101026 |