CN1400228A - Preparation method of polyvinyl chloride/laminate silicate nano composite material - Google Patents
Preparation method of polyvinyl chloride/laminate silicate nano composite material Download PDFInfo
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- CN1400228A CN1400228A CN 02112255 CN02112255A CN1400228A CN 1400228 A CN1400228 A CN 1400228A CN 02112255 CN02112255 CN 02112255 CN 02112255 A CN02112255 A CN 02112255A CN 1400228 A CN1400228 A CN 1400228A
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Abstract
The present invention provides a method for preparing polyvinyl chloride/laminate silicate nano composite material. It adopts solution comixing or melting comixing technology to implement effective combination of polyvinyl chloride and laminate silicate on nano size, and utilizes addition of other polymer or plasticizer with different propertion to obtain various polyvinyl chloride alloys or a serier of nano composite materials from hard to soft and from transparent to non-transparent composite formed from polyvinyl chloride elastic body and silicate. Said ivnented polyvinyl chloride/laminated silicate nano composite material can meed various application requirements, and its production process is simple and its production efficiency is high and cost is low.
Description
Technical field: the present invention relates to the preparation method of a kind of polyvinyl chloride (PVC) matrix material, particularly a kind of preparation method of the nano composite material of forming by polyvinyl chloride and inorganic laminated silicate.
Background technology: the single-layer sheet thickness of laminar silicic acid salt particle is about 1nm, and lamellar spacing changes between 0.96～2.14nm with the difference of interlayer cation kind, links to each other by Van der Waals force or hydrogen bond between each synusia.The interlayer inorganic cation of layered silicate can be replaced by organic cation by cation exchange reaction, makes lamellar spacing enlarge and close organic property enhancing of layered silicate.Studies show that in polymer processing, the polymer macromolecule chain can enter between the layered silicate synusia that organises at intercalation under the effect of high temperature or shearing force, lamellar spacing is further enlarged, even with its cleavage.The single-layer sheet of layered silicate is dispersed in the polymeric matrix like this, and promptly nano level wild phase original position forms.The polymer nanocomposites that adopts this method to obtain can combine rigidity, dimensional stability and the thermostability of inorganics and toughness, processibility and the dielectric properties etc. of polymkeric substance, makes the physical and mechanical property of such matrix material be better than the conventional performance of composites of same composition.
PVC is a kind of broad-spectrum universal resin, but because melt viscosity is big, shortcomings such as shock resistance difference have limited the application of PVC as structured material.Adopt at present existing report of research of thermoplastic resin (as acrylic acid esters co-polymer, SAN, SMA, E-VA-CO terpolymer and polyester etc.), thermosetting resin (as Resins, epoxy etc.) and elastomerics (as EVA, NBR, ABS, MBS, ACR, CPE etc.) modified PVC.
Described among the U.S. Pat P 6271297 and adopted organic complex ion or coupling agent that layered silicate is carried out organic decoration, with the auxiliary intercalator of Resins, epoxy conduct, then with the polymer melt blend, obtained the polymer/laminated silicate matrix material of intercal type or exfoliated structure, wherein mentioned nano composite material of polyvinyl chloride/layer silicate, be mainly concerned with Resins, epoxy improving the effect of PVC and the layered silicate thermal destruction in the course of processing.
Chinese patent CN 1340564A has described a kind of preparation method of nm-class particles toughened and reinforced polyvinyl chloride composite material, and nanoparticle wherein mainly is meant the particulate inorganic particle, as lime carbonate, and silicon-dioxide etc.
Summary of the invention: the preparation method who the purpose of this invention is to provide a kind of nano composite material of polyvinyl chloride/layer silicate of mechanical property excellence.
Nano composite material of polyvinyl chloride/layer silicate of the present invention prepares by solution blending and two kinds of methods of melt blending.The preparation method is as follows: the processing that organises of (1) layered silicate
0.5～20 part of layered silicate, 10～1000 parts in dispersion medium water, 0.1～10 part of organic agent 25～90 ℃ of following violent stirring, carries out cation exchange reaction, and the laminar silicic acid salt particle that obtains organising and handle is with its dry for standby.(2) Prepared by Solution Mixing Method nano composite material of polyvinyl chloride/layer silicate
The good solvent that adopts polyvinyl chloride is in advance with 100 parts of polyvinyl chloride (PVC) RESINS, 1～10 part of stablizer, 0～125 part of fully dissolving of softening agent, the layered silicate that organises that step (1) is obtained is with the abundant swelling of the good solvent of polyvinyl chloride and be uniformly dispersed, and it is joined in the solution of polyvinyl chloride system, stirring and refluxing is 20～300 minutes under the boiling point of good solvent, each component is mixed in solution, in glass plate top casting film forming, make nano composite material of polyvinyl chloride/layer silicate then.(3) melt-blending process prepares nano composite material of polyvinyl chloride/layer silicate
With purified laminar silicic acid salt particle or by step (1) obtain organise 0.1～15 part of layered silicate respectively with 100 parts of polyvinyl chloride (PVC) RESINS, 1～10 part of stablizer, 0～125 part in softening agent, 0.1～5 part of lubricant, 0～20 part of processing aid and other components equal in Banbury mixer or the forcing machine to prepare nano composite material of polyvinyl chloride/layer silicate in 145～190 ℃ of melting mixing.
Polyvinyl chloride of the present invention is the polymerization degree at 500～4000 polyvinyl chloride (PVC) RESINS or vinyl chloride copolymer.
Layered silicate of the present invention comprises montmorillonite, nontronite, beidellite, volkonskoite, hectorite, talcum, sauconite, magadiite, fibrous morphology crystals and vermiculite, and its cation exchange capacity (CEC) is 80～200meq/100g.
The organic agent of layered silicate of the present invention is the organic ion compound, comprising alkylammonium salt and alkyl phosphonium salt; Or suitable functionalized coupling agent, comprising silane, titanic acid ester, aluminate coupling agent, alkyl hydrochlorate and lipid acid.
Among the solution blending preparation method of the present invention, the good solvent of polyvinyl chloride comprises chlorinated hydrocarbons, pimelinketone, methylethylketone, dimethyl formamide, nitro benzene,toluene,xylene, acetonitrile and tetrahydrofuran (THF).
Among the described melt blending preparation method, stablizer comprises that lead salts stablizer, metallic soap class stablizer organic tin stablizer and organic auxiliary stabilizer cooperate or use separately; Softening agent is a phthalate, trimellitic acid ester class and polymeric plasticizer; Lubricant is a kind of in saturated hydrocarbons, fatty acid and the fatty stearic class; Processing aid is polyacrylate(s) modifier (ACR) or chlorinatedpolyethylene (CPE).
Described polyvinyl chloride composite materials comprises various polyvinyl chloride alloys, comprising alloy and the polyvinyl chloride elastomerics formed with chlorinatedpolyethylene, paracril, nylon, Resins, epoxy, MBS, EVA, NBR, ABS and ACR.
The present invention is owing to adopt the method for solution blending and melt blending to make the wild phase (silicate synusia) of nanoscale form in position, polyvinyl chloride matrix Central Plains, realize compound at nanoscale of polyvinyl chloride and layered silicate, thereby can give this nano composite material of polyvinyl chloride/layer silicate excellent mechanical property and barrier property; When adopting transparent thermo-stabilizer such as organic tin, layered silicate can further improve the transparency of material.
The present invention the has adopted Prepared by Solution Mixing Method polyvinyl chloride/laminate silicate film of exfoliated structure, tensile strength have improved 10～30%, the transparency and barrier are improved.Adopt the rigid polyvinyl chloride/laminated nm-silicate composite material of the intercal type structure of melt-blending process preparation, have the good transparency and mechanical property, in the layered silicate consumption is the scope of 0.5～3wt%, tensile strength has improved 10～30%, notched Izod impact strength has improved 5～20%, modulus in flexure has improved 10～50%, and processing characteristics and ordinary rigid and semi-rigid polrvinyl chloride product are suitable.Polyvinyl chloride alloy/the laminated nm-silicate composite material of preparation can further improve performance of composites.The elastomer/laminated silicate nanometer composite material of polyvinyl chloride of preparation can improve raw-material barrier and mechanical property.
Enforcement of the present invention is for the high performance PVC advanced composite material of exploitation, improve the PVC value-added content of product, the Application Areas of developing PVC, replace expensive engineering plastics in some occasions, reduce cost and the research contents etc. of enriching nano composite polymer/laminated silicate material has certain practical significance.
Embodiment: the following examples are to further specify of the present invention, do not limit the scope of the invention.
Embodiment 1:
Adopt the 45ml pimelinketone that the 10gPVC powder is fully dissolved, the 5ml pimelinketone is with 0.5g organic montmorillonoid swelling, after both mixing, 80 ℃ of following stirring and refluxing 60 minutes, each component is mixed in solution, in glass plate top casting film forming, make transparent polyvinyl chloride/montmorillonite-based nano laminated film of 0.1～0.3mm then.Adopt X-ray diffraction to measure the lamellar spacing of polynite in the material, and sample is carried out transmission electron microscope observing, the result shows that the polynite particle disperses with nanoscale in this material, and the performance test parameter of gained material sees Table 1.
Embodiment 2:
With the polymerization degree 800 powder material of polyvinyl chloride 60g, purified sodium-based montmorillonite 0.3g, organotin stabilizer 3g, DOP 3g, other auxiliary agents 1g mixes, in the mixing section of Haake torque rheometer,, mix discharging in 5 minutes under the condition of 50rpm, make transparent rigid polyvinyl chloride/Nano composite material of montmorillonite in 170 ℃.Adopt X-ray diffraction to measure the lamellar spacing of polynite in the material, and sample is carried out transmission electron microscope observing, the result shows that the polynite particle disperses with nanoscale in this material, and the performance test parameter of gained material sees Table 2.
Embodiment 3:
With the polymerization degree 800 powder material of polyvinyl chloride 60g, organic montmorillonoid 0.3g, organotin stabilizer 3g, DOP 3g, other auxiliary agents 1g mixes, in the mixing section of Haake torque rheometer,, mix discharging in 5 minutes under the condition of 50rpm, make transparent rigid polyvinyl chloride/Nano composite material of montmorillonite in 170 ℃.Adopt X-ray diffraction to measure the lamellar spacing of polynite in the material, and sample is carried out transmission electron microscope observing, the result shows that the polynite particle disperses with nanoscale in this material, and the performance test parameter of gained material sees Table 2.
Embodiment 4:
With the polymerization degree 800 powder material of polyvinyl chloride 60g, organic montmorillonoid 0.3g, Resins, epoxy 1.2g, organotin stabilizer 3g, DOP 3g, other auxiliary agents 1g mixes, in the mixing section of Haake torque rheometer in 170 ℃, mix discharging in 5 minutes under the condition of 50rpm, make transparent rigid polyvinyl chloride/Nano composite material of montmorillonite.Adopt X-ray diffraction to measure the lamellar spacing of polynite in the material, and sample is carried out transmission electron microscope observing, the result shows that the polynite particle disperses with nanoscale in this material, and the performance test parameter of gained material sees Table 2.
Embodiment 5:
With the polymerization degree 1300 powder material of polyvinyl chloride 60g, organic montmorillonoid 0.3g, lead salt one package stabilizer 3g, DOP 24g, other auxiliary agents 1g mixes, in the mixing section of Haake torque rheometer,, mix discharging in 5 minutes under the condition of 50rpm, make soft PVC/Nano composite material of montmorillonite in 150 ℃.Adopt X-ray diffraction to measure the lamellar spacing of polynite in the material, and sample is carried out transmission electron microscope observing, the result shows that the polynite particle disperses with nanoscale in this material, and the performance test parameter of gained material sees Table 3.
The performance perameter of table 1 polyvinyl chloride/Nano composite material of montmorillonite
The performance perameter of table 2 polyvinyl chloride/Nano composite material of montmorillonite
The performance perameter of table 3 polyvinyl chloride/Nano composite material of montmorillonite
Claims (7)
1, the preparation method of nano composite material of polyvinyl chloride/layer silicate is characterized in that described matrix material prepares as follows:
(1) processing that organises of layered silicate
0.5～20 part of layered silicate, 10～1000 parts in dispersion medium water, 0.1～10 part of organic agent 25～90 ℃ of following violent stirring, carries out cation exchange reaction, and the laminar silicic acid salt particle that obtains organising and handle is with its dry for standby;
(2) Prepared by Solution Mixing Method nano composite material of polyvinyl chloride/layer silicate
The good solvent that adopts polyvinyl chloride is in advance with 100 parts of polyvinyl chloride (PVC) RESINS, 1～10 part of stablizer, 0～125 part of fully dissolving of softening agent, the layered silicate that organises that step (1) is obtained is with the abundant swelling of the good solvent of polyvinyl chloride and be uniformly dispersed, and it is joined in the solution of polyvinyl chloride system, stirring and refluxing is 20～300 minutes under the boiling point of good solvent, each component is mixed in solution, in glass plate top casting film forming, make nano composite material of polyvinyl chloride/layer silicate then;
(3) melt-blending process prepares nano composite material of polyvinyl chloride/layer silicate
With purified laminar silicic acid salt particle or by step (1) obtain organise 0.1～15 part of layered silicate respectively with 100 parts of polyvinyl chloride (PVC) RESINS, 1～10 part of stablizer, 0～125 part in softening agent, 0.1～5 part of lubricant, 0～20 part of processing aid and other components equal in Banbury mixer or the forcing machine to prepare nano composite material of polyvinyl chloride/layer silicate in 145～190 ℃ of melting mixing.
2,, it is characterized in that described polyvinyl chloride is the polymerization degree at 500～4000 polyvinyl chloride (PVC) RESINS or vinyl chloride copolymer according to the preparation method of the described nano composite material of polyvinyl chloride/layer silicate of claim 1.
3, according to the preparation method of the described nano composite material of polyvinyl chloride/layer silicate of claim 1, it is characterized in that described layered silicate comprises montmorillonite, nontronite, beidellite, volkonskoite, hectorite, talcum, sauconite, magadiite, fibrous morphology crystals and vermiculite, its cation exchange capacity (CEC) is 80～200meq/100g.
4, according to the preparation method of the described nano composite material of polyvinyl chloride/layer silicate of claim 1, the organic agent that it is characterized in that described layered silicate is the organic ion compound, comprising alkylammonium salt and alkyl phosphonium salt; Or suitable functionalized coupling agent, comprising silane, titanic acid ester, aluminate coupling agent, alkyl hydrochlorate and lipid acid.
5,, it is characterized in that the good solvent of described polyvinyl chloride comprises chlorinated hydrocarbons, pimelinketone, methylethylketone, dimethyl formamide, nitro benzene,toluene,xylene, acetonitrile and tetrahydrofuran (THF) according to the preparation method of the described nano composite material of polyvinyl chloride/layer silicate of claim 1.
6,, it is characterized in that described stablizer comprises that lead salts stablizer, metallic soap class stablizer, organic tin stablizer and organic auxiliary stabilizer cooperate or use separately according to the preparation method of the described nano composite material of polyvinyl chloride/layer silicate of claim 1; Softening agent is a phthalate, trimellitic acid ester class and polymeric plasticizer; Lubricant is a kind of in saturated hydrocarbons, fatty acid and the fatty stearic class; Processing aid is polyacrylate(s) modifier (ACR) or chlorinatedpolyethylene (CPE).
7, according to the described nano composite material of polyvinyl chloride/layer silicate of claim 1 and make each method, it is characterized in that described polyvinyl chloride composite materials comprises various polyvinyl chloride alloys, comprising alloy and the polyvinyl chloride elastomerics formed with chlorinatedpolyethylene, paracril, nylon, Resins, epoxy, MBS, EVA, NBR, ABS and ACR.
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| CN101935426A (en) * | 2010-09-03 | 2011-01-05 | 天津科技大学 | Aid low-mobility polyvinyl chloride preservative film |
| CN102061026A (en) * | 2010-11-26 | 2011-05-18 | 中国科学院宁波材料技术与工程研究所 | Diathermanous and moisture permeable composite film and preparation method thereof |
| CN1687221B (en) * | 2005-04-06 | 2011-06-08 | 华南理工大学 | Method for preparing nano composite material of polyvinyl chloride/layer silicate |
| CN102127297A (en) * | 2010-01-12 | 2011-07-20 | 财团法人工业技术研究院 | Organic/inorganic hybrid material and method for producing same |
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| CN102558714A (en) * | 2011-06-24 | 2012-07-11 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| US8674011B2 (en) | 2009-11-27 | 2014-03-18 | Industrial Technology Research Institute | Organic/inorganic hybrid material and fabrication method thereof |
| CN106519498A (en) * | 2016-10-28 | 2017-03-22 | 无锡市永兴金属软管有限公司 | Blended toughened PVC (polyvinyl chloride) elastomer and preparation method thereof |
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- 2002-06-27 CN CN 02112255 patent/CN1202145C/en not_active Expired - Fee Related
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| CN1687221B (en) * | 2005-04-06 | 2011-06-08 | 华南理工大学 | Method for preparing nano composite material of polyvinyl chloride/layer silicate |
| US8674011B2 (en) | 2009-11-27 | 2014-03-18 | Industrial Technology Research Institute | Organic/inorganic hybrid material and fabrication method thereof |
| CN102127297A (en) * | 2010-01-12 | 2011-07-20 | 财团法人工业技术研究院 | Organic/inorganic hybrid material and method for producing same |
| CN102127297B (en) * | 2010-01-12 | 2014-08-27 | 财团法人工业技术研究院 | Organic/inorganic hybrid material and method for producing same |
| CN101935426A (en) * | 2010-09-03 | 2011-01-05 | 天津科技大学 | Aid low-mobility polyvinyl chloride preservative film |
| CN102061026A (en) * | 2010-11-26 | 2011-05-18 | 中国科学院宁波材料技术与工程研究所 | Diathermanous and moisture permeable composite film and preparation method thereof |
| CN102061026B (en) * | 2010-11-26 | 2013-04-24 | 中国科学院宁波材料技术与工程研究所 | Use of composite fast ion conductive film as heat and moisture permeable composite film |
| CN102558714A (en) * | 2011-06-24 | 2012-07-11 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| CN102558714B (en) * | 2011-06-24 | 2013-09-18 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| CN102504618A (en) * | 2011-11-22 | 2012-06-20 | 华南理工大学 | Imvite modifying method and nanometer composite micro foaming material preparation method |
| CN102516654B (en) * | 2011-11-24 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Out-phase ion exchange composite film and preparation method thereof |
| CN102516654A (en) * | 2011-11-24 | 2012-06-27 | 中国科学院宁波材料技术与工程研究所 | Out-phase ion exchange composite film and preparation method thereof |
| WO2018006728A1 (en) * | 2016-04-28 | 2018-01-11 | 华南理工大学 | Environmentally friendly imitation shell composite membrane in "interpenetrating petal" structure and preparation method therefor |
| US10781269B2 (en) | 2016-04-28 | 2020-09-22 | South China University Of Technology | Nacre-mimetic environmentally friendly composite membrane with “interpenetrating petal” structure and preparation method thereof |
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| CN109134722A (en) * | 2018-07-28 | 2019-01-04 | 塔里木大学 | A kind of compound barrier film of vermiculite and preparation method thereof |
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