CN105885022B - A kind of novel clay soil method of modifying and the method that polymer composites are prepared using the clay - Google Patents
A kind of novel clay soil method of modifying and the method that polymer composites are prepared using the clay Download PDFInfo
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- CN105885022B CN105885022B CN201610307259.XA CN201610307259A CN105885022B CN 105885022 B CN105885022 B CN 105885022B CN 201610307259 A CN201610307259 A CN 201610307259A CN 105885022 B CN105885022 B CN 105885022B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Medicinal Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A kind of method that polymer composites are prepared the present invention relates to novel clay soil method of modifying and using the clay.Comprise the following steps：1）Clay is uniformly scattered in paraffin oil, forms stable mixture；2）Irradiated by UV/O3, activated clay surface, reacted with clay treating chemicals, introduce group；Described clay, it is that main component is SiO2And Al2O3, granularity is less than 200 mesh, structure is stratiform or threadiness aluminosilicate mineral powder, including montmorillonite.By obtained modified clay and mixed with polymers, nano composite material is prepared by way of solution blending, in-situ polymerization or melt blending.The present invention can introduce functional group in a manner of very simple and effective in surface of clay, improve the compatibility of clay in the polymer and dispersiveness, so as to build stronger interaction between polymer and clay filler, nano composite material is being prepared by the methods of melt blending, solution blending or in-situ polymerization in the case of without using any compatilizer.
Description
Technical field
, can using this method energy activated clay surface the present invention relates to a kind of new surface of clay processing method
Enough efficient and easy grafting organic molecules, pass through the design to course of reaction parameter, the kind of control surface of clay organic molecule
Class and grafting amount, so that modified clay is applied to prepare different types of polymer nanocomposites.
Background technology
In recent years, in order to improve the performances such as the mechanics of polymer, barrier properties for gases, many scientific research institutions attempt to make with company
Standby composite nano polymer/clay material.Clay layer possesses high modulus in itself and intensity, very big specific surface area etc. are excellent
Different characteristic.The performance of products obtained therefrom can be greatly improved by it being added with suitable process in polymer, expanded it and used neck
Domain.It is bad with the main polymer chain compatibility of low polarity but the lamella polarity of clay is very high；And clay layer and interlayer from
Son has very strong interaction, therefore, it is difficult to make it be dispersed into polymeric matrix with the state of monolithic layer, so that clay
Modified effect cannot fully play.In order to solve above problem, widespread practice is to pass through ion using quaternary ammonium salt at present
The method of exchange is modified to clay.Quaternary ammonium salt can reduce surface of clay polarity, and expand the interlamellar spacing of clay to drop
Interaction between low layer, so as to improve clay in the polymer scattered.
Although the above method improves the dispersiveness of clay, but ignore the interaction between clay and polymer.It is viscous
The native naturally occurring functional group in surface is less, causes the interface performance of clay and polymeric matrix poor, the external force suffered by material
Rigid filler can not be delivered to, so that the humidification of filler significantly weakens.Filler can even change in extreme circumstances
Into additional impurity, the too early failure of induced material, fracture.Meanwhile the thermostabilization of quaternary ammonium salt is relatively low, it is seriously limited at certain
Application in a little high-melting-point polymers.Especially when composite nano polymer/clay material is by solution blending or original position
When prepared by the method for polymerization, quaternary ammonium salt can due to long-time contacts with solvent or polymer monomer and from montmorillonite layer dissolution.
It is also, also very high for high-melting-point polymer, its melt blending temperature（Such as nylon, PET）, therefore quaternary ammonium salt modified montmorillonoid
When preparing nano composite polymer-montmorillonoid material, use range is severely limited.And pass through coupling agent and clay layer
The methods of section hydroxyl directly reacts introduces limiting for the hydroxyl quantity that active group is then available for reacting by surface of clay, it is difficult to
The interfacial characteristics of clay is greatly improved.Simultaneously as the polarity difference of clay and polymer, during composite is prepared
Generally require to add compatilizer to improve the dispersiveness of filler and compatibility, such as maleic anhydride grafted polymer.These auxiliary agents
Although can improve the microscopic appearance of composite to a certain extent, enhancing modified effect is not notable, and equally
It result in stability problem and add production cost.
The content of the invention
The invention provides a kind of new surface of clay processing mode, can not only in a manner of very simple and effective
Surface of clay introduces functional group, can more improve the compatibility of clay in the polymer and dispersiveness, so as in polymer and clay
Stronger interaction is built between filler, in the case of without using any compatilizer by melt blending, solution blending or
The methods of person's in-situ polymerization, prepares nano composite material, and the performance of gained composite is substantially improved.
It is for this technical solution adopted by the present invention：A kind of method of clay alteration, comprises the following steps：
1）Clay is uniformly scattered in paraffin oil, forms stable mixture；
2）Irradiated by UV/O3, activated clay surface, reacted with clay treating chemicals, introduce group；
The active group is amino, acid anhydrides；
Described clay, it is that main component is SiO2 and Al2O3, granularity are less than 200 mesh, structure is stratiform or threadiness
The mixture of aluminosilicate mineral powder, including montmorillonite, preferably sodium-based montmorillonite, calcium-base montmorillonite or their arbitrary proportions.
The molecular weight of paraffin oil is between 200-4000, and for fusing point less than 120 DEG C, the part by weight of clay and paraffin oil is viscous
Soil：Paraffin oil=10:1~1:100, the two mixed media includes stirring, concussion, ultrasound or emulsification.
Ultraviolet irradiation power is 5W-500W, irradiation time 1-240 minutes.
Clay treating chemicals includes the silane coupler containing various functional groups, titanate coupling agent, and amino acid, isocyanide
Acid esters, containing one or more amino or carboxyl, the aliphatic compound of hydroxyl, contain the functions such as hydroxyl, amino, carboxyl
One or more aromatic compound in group.
A kind of preparation method of polymer complex, comprises the following steps：
By obtained modified clay and mixed with polymers, by way of solution blending, in-situ polymerization or melt blending
Prepare nano composite material.
The polymer includes polymer and its derivative such as polyolefin, polyester, polyamide, and above-mentioned polymer is mixed
Compound or copolymer.
The content of clay in the composite is 0.1wt%-10wt%.
In the present invention, clay without being uniformly scattered in appropriate paraffin oil first with quaternary ammonium reactant salt, clay, shape
It is then innovative to be irradiated by UV/O3 into stable mixture, activated clay surface, and introduce functional group.And in UV/O3
Handle the organic clay obtained afterwards further can react with other inorganic agents, introduce active group（Such as amino, acid anhydrides
Deng）, expand the enhancing effect and use range for being modified clay.
Paraffin oil used in the present invention is mainly made up of hydrocarbon, may contain the element such as a small amount of oxygen, nitrogen with
Corresponding functional group, for molecular weight between 200-4000, fusing point is less than 120 DEG C.
The processing of clay comprises the following steps：
1）Clay is well mixed with paraffin oil with certain proportion, is filtered to remove unnecessary paraffin oil.
2）By step 1）In obtained clay UV ozone processing instrument irradiate, obtain being modified clay.
3）Modified clay can be directly entered step 4）Prepare nano composite material.And for some polymer, it is modified viscous
Soil needs further reaction to improve the compatibility with polymer.Reaction can be carried out in the solution, or directly be walked in blending
Suddenly obtained by reactively blending.
4）Modified clay is mixed with polymer with certain proportion, passes through solution blending, in-situ polymerization or melt blending
Mode prepare nano composite material.
Step 1）The ratio of clay and paraffin oil is clay：Paraffin oil=10:1~1:100（Weight ratio）.The two mixed media
Including stirring, shaking, ultrasound, emulsification etc..
Step 2）Middle ultraviolet irradiation power is 5W-500W, irradiation time 1-240 minutes.
Step 3）Solvent used in middle solution reaction includes water, alcohols, Benzene and Homologues, acetone, tetrahydrofuran, N,
The common solvents such as dinethylformamide or its mixture.Clay treating chemicals includes the silane coupler containing various functional groups,
Titanate coupling agent, and amino acid, isocyanates, contain one or more amino（Or carboxyl, hydroxyl）Aliphatic
Compound, contain aromatic compound one or more in the functional groups such as hydroxyl, amino, carboxyl（As 4- (2- ethylamino-s) benzene-
1,2- diphenol）Deng.Solution concentration is controlled in 0.001 mol/L-2 mol/L.
Step 4）In polymer used include polymer and its derivative such as polyolefin, polyester, polyamide, it is and above-mentioned poly-
The mixture or copolymer of compound.The content of clay in the composite is 0.1wt%-10wt%.
The present invention prepares polymer nanocomposites using the modification clay of the present invention, can use melt blending, molten
Liquid is blended or the method for in-situ polymerization.Melt-blending process needs that clay and polymer will be modified on melting point polymer with one
Fixed condition is blended.Solution blended process needs polymer and clay being uniformly scattered in appropriate solvent, then will be molten
Agent removing prepares composite.And whenever can be added before the beginning of the polymerization using situ aggregation method clay, closing
Nano composite material is prepared while into polymer.
Brief description of the drawings
Fig. 1 is the thermogravimetric curve of the clay under the conditions of different disposal（Na-MMT：Undressed clay；MMT-Wax：Through
Cross the clay of UV/O3 processing；Sample E：With the clay after reacting ethylenediamine）；
Fig. 2 is nano composite material H TEM photos；
Fig. 3 is nano composite material I TEM photos.
Embodiment
Embodiment：
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Mechanic property test method is as follows in following examples：
The mechanical property testers of Instron 5567,50KN sensors, draw speed 50mm/min, test temperature 25
DEG C, specimen shape meets ASTM D638V standards.
The modification of one, clays
1g sodium-based montmorillonites are well mixed with 100g paraffin oils, are removed after unnecessary paraffin oil in UV ozone processing instrument
Irradiate 2h.0.03mol KH560 silane couplers are dissolved in 150ml deionized waters and the in the mixed solvent of ethanol（Water：Ethanol=
1:9）, and 2h is stirred at room temperature.Montmorillonite after UV/O3 is handled mixes with KH560 solution and stirs 8h at 60 DEG C.
Gained mixture centrifuge washing 3 times.80 DEG C of vacuum dryings ground 300 mesh sieve, obtain product A to constant weight.
2g sodium-based montmorillonites are well mixed with 0.2g paraffin oils, are removed after unnecessary paraffin oil in UV ozone processing instrument
Irradiate 0.7h.0.03mol alpha-amido glutaric acids are dissolved in 50ml deionized waters, and 3h is stirred at room temperature.By what is be disposed
Montmorillonite mixes with alpha-amido glutaric acid solution and stirs 18h at 90 DEG C.Gained mixture centrifuge washing 3 times.80 DEG C of vacuum
Constant weight is dried to, ground 300 mesh sieve, obtains product B.
3g sodium-based montmorillonites mix with 30g paraffin oils, remove unnecessary paraffin oil and are irradiated afterwards in UV ozone processing instrument
24h.Benzene -1,2- diphenol is dissolved in 120ml deionized waters 0.21mmol 4- (2- ethylamino-s), and 10min is stirred at room temperature.
The montmorillonite of activation is mixed with the phenol solutions of 4- (2- ethylamino-s) benzene -1,2- two and 2.5h is stirred at room temperature.Gained mixture
Centrifuge washing 3 times.80 DEG C of vacuum dryings ground 300 mesh sieve, obtain product C to constant weight.
5g calcium-base montmorillonites are well mixed with 5g paraffin oils, are removed unnecessary paraffin oil and are shone afterwards in UV ozone processing instrument
Penetrate 0.5h.80 DEG C of vacuum dryings ground 300 mesh sieve, obtain product D to constant weight.
10g calcium-base montmorillonites are mixed with 2g paraffin oils, and 5h and true at 150 DEG C is then irradiated in UV ozone processing instrument
Sky drying 6 hours.10mol ethylenediamines mix with above-mentioned clay, and stir 1h at 50 DEG C.Catalyst HATU is added afterwards to continue
Ultrasonic wave is utilized at 50 DEG C（Power 100-2000W）Handle 10-20 hours.Products therefrom centrifuge washing 3 times.80 DEG C of vacuum are dried
Do to constant weight, ground 300 mesh sieve, obtain product E.In order to show the feasibility of clay alteration method, to product E and among it
Product has carried out EPMA and TGA sign,
To Na-MMT, MMT-Wax and the product E with being obtained after reacting ethylenediamine carries out thermogravimetric analysis, the results showed that
Product E is relative to modified montmorillonoid（MMT-Wax）Weightlessness 10%, illustrates have more organic molecules to graft on illiteracy more than at 700 DEG C
Native surface is taken off, the reaction of ethylenediamine is successful.It is remote super general poly- meanwhile the heat decomposition temperature of modified clay reaches nearly 400 DEG C
The processing temperature of compound, quaternary ammonium salt-modified clay is significantly better than in terms of heat endurance.We use electron probe microscope
（EPMA）Semi-quantitative analysis is carried out to Na-MMT and product E constituent contents, the results showed that contain N element in product E, tied with expected
Fruit coincide.
In order to protrude the importance of UV ozone processing, following control sample is prepared for：
0.05mol KH560 silane couplers are dissolved in 200ml deionized waters and the in the mixed solvent of ethanol（Water：Ethanol=
1: 9）, and 4h is stirred at room temperature.10g sodium-based montmorillonites are mixed with KH560 solution and stir 12h at 60 DEG C.Gained mixes
Thing centrifuge washing 3 times.80 DEG C of vacuum dryings ground 300 mesh sieve, obtain product F to constant weight（Contrast product A）.
10g sodium-based montmorillonites stir 4h with 1.2mol cetabs in 90 DEG C of deionized waters, cross and filter out
Remove excess of solvent.0.05mol KH560 silane couplers are dissolved in 200ml deionized waters and the in the mixed solvent of ethanol（Water：Second
Alcohol=1:9）, and 4h is stirred at room temperature.The montmorillonite that quaternary ammonium salt treats is mixed with KH560 solution and stirred at 60 DEG C
12h.Gained mixture centrifuge washing 3 times.80 DEG C of vacuum dryings ground 300 mesh sieve, obtain product G to constant weight（Contrast product
A）.
The preparation of two, nano composite materials：
1g products A uniformly mixes with 19g lactides, octoate catalyst stannous, in 170oC, nitrogen protection and mechanical agitation
Under conditions of react 12 hours, obtain PLA/clay nanocomposites H.
A is substituted for F or G, it is multiple with obtaining PLA/clay nano under preparation condition in identical clay content
Condensation material I and J（Contrast product H）.
The modification clay B that 2g was dried in vacuo and 200g BHET, catalyst Sb2O3 mixing, are added in vacuum reaction kettle.
It is warming up to 260-290 DEG C and stirs, polycondensation reaction is carried out under below 50Pa pressure conditions, is obtained by in-situ polymerization
PET/ clay nanocomposites K.
3g products C, 117g PVDF is dissolved in 1000g DMF solvents at 50 DEG C, and is sufficiently stirred 2 hours.By gained mixture
Under conditions of 50Pa, 150-200 DEG C of pressure, solvent is removed, obtains PVDF/ clay composite materials L.
5g products D uniformly mixes with 95g 6-caprolactone octoate catalyst stannous, is stirred in 110oC, nitrogen protection with machinery
React 12 hours, gathered under conditions of mixing（6-caprolactone）/ clay nanocomposites M.
The modification clay E that 5g was dried in vacuo is mixed with 45g HDPE, and 12h is dried in vacuo under 100oC.By above-mentioned raw materials
Add in double screw extruder and carry out melt blending, obtain HDPE/ clay nanocomposites N.Screw speed：Per minute 80
Turn；Blending temperature：210oC；Screw slenderness ratio（L/D）：40.
Three, properties of product
Table one：The mechanical property of nano composite material
| Sample | Stretch modulus（MPa） | Tensile strength（MPa） | Elongation at break（%） |
| H | +67% | +35% | -34% |
| I | +19% | -11% | -83% |
| J | +13% | -20% | -78% |
| K | +26% | +14% | -15% |
| L | +70% | +38% | -5% |
| M | +83% | +25% | -3% |
| N | +99% | +46% | -57% |
（Percentage in form for nano composite material relative to straight polymer substrate performance lifting or reduction hundred
Divide ratio.
Pure PLA：Stretch modulus 2.7GPa, tensile strength 107MPa, elongation at break 50%.
Pure PET：Stretch modulus 2.3GPa, tensile strength 58MPa, elongation at break 105%.
Pure PVDF：Stretch modulus 1.1GPa, tensile strength 43MPa, elongation at break 200%.
Pure polycaprolactone：Stretch modulus 270MPa, tensile strength 9.3MPa, elongation at break 220%.
Pure HDPE：Stretch modulus 1.0GPa, tensile strength 23.3MPa, elongation at break 620%）
From the mechanical property of nano composite material it can clearly be seen that using the modification clay prepared by the present invention, gained
The mechanical property of nano composite material is increased dramatically, and elongation at break loss is smaller（Sample H, K, L, M and N）.For
83% and 25% has been respectively increased with intensity in PCL, only 2.5wt% clays addition, stretch modulus；For PET, PLA and PVDF etc.,
The lifting of significantly mechanical property has also been obtained in the case of relatively low clay addition.And for the said goods, elongation at break
Reduction it is but relatively slight, do not occur the situation that general composite is greatly reduced with strength enhancing toughness.As right
Than, the clay being modified using conventional method, mechanical property lifting unobvious, or even reduce（Product I and J）, this also show this
The great function of clay alteration mode used in invention.
TEM photos（Accompanying drawing 2）Then indicate the influence dispersed to its of different clay treatment modes.Left-side images are use
The inventive method, the nano composite material H prepared by modification clay obtained by paraffin oil and UV/O3 processing TEM photos.
From the graph, it is apparent that clay layer, which is presented, peels off state distribution；And right side filler clay is without UV/O3 processing, directly with
Coupling agent reacts to obtain corresponding sample（I）, clay layer thickness reaches 200-300nm, it will be apparent that aggregate structure.Different clays
Dispersiveness shows：The clay prepared using traditional approach, it is very weak with interpolymer interaction, it is difficult to pass through the modes such as melt blending
It is dispersed in the polymer and with improve material property；And the clay for using the surface treatment mode of the present invention to prepare, with gathering
Compound compatibility, interaction are preferable, so as to preferably show the humidification of clay layer.
Claims (8)
1. a kind of novel clay soil method of modifying, it is characterised in that comprise the following steps：
1）Clay is uniformly scattered in paraffin oil, forms stable mixture；
2）Pass through UV/O3Irradiation, activated clay surface, reacted with clay treating chemicals, introduce group；
The group is amino, acid anhydrides；
Described clay, it is that main component is SiO2And Al2O3, granularity be less than 200 mesh, structure be stratiform or threadiness sial
Hydrochlorate mineral dust, including montmorillonite.
2. a kind of novel clay soil method of modifying according to claim 1, it is characterised in that the montmorillonite is sodium Ji Mengtuo
The mixture of soil, calcium-base montmorillonite or their arbitrary proportions.
3. a kind of novel clay soil method of modifying according to claim 1, it is characterised in that the molecular weight of paraffin oil is in 200-
Between 4000, for fusing point less than 120 DEG C, the part by weight of clay and paraffin oil is clay：Paraffin oil=10:1~1:100, the two is mixed
Conjunction means include stirring, concussion, ultrasound or emulsification.
4. a kind of novel clay soil method of modifying described in claim 1, it is characterised in that ultraviolet irradiation power is 5W-500W, is shone
Penetrate minute time 1-240.
5. a kind of novel clay soil method of modifying according to claim 1, it is characterised in that clay treating chemicals is included containing each
The silane coupler of kind of functional group, titanate coupling agent, and amino acid, isocyanates, containing one or more amino or
The aliphatic compound of person's carboxyl, hydroxyl, contain aromatic compound one or more in hydroxyl, amino, carboxyl functional group.
6. a kind of preparation method of polymer composites, it is characterised in that comprise the following steps：
Will modified clay and mixed with polymers made from claim 1-4 either method, by solution blending, in-situ polymerization or
The mode of melt blending prepares nano composite material.
A kind of 7. preparation method of polymer composites according to claim 6, it is characterised in that the polymer bag
Include polyolefin, polyester, polyamide polymer and its derivative, and the mixture or copolymer of above-mentioned polymer.
8. the preparation method of a kind of polymer composites according to claim 6 or 7, it is characterised in that clay is multiple
Content in condensation material is 0.1wt%-10wt%.
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Citations (4)
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|---|---|---|---|---|
| WO2001066627A1 (en) * | 2000-03-08 | 2001-09-13 | Omnova Solutions Inc. | Flame resistant polyolefin compositions containing organically modified clay |
| CN103937232A (en) * | 2014-04-30 | 2014-07-23 | 中仑塑业（福建）有限公司 | Method for preparing montmorillonite nylon 6 composite material |
| CN104262534A (en) * | 2014-09-10 | 2015-01-07 | 江南大学 | Montmorillonite composite cationic hydrogel and preparation method thereof |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
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2016
- 2016-05-10 CN CN201610307259.XA patent/CN105885022B/en active Active
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|---|---|---|---|---|
| WO2001066627A1 (en) * | 2000-03-08 | 2001-09-13 | Omnova Solutions Inc. | Flame resistant polyolefin compositions containing organically modified clay |
| CN103937232A (en) * | 2014-04-30 | 2014-07-23 | 中仑塑业（福建）有限公司 | Method for preparing montmorillonite nylon 6 composite material |
| CN104262534A (en) * | 2014-09-10 | 2015-01-07 | 江南大学 | Montmorillonite composite cationic hydrogel and preparation method thereof |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
Non-Patent Citations (1)
| Title |
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