CN1216096C - Polyiner/laminate inorganic nano composite material and its milling shearing preparation method - Google Patents
Polyiner/laminate inorganic nano composite material and its milling shearing preparation method Download PDFInfo
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- CN1216096C CN1216096C CN 02133588 CN02133588A CN1216096C CN 1216096 C CN1216096 C CN 1216096C CN 02133588 CN02133588 CN 02133588 CN 02133588 A CN02133588 A CN 02133588A CN 1216096 C CN1216096 C CN 1216096C
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Abstract
A strong extrusion and shearing force field supplied by a unique three-dimensional shearing structure of a force chemical reactor in the milling disc shape is used for realizing slide and stripping between inorganic solid phase shearing layers with a weak interlaminar structure and preparing a nanometer lamellar filling material with a large width and thickness ratio. The multifunction of the milling pulverization, the dispersion, the mixture and the force activation of a milling disc is used for simultaneously realizing the pulverization and the lamella slide and stripping of lamellar inorganic matter, the pulverization and the embedding of a polymer and the solid phase dispersion and the mixture of the polymer and an inorganic filling material and preparing polymer or lamellar inorganic composite powder. Then, the polymer or lamellar inorganic nano composite material is prepared by a universal processing method.
Description
One, technical field
The present invention relates to a kind of polymer/laminated inorganics nano composite material and mill shearing preparation method thereof.
Two, background technology
Polymer/laminated inorganics nano composite material is that a kind of laminated inorganic matter filler that will have weak interlayer structure by suitable means is scattered in the formed a kind of nano composite material of polymeric matrix with nanometer layer thickness.According to the degree of scatter of laminated inorganic matter filler in matrix resin, it is divided into intercal type and exfoliated two classes.Owing to combine the advantage of polymkeric substance and laminated inorganic matter material, economical, effectively the laminated inorganic matter material with potential nanostructure is not fully exerted in performances such as light, electricity, magnetic, heat, power, obstruct, chemically reactive and catalysis, be subjected to the great attention of countries in the world scholar and business circles surplus in the of nearly ten over year always, become one of material area research and hot of research and development.
At present, the method for preparing polymer/laminated inorganics nano composite material is an intercalation compounding, comprising:
The monomer intercalation polymerization: the volumetric expansion when it utilizes the special laminate structure of natural laminated inorganic matter (as clay) and monomer intercalation polymerization realizes the splitting of laminated inorganic matter, the nanometer lamella is dispersed in the polymeric matrix, gives mechanical property, thermal characteristics and the barrier property etc. of material excellence.Multiple intercalation composite materials such as polyamide/laminated clay, PI/ layered silicate, PS/ polynite and PET/ polynite have been prepared with this method.In addition Ziegler-Natta catalyst is carried between the organo montmorillonite lamella, realizes propylene gas phase catalyzed polymerization, the preparation composite nanometer-level polypropylene/montmorillonoid material.
The polyalcohol intercalation method: polymers soln or emulsion or polymer melt intercalation enter the laminated inorganic matter interlayer through the special processing that organises, and realize that the laminated inorganic matter filler is scattered in the polymeric matrix with the nanometer lamella.
But also face a following difficult problem by the compound preparation polymer/inorganic nanometer of intercalation matrix material:
(1) layer compound thermodynamics requires polymkeric substance and laminated inorganic matter that strong interaction is arranged, and the intercalation that has limited non-polar polymer is compound;
(2) the monomer intercalation polymerization relates to complicated chemical reaction;
(3) laminated inorganic matter organises and relates to complicated chemical reaction and solid-liquid separating technology;
(4) the melt intercalation requires polymer malt viscosity low;
(5) little, the laminated inorganic matter that do not possess ion exchanging function of interlamellar spacing such as graphite, V
2O
5, MoS
2Deng, be difficult to handle the enlargement layer spacing and realize that intercalation is compound by organising.
Three, summary of the invention
A kind of polymer/laminated inorganics nano composite material and the mill shearing preparation method thereof that provide at the deficiencies in the prior art is provided, is characterized in the solid state mechanochemistry method is introduced polymer/laminated inorganics nano composite material frontier.Utilize the powerful extrusion shearing field of force that three-dimensional shear structure provided and pulverizing, mixing, dispersion and the solid state mechanochemistry response function of pan type physico chemical reactor uniqueness, in the pan-milling process, realize pulverizing, the lamella slippage of laminated inorganic matter simultaneously and peel off, the pulverizing of polymkeric substance and embedding, polymkeric substance disperses with the solid phase of mineral filler and mixes, prepare polymer/laminated inorganics composite granule, through further machine-shaping, prepare polymer/laminated inorganics nano composite material.
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.
The recipe ingredient of polymer/laminated inorganics nano composite material is:
99.5～50 parts in polymkeric substance
0.5～30 part of laminated inorganic matter
0～20 part of auxiliary agent
Polymkeric substance wherein is thermoplastic polyethylene, polypropylene, polystyrene, ABS, polyethylene oxide, polymeric amide, polyester, polyvinyl chloride, polymethylmethacrylate; At least a in thermoplastic elastomer such as SBS, the ethylene-propylene copolymer.
Laminated inorganic matter in the polymer/laminated inorganics nano composite material is a graphite; Layered silicate is talcum, mica, clay, vermiculite and chrysotile; Layered metal oxide is V
2O
5, MoO
3, WO
3In at least a.
The mill shearing preparation method of polymer/laminated inorganics nano composite material:
(1) be that 0.5～30 part of the layered inorganic powder of 1～100 μ m mixes for 0～20 part with auxiliary agent with median size;
(2) the solid particulate polymkeric substance is made powdery, the powder with layered inorganic powder or (1) mixes then;
(3) start the millstone type force chemical reactor, Chinese patent ZL 95 1 11258.9, adjusting rotating speed is 5～100 rev/mins, logical water coolant is taken the heat that mill processes produces out of, above-mentioned mixture is entered pan type physico chemical reactor by charging opening, back through once milling by the discharge port blanking, enter the circulation of next time milling, pressure between regulation and control Moving plate and the quiet dish, the Moving plate rotating speed, realize shearing force field to the pulverizing of polymkeric substance and the splitting of laminated inorganic matter,, obtain to embed mutually by 10～60 circulations of milling, the polymer/laminated inorganics composite granule of uniform mixing and dispersive;
(4) polymer/laminated inorganics composite granule mixes with polymeric matrix and various processing aid with various processing aids or polymer/laminated inorganics composite granule, through the twin screw extruder extruding pelletization, get polymer/laminated inorganics nano composite material.
(5) polymer/laminated inorganics nano composite material through mold pressing, injection moulding, extrude and the blow moiding method moulding, obtain various plastics.
Used auxiliary agent comprises coupling agent, compatilizer or tensio-active agent among the present invention.Wherein coupling agent is the known silane coupling agent of prior art, titanate coupling agent, aluminate coupling agent and aluminium titanium composite coupler etc.; Compatilizer is known polymer graft multipolymer of prior art or segmented copolymer; Tensio-active agent is the known positively charged ion of prior art, negatively charged ion or nonionogenic tenside.Can be used, its precondition is that these auxiliary agents are realized purpose of the present invention and obtaining of excellent results of the present invention do not have a negative impact.
Used processing aid is the known oxidation inhibitor of prior art, stablizer, lubricant etc. among the present invention.
The present invention has following advantage:
1. normal temperature, normal pressure, solid phase is compound, does not need solvent, does not produce environmental pollution;
2. wider to the laminated inorganic matter adaptive surface, selectivity is big;
3. wide to the polymkeric substance adaptation, selectivity is big;
4. can obtain broad-spectrum polymer/laminated inorganics nano composite material easily, as have the structured material of excellent mechanical performances and have functional materialss such as conduction, heat conduction, electromagnetic shielding, obstruct or sound insulation and noise reduction.
Four, description of drawings
Fig. 1 pan-milling shearing force field prepares the SEM photo of PP/EP250 (95/5) matrix material
Fig. 2 pan-milling shearing force field prepares the TEM photo of PP/EP250 (95/5) matrix material
The PP/FG (60/40) of Fig. 3 pan-milling shearing force field preparation adheres to the SEM photo of secondary structure composite granule
The TEM photo of the PP/FG matrix material of Fig. 4 pan-milling shearing force field preparation
The SEM photo of SBS/PP/ clay (90/8/2) nano composite material of Fig. 5 pan-milling shearing force field preparation
The TEM photo of SBS/PP/ clay (90/8/2) nano composite material of Fig. 6 pan-milling shearing force field preparation
The PP/ talcum powder (50/50) of Fig. 7 pan-milling shearing force field preparation adheres to the SEM photo of secondary structure composite granule
The SEM photo of PP/ talcum powder (50/50) matrix material of Fig. 8 pan-milling shearing force field preparation
Fig. 9 PA6/MTT nano material TEM photo
Five, 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.PP/ expanded graphite conductive nano composite material: earlier particle diameter 2～5mm polypropylene (F401) 80kg is added the millstone type force chemical reactor of having opened by charging opening, mill through 7 times, polypropylene powder that must be thicker, continue to mill 25 times with 250 times of expanded graphite 5kg that handle through sodium oleate, get PP/ expanded graphite composite powder, mix through twin-roll masticator mastication with polypropylene (trade mark 4220) 15kg then, in 190 ℃ of temperature, pressure 10MPa compression molding gets 3mm and 1.5mm sheet material.The Mechanics Performance Testing result is: when content of graphite is 5% tensile yield strength 32.5MPa, and Young's modulus 1.8GPa, the powerful 13.4kJ/m of notch shock
2, realized strengthening toughness reinforcing; Specific conductivity 1.1 * 10
-6Scm
-1, improved 10 orders of magnitude with compound the comparing of simple blend, reached the requirement of antistatic material.Scanning electron microscope Fig. 1 and transmission electron microscope Fig. 2 observe and show that graphite flake layer is dispersed in the polypropylene matrix with 5～10nm thickness.
2.PP/ crystalline flake graphite conduction, heat-conductive composite material: PP is just mixed according to (60+40) with crystalline flake graphite (FG), select suitable rotating speed and pressure, in pan type physico chemical reactor, mill altogether 35 times, making median size is the PP/FG composite granule that 227.6 μ m have laminar shape characteristic Fig. 3, compound with PP blend on the twin-roll masticator then, make PP/FG conduction, heat conducting nano composite material.When content of graphite was 20wt%, tensile yield is powerful to be 30.68MPa, and notched Izod impact strength is 9.65kJ/m
2, specific conductivity 5.2 * 10
-4Scm
-1, fill compound 8 orders of magnitude that improved than simple blend; Thermal conductivity is 0.69Wm
-1K
-1, improved more than 2 times than matrix resin.TEM Fig. 4 observes proof, and in the PP/FG matrix material, crystalline flake graphite has been peeled off into the nanometer lamella and has been uniformly distributed in the matrix, graphite flake layer thickness 10～50nm, and length is below 0.5 μ m.
Make HDPE/ crystalline flake graphite heat conducting nano composite material with same method, when content of graphite was 30wt.%, thermal conductivity was 2.2W/Km, and specific conductivity reaches 10
-3S/cm.Fill compound comparing with simple mixing, thermal conductivity is high by 30%, and specific conductivity exceeds 8 orders of magnitude.High heat conduction and conduction have been realized.Tensile yield strength is brought up to 34.5MPa by 28.5MPa, and shock strength and elongation at break descend to some extent.
3.SBS/MTT nano composite material: mix at the beginning of 95 parts of 5 parts of organo montmorillonites and the SBS, select suitable rotating speed and pressure, in pan type physico chemical reactor, mill altogether, make the SBS/MTT composite granule, compression molding.When polynite soil content was 5wt%, tensile strength was brought up to 20MPa by the 4.2MP of SBS, and 500% stretches modulus surely brings up to 7.2MPa by the 5.1MPa of SBS, and tear strength and elongation at break almost do not change.Tem observation shows that milling altogether of polynite and SBS realized the limellar stripping of polynite, has produced the laminated structure of 40nm left and right thickness, and in the SBS matrix homodisperse.
4.SBS/PP/ clay nanocomposites: PP is pulverized, just mix according to 80/20 ratio with organic clay, select suitable rotating speed and pressure, in pan type physico chemical reactor, mill altogether, making median size is the PP/ clay composite granule of 5.57 μ m, compound with SBS blend on the twin-roll masticator of proportional then, make the SBS/PP/ clay nanocomposites.Tensile strength is brought up to 20.2MPa by the 4.2MPa of SBS when PP/ clay composite powder content is 10wt%, tear strength is brought up to 67.3kN/m by the 37.6kN/m of SBS, 300% stretches modulus surely brings up to 4.6MPa by 2.0MPa, elongation at break brings up to 848% by 664%, and the maximum heat weightless temperature is brought up to 468.3 ℃ by 447.3 ℃.SEM Fig. 5 and TEM Fig. 6 observe proof, and in the SBS/PP/ clay composite material, clay has been peeled off into the nanometer lamella and has been uniformly distributed in the matrix, clay layer thickness 30～80nm, and length is below 0.5 μ m.
Can prepare the SBS/PS/ clay nanocomposites with same method, when (SBS+PS+MTT=92.0+5.6+2.4), its mechanical property is: tensile strength 19.5MPa, tear strength 51kN/m, elongation at break 650%, 300% is stretched modulus 4.5MPa surely, and 500% stretches modulus 7.3MPa surely.
5.PP/ talcum powder nano composite material: with PP powder and median size after the mixed of talcum powder less than 10 μ m according to (50+50), in pan type physico chemical reactor, mill altogether 30 times, getting median size is 3 μ m, has the PP/ talcum powder composite granule Fig. 7 that adheres to secondary structure, sheet shape characteristic, with PP blend granulation in twin screw extruder, get PP/ talcum powder nano composite material then through compression molding.When talcum powder content was 10wt.%, mechanical property is: tensile yield strength was brought up to 28MPa by 23MPa, and Young's modulus is brought up to 1.5GPa by 1.0GPa, and notched Izod impact strength is by 7.4kJ/m
2Bring up to 9.8kJ/m
2TEM photo such as Fig. 8 of the direct compression molding sheet material of PP/ talcum powder (50/50) composite granule ultrathin section(ing), as can be seen, talcum powder has been stripped from into 30～50nm lamella, and is isolated by matrix PP, obtains homodisperse.
6.PA6/MTT nano composite material: the PA6 meal that pan-milling is obtained is with after the organo montmorillonite of median size 34 μ m mixes by (50+50), in pan type physico chemical reactor, mill altogether 30 times, obtaining median size is the PA6/MTT composite granule of 80nm, through the twin screw extruder extruding pelletization, get the PA6/MMT nano composite material.When polynite content was 3.5wt.%, its mechanical property is: tensile yield strength was brought up to 95MPa by 68MPa, and modulus is brought up to 4.3GPa by 3.0GPa, and heat-drawn wire is brought up to 113 ℃ by 62 ℃, and notched Izod impact strength is brought up to 38J/m by 28J/m.The monomer polymerization method gained PA6/MTT nano composite material that is higher than bibliographical information.Tem observation shows Fig. 9, and polynite is dispersed in the PA6 matrix with the lamellar spacing of 10～30nm.
7.HDPE/ vermiculite nano composite material: with median size is the industrial vermiculite power of 10 μ m, 850 ℃ of thermal expansions, gets expanded vermiculite.Then powdery HDPE, maleic anhydride grafts (MAH-g-HDPE) are mixed with the prescription of expanded vermiculite according to (50+10+40), in pan type physico chemical reactor, mill altogether 30 times, get embedding, homodisperse mutually, has the HDPE/ vermiculite composite granule that adheres to secondary structure and sheet shape characteristic, then with the HDPE of formula ratio through twin screw extruder blend extruding pelletization, the HDPE/ vermiculite nano composite material.Vermiculite power content is that 10% compression molding sheet material tensile strength, shock strength and Young's modulus all have raising by a relatively large margin.Prove that through means such as XRD, TEM the vermiculite wafer pitch surpasses 40nm, lamellar spacing 15～45nm, and in the HDPE matrix homodisperse.
Claims (2)
1, a kind of mill shearing preparation method of polymer/laminated inorganics nano composite material is characterized in that:
(1) be that layered inorganic powder 0.5～30 weight part of 1～100 μ m mixes with auxiliary agent 0～20 weight part with median size;
(2) solid particulate polymkeric substance 99.5～50 weight parts are made powdery, the powder with (1) mixes then;
(3) start the millstone type force chemical reactor, adjusting rotating speed is 5～100 rev/mins, logical water coolant is taken the heat that process of lapping produces out of, mixture is added pan type physico chemical reactor, back through once milling by the discharge port blanking, enter the circulation of next time milling, pressure, Moving plate rotating speed between regulation and control Moving plate and the quiet dish, realize that shearing force field is to the pulverizing of polymkeric substance and the splitting of laminated inorganic matter, by 10～60 circulations of milling, embedded mutually, uniform mixing and the polymer/laminated inorganics composite granule of dispersive;
(4) polymer/laminated inorganics composite granule mixes with various processing aids, through the twin screw extruder extruding pelletization, gets polymer/laminated inorganics nano composite material;
(5) polymer/laminated inorganics nano composite material through mold pressing, injection moulding, extrude and the blow moiding method moulding, obtain various plastics;
Wherein polymkeric substance is thermoplastic polyethylene, polypropylene, polystyrene, ABS, polyethylene oxide, polymeric amide, polyester, polyvinyl chloride, polymethacrylate; At least a in thermoplastic elastomer SBS, the ethylene-propylene copolymer, laminated inorganic matter comprises graphite, layered silicate and layered metal oxide.
2, by the mill shearing preparation method of the described polymer/laminated inorganics nano composite material of claim 1, it is characterized in that laminated inorganic matter is a graphite; Layered silicate is talcum, mica, clay, vermiculite and chrysotile; Layered metal oxide is V
2O
5, MoO
3, WO
3In at least a.
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| CN1216096C true CN1216096C (en) | 2005-08-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2915749A1 (en) * | 2007-05-03 | 2008-11-07 | Multibase Soc Par Actions Simp | COMPOSITIONS FORMED OF A POLYOLEFIN MATRIX AND A LAMELLAR MINERAL CHARGE AND ASSOCIATED COMPOUNDAGE EXTRUSION PROCESS |
| CN101633740B (en) * | 2008-07-22 | 2011-11-09 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing transparent heat-resistant polymethyl methacrylate nano-composite membrane |
| CN104071848B (en) * | 2014-06-23 | 2016-01-20 | 浙江大学 | A kind of talcum-ferrite nano matrix material and preparation method thereof |
| CN104058467B (en) * | 2014-07-06 | 2016-02-24 | 浙江大学 | A kind of layer mineral and nanometer iron carbonyl intercalation composite material and preparation method thereof |
| CN105482320B (en) * | 2016-01-28 | 2017-10-13 | 西安科技大学 | A kind of polyvinyl chloride plasticizing enhanced agglomerate and its preparation method and application |
| CN106046659B (en) * | 2016-07-14 | 2018-08-10 | 东莞市常平信安实业有限公司 | A kind of heat conduction ABS products and preparation method thereof |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
| CN109912887A (en) * | 2019-03-15 | 2019-06-21 | 广东工业大学 | A kind of nanometer of removing composite material, preparation method and applications |
| CN110642295B (en) * | 2019-10-25 | 2021-08-03 | 四川大学 | Molybdenum disulfide nanosheet layer stripping preparation method based on solid-phase mechanochemical reactor |
| CN114832907B (en) * | 2021-02-01 | 2023-10-03 | 深圳大学 | Method for preparing lamellar nano particles in large scale by rapid cutting |
| CN115490889A (en) * | 2022-08-26 | 2022-12-20 | 四川大学 | Method for realizing in-situ stripping of two-dimensional filler by using high-elasticity polymer |
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