SG192502A1 - Thermoplastic polymer based nanocomposites - Google Patents
Thermoplastic polymer based nanocomposites Download PDFInfo
- Publication number
- SG192502A1 SG192502A1 SG2013053434A SG2013053434A SG192502A1 SG 192502 A1 SG192502 A1 SG 192502A1 SG 2013053434 A SG2013053434 A SG 2013053434A SG 2013053434 A SG2013053434 A SG 2013053434A SG 192502 A1 SG192502 A1 SG 192502A1
- Authority
- SG
- Singapore
- Prior art keywords
- reactive
- carrier
- nanocomposite
- polymer
- clay
- Prior art date
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 51
- 239000013339 polymer-based nanocomposite Substances 0.000 title claims description 8
- 239000004927 clay Substances 0.000 claims abstract description 145
- 239000002114 nanocomposite Substances 0.000 claims abstract description 99
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 239000011159 matrix material Substances 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 229920003023 plastic Polymers 0.000 claims abstract description 53
- 239000004033 plastic Substances 0.000 claims abstract description 53
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 29
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 26
- 238000013329 compounding Methods 0.000 claims abstract description 24
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 22
- 229920013730 reactive polymer Polymers 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 8
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- 150000001412 amines Chemical class 0.000 claims description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
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- -1 polypropylene Polymers 0.000 description 23
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- 238000002360 preparation method Methods 0.000 description 3
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
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- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
: THERMOPLASTIC POLYMER BASED NANOCOMPOSITESThermoplastic nanocomposites are prepared by reactive compounding of a nanocomposite versatile masterbatch comprising a partially modified pristine clay and a reactive carrier plastics compound with a5 thermoplastics matrix polymer wherein the matrix polymer has a main chain directly or indirectly miscible with or reactive with said carrier plastics compound. The matrix polymer may include functional groups reactive with the carrier plastics compound to form a copolymer or a copolymer having at least one region thermodynamically miscible with said matrix polymer and at10 least one functional group reactive with said reactive carrier plastics compound to form a block copolymer therebetween.Fig. 23 Amended Sheet IPEAJAU
Description
"THERMOPLASTIC POLYMER BASED NANOCOMPOSITES”
This invention is concerned with the manufacture of polymer/ciay nanocomposites produced by a reactive compounding process.
The invention is concerned particularly, although not exclusively, with the manufacture of polymer/clay nanocomposites by reactive compounding of a matrix polymer with an exfoliated clay-containing ‘versafile masterbatch having a reactive plastics carrier compound. ~~
Clay-based polymer nanocomposites offer substantial improvements in physical properties over conventional polymeric materials. in particular, improvements in mechanical, thermal, fire retardancy and gas barrier properties already have been exhibited in a wide range of polymeric materials where layered inorganic fillers can be dispersed as plate-like nanoparticles throughout a polymer matrix. in order to maximize the physical properties of polymer/clay nanocomposites it is necessary to maximize the degree of delamination or exfoliation of clay platelets to obtain an even dispersion thereof through the polymer matrix. An ideal dispersion comprises an even substantially random distribution of individual platelets of say, montmorillonite which have a thickness of about 1 nm and a diameter of 1 um thereby giving aspect ratios in the range of about 1000:1 thus providing an extremely high surface area to volume ration. The presence of undispersed clumps of clay particles or 25 . “factoids” can substantially reduce the physical properties otherwise available where dispersion approaches an “ideal” or complete exfoliation.
It is well known in the prior art that cost effective dispersion of fully exfoliated clay platelets is both difficult and rarely achieved. Early nanocomposites were based on Nylon 6 produced in the polymerization reactor. Of more recent times, the focus has been on achieving exfoliation in a melt compounding process to enable a wider range of polymeric clay nanocomposite species. Unfortunately, of the many melt compounding processes described in the literature, many of these do not permit a sufficient degree of exfoliation of clay particles or otherwise are limited to a narrow range of polymeric matrices.
Many of the prior art processes employ an organically modified clay wherein otherwise hydrophilic clays are treated with organic modifiers to render the clay particles organophilic or more miscible with hydrophobic polymers in particular. Alkyl ammonium surfactants are the most commonly employed organic modifiers which effect an ionic exchange with hydrated cations bound between platelet stacks in regions known as “interlayers” or oo “galleries”. The alkyl-ammonium exchanged clay can then be intercalated by an organic swelling agent such as ethylene glycol, naphtha or heptane which can then be melt processed to allow polymer penetration into the clay galleries. Typically these clay filled polymers can include up to 60 weight per : cent of organoclay dispersed as exfoliated platelets, disordered clumps and intercalated tactoids.
In other prior art processes it has been proposed to utilize a hydroxy functionalized polypropylene oligomer and an organoclay, or a maleic anhydride-modified polypropylene oligomer and a stearylammonium — intercalated clay.
Yet another prior art process proposed the use of ammonium — functionalized polymers or oligomers wherein the ammonium ~ functionalized polymer or oligomer was first melt compounded with up to 60 weight per cent clay to form a concentrate which was then melt compounded with a matrix polymer compatible with the functionalized oligomer or polymer, both preferably having the same monomer unit.
One of the difficulties in forming highly exfoliated dispersions of clay in nanocomposites is that for certain polymeric matrices, such nanocomposites are thermodynamically unstable and do not readily lend themselves to further processing in, for example, thermoplastics matrices.
Effective dispersion of highly exfoliated clays in non-polar thermoplastics polymers such as polyolefins and polystyrenes has been quite difficult and not cost effective. From the outset, modified organoclays were required to permit intercalation of the polymeric matrix and, depending upon the nature
Co oo | PCTISG2005/00000 , : Received 16 April 200’ ; : : 3 . of the polymeric species, low molecular weight compatibilizers wers required to facilitate intercalation of the polymeric species into the clay galleries.
Typically, an organoclay comprises from 25 to 45 wt % of a : modifier such as an alkylammonium salt to render the clay more organophilic : 5 and thus susceptible to intercalation. : - Toimprove dispersion and exfoliation of an organoclay innon- polar polymers a low molecular weight copolymer such as maleic anhydride . grafted polypropylene (PP—g—MAH) is often employed. A difficulty with such "- prior art nanocomposites is that the presence of low molecular weight modifier molecules and low molecular weight polymers substantially
Co deteriorates both mechanical and thermal properties of the resultant " nanocomposite. 0 © While generally effective, fo a greater or lesser extent, for their intended purpose, these prior art polymet/clay nanocomposites have all suffered from the requirement for expensive organically modified clays, limitations on polymer choices and processing limitations to avoid degradation of the polymer matrix. At the same time, the degree of oo exfoliation of the clay filler varies greatly from one prior art process to ~ another, : 20 One of the more serious shortcomings associated with the use of organoclays is the presence of residual small organic modifier molecules . in the resultant nanocomposite, which residual small molecules can detract hy "from the thermal and mechanical properties otherwise obtainable.
Accordingly, itis an aim of the present invention to overcome or ameliorate at least some of the disadvantages of the prior art and otherwise provide greater degree of choice in the preparation. of nanocomposites and the nanocomposites so obtained. ~~ oo oo SUMMARY OF THE INVENTION i. Co In accordance with one aspect of the invention there is : 30 provided a thermoplastic polymer based nanocomposite comprising:- - - Amended Sheet
IPEA/AU oo cn re PCT/SG2005/000006
Received 30 August 2005 ’ a oo | 4 : a nanocomposite masterbatch comprising a carrier plastics
Ce | compound having one or more carrier functional groups and an exfoliated } clay dispersed throughout said carrier plastics compound; and, : -a thermoplastic matrix polymer reactively compounded with said nanocomposite masterbatch, said matrix polymer having a main chain - directly or indirectly miscible with or reactive with said carrier plastics : compound, said thermoplastic polymer based nanocomposite characterized oo ~~ + inthat said nanocomposite masterbatch is formed by treatment of pristine oo : Co B clay with water to swell said clay, exchanging said water with an organic oo 10 solvent while maintaining said clay in a swollen state, treating said solvent ) yo exchanged swollen clay with a modifier selected from a surfactant, a < coupling agent, a compatibilizer or any combination thereof ‘and - subsequently mixing said clay so treated with a monomer, oligomer, polymer
SE or combinations and selectively removing said solvent from said nanocomposite masterbatch. oo oo . Suitably, said carrier plastics compound may comprise a oo monomer, oligomer or-polymer or any combination thereof. B
EE | + If required said one or more carrier functional groups may be : selected from epoxy, hydroxyl, amine, isocyanate, carboxyl or any
Lo © 20 combination thereof. oo oo : Preferably, said cartier plastics compound comprises an epoxy ; prepolymer or polyethylene oxide. : -
BE Co ~ Said thertnoplastic matrix polymer may be directly miscible with
BE -said carrier plastics compound and where said carrier plastics compound ; comprises a monomer, oligomer, prepolymer or any combination thereof, a oe Ee curing agent may be provided to effect cross linking of said monomer,
B Co | oligomer, prepolymer or any combination thereof during reactive | - oo compounding of said nanocomposite. EE : a so | "Hf required, said thermoplastic matrix polymer may include one :
B - "30 or more matrix functional groups reactive with carrier functional groups via i ) ‘chain extension or cross linking during reactive compounding fo form a _ ~ cartler/matrix copolymer between said carrier plastics compound and said matrix polymer. : | :
To PCT/SG2005/00000¢
Ct Received 16 April 200° i : Suitably, the thermoplastic polymer is selected from the group comprising:- crystalline polar thermoplastic polymers, crystalline non-polar : thermoplastic polymers, non-crystalline non-polar thermoplastic polymers, " 5 non-crystalline polar thermoplastic polymers; copolymers thereof or any combination of the aforesaid polymers.
Said nanocomposite may include a reactive polymer having at least one segment thermodynamically miscible with said matrix polymer and at least one region having at least one reactive polymer functional group reactive with a carrier functional group during reactive compounding to form 0) a carrierfreactive copolymer between said carrier plastics compound and BN oo said reactive polymer. :
Suitably, said atleast one reactive polymer functional group is : selected from carboxyl, hydroxyl, isocyanate, amine, epoxy or any combination thereof.
The reactive polymer may be selected from a group comprising : : blocks, segments or chains having the same monomer unit as said matrix polymer or are thermodynamically miscible therewith.
The nanocomposite masterbatch may include clay in an amount of from between 2% and 80% by weight of the masterbatch. ] oo Preferably, said thermoplastic polymer based nanocomposite 1 Co comprises from 0.1% to 20% by weight of clay based on the total weight of
SE the nanocomposite.
According to another aspect of the invention there is provideda process for the formation of a thermoplastic nanocomposite said process
ST “including reactive compounding ofa nanocomposite masterbatch comprising a plastics carrier compound having one or more carrier functional groups and an exfoliated clay dispersed throughout said carrier plastics compound and a - 30 thermoplastic matrix polymer, said matrix polymer having a main chain : ~~ = directly or indirectly miscible with or reactive ‘with said carrier plastics compound.
Suitably, said carrier plastics compound is selected from monomers, oligomers, polymers or any combination thereof. oo Amended Sheet
TPEA/AU
If required, said carrier functional groups may be selected from epoxy, hydroxyl, amine, isocyanate, carboxyl or any combination thereof.
Preferably said carrier plastics compound comprises an epoxy prepolymer or polyethylene oxide.
Where said thermoplastic matrix polymer is directly miscible with said carrier plastics compound and where said carrier plastics compound comprises a monomer, oligomer, prepolymer or any combination thereof, a curing agent may be provided to effect cross linking of said carrier plastics compound during reactive compounding.
If required, said thermoplastic matrix polymer may comprise one or more matrix functional groups reactive with said carrier functional groups via chain extension or cross linking during reactive compounding to form a carrier/matrix copolymer between said carrier plastics compound and said matrix polymer.
Suitably, the thermoplastic polymer is selected from the group comprising~ crystalline polar thermoplastic polymers, crystalline non-polar thermoplastic polymers, non-crystalline non-polar thermoplastic polymers non-crystalline polar thermoplastic polymers; copolymers thereof or any combination of the aforesaid polymers.
The process may comprise the reaction, during reactive compounding, of a reactive polymer having at least one segment thermodynamically miscible with said matrix polymer and at least one ] | segment having at least one reactive polymer functional group reactive with a carrier functional group to form a carrier/reactive copolymer between said carrier plastics compound and said reactive polymer.
The reactive polymer may be selected from a group comprising blocks, segments or chains having the same monomer unit as said matrix polymer or are thermodynamically miscible with said matrix polymer.
Suitably said carrierfreactive copolymer functions as a compatibilizer for said carrier plastics compound and said matrix polymer.
If required said reactive polymer may function as a curing agent for said plastics carrier compound during reactive compounding.
In order that the various aspects of the invention may be more fully understood and put into practical effect, reference will now be made to various embodiments described and exemplified herein and with further reference to the accompanying drawings in which:-
Figure 1 shows an optical micrograph of polished surface of epoxy DER332/organoclay (epoxy/Cloisite 93A) nanocomposites (clay content of 2.5 wt %), of the prior art. (Scale bar: right: 50 um);
So Figure 2 shows an optical micrograph of polished surface of ~~ epoxy DER332/pristine clay nanocomposites (clay content of 2.5 wt %). (Scale bar: right: 50 pm),
Figure 3 shows a TEM micrograph of the epoxy
DER332/organoclay (epoxy/Cloisite 93A) nanocomposites (clay content of 2.5 wt %) of the same prior art shown in Figure 1; 16 FIG. 4 shows a TEM micrograph of epoxy DER332/pristine clay nanocomposites (clay content of 2.5 wt %);
FIG. 5 shows the mechanical properties of epoxy
DER332/pristine clay nanocomposites exhibited by Young's modulus values;
Figure 6 shows the mechanical properties of epoxy . 20 DER332/pristine clay nanocomposites exhibited by fracture toughness;
Figure 7 shows the comparison of the Young's Modulus of pristine clay nanocomposites prepared with different method;
Figure 8 shows the comparison of the fracture toughness of pristine clay nanocomposites prepared with different method;
Figure 9 comprises the storage modulus, E’ versus temperature - for neat epoxy, epoxy DER332/pristine clay nanocomposites and that of an epoxy DER332/organoclay nanocomposite (epoxy/Cloisite 93A) of the prior art; .
Figure 10 comprises the fan & versus temperature for epoxy
DER332/pristine clay nanocomposites and that of an epoxy
DER332/organoclay nanocomposite (epoxy/Cloisite 93A);
Figure 11 shows light transmittance of pristine clay nanocomposites various clay concentrations. Curves ab,cand dare at 1.0, 2.5, 3.5 and 5.0 wt % clay respectively;
Figure 12 shows a comparison of light transmittance according to prior art approach. (Ref: Deng, etal., Polymer International, 2004, 53, 85- 91);
Figure 13 shows a TEM micrograph of epoxy LY5210/pristine clay nanocomposites (clay content of 2.5 wt %);
Figure 14 shows the storage modulus, E’ versus temperature for epoxy LY5210/pristine clay nanocomposites;
Figure 15 shows the tan 8 versus temperature for epoxy
LY5210/pristine clay nanocomposites of the invention. in Figures 13 and 14, curve a is neat epoxy, curves b and c are 2.5 and 5.0 wt % clay respectively;
Figure 16 shows the mechanical properties of epoxy
LY5210/pristine clay nanocomposites using fracture toughness;
Figure 17 shows a TEM micrograph of epoxy DER332/pristine clay nanocomposites (clay content of 2.5 wt %);
Figure 18 shows a TEM micrograph of epoxy DER332/pristine clay nanocomposites (clay content of 2.5 wt %);
Figure 19 compares XRD analyses of raw clay, a polypropylene/pristine clay nanocomposite according to the invention and a polypropylene/organoclay nanocomposite;
Figure 20 shows comparative optical micrographs of
PP/organoclay and PP/pristine clay nanocomposites according to the invention; and
Figure 21 shows TEM micrographs of PP/organoclay and
PP/pristine clay according to the invention.
Figure 22 shows XRD patterns of raw clay and a SMA/pristine clay nanocomposite sample according to the invention;
Figure 23 shows a TEM micrograph of styrene-maleic anhydride (SMA) copolymer/pristine clay according to the invention.
In the accompanying drawings, Figures 1 to 18 deal with prior art comparisons and illustrations of a novel method of preparing a clay masterbatch from a pristine clay and a carrier plastics compound having one or more functional groups.
The manufacture of pristine clay masterbatches is described in co-pending patent application PCT/SG2004/000212 to the same applicant and the contents thereof are incorporated herein by cross-reference and disclosure. ©" Figures 19 to 23 are directed to the preparation of thermoplastic polymer/pristine clay composites according to the present invention.
In preparation of the clay masterbatch, the pristine clay is first dispersed in water to form a dispersion. This causes swelling of the individual clay particles by penetration of the water into the clay gallery 156 spaces.
The water dispersion is then exchanged with an organic solvent. The choice of solvent and the conditions of exchange are such that the swollen state of the clay is maintained. By using an organic solvent, the amount of modifiers can be reduced while exfoliation of the clay particles is improved. Substantially complete exfoliation can be achieved in at least the preferred forms of the process.
The organic solvent used in this process facilitates the reaction between the modifier and the clay and also facilitates the uniform dispersion of the clay layers in the monomers, oligomers or polymers. The organic solvent can also act as a solvent for such monomers, oligomers or polymers.
The organic solvent can be a polar or non-polar solvent. Ifitis non-polar and is not miscible with water, it will usually be used with a polar solvent. By such a solvent system, compatibility of the system with the hydrophilic clay layers and the hydrophobic molecules which may be used as a modifier or as the monomer, polymer or oligomer can be achieved.
The organic solvent is preferably of a low boiling point in order that the reactions are conducted at a low temperature and so that the solvent after performing its function can be easily removed by evaporation.
The organic solvents will thus be preferred including, but are not limited to ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as methanol, ethanol, propanol, n- butanol, i-butanol, sec-butanol and tert-butanol; glycols such as ethylene glycol, propylene glycol and butylene glycol; esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and diethyl malonate; ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and o-dichlorobenzene; hydrocarbons such as hexane, heptane, octane, benzene, toluene and xylene. Others include N-methyl-2- oo pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric friamide, and gamma- butyrolactone. These solvents may be used either singly or in any combination thereof. A solvent or a combination thereof with a boiling point below 100° C is generally preferred for ease of handling and low cost.
In the process, the clay is first mixed with water. The ratio of clay to water can vary from 1:1 to 1:1000. Preferably from 1:2 fo 1:500, more preferably from 1:5 to 1:200. :
The ratio of the amount of water to the amount of organic solvent can vary widely as long as the clay remains in a swollen state. The amounts can vary from 1:1 to 1:50.
The clay used in the formation of the nanocomposiies is one generally utilised in the prior art. Thus it can be selecied from the group consisting of smectite and kaolin clays. Smectite clays for use in the current invention can be selected from the group consisting of montmorillonite, hectorite, saponite, sauconite, beidellite, nontronote, and combinations of two or more thereof. More preferably the clay is selected from the group consisting of hectorite, montmorillonite, beidellite, stevensite, and saponite.
Typically the clay used in the current invention will have a cation-exchange capacity ranging from about 7 to 300 meqg/100 g.
The amount of clay used in the nanocomposites of the current invention will vary depending upon the desired properties in the final nanocomposite and generally range from about 0.1% to 80% by weight based on the total weight of the composition with the higher values, 40 weight % to 80 weight % being employed in clay masterbatch compositions.
The organic modifiers used in the process can be those referred to in the prior art. The modifiers hormally have a function to react with the clay surface and with the polymer chains. The clay surfaces are hydrophilic. The polymer chain can vary from hydrophobic to having some degree of hydrophilicity. The modifier will have both a hydrophilic and a "hydrophobic functional group. Hence the modifier can be selected fromthe group consisting of surfactants, coupling agents and compatibilizers.
Suitable modifiers can be selected from alkylammonium salts, organosilanes, alkyl acids (or functional derivatives thereof, such as an acid chloride or anhydride), grafted copolymers and block copolymers. in each case the modifier will be selected so that it has a functionai group that can bond to the clay layers and another functional group that can bond.to the polymer. ltis a feature of the masterbatch process that the modifier can be used in a much lower amount than proposed in the prior art methods.
Hence, the amount of modifier can be reduced to an amount within the range 0.15 to 15 weight percent.
The polymer can be selected from any polymers normally used in a composite in the prior art. Hence polymers chosen from thermosetting polymers, thermoplastic polymers, and combinations thereof can be employed. The polymers can be incorporated in the process as a polymerizable monomer, oligomer or prepolymer and then later polymerized in a reactive compounding process. Such polymers include thermosetting polymers such as epoxies, polyester resins and curing rubbers; thermoplastic polymers such as polyolefins which can consist of polyethylenes, polypropylenes, polybulylenes, polymethylpentene, polyisoprenes and copolymers thereof, copolymers of olefins and other monomers such as : 30 ethylene-vinyl acetate, ethylene acid copolymers, ethylene-vinyl alcohol, ethylene-ethyl acrylate, and ethylene-methyl acrylate, polyacrylates such as polymethyl methylacrylate, polybutyl acrylate, polyethyl methacrylate, polyisobutyl acrylate, poly(2-ethylhexyl acrylate), poly(amino acrylates),
poly(hydroxyethylmethacrylate), poly(hydroxypropyl methacrylate), or other : polyalkyl acrylates; polyesters such as polyarylates, polybutylene terephthalate and polyethylene terephthalate; polystyrene and copolymers such as ABS, SAN, ASA and styrene-butadiene; engineering resins such as polycarbonate, polyetherimide, polyetheretherketone, polyphenylene sulphide and thermoplastic polyimides; elastomers such as olefinic TPE’s, polyurethane TPE's, and styrenic TPE's; chlorinated polymers such as PVC and polyvinylidene dichloride; silicones such as polydimethyl siloxane, silicone rubber, silicone resin; fluoropolymers and copolymers with other ~~ monomers are useful such as polytetrafluoroethylene, fluorinated ethylene-propylene, perfluoroalkoxy resins, polychlorotrifiuoroethylene, ethylene-chlorofluorosthylene copolymer, polyvinylidene fluoride and polyvinylfluoride. Additional polymers are nitrile resins, polyamides (nylons), polyphenylene ether and polyamide-imide copolymers. Also included are the sulfone based resins such as polysulfone, polyethersulfone and polyarylsulfone. Other families of thermoplastic resins useful in this process are acetals, acrylics and cellulosics. Liquid crystal polymers, a family of polyester copolymers, can also be used. In addition, miscible or immiscible blends and alloys of any of the above resin combinations are useful.
The amount of polymer in the composite masterbatch can vary from about 20% up to about 80% by weight of the total composition depending on the desired application. The preferred polymer content can be 40% to 80%; more preferably 50% to 60%.
Example 1 illustrates the manufacture of a clay masterbatch using a prior art modified clay.
Examples 2 to 5 illustrate the manufacture of clay masterbatches for use with nanocomposites and processes for the manufacture thereof in accordance with the present invention.
Examples 6 and 7 illustrate the manufacture of thermoplastic nanocomposites according to the present invention.
Example 1
2 grams of Cloisite 93A, an commercial organoclay containing 40 wt % of an alkylammonium surfactant was mixed with 60.8 g of Dow epoxy resin DER 332 by using a homogenizer for 2 hours at a speed of 10000 rpm. The mixture then mixed with 16g curing agent (ETHACURE 100
LC) by stirring and cured at 100° C for 2 hours and 180° C for 5 hours. The final product was a plate and subject to a number of fess.
The optical micrograph is shown in Figure 1. The TEM micrograph is shown in Figure 3.
Example 2 oo I 0 2 grams of purified sodium montmorillonite having a cation exchange capacity of 145 meq/100g, was mixed with 100 ml of water, with stirring for 24 hours at room temperature to form a suspension. The suspension was precipitated in 1000 ml of acetone at room temperature with stirring and washed: with acetone at room temperature for 3 times. 3-aminopropyltrinethoxy-silane was added as the coupling agent in an amount of 0.1 g. The mixture was then stirred for 12 hours at room temperature. Then 60.8 g of Dow epoxy resin DER 332 was mixed with the modified clay thoroughly by using a homogenizer for 2 hours at a speed of 10000 rpm. The mixture was dried in a vacuum oven at 50° C for 48 hours and then mixed with 16g curing agent (ETHACURE 100 LC) by sfirring and cured at 100° C for 2 hours and 180° C for 5 hours. The final product was a plate and subject to a number of tests. : The optical micrograph is shown in Figure 2. The TEM : micrograph is shown in Figure 4.
Optical microscope (OM) observations confirmed that the clay particles have uniformly dispersed in the matrix in the nanocomposites prepared with the dispersion technique. In an epoxy/organoclay composite prepared with a prior art technique, the aggregate size is 10-20 micion (Figure 1). In the above-mentioned epoxy/clay nanocomposite, clay particles are uniformly dispersed in the matrix and the size of the aggregates is less than 1 micron (Figure 2).
The results of a transmission electron microscopic (TEM) study show that the clay is highly exfoliated and the clay layers are uniformly dispersed in the epoxy matrix (Figure 4), which is significantly superior to that of the samples made with the prior art technique (Figure 3).
The incorporation of clay into epoxy improves both the Young's modulus (Figure 5) and fracture toughness (Figure 6). At a clay load of 2.5 wt %, the fracture toughness shows a maximum value (Figure 6).
Compared with the data reported in literature, the nanocomposites prepared ‘with this approach show better performance in terms of both Young's modulus and fracture toughness. Figures 7 and 87 show, respectively, the comparison of the Young's Modulus and fracture toughness of the nanocomposites of the invention prepared in accordance with a different method. (Ref: Becker, Cheng, Varley, Simon. Macromolecules, 2003, 36, 1616-1625). Ref A was cured at 100°C 2h, 130°C 1h, 160° 12h, 200°C 2h.
Ref B was cured at 160°C 12h, 200°C 2h. it is obvious that the nanocomposites prepared with this approach show higher Young's modulus regardless of the clay content. The maximum value of fracture toughness is higher than that of the samples prepared with the prior art approach.
The dynamic mechanical properties of the nanocomposites are shown in Figures 9 and 10, together with that of an epoxy/organoclay nanocomposite (epoxy/83A). In Figures 9 and 20, curve a is neat epoxy, curves b, ¢, d and e are 1.0,2.5,3.5and & wt % clay respectively. Curve f represents 5.0 wt % of Cloisite 93A. lt can be seen that the storage modulus of the nanocomposites with this approach increase with the clay load, while the Tg didn’t change much. For epoxy/organoclay, however, the storage modulus is lower at the same load, and the Tg decrease dramatically.
Figures 11 and 12 show a comparison of high transmittance.
Because the clay dispersion and exfoliation have been improved with this approach, the transmittance of the new epoxy/clay nanocomposites (Figure 11) is better than that of the nanocomposites prepared with the prior art approaches (Figure 12). co
Example 3 2 grams of purified sodium montmorillonite having a cation exchange capacity of 145 meg/100g, was mixed with 100 ml of water, with stirring for 24 hours at room temperature to form a suspension. The suspension was precipitated in 1000 ml of acetone at room temperature with stirring and washed with acetone at room temperature for 3 times. 3-glycidopropyltrimethoxy-silane was added as the coupling agent in an amount of 0.1 g. The mixture was then stirred for 12 hours at room temperature. Then 50 g of Ciba epoxy resin LY5210 was mixed with the modified clay thoroughly by using a homogenizer for 2 hours at a speed of 10000 rpm. The mixture was dried in a vacuum oven at 50° C for 48 hours and then mixed with 25g curing agent (Ciba HY2954) by stirring and cured at 160° C for 2 hours and 220° C for 2 hours. The final product was a plate and subject to a number of tests.
The TEM micrograph shows that the clay is highly exfoliated and the clay layers are uniformly dispersed in the epoxy matrix (Figure 13), which is significantly superior to that of the samples made with the prior art technique (Figure 3). :
The dynamic mechanical properties of the nanocomposites are shown in Figures 14 and 15. It can be seen that both the storage modulus and Tg of the nanocomposites made by this approach increase with the clay load. i
The incorporation of clay into epoxy improves fracture toughness (Figure 16). At a clay load of 2.5 wt %, the fracture toughness shows a maximum value. :
Example 4 2 grams of purified sodium montmorillonite having a cation exchange capacity of 145 meq/100g, was mixed with 100 mi of water, with stirring for 24 hours at room temperature fo form a suspension. The suspension was precipitated in 1000 ml of ethanol at room temperature with stiming and washed with ethanol at room temperature for 3 times. 3-aminopropyltrimethoxy-silane was added as the coupling agent in an amount of 0.1 g. The mixture was then stirred for 12 hours at room. temperature. Then 60.8 g of Dow epoxy resin DER 332 was mixed with the modified clay thoroughly by using a homogenizer for 2 hours at a speed of 10000 rpm. The mixture was dried in a vacuum oven at 60° C for 48 hours and then mixed with 16g curing agent (ETHACURE 100 LC) by stirring and cured at 100° C for 2 hours and 180° C for 5 hours. The final product was a © plate and subject to a number of tests. Bh Coo
The TEM micrograph show that the clay is highly exfoliated and the clay layers are uniformly dispersed in the epoxy matrix (Figure 17), which is significantly superior to that of the samples made with a prior art technique (Figure 3).
Example 5 2 grams of purified sodium montmorillonite having a cation exchange capacity of 145 meq/100g, was mixed with 100 ml of water, with stirring for 24 hours at room temperature to form a suspension. The suspension was precipitated in 1000 ml of acetone at room temperature with : stiming and washed with acetone at room temperature for 3 times. 3-glycidopropyltrimethoxy-silane was added as the coupling agent in an amount of 0.1 g. The mixture was then stirred for 12 hours at room temperature. Then 60.8 g of Dow epoxy resin DER 332 was mixed with the modified clay thoroughly by using a homogenizer for 2 hours at a speed of 10000 rpm. The mixture was dried in a vacuum oven at 50° C for 48 hours and then mixed with 16g curing agent (ETHACURE 100 LC) by sfirring and cured at 100° C for 2 hours and 180° C for 5 hours. The final product was a plate and subject to a number of tests. :
The TEM micrograph show that the clay is highly exfoliated and the clay layers are uniformly dispersed in the epoxy matrix (Figure 18), which is significantly superior to that of the samples made with a prior art technique (Figure 3).
The following table summarises the main components used in each of the Examples and the relevant Figures illustrating the properties of the final product.
TABLE 1
Examples | Polymer | Clay Solvent | Modifier Figures fe 1 DER332 | Organo None 1,3
Ce
DER332 | Pristine | Acetone | 3-aminopropylimethoxy- | 24-12 od 3 LY 5210 | Pristine | Ethanol | 3-glycidopropyitrimethoxy; 13-16
IPE
4 DER332 | Pristine | Ethanol | 3-aminopropyltiimethoxy- | 17
A x wl Pd
DER332 | Pristine | Acetone | 3-glycidopropyltrimethoxy; 18
CET
;
Example 6 (a Initially, a 20 weight % masterbatch was prepared in accordance with the method described in EXAMPLE 5 except thatthe curing : agent was omitted. As in EXAMPLE 5, the carrier plastics compound was an epoxy (DER 332) compound. 5 grams of the masterbaich so prepared was then melt compounded with 32 grams of a general purpose (Titanpro) 6331 grade polypropylene (PP) homopolymer and 8 grams of (Eastman Epolene) maleic anhydride grafted polypropylene (PP—g-MAH) grade G3003 in a Brabendar mixer at 190°C with a rotational speed of 100 rpm for 10 minutes. (b) For comparative purposes, a reference sample was prepared by melt compounding 1 gram of (Nanocor Nanomer) 130P organoclay with 40 grams of (Titanpro) 6331 grade PP and 4 grams of (Eastman Epolene
G3003) PP-g-MAH at 190°C with a rotational speed of 100 rpm for 10 minutes.
Referring to Figure 19, which represents XRD spectra for raw clay (curve 1), sample a (curve 2) and sample b (curve 3), it can be concluded that the organoclay containing sample (b) exhibits a highly intercalated structure because the (001) peak of clay reflects strongly albeit at a lesser angle than for raw clay. In contrast the (001) peak disappears from the reflectance curve for the pristine clay example (a) thus suggesting an absence of intercalated tactoids and the likelihood of a highly exfoliated clay dispersion in sample a according to the invention. © Figure 20 shows comparative optical micrographs for samples ~~ a and b wherein the aggregate particle size of the clearly visible tactoids or undispersed disordered layers for sample b is in the range of from 10 to 20 pm compared with far more uniformly dispersed clay particles in sample a wherein the aggregate particle size is less than 1 pm.
Figure 21 is a comparison between TEM micrographs for - samples a and b showing clearly that the clay particles in sample a are more highly exfoliated and more uniformly dispersed than in sample b which represents a prior art technique for nanocomposite manufacture using an organoclay filler.
Example 7
A 20 weight % masterbaich was prepared in accordance with the method described in EXAMPLE 5 except that the curing agent was omitted. As in EXAMPLE 5, the carrier plastics compound was an epoxy (DER 332) compound. 5 grams of the masterbatch so prepared was then melt : compounded with 45 grams of a styrene-maleic anhydride (SMA) copolymer (Dylark 322, Nova Chemicals) in a Brabendar mixer at 180°C with a rotational speed of 100 rpm for 10 minutes.
Referring to Figure 22, which represents XRD spectra for raw clay (curve 1) and the SMA/clay nanocomposite (curve 2), it can be concluded that the SMA/clay nanocomposite exhibits a highly exfoliated structure because the (001) peak of clay reflects disappears.
Figure 23 shows a TEM micrograph of the SMA/clay hanocomposite sample. Clearly, the clay particles in the sample are highly exfoliated. it readily will be apparent to a person skilled in the art that many modifications and variations may be possible without departing from the spirit and scope of the various aspects of the invention.
Similarly, equally it will be apparent to a person skilled inthe art that the nanocomposites of the present invention offer substantial advantages over prior art nanocomposite materials and processes forthe production thereof.
By employing the novel and versatile masterbatch of our co- pending patent application PCT/SG2004/000212 with a thermoplastic polymer matrix, with or without a reactive copolymer, in a reactive compounding process, a wide range of thermoplastic polymer matrices may be employed including non-polar polymers such as polyolefins including polyethylenes, polypropylenes, polystyrenes, polyurethanes as well as styrene based thermoplastic elastomers including acrylonitrile butadiene styrene (ABS) and the like. Moreover the invention is also applicable to poly (methyimethacrylate) (PMMA), poly (ethyleneterephthalate) (PET), poly (butyleneterephthalate) (PBT), polycarbonates, polyamides and the like.
A particular advantage arises from the use of pristine clay masterbatches made in accordance with our co-pending patent application
PCT/SG2004/000212 in that notonly are the minimally modified substantially pristine clays substantially less expensive than prior art organoclays, they are not contaminated with low molecular weight modifiers to the same extent as prior art products. Moreover, because the plastics carrier compound for the pristine clay masterbatch has a highly exfoliated clay dispersed within and because the plastics carrier compound is thermodynamically miscible or reactive with a wide variety of polymer matrices, the resultant thermoplastic nanocomposite is thermodynamically stable with superior physical properties arising from an evenly dispersed highly exfoliated pristine clay throughout.
A further advantage is that by utilizing a low clay modifier content in combination with a reactive plastics carrier compound, selective chain extension or cross linking reactions between carrier compounds and matrix polymers, with or without the presence of a reactive copolymer, substantially minimize the presence of low molecular weight polymer species in the nanocomposite material.
Table 2 represents a comparison of prior art nanocomposite materials with nanocomposites according to the invention.
TABLE 2 ~ Prior Art Nanocomposite | Nanocomposites of the
IEE
Amount of organic |1.71io4.1wt% 0.1to 0.5wt% ©
Function of copolymer | Compatibilizer Curing agent and oy fom
Reaction during Yes es ||" " 'Low MW additives in | Unchanged Chemically bonded rs
Comrorpo [Bom [Coneey oe [A few * in final nanocomposite if true clay content is 5.0 wt %.
Nanocomposites according to the invention will have wide application in injection moulded, extruded or thermoformed articles where high elastic modulus, high tensile strength, high impact resistance, high hardness, high heat distortion temperatures, high thermal stability, good clarity and improved gas barrier properties are required. Such articles may find application as parts and components in the automotive, autornobile or general engineering industries as well as beverage and food packaging.
Claims (1)
- . | PCT/SG2005/000006 ol Received 16 April 2007 21 CLAIMS1. A thermoplastic polymer based nanocomposite comprising:- : a nanocomposite masterbatch comprising a carrier plastics. - compound having one or more carrier functional groups and an exfoliated : 5 clay dispersed throughout said cartier plastics compound; and, a thermoplastic matrix polymer reactively compounded with said nanocomposite masterbatch, said matrix polymer having a main chain directly or indirectly miscible with or reactive with said carrier plastics compound, said thermoplastic polymer based nanocomposite characterized 10 in that said nanocomposite masterbatch is formed by treatment of pristine { J clay with water to swell said clay, exchanging said water with an organic } solvent while maintaining said clay in a swollen state, freating said solvent exchanged swollen clay with a modifier selected from a surfactant, a : coupling agent, a compatibilizer or any combination thereof and : 15 subsequently mixing said clay so treated with a monomer, ofigomer, polymer : or combinations and selectively removing said solvent from said nanocomposite masterbatch.2. A nanocomposite as claimed in claim 1 wherein said modifier is present in an amount of between 0.05 — 10 wt % of clay in said ’ 20 nanocomposite. | oo3. A nanocomposite as claimed in claim 1 wherein said carrier . plastics compound comprises a monomer, oligomer or polymer or any Lf combination thereof, 4, A nanocomposite as claimed in claim 1 wherein said one or 25 mare carrier functional groups are selected from epoxy, hydroxyl, amine, : isocyanate, carboxyl or any combination thereof. : A nanocomposite as claimed in claim 1 wherein sald carrier plastics compound comprises an epoxy prepolymer ar polyethylene oxide.6. A" nanocomposite as claimed in claim 1 wherein said thermoplastic matrix polymer is directly miscible with said carrier plastics compound and where said carrier plastics compound comprises a monomer, oligomer, prepolymer or any combination thereof, a curing agent is provided oo | | Amended Sheet 'IPEA/AUPCT/SG2005/00000¢ Co | Received 16 April 200’ ! to effect cross: linking of said monomer, oligomer, prepolymer or any combination thereof during reactive compounding of sajd Nanocomposite. . 7. A nanocomposite as claimed in claim 1 wherein sajd : thermoplastic matrix polymer includes One or more matrix functional groups reactive with carrier functional groups via chain extension or cross linking during reactive compounding to form a carrier/matrix copolymer between said carrier plastics compound and said matrix polymer.: 8. A nanocomposite as claimed in ciaim 1 wherein said thermoplastic polymer is selected from the group comprising: : Crystalline polar thermoplastic polymers, crystalline non-polar s | thermoplastic polymers, non-crystalline non-polar thermoplastic polymers, be : non-crystalline polar thermoplastic polymers; copolymers thereof or any : Combination of the aforesaid polymers, Co g, A nanocomposite as claimed in claim 1 wherein said ‘nanocomposite includes & reactive polymer having at least one segment thermodynamicatly miscible with said matrix polymer and at least one region N - having atleast one reactive polymer functional group reactive with a carrier - functionaj group during reactive Compounding to form g carrier/reactive : copolymer between said carrier plastics Compound and said reactive polymer. : 10. A nanocomposite as claimed in claim 9 wherein said at least oo © one reactive polymer functional group is selected from carboxyl, anhydride, Cy | hydroxyl, isocyanine, amine, epoxy or any combination thereof,oo . 11 A nanocomposite as claimed In claim 9 wherein said reactive polymer is selected from a group comprising blocks, segments or chains oo having the same monomer unit as said matrix polymer OF are CT ‘thermodynarmically miscible therewith, :12. A nanocomposite as claimed in claim 1 wherein saig :. masterbatch includes clay in-an amount of from between 2%, and 80% by ; weight of said masterbatch, | | i13. A nanocomposite as claimed in claim 1 comprising from 0.1% : to 20% by weight of clay based on a total weight of the Nanocomposite. : Co | Amended Sheet IPEA/AU- oo nt - Smee ee - PCT/SG2005/000006 oo Received 16 April 2007 ‘ 23 : 14, A process for the formation of a thermoplastic polymer based nanocomposite according to claim 1, said process including reactive compounding of said nanocomposite masterbatch comprising a carrier ) plastics compound having one or more camier functional groups and an exfoliated clay dispersed throughout said carrier plastics cornpound and a thermoplastic matrix polymer, said matrix polymer having a main chain directly or indirectly miscible with or reactive with said carrier plastics compound,15. A process as claimed in claim 14 wherein said carrier plastics compound is selected from monomers, oligomers, polymers or any D) combination thereof. oo16. A process as claimed in claim 14 wherein said carrier functional : groups are selected from epoxy, hydroxyl, amine, isocyanate, carboxyl or any combination thereof. : 15 17. A process as claimed in claim 14 wherein said carrier plastics compound comprises an epoxy prepolymer or polyethylene oxide.18. A process as claimed in claim 14 wherein said thermoplastic . : matrix polymer Is directly miscible with said carrier plastics compound and where said carrier plastics compound comprises a monomer, oligomer, prepolymer or any combination thereof, a curing agent is provided to effect cross linking of said carrier plastics compound during reactive compounding. a 19. A process as claimed in claim 14 wherein said thermoplastic ~ i | “matrix polymer comprises one or more matrix functional groups reactive with ~ said carrer functional groups via chain extension or cross linking during - 25 reactive compounding fo form a carrier/matrix copolymer between said carrier plastics compound and said matrix polymer.Lo. TK process as claimed in claim 14 wherein said thermoplastic polymer is selected from the group comprising:- : crystalline polar thermoplastic polymers, crystalline non-polar thermoplastic polymers, non-crystalline non-polar thermoplastic polymers, Co - non-crystalline polar. thermoplastic polymers; copolymers thereof or any combination of the aforesaid polymers. Amended Sheet IPEA/AU- | | PCT/SG2005/000006 voc Received 16 April 2007 24 - 21. A process as claimed in claim 14 comprising a reaction, during reactive compounding, of a reactive polymer having at least one segment thermodynamically miscible with said matrix polymer and at least one segment having at least one reactive polymer functional group reactive with a : carrier functional group to form a carrierfreaciive copolymer between said carrier plastics compound and said reactive copolymer. : oo 22. A process as claimed in claim 14 wherein said reactive polymer is selected from a group compiising blacks, segments or chains having the : same monomer unit as said matrix polymer or are thermodynamically miscible therewith. ) 23. A process as claimed in claim 14 wherein said cartier/reactive : : copolymer functions as a compatibilizer for said carrier plastics compound and said matrix polymer. :; . 24. A process as claimed in claim 14 wherein said reactive polymer : 16 functions as a curing agent for said plastics carrier compound during reactive compounding. : Amended Sheet IPEA/AU
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