CN1114634C - Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles - Google Patents
Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles Download PDFInfo
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- CN1114634C CN1114634C CN 99115028 CN99115028A CN1114634C CN 1114634 C CN1114634 C CN 1114634C CN 99115028 CN99115028 CN 99115028 CN 99115028 A CN99115028 A CN 99115028A CN 1114634 C CN1114634 C CN 1114634C
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Abstract
The present invention relates to a method for preparing a polymer/inorganic nanometer particle compound material by ultrasonic irradiation, which is characterized in that multiple action of dispersion, pulverization, activation, initiation, etc. of ultrasonic waves is used; the polymerization of monomers on the surfaces of nanometer particles is realized when the nanometer dispersion of inorganic nanometer particles in a liquid phase is realized, and thus, the stabilization and the compound of the inorganic nanometer particles are realized. Prepared products are nanometer compound emulsion particle polymers, and the thickness of a wrapping layer is from 5 to 65mm. Thus, the prepared products can be directly used as paint and adhesive agents. After the processes of separation and drying, functional polymer/inorganic nanometer compound materials are obtained.
Description
The present invention relates to a kind of method for preparing the polymer/inorganic nanometer particle composite material.
The polymer/inorganic nanometer particle composite material is that inorganic nano-particle is scattered in a kind of nano composite material in the polymeric matrix.Owing to combine the advantage of polymkeric substance and inorganic nano material, performances such as economic, as to effectively utilize nanoparticle uniqueness light, electricity, heat, magnetic, power, chemically reactive, catalysis, be subjected to various countries scholar's great attention in recent years, become one of the research focus in material field.But because the inorganic nano-particle surface energy is high, conglomerate very easily is difficult to really to realize the nano-dispersed of nanoparticle in polymeric matrix and nano combined by general blend is compound.For addressing this problem, people mainly adopt following several method: (1) physical deposition method: (2) precursor process (3) nanoparticle original position method of formation (4) intercalation compounding (5) supramolecule self-assembly forms nano composite material method (6) parcel polymerization (E.Bourgeat-Lami, Ph.Espiard, A.Guyot, Polymer, 36 (23), 4385,1995).Wherein, parcel polymerization alternative is big, applied widely, is subjected to people and pays much attention to.But the difficult point of parcel polymerization is: the nano-dispersed of (1) nanoparticle in polymerisation medium; (2) monomer is in the polymerization of nanoparticle surface.
The method that provides a kind of ultrasound wave irradiation to prepare the polymer/inorganic nanometer particle composite material at the deficiencies in the prior art is provided, is characterized in the ultrasound wave irradiation technology is introduced nano combined frontier.Utilize multiple actions such as hyperacoustic dispersion, pulverizing, activation, initiation, realizing that inorganic nano-particle is in liquid phase in the nano-dispersed, realize that monomer is in the nanoparticle surface polymerization, realize the stabilization and compoundization of inorganic nano-particle, preparation has the matrix material of polymkeric substance parcel inorganic nano-particle.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Ultrasound wave irradiation prepares the method for polymer/inorganic nanometer particle composite material:
1. with 0.1～5 part of inorganic nano-particle, 5～20 parts of monomers are in 0.2～5 part of adding of 70～90 parts of solvents and other auxiliary agent ultrasound wave irradiation reactor, again with in the ultrasonic wave horn,amplitude transformer insertion reaction device.
2. fed nitrogen about 2～10 minutes, logical nitrogen speed is 0.1～50 ml/min, and feeding the circulator bath temperature is 10～70 ℃.
3. the startup ultrasonoscope carries out polyreaction, and the ultrasonic power regulation range is at 50～1500w, frequency, 2 * 10
4～10
9Hz, 10 minutes～5 hours reaction times.
The inorganic nano-particle particle diameter is 1-100nm, and Nano compound is SiO
2, TiO
2, Al
2O
3, CdS, BaTiO
3And/or nano metal particles such as Ag, Au, Pt is at least a.
Monomer is that methyl methacrylate, ethyl propenoate, butyl acrylate, vinylbenzene, vinyl cyanide, acrylamide and/or the vinyl monomer that has surface-active sulfonic acid group, quaternary amines, phosphate group are at least a.
Solvent be water and/or with other solvents of water arbitrary proportion blended as alcohol, ketone etc., for the consideration of economy and environment aspect, the most preferred with water.
Tensio-active agent in the reactant of the present invention is at least a of the known positively charged ion of prior art, negatively charged ion or nonionogenic tenside, use jointly with auxiliary agent such as pH regulator agent, to be these auxiliary agents to order of the present invention realize obtaining with the good effect of the present invention its precondition does not have a negative impact.
The product of the present invention's preparation is nano combined emulsion particle polymkeric substance, is 5～65nm through transmissioning electric mirror determining polymkeric substance integument thickness, can directly be used as coating, binding agent; After separation, drying, obtain functional polymer/inorganic nano composite material.
The present invention has following advantage:
(1) polymerization does not need initiator;
(2) can realize that the nanoparticle dispersive carries out the polymerization encapsulation reaction simultaneously;
(3) temperature of reaction is lower;
(4) suitability to nanoparticle is wider;
(5) monomeric selectivity is bigger;
(6) can obtain broad-spectrum polymer/inorganic nanometer particle composite material easily.
Embodiment:
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
1. with nanoporous shape SiO
2Particle (particle diameter is 10nm) 500mg, butyl acrylate 27g and 1% hexadecyl amine bromide aqueous solution 270g join in the reactor, and adjusting the pH value with sodium hydroxide is 7～9.Feed about 5 minutes of nitrogen with the oxygen in the eliminating system, and 45 ℃ of control bath temperatures.Start Fisher Sonic DismemberatorModel 550 ultrasonic instruments (Fisher Scientific Co.) then, the beginning polyreaction, ultrasonic power is 137.5w in the reaction process, and frequency is 20kHz, and nitrogen speed is that the maintenance of 10 ml/min is constant.React and finished in 30 minutes.The nano combined emulsion particle polymkeric substance integument thickness of preparation is 5～65nm.
2. with nanometer Al
2O
3Particle (particle diameter is 17nm) 300mg, methyl methacrylate 28g and 1% lauryl sodium sulfate aqueous solution 270g join in the reactor, and adjusting the pH value with hydrochloric acid is 5～6.5.Feed about 5 minutes of nitrogen with the oxygen in the eliminating system, and 45 ℃ of control bath temperatures.Open Fisher Sonic Dismemberator Model550 ultrasonic instrument (Fisher Scientific Co.) then, the beginning polyreaction.Ultrasonic power is 137.5w in the reaction process, and frequency is 20kHz, and nitrogen speed is that the maintenance of 10 ml/min is constant.React and finished in 30 minutes.The nano combined emulsion particle polymkeric substance integument thickness of preparation is 5-65nm.
3. with nano-TiO
2Particle (particle diameter is 27nm) 300mg, vinylbenzene 16g and 1% hexadecyl amine bromide aqueous solution 144g join in the reactor.Adjusting the pH value with sodium hydroxide is 7～9.Feed earlier about 5 minutes of nitrogen with the oxygen in the eliminating system, and 30 ℃ of control bath temperatures.Open VC-1500 ultrasonic instrument (Sonic ﹠amp then; Materials Inc.) beginning polyreaction.Ultrasonic power is 600w in the reaction process, and frequency is 20kHz, and it is constant that nitrogen speed 10 ml/min keep.React and finished in 30 minutes.The nano combined emulsion particle polymkeric substance integument thickness of preparation is 5-65nm.
Claims (2)
1. ultrasound wave irradiation prepares the method for polymer/inorganic nanometer particle composite material.It is characterized in that:
(1) with inorganic nano-particle 0.1～5 weight part, monomer 5～20 weight parts, solvent 70～90 weight parts and other auxiliary agent 0.2～5 weight part add in the ultrasound wave irradiation reactor, again with in the ultrasonic wave horn,amplitude transformer insertion reaction device,
(2) fed nitrogen about 2～10 minutes, logical nitrogen speed is 0.1～50 ml/min, and logical circulator bath temperature is 10-70 ℃,
(3) start ultrasonoscope, carry out polyreaction, the ultrasonic power regulation range is at 50-1500w, frequency, 2 * 10
4～10
9Hz, 10 minutes～5 hours reaction times.
Wherein, monomer is at least a in methyl methacrylate, ethyl propenoate, butyl acrylate, vinylbenzene, vinyl cyanide, acrylamide and/or the vinyl monomer that has surface-active sulfonic acid group, quaternary amines, phosphate group.
2. prepare the method for polymer/inorganic nanometer particle composite material according to the described ultrasound wave irradiation of claim 1, the particle diameter that it is characterized in that inorganic nano-particle is 1～100nm, and Nano compound is SiO
2, TiO
2, Al
2O
3, CdS, BaTiO
3And/or nano metal particles such as Ag, Au, at least a among the Pt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115028 CN1114634C (en) | 1999-07-20 | 1999-07-20 | Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115028 CN1114634C (en) | 1999-07-20 | 1999-07-20 | Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280993A CN1280993A (en) | 2001-01-24 |
| CN1114634C true CN1114634C (en) | 2003-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99115028 Expired - Lifetime CN1114634C (en) | 1999-07-20 | 1999-07-20 | Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346951C (en) * | 2002-09-27 | 2007-11-07 | 北京化工大学 | Disperseing process of abio-particle in polymers |
| CN100391840C (en) * | 2004-03-12 | 2008-06-04 | 河南大学 | Reactive nanometer particle of silica dioxide |
| CN1331651C (en) * | 2004-11-15 | 2007-08-15 | 四川大学 | Method for improving mechanical properties of fusion seam of polymer injection articles and injection article die |
| JP5188045B2 (en) * | 2006-08-30 | 2013-04-24 | キヤノン株式会社 | Nano-oxide particles and method for producing the same |
| CN101864098B (en) * | 2010-06-03 | 2012-01-04 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN103372652A (en) * | 2012-04-16 | 2013-10-30 | 合肥杰事杰新材料股份有限公司 | Method for using ultrasound irradiation to prepare nano Ag/PVP (Ag/ polyvinyl pyrrolidone) composite |
| CN102775548B (en) * | 2012-07-30 | 2014-05-28 | 安徽理工大学 | Method for polymerizing and preparing nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion |
| CN106633511A (en) * | 2016-12-12 | 2017-05-10 | 芜湖市天雄新材料科技有限公司 | Preparation method of polyvinyl chloride wood-plastic composite material granules for profiles |
-
1999
- 1999-07-20 CN CN 99115028 patent/CN1114634C/en not_active Expired - Lifetime
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Granted publication date: 20030716 |