CN1384130A - Prepn process of nano composite polymer/laminated silicate material - Google Patents
Prepn process of nano composite polymer/laminated silicate material Download PDFInfo
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- CN1384130A CN1384130A CN 01114907 CN01114907A CN1384130A CN 1384130 A CN1384130 A CN 1384130A CN 01114907 CN01114907 CN 01114907 CN 01114907 A CN01114907 A CN 01114907A CN 1384130 A CN1384130 A CN 1384130A
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Abstract
Active organic matter capable of being polymerized through reaction and extrusion process and corresponding initiator or catalyst as well as organically modified laminar silicate are mixed and in-situ insertion polymerized together with other supplementary material in a reactive extruder to prepare the composite polymer/laminar silicate nano-material directly and pelletize. The said process is one simple technological process, has low cost and continuous production and can realize the stripping between layer and improve the performance of the composite material.
Description
The technical field of the invention is a macromolecular material.
Polymer based nanocomposites is the important branch that nano material is used.Its superiority is in common knowledge by people.But, because during the very big and energy charge of nano material preparation difficulty, the cost costliness, big with the compound difficulty of polymkeric substance, seriously hindered the large scale application of this matrix material.Therefore, seek inexpensive nano material and become the focus that current polymer based nanocomposites is paid close attention to the complex method of polymkeric substance.Layered silicate is exactly a kind of so inexpensive natural inorganic material that people have searched out, and raw material sources are very abundant.With different polymkeric substance (as nylon, polyester, Resins, epoxy, acrylate or the like) and the compounded nano composite material of layered silicate, have excellent thermal property, mechanical property, flame retardant properties, gas barrier property etc.Can do high-performance industrial part, smart material and medical material etc.Be the easiest realization industrialization, the most inexpensive and polymer based nanocomposites that application prospect is the most wide.
Layered silicate is a kind of natural mineral, and the about 1nm of each crystal layer of the layered silicate of natural generation is thick, has only that each layer separately just becomes the nano-grade particle with it.The existing at present method for preparing nano composite polymer/laminated silicate material is that polymkeric substance is inserted between the stratiform silicate layer, realizes splitting, and layered silicate is dispersed in the polymkeric substance with the nano level lamella.Concrete grammar is broadly divided into three classes, ie in solution graft process, melt intercalated method and monomer intercalation method.Have partial monopoly at present both at home and abroad.But these methods are all not ideal enough from technology and intercalation effect aspect.
The solution intercalation method is that polymkeric substance and layered silicate are dissolved in the solvent simultaneously, and the intercalation by stirring because polymericular weight is very big, is difficult to enter interlayer, and the interlayer degrees of expansion is undesirable, and needs a large amount of solvents, and is complicated time-consuming, seriously polluted; Melt intercalated method is difficult to enter the layered silicate interlayer in all directions because polymericular weight is very big, and the interlayer degrees of expansion of layered silicate is not enough behind the intercalation, and the ratio of peeling off fully is less, is difficult to reach the ideal nano composite material; By contrast, monomer intercalation is a kind of comparatively ideal method.This method normally earlier with after polymer monomer and the organic modified sheet silicate mixing stirring, is carried out polymerization with reactor more under suitable condition.Because monomer at first enters interlayer, the re-initiation polymerization realizes that by monomeric polymerization expansion the bigger interlayer of layered silicate expands, and the ratio of peeling off fully increases greatly.Compare with other method, mechanical property, thermal stability, the interface cohesive force of this this method gained matrix material all improve a lot.Although it is a kind of relatively effective means that the monomer intercalation legal system is equipped with the polymer/laminated silicate based nano composite material, but still do not break away from traditional synthetic method of polymers, can only be undertaken by polymerization reaction kettle, the shortcoming of this method is: 1. owing to need powerful stirring more monomer could be inserted between the stratiform silicate layer, common polymkeric substance synthesis reaction vessel stirs powerful not high enough, especially the big reactor of suitability for industrialized production is all the more so, is difficult to realize suitability for industrialized production; 2. batch production can only be realized, automatization and serialization production can not be realized.
United States Patent (USP) 4,739,007 has reported the method for preparing nano-class polyamide/laminated silicate composition by the monomer intercalation polymerization.Chinese patent 1138593A discloses the method that another kind of monomer intercalation polymerization prepares nano-class polyamide/laminated silicate composition, adopts reactor polymerization 6-10 hour.Chinese patent 1272513A discloses the method for preparing polyester/phyllosilicate nano-composite material by the intercalation copolymerization, adopts reactor polymerization 8-13 hour.Chinese patent 1242392 (notification number) discloses a kind of method of monomer intercalation polystyrene/laminated nm-silicate composite material, United States Patent (USP) 6136909,6057396 grades have all related to the preparation method that intercalation prepares nano composite polymer/laminated silicate material, but these methods are common reactor intercalation polymeric, reaction times is usually in a few hours, and is that have even tens of hours.
The objective of the invention is to propose a kind of preparation method of nano composite polymer/laminated silicate material, it comprise with available reaction extrusion molding polymeric organic active thing and corresponding initiator or catalyzer etc. mix with organic modified sheet silicate etc. handle after, putting into screw extrusion press with other attached material reacts and extrudes, realize in-situ inserted polymerization, directly prepare nano composite polymer/laminated silicate material and granulation.Extrude by the response type twin screw extruder, the high shear field of screw rod can realize that the organic active thing fully enters the layered silicate interlayer, realize the more effective splitting of layered silicate, can reach the unapproachable effect of other method, increase substantially performance of composites; This novel method combines the granulation of monomer intercalation, polymerization, target compound together, realizes automatization serialization production, simplifies technology greatly, reduce cost, and pollution-free.
The inventive method is when extruding machine-shaping, finishes predetermined intercalation and chemical reaction process.The high-shear of screw rod makes and melts the body laminating in forcing machine, has increased the surface-area and the volume ratio of melting body greatly, helps the intercalation polymeric of organic active thing and layered silicate.The upper layer that approaches simultaneously and bring in constant renewal in helps the material transfer and the heat exchange of polyreaction, makes material can finish predetermined intercalation polymeric reaction quickly and accurately when carrying.The inventive method speed of response is fast, and the production efficiency height can be continuously produced.Production unit is simple, the level of automation height, and energy consumption is low.Residual monomer can directly remove in process of production, and can recycle.Product residence time in forcing machine is short, and extent of thermal degradation is low.Can directly strengthen toughness reinforcing or chemical modification in process of production.The product performance price is than high.The inventive method can be carried out the integrated production from the monomer intercalation polyreaction to product molding, as section bar, calendering, spinning, injection moulding and hollow blow molding etc. if be connected with post-treatment equipment.This shows that this preparation method is not only a kind of fabulous production technique, and widened the range of application of production technique, improve the performance of material, make it to have bigger development potentiality.
For realizing target of the present invention, the screw extrusion press described in this preparation method can be single screw rod, twin screw or multiple screw extruder.According to the difference of selected organic active thing, the forcing machine length-to-diameter ratio is in the 20-80 scope, and rotating speed is 10-150 rev/min, temperature is controlled at 30 ℃-300 ℃, can adopt a plurality of charging openings in case of necessity, and additional side is to drawing-in device, the liquid quantitative feeding device is beneficial to the adding of different attached material.But addition of vacuum gas barrier when being necessary is to get rid of the low molecular weight volatile thing that reaction generates.
Mixture of mixture, organic monomer and living oligomer that available reaction extrusion molding polymeric organic active thing of the present invention can be organic monomer, living oligomer, multiple organic monomer or the like.Organic monomer can be hexanolactam, diamine, diprotic acid, methyl methacrylate, dibasic alcohol, methylsiloxane, vinylbenzene, vinyl cyanide, cyanoacrylate or the like, and the organic active thing can be estrodur performed polymer, polyethers performed polymer, epoxy resin prepolymer or the like.These organic active monomers and organic active thing can react by condensation polymerization, radical polymerization, addition polymerization, anionoid polymerization, cationoid polymerisation and polycoordination etc.Layered silicates such as this employing clay, carclazyte, polynite or Meccah stone, be crushed to 200-400 order size particles, use intercalator, dispersion medium etc. by processing such as ion-exchanges then, make organic modified sheet silicate, be beneficial to the infiltration and the intercalation polymeric of organic active thing and layered silicate.Used intercalator can be a lauryl amine, octadecylamine, thanomin, diethanolamine, trolamine, lauric acid amine, hexanolactam, hexanediamine, trimethylammonium ammonia chloride, quaternary amine, phenyl-ethyl amine, Ursol D etc., preferably alkyl amine.Used dispersion medium can be a water, ethanol, ethylene glycol, 1,3-propyl alcohol, 1,4-butyleneglycol, acetone, chaff ketone etc., preferably water and ethanol.
The essentially consist of composite nano polymer/clay material of the present invention is, (A) organic active thing 40-99.5 weight part, (B) organic modified sheet silicate 0.5-60 weight part, (A) and gross weight (B) be 100 weight parts.(C) initiator 0.1-3 weight part, (D) activator 0.05-5 weight part (if being necessary), (E) toughner 1-20 weight part (if being necessary), (F) nucleator 0.1-5 weight part (if being necessary), (G) lubricant 0.2-5 weight part (if being necessary), (H) toughener 5-50 weight part (if being necessary), (I) stablizer 0.1-5 weight part (if being necessary), (J) tinting material 0.01-5 weight part (if being necessary).
The preparation method of composite nano polymer/clay material of the present invention is at first with mixing such as above-mentioned organic modified sheet silicate and organic active thing and corresponding initiators, can carry out suitable drying in case of necessity.Then the attached material feeding of this mixture and other forcing machine is reacted and extrude intercalation polymeric and granulation.
The present invention is a kind of preparation method of polymer based nanocomposites, its target product is a nano composite polymer/laminated silicate material, this target product can be a plurality of kinds, as nano-class polyamide/laminated silicate composition, polyester/phyllosilicate nano-composite material, Resins, epoxy stratiform silicate nanometer composite material, matrix material that polymethylmethacrylate/laminated nm-silicate composite material is relevant with all.
Embodiment
With the example that is prepared as of nylon 6/ laminated nm-silicate composite material, the preparation method and the performance of nano composite material of the present invention is described.
1, starting material component
Component A is ε-Ji Neixianan (hereinafter to be referred as a hexanolactam), component B is that organic modified sheet silicate is (hereinafter to be referred as silicate, see the preparation of organic modified sheet silicate for details), component C is sodium hydroxide (hereinafter to be referred as NaOH), component (D) is 2,4-tolylene diisocyanate (TDI is hereinafter to be referred as TDI).
2, the preparation of organic modified sheet silicate: after with ball mill layered silicate being ground, with 325 purpose sieve, the ion exchange capacity of the layered silicate that obtains is 96.4meq/100g.The 0.01M HCL that the 1.8g amino dodecane is dissolved in 60 ℃ 1000ml makes solution, the 10g layered silicate adds in this solution gradually, the suspension concuss 3h that obtains, repeatedly wash with deionized water again, filtered residue is at 80 ℃ of following vacuum-drying 12h, and regrinding carefully just gets organic modified sheet silicate through 325 purpose sieve.
3, screw extrusion press and expressing technique condition:
Adopt and rotate cord wood engagement type twin screw extruder in the same way, model is SJ-35, and screw diameter is 35mm, and length-to-diameter ratio is 32,140 rev/mins of control screw speeds.Adopt seven sections heating temperature controls, high temperature oil cooling is carried out vacuum exhaust the 6th section of forcing machine, and each section temperature is controlled to be 195 ℃, and 200 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃, 265 ℃.
4, the preparation of nylon 6/ laminated nm-silicate composite material:
After earlier hexanolactam being melted, add initiator and organic modified sheet silicate and mix, feed forcing machine behind the cooling drying continuously, activator TDI quantitatively feeds with second charging opening of micro liquid volume pump from forcing machine, extruding pelletization promptly gets product continuously.Composition of raw materials and product performance see Table 1.
Table 1 examples of implementation 123456 caprolactams (part) 100 99 98 97 96 95 silicate (part) 01234 5NaOH (part) 0.170 0.168 0.167 0.165 0.163 0.162TDI (part) 0.93 0.92 0.91 0.90 0.89 0.88 yield strength (MPa) 68 80 86 90 98 106 elongation at breaks (%) 83 78 66 53 48 38 stretch moduluses (GPa) 2.9 3.1 3.5 3.8 4.1 4.4 bending strengths (MPa) 93.5 98.3 109.0 125.1 138.4 148.0 composite bending modulus (GPa) 2.5 2.8 3.0 3.5 3.8 4.2 thermal denaturation temperature (℃, 1.82MPa) 86 95 112 125 140 152
Claims (11)
- A kind of preparation method of polymer based nanocomposites.It is with after organic modified sheet silicate mixes with available reaction extrusion molding polymeric organic active thing and corresponding initiator or catalyzer etc., add with other attached material and to carry out in-situ inserted polymerization in the reactive extruder, directly prepare nano composite polymer/laminated silicate material and granulation.1. the preparation method of a nano composite polymer/laminated silicate material, it is characterized in that with available reaction extrusion molding polymeric organic active thing and corresponding initiator or catalyzer etc. mix with organic modified sheet silicate etc. handle after, putting into screw extrusion press with other attached material reacts and extrudes, controlled temperature is at 30 ℃-300 ℃, realize in-situ inserted polymerization, directly prepare nano composite polymer/laminated silicate material and granulation.
- 2. according to the described preparation method of claim 1, wherein said screw extrusion press can be single screw rod, twin screw or multiple screw extruder.
- 3. according to claim 2, wherein said screw extrusion press length-to-diameter ratio is in the 20-100 scope, and rotating speed is 10-250 rev/min, controllable temperature can adopt a plurality of charging openings in case of necessity between 30 ℃-500 ℃, additional side is to drawing-in device, the liquid quantitative feeding device, vacuum pumping hardware etc.
- 4. the preparation method of claim 1, mixture of mixture, organic monomer and living oligomer that wherein said available reaction extrusion molding polymeric organic active thing can be organic monomer, living oligomer, multiple organic monomer or the like.
- 5. the preparation method of claim 1, wherein said organic modified sheet silicate is meant the layered silicate of handling by ion-exchange etc. with intercalator, dispersion medium etc.
- 6. according to claim 5, wherein said layered silicate is meant clay, carclazyte, polynite or Meccah stone.
- 7. according to claim 5, wherein said intercalator can be a lauryl amine, octadecylamine, thanomin, diethanolamine, trolamine, lauric acid amine, hexanolactam, hexanediamine, trimethylammonium ammonia chloride, quaternary amine, phenyl-ethyl amine, Ursol D etc.
- 8. according to claim 5, wherein said dispersion medium can be a water, ethanol, ethylene glycol, 1,3-propyl alcohol, 1,4-butyleneglycol, acetone, chaff ketone etc.
- 9. the preparation method of claim 1, wherein said in-situ inserted polyreaction can be condensation polymerization, radical polymerization, addition polymerization, ionic polymerization, polycoordination or the like.
- 10. the preparation method of claim 1, the essentially consist of wherein said composite nano polymer/clay material is, (A) organic active thing 40-99.5 weight part, (B) organic modified sheet silicate 0.5-60 weight part, gross weight (A) and (B) is 100 weight parts.(C) initiator 0.1-3 weight part, (D) promoting agent 0.05-5 weight part (if being necessary) if be necessary, can add toughner, nucleator, lubricant, toughener, stablizer, tinting materials etc. are some.
- 11. the preparation method of claim 1, its target product is a nano composite polymer/laminated silicate material, as nano-class polyamide/laminated silicate composition, polyester/phyllosilicate nano-composite material, Resins, epoxy stratiform silicate nanometer composite material, matrix material that polymethylmethacrylate/laminated nm-silicate composite material is relevant with all.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318455C (en) * | 2003-06-05 | 2007-05-30 | 中国科学技术大学 | Polymer/laminated dihydroxide inserting layered nano composite material and its preparation |
| CN1326931C (en) * | 2004-12-12 | 2007-07-18 | 青岛大学 | Preparation method of polyolefin/layered silicate nano-composition |
| CN102952393A (en) * | 2011-08-29 | 2013-03-06 | 奇菱科技股份有限公司 | Organic modification laminated composite material |
| CN103435875A (en) * | 2013-09-10 | 2013-12-11 | 青岛华夏橡胶工业有限公司 | High-abrasion-resistance rubber/phyllosilicate nano composite material fabric core conveyer belt cover rubber and preparation method thereof |
| CN105968375A (en) * | 2016-05-27 | 2016-09-28 | 江苏科技大学 | Reactive extrusion preparation method for polyamide nanometer master batches |
| CN107099116A (en) * | 2017-05-18 | 2017-08-29 | 湖南省达琪新材料有限公司 | The preparation method of polyamide polyamines intercalation phyllosilicate composite |
| CN108003609A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of bromination intercalated montmorillonite modified nylon materials and preparation method thereof |
-
2001
- 2001-04-27 CN CNB011149078A patent/CN1155643C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318455C (en) * | 2003-06-05 | 2007-05-30 | 中国科学技术大学 | Polymer/laminated dihydroxide inserting layered nano composite material and its preparation |
| CN1326931C (en) * | 2004-12-12 | 2007-07-18 | 青岛大学 | Preparation method of polyolefin/layered silicate nano-composition |
| CN102952393A (en) * | 2011-08-29 | 2013-03-06 | 奇菱科技股份有限公司 | Organic modification laminated composite material |
| CN103435875A (en) * | 2013-09-10 | 2013-12-11 | 青岛华夏橡胶工业有限公司 | High-abrasion-resistance rubber/phyllosilicate nano composite material fabric core conveyer belt cover rubber and preparation method thereof |
| CN103435875B (en) * | 2013-09-10 | 2015-10-28 | 青岛华夏橡胶工业有限公司 | A kind of high wear-resistant rubber/laminated nm-silicate composite material fabric core conveyor belt rubber cover and preparation method thereof |
| CN105968375A (en) * | 2016-05-27 | 2016-09-28 | 江苏科技大学 | Reactive extrusion preparation method for polyamide nanometer master batches |
| CN105968375B (en) * | 2016-05-27 | 2019-06-14 | 丹阳新华美塑料有限公司 | A kind of reactive extrursion preparation method of polyamide nano master batch |
| CN107099116A (en) * | 2017-05-18 | 2017-08-29 | 湖南省达琪新材料有限公司 | The preparation method of polyamide polyamines intercalation phyllosilicate composite |
| CN108003609A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of bromination intercalated montmorillonite modified nylon materials and preparation method thereof |
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