CN105885022A - Novel clay modification method and method of preparing composite polymer material from the clay - Google Patents

Novel clay modification method and method of preparing composite polymer material from the clay Download PDF

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CN105885022A
CN105885022A CN201610307259.XA CN201610307259A CN105885022A CN 105885022 A CN105885022 A CN 105885022A CN 201610307259 A CN201610307259 A CN 201610307259A CN 105885022 A CN105885022 A CN 105885022A
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clay
polymer
paraffin oil
novel
montmorillonite
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CN105885022B (en
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殷明
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Dongbuwan (Yangzhou) Biological New Material Co.,Ltd.
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Yangzhou Zhongcheng Nano Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a novel clay modification method and a method of preparing a composite polymer material from the clay, comprising the following steps: 1) uniformly dispersing the clay into a paraffin oil to form a stable mixture; 2) activating surfaces of the clay through UV/O3 irradiation, reacting with a clay treating agent, introducing radical groups, wherein the clay is aluminosilicate mineral powder that main components are SiO2 and Al2O3, particle size is less than 200 meshes, and a structure is lamellar or a fibrous structure, including montmorillonite; mixing the prepared modified clay with a polymer, and preparing a nanometer composite material by means of solution mixing, in-situ polymerization or melt blending. The invention can introduce functional groups into the surface of the clay in a very simple and efficient way, so as to increase the compatibility and dispersity of the clay inside the polymer, thereby building a stronger interaction between the polymer and the clay filler, and preparing the nanometer composite material by means of melt blending, solution mixing or in-situ polymerization, without using any compatilizer.

Description

A kind of novel clay soil method of modifying and utilize this clay to prepare polymer composites Method
Technical field
The present invention relates to a kind of novel surface of clay processing method, use the method energy activated clay surface so that it is energy Enough efficient and easy grafting organic molecules, by the design to course of reaction parameter, control the kind of surface of clay organic molecule Class and grafting amount, so that modified clay is applicable 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, a lot of scientific research institutions attempt system with company Standby composite nano polymer/clay material.It is excellent with intensity, the biggest specific surface area etc. that clay layer itself has high modulus Different characteristic.It is added with suitable process the serviceability that products obtained therefrom can be greatly improved in polymer, expands it and use neck Territory.But, the lamella polarity of clay is the highest, and the main polymer chain compatibility with low polarity is bad；And clay layer and interlayer from Son has the strongest interaction, therefore, it is difficult to make it be dispersed into polymeric matrix with the state of monolithic layer, so that clay Modified effect can not get fully playing.In order to solve an above difficult problem, current widespread practice is to use quaternary ammonium salt to pass through ion Clay is modified by the method for exchange.Quaternary ammonium salt can reduce surface of clay polarity, and expands the interlamellar spacing of clay with fall Interaction between low layer, thus improve clay dispersion in the polymer.
Although said method improves the dispersibility of clay, ignore the interaction between clay and polymer.Viscous The soil naturally occurring functional group in surface is less, causes clay poor with the interface performance of polymeric matrix, the external force suffered by material The filler of rigidity cannot be delivered to, so that the potentiation of filler significantly weakens.Filler even can change in extreme circumstances Become additional impurity, the too early inefficacy of induced material, fracture.Meanwhile, quaternary ammonium salt thermally-stabilised relatively low, seriously limit it at certain Application in a little high-melting-point polymers.It is especially by solution blending or in situ when composite nano polymer/clay material The method of polymerization is when preparing, and quaternary ammonium salt can be due to long-time contact with solvent or polymer monomer from montmorillonite layer dissolution. Further, for high-melting-point polymer, its melt blending temperature the highest (such as nylon, PET etc.), therefore quaternary ammonium salt modified montmorillonoid When preparing nano composite polymer-montmorillonoid material, range is severely limited.And by coupling agent and clay layer The methods such as section hydroxyl direct reaction introduce active group and are then available for the hydroxyl value quantitative limitation of reaction by surface of clay, it is difficult to The interfacial characteristics of clay is greatly improved.Simultaneously as clay and the polarity difference of polymer, during preparing composite Generally require interpolation compatilizer to improve dispersibility and the compatibility of filler, such as maleic anhydride grafted polymer etc..These auxiliary agents Although the microscopic appearance of composite can be improved to a certain extent, but enhancing modified effect is not notable, and equally Result in stability problem and add production cost.
Summary of the invention
The invention provides a kind of novel surface of clay processing mode, can not only in the way of the most simple and effective Surface of clay introduces functional group, more can improve the clay compatibility in the polymer and dispersibility, thus at polymer and clay Build stronger interaction between filler, in the case of not using any compatilizer by melt blending, solution blending or The methods such as person's in-situ polymerization prepare nano composite material, and the performance of gained composite is substantially improved.
For this technical solution used in the present invention it is: a kind of method of clay alteration, comprises the steps:
1) clay is scattered in paraffin oil uniformly, forms stable mixture；
2) irradiated by UV/O3, activated clay surface, react with clay treating chemicals, introduce group；
Described active group is amino, anhydride；
Described clay, for being mainly composed of SiO2And Al2O3, granularity be stratiform or fibrous sial less than 200 mesh, structure Hydrochlorate mineral dust, including montmorillonite, preferably sodium-based montmorillonite, calcium-base montmorillonite or the mixture of their arbitrary proportion.
The molecular weight of paraffin oil is between 200-4000, and fusing point is less than 120 DEG C, and clay is viscous with the part by weight of paraffin oil Soil: paraffin oil=10:1 ~ 1:100, the two mixed media includes stirring, concussion, ultrasonic or emulsifying.
Ultra-vioket radiation power is 5W-500W, irradiation time 1-240 minute.
Clay treating chemicals includes the silane coupler containing various functional groups, titanate coupling agent, and aminoacid, isocyanide Acid esters, containing one or more amino or carboxyl, the aliphatic compound of hydroxyl, containing official's energy such as hydroxyl, amino, carboxyls The aromatic compound of one or more in group.
The preparation method of a kind of polymer complex, comprises the steps:
By prepared modified clay and polymer mixed, prepare by the way of solution blending, in-situ polymerization or melt blending Nano composite material.
Described polymer includes polymer and the derivants thereof such as polyolefin, polyester, polyamide, and above-mentioned polymer is mixed Compound or copolymer.
Clay content in the composite is 0.1wt%-10wt%.
In the present invention, clay is without reacting with quaternary ammonium salt, and clay is scattered in suitable paraffin oil the most uniformly, shape Become stable mixture, then novelty pass through UV/O3Irradiate, activated clay surface, and introduce functional group.And at UV/O3Place The organic clay obtained after reason can react with other inorganic agents further, introduces active group (such as amino, anhydride etc.), expands The reinforced effects of big modified clay and range.
Paraffin oil used in the present invention is mainly made up of Hydrocarbon, may containing the elements such as a small amount of oxygen, nitrogen with Corresponding functional group, molecular weight is between 200-4000, and fusing point is less than 120 DEG C.
The process of clay comprises the following steps:
1) clay is mixed homogeneously with certain proportion with paraffin oil, is filtered to remove unnecessary paraffin oil.
2) the clay UV ozone processing instrument obtained in step 1) is irradiated, obtain modified clay.
3) modified clay can be directly entered step 4) and prepares nano composite material.And for some polymer, modified viscous Soil needs reaction further to improve the compatibility with polymer.Reaction can be carried out in the solution, or directly in blended step Suddenly obtained by reactively blending.
4) modification clay is mixed with certain proportion with polymer, by solution blending, in-situ polymerization or melt blending Mode prepare nano composite material.
Step 1) clay is clay with the ratio of paraffin oil: paraffin oil=10:1 ~ 1:100(weight ratio).The two mixed media Including stirring, concussion, ultrasonic, emulsifying etc..
Step 2) medium ultraviolet irradiation power is 5W-500W, irradiation time 1-240 minute.
In step 3), solvent used in solution reaction includes water, alcohols, Benzene and Homologues, acetone, oxolane, N, The common solvent such as dinethylformamide or its mixture.Clay treating chemicals includes the silane coupler containing various functional groups, Titanate coupling agent, and aminoacid, isocyanates, containing the aliphatic of one or more amino (or carboxyl, hydroxyl) Compound, containing in the functional groups such as hydroxyl, amino, carboxyl one or more aromatic compound (as 4-(2-ethylamino-) benzene- 1,2-diphenol) etc..Solution concentration controls at 0.001 mol/L-2 mol/L.
In step 4), polymer used includes polymer and the derivants thereof such as polyolefin, polyester, polyamide, and above-mentioned poly- The mixture of compound or copolymer.Clay content in the composite is 0.1wt%-10wt%.
The present invention uses the modified clay of the present invention to prepare polymer nanocomposites, it is possible to use melt blending, molten Liquid is blended or the method for in-situ polymerization.Melt-blending process need by modification clay and polymer on melting point polymer with one Fixed condition is blended.Solution blended process needs to be scattered in suitable solvent polymer and clay uniformly, then by molten Composite is prepared in agent removing.And use situ aggregation method clay the most whenever to add, closing Nano composite material is prepared while becoming polymer.
Accompanying drawing explanation
Fig. 1 is thermogravimetric curve (Na-MMT: the undressed clay of clay under the conditions of different disposal；MMT-Wax: warp Cross UV/O3The clay processed；Sample E: with the clay after reacting ethylenediamine)；
Fig. 2 is the TEM photo of nano composite material H；
Fig. 3 is the TEM photo of nano composite material I.
Detailed description of the invention
Embodiment:
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following example.
In following example, mechanic property test method is as follows:
Instron 5567 mechanical property tester, 50KN sensor, draw speed 50mm/min, test temperature is 25 DEG C, examination Sample shape meets ASTM D638V standard.
One. the modification of clay
1g sodium-based montmorillonite is mixed homogeneously with 100g paraffin oil, irradiates after removing unnecessary paraffin oil in UV ozone processing instrument 2h.0.03mol KH560 silane coupler is dissolved in 150ml deionized water and (water: ethanol=1:9) in the mixed solvent of ethanol, And 2h is stirred at room temperature.By UV/O3Montmorillonite after process is mixed with KH560 solution is incorporated at 60 DEG C stirring 8h.Gained mixes Compound centrifuge washing 3 times.80 DEG C of vacuum dryings to constant weight, ground 300 mesh sieves, obtain product A.
2g sodium-based montmorillonite is mixed homogeneously with 0.2g paraffin oil, removes after unnecessary paraffin oil in UV ozone processing instrument Irradiate 0.7h.0.03mol alpha-amido 1,3-propanedicarboxylic acid is dissolved in 50ml deionized water, and 3h is stirred at room temperature.By be disposed Montmorillonite is mixed with alpha-amido 1,3-propanedicarboxylic acid solution is incorporated at 90 DEG C stirring 18h.Gained mixture centrifuge washing 3 times.80 DEG C of vacuum Dry to constant weight, ground 300 mesh sieves, obtain product B.
3g sodium-based montmorillonite mixes with 30g paraffin oil, irradiates after removing unnecessary paraffin oil in UV ozone processing instrument 24h.0.21mmol 4-(2-ethylamino-) benzene-1,2-diphenol is dissolved in 120ml deionized water, and 10min is stirred at room temperature. The montmorillonite of activation is mixed with 4-(2-ethylamino-) benzene-1,2-two phenol solution and is stirred at room temperature 2.5h.Gained mixture Centrifuge washing 3 times.80 DEG C of vacuum dryings to constant weight, ground 300 mesh sieves, obtain product C.
5g calcium-base montmorillonite is mixed homogeneously with 5g paraffin oil, shines after removing unnecessary paraffin oil in UV ozone processing instrument Penetrate 0.5h.80 DEG C of vacuum dryings to constant weight, ground 300 mesh sieves, obtain product D.
10g calcium-base montmorillonite mixes with 2g paraffin oil, then irradiates 5h true at 150 DEG C in UV ozone processing instrument Empty drying 6 hours.10mol ethylenediamine mixes with above-mentioned clay, and stirs 1h at 50 DEG C.Continue after adding catalyst HATU Ultrasound wave (power 100-2000W) is utilized to process at 50 DEG C 10-20 hour.Products therefrom centrifuge washing 3 times.80 DEG C of vacuum are dried Do to constant weight, ground 300 mesh sieves, obtain product E.In order to show the feasibility of clay alteration method, to product E and centre thereof Product has carried out the sign of EPMA and TGA, and concrete outcome is shown in Figure of description.
To Na-MMT, MMT-Wax and with reacting ethylenediamine after the product E that obtains carry out thermogravimetric analysis, result shows Product E when 700 DEG C how weightless 10%, has illustrated that more organic molecule grafts on illiteracy relative to modified montmorillonoid (MMT-Wax) De-soil surface, the reaction of ethylenediamine is successful.Meanwhile, the heat decomposition temperature of modified clay reaches nearly 400 DEG C, super general poly- The processing temperature of compound, is significantly better than quaternary ammonium salt-modified clay in terms of heat stability.We use electron probe microscope (EPMA) with product E constituent content, Na-MMT being carried out semi-quantitative analysis, result shows containing N element in product E, with expection knot Fruit coincide.
In order to highlight the importance that UV ozone processes, it is prepared for following control sample:
0.05mol KH560 silane coupler be dissolved in the mixed solvent of 200ml deionized water and ethanol (water: ethanol=1: , and 4h is stirred at room temperature 9).Stirring 12h it is incorporated at 60 DEG C by mixed to 10g sodium-based montmorillonite and KH560 solution.Gained mixture Centrifuge washing 3 times.80 DEG C of vacuum dryings to constant weight, ground 300 mesh sieves, obtain product F(contrast product A).
10g sodium-based montmorillonite and 1.2mol cetab stir 4h in 90 DEG C of deionized waters, cross and filter Remove excess of solvent.0.05mol KH560 silane coupler is dissolved in 200ml deionized water and (water: second in the mixed solvent of ethanol Alcohol=1:9), and 4h is stirred at room temperature.The montmorillonite processed by quaternary ammonium salt is mixed with KH560 solution is incorporated at 60 DEG C stirring 12h.Gained mixture centrifuge washing 3 times.80 DEG C of vacuum dryings to constant weight, ground 300 mesh sieves, obtain product G(contrast product A).
Two. the preparation of nano composite material:
1g product A and 19g lactide, octoate catalyst stannous uniformly mix, 170oThe protection of C, nitrogen and churned mechanically bar React 12 hours under part, obtain polylactic acid/clay nanocomposites H.
A is replaced to F or G, under identical clay content with preparation condition, obtains polylactic acid/clay nano multiple Condensation material I Yu J(contrasts product H).
The modified clay B that 2g was vacuum dried and 200g BHET, catalyst Sb2O3Mixing, adds in vacuum response still.Rise Temperature is to 260-290 DEG C and stirs, and carries out polycondensation reaction under the pressure conditions of below 50Pa, obtains PET/ by in-situ polymerization and glues Soil nano composite material K.
3g product C, 117g PVDF are dissolved in 1000g DMF solvent at 50 DEG C, and are sufficiently stirred for 2 hours.By gained mixture Under conditions of pressure 50Pa, 150-200 DEG C, remove solvent, obtain PVDF/ clay composite material L.
5g product D and 95g 6-caprolactone octoate catalyst stannous uniformly mixes, 110oThe protection of C, nitrogen is stirred with machinery React 12 hours under conditions of mixing, obtain poly-(6-caprolactone)/clay nanocomposites M.
Modified clay E and the 45g HDPE that 5g was vacuum dried mixes, 100o12h it is vacuum dried under C.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) Hot 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 ratio in form is the nano composite material percentage promoting or reducing relative to straight polymer substrate performance Ratio.
Pure polylactic acid: stretch modulus 2.7GPa, hot strength 107MPa, elongation at break 50%.
Pure PET: stretch modulus 2.3GPa, hot strength 58MPa, elongation at break 105%.
Pure PVDF: stretch modulus 1.1GPa, hot strength 43MPa, elongation at break 200%.
Pure polycaprolactone: stretch modulus 270MPa, hot strength 9.3MPa, elongation at break 220%.
Pure HDPE: stretch modulus 1.0GPa, hot strength 23.3MPa, elongation at break 620%)
From the mechanical property of nano composite material it can clearly be seen that use the modified clay prepared by the present invention, gained nanometer The mechanical property of composite is increased dramatically, and elongation at break loses less (sample H, K, L, M and N).For PCL, The addition of only 2.5wt% clay, stretch modulus and intensity have been respectively increased 83% and 25%；For PET, PLA and PVDF etc., relatively The lifting of significantly mechanical property is have also been obtained in the case of low clay addition.And for the said goods, the fall of elongation at break Low the slightest, the situation that general composite is greatly reduced along with strength enhancing toughness does not occur.As a comparison, make With the modified clay of traditional method, mechanical property promotes inconspicuous, even reduces (product I and J), and this also show institute of the present invention The great function of the clay alteration mode used.
TEM photo (accompanying drawing 2) then indicates the different clay treatment mode impact on its dispersibility.Left-side images is for using The inventive method, through paraffin oil and UV/O3Process the TEM photo of nano composite material H prepared by modified clay obtained. From the graph, it is apparent that clay layer presents stripping state distribution；And right side filler clay is without UV/O3Process, directly with The sample (I) that coupling agent reacts corresponding, clay layer thickness reaches 200-300nm, it will be apparent that aggregate structure.Different clays Dispersibility shows: use clay prepared by traditional approach, the most weak with interpolymer interaction, is difficult to by modes such as melt blendings The most dispersed and with improve material property；And use clay prepared by the surface treatment mode of the present invention, with poly- The compound compatibility, interaction are preferably such that it is able to preferably represent the potentiation of clay layer.

Claims (7)

1. a novel clay soil method of modifying, it is characterised in that comprise the steps:
1) clay is scattered in paraffin oil uniformly, forms stable mixture；
2) irradiated by UV/O3, activated clay surface, react with clay treating chemicals, introduce group；
Described active group is amino, anhydride；
Described clay, for being mainly composed of SiO2And Al2O3, granularity be stratiform or fibrous sial less than 200 mesh, structure Hydrochlorate mineral dust, including montmorillonite, preferably sodium-based montmorillonite, calcium-base montmorillonite or the mixture of their arbitrary proportion.
A kind of novel clay soil method of modifying the most according to claim 1, it is characterised in that the molecular weight of paraffin oil is at 200- Between 4000, fusing point is less than 120 DEG C, and clay is clay with the part by weight of paraffin oil: paraffin oil=10:1 ~ 1:100, and the two mixes Conjunction means include stirring, concussion, ultrasonic or emulsifying.
3. a kind of novel clay soil method of modifying described in claim 1, it is characterised in that ultra-vioket radiation power is 5W-500W, shines Penetrate the time 1-240 minute.
A kind of novel clay soil method of modifying the most according to claim 1, it is characterised in that clay treating chemicals includes containing each The silane coupler of kind of functional group, titanate coupling agent, and aminoacid, isocyanates, containing one or more amino or Person's carboxyl, the aliphatic compound of hydroxyl, containing the aromatic compound of one or more in the functional groups such as hydroxyl, amino, carboxyl Thing.
5. the preparation method of a polymer composites, it is characterised in that comprise the steps:
The modified clay that claim 1-4 either method is prepared and polymer mixed, by solution blending, in-situ polymerization or The mode of melt blending prepares nano composite material.
The preparation method of a kind of polymer composites the most according to claim 5, it is characterised in that described polymer bag Include polymer and the derivants thereof such as polyolefin, polyester, polyamide, and the mixture of above-mentioned polymer or copolymer.
7. according to the preparation method of a kind of polymer composites described in claim 5 or 6, it is characterised in that clay is multiple Content in condensation material is 0.1wt%-10wt%.
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