CN1918227A - Nanoclay-containing composites and methods of making them - Google Patents
Nanoclay-containing composites and methods of making them Download PDFInfo
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- CN1918227A CN1918227A CN 200480029263 CN200480029263A CN1918227A CN 1918227 A CN1918227 A CN 1918227A CN 200480029263 CN200480029263 CN 200480029263 CN 200480029263 A CN200480029263 A CN 200480029263A CN 1918227 A CN1918227 A CN 1918227A
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Abstract
A composite of nanoclay and thermoplastic matrix polymer is disclosed, optionally containing a polyolefin elastomer and also optionally containing a dispersion agent for the nanoclay. The nanocomposite is prepared for use with thermoplastic polyolefins (TPO's). The polyolefin elastomer, preferably an ethylene-octene copolymer, is added into a mixing extruder downstream of the other ingredients. The nanoconcentrate contributes increased stiffness and toughness to a TPO, which can be used form molded articles such as automotive parts.
Description
Prioity claim
The application requires the right of priority of following United States Patent (USP) provisional application:
60/509,679 (business quarters's file number 12003023 was submitted on October 8th, 2003);
60/538,534 (business quarters's file number 12004001 was submitted on January 22nd, 2004);
60/539,250 (business quarters's file number 12004002 was submitted on January 26th, 2004).
Invention field
The present patent application relates to the polymeric blends that contains nanoclay.
Background technology
Nanotechnology is an emerging scientific domain.Think always and use the phyllosilicate (being also referred to as montmorillonitic clay) that embeds, particularly the montmorillonite clay is as valuable reinforcing filler.
Nanocor company maintains the leading position at produce and market montmorillonite nanoclay and aspect the enriched material that wherein clay platelet comes off.Further technology and business information can be found on www.nanocor.com..U.S. Patent No. 6,632,868 (Qian etc.) openly use the intercalated material that polypropylene/maleic anhydride modified polypropylene intercalating agent forms.
A kind of polymkeric substance that has wherein added the montmorillonite nanoclay is TPO (TPO), and particularly described polymkeric substance is polypropylene (PP).
Summary of the invention
Be the object of the invention, " nano-complex " refers to comprise the mixture of the nanoclay of thermoplasticity matrix polymer and embedding, uses with enriched material or mixture.Optional but preferably nano-complex contain compatible dispersion agent, as the polyolefine of maleinization.Optional but preferably nano-complex contain polyolefin elastomer, to improve shock resistance.
One aspect of the invention provides a kind of nano-complex, and the weight ratio of its nanoclay and compatible dispersion agent is less than 2.2: 1, and greater than 1: 1.9.At this ratio range, this nano-complex can be used for by molding or extrude forming end article with mixture.Preferably, this nano-complex has the nanoclay of minimum 9 weight % to be dispersed in the mixture of this nano-complex.Better, the concentration of nanoclay is 10 weight % or higher.The concentration of best described nanoclay is at least 12 weight %.When 12 weight % nanoclays, the amount of compatible dispersion agent is greater than about 5.5 weight %, but less than 22.8 weight %.
The present invention provides a kind of nano-complex on the other hand, and the weight ratio of its nanoclay and compatible dispersion agent is greater than 3.1: 1 and less than 10: 1.Better, described weight ratio is 3.5: 1 to 5: 1.This nano-complex can with enriched material be used for after a while dilution or " disperse (let-down) " to polymkeric substance, or be used for the TPO that classification is extruded with final mixture.
The present invention provides the nano-complex that contains polyolefin elastomer on the other hand.
The present invention provides the method for making nano-complex on the other hand, wherein, adds polyolefin elastomer in the downstream of forcing machine, adds other component from this forcing machine.
The present invention provides the method for making the nano-complex mixture on the other hand, wherein, import at forcing machine, thermoplasticity matrix polymer, nanoclay, compatible dispersion agent and optional additive add with component independently, add polyolefin elastomer (being used to improve impact) in the downstream part of this forcing machine subsequently.In such a way, TPO is by whole raw materials, rather than the enriched material of TPO or nano-complex constitutes.
Advantage of the present invention is by using the nano-complex by the inventive method preparation to reach balanced rigidity and toughness in TPO.This rigidity and flexible equilibrium are better than wherein not having the TPO of nanoclay.
Another advantage of the present invention is that a kind of delay adds optional polyolefin elastomer, is dispersed in matrix polymer up to nanoclay, the method after normally among the PP.The polyolefine of optional compatible dispersion agent, especially maleinization has improved optional polyolefin elastomer the integral body dispersion of nanoclay in matrix polymer before of any interaction has taken place.Believe that this delay can guarantee that the nanoclay that exists can not be in the disperse phase of polyolefin elastomer.Therefore, these valuable nanoclays are useful by the performance of the end article of the combination forming of TPO and nano-complex of the present invention to raising.
The working of an invention mode
TPO can obtain by transnational source, as obtaining from Basell Polyolefin.As is known to persons skilled in the art, TPO can have the polyolefin copolymer of various character supply shock modifications, from the rigidity to toughness.The end-use of the goods of being made by TPO can benefit from these improved character.
Thermoplasticity matrix polymer of the present invention can be any thermoplastic material that is applicable to molding or extrudes operation, requires brightness, rigidity and toughness as performance in these operations.The non-limitative example of this polymkeric substance is polyolefine, polyamide-based, polyester, polyurethanes, styrenic polymer, polycarbonate-based, polyvinylhalide class, and their combination.
Nanoclay is the clay from montmorillonite family.Montmorillonite has the unique form, it is characterized in that a size of nanometer range.The montmorillonite clay is prevailing a kind of in the montmorillonitic clay family.The montmorillonite clay particle often is known as platelets, refers to that size on the both direction is much larger than the slab organization of grain thickness.
If embed with intercalating agent, nanoclay is commercial more useful.Intercalating agent is clay-chemical complex, wherein, because carried out surface working with intercalating agent, passage (gallery) space of clay is increased.Under suitable temperature and shearing condition, intercalating agent can come off by slabbing in resinous substrates.Intercalating agent is a kind of organic or half-organic compound, can enter the passage of montmorillonite clay and be attached to the surface.Flaking has been described surface treated nanoclay and has been dispersed in dispersion in the plastic substrate.
When slabbing came off form, the platelets of nanoclay had flexible sheets type structure, and the notable attribute of this structure is its very little size, especially the thickness of sheet.Particulate length and width range are 1.5 microns to tens microns.But its thickness is minimum, measured value 1 nanometer (part per billion meter) of only having an appointment.These sizes produce high average slenderness ratio (aspect ratio) (75-500).In addition, small size and thickness mean as long as 1 gram just contains the independently particle more than 100 ten thousand.
As defined above, nano-complex is the treated nanoclay in surface and the combination of plastics substrate.When mixed polymer, it is that nanoclay is distributed to mode commonly used in the final mixture that nano-complex concentrates, as long as the main polymer resin components of the plastics substrate of this nano-complex enriched material and this mixture is compatible.By this way, nano-complex can enriched material, masterbatch (masterbatch) and mixture, from Nanocor, Inc.of Arlington Heights, Illinois (www.nanocor.com) and PolyOne Corporation of AvonLake, Ohio (www.polyone.com) obtains.
Nano-complex often can provide flame retardant resistance, because this nano-complex ingredients can burn with the combustionvelocity that significantly slows down, and forms hard Jiao of one deck on the surface.And its drippage and flame flicking minimum.
When making nanoclay with Nanocor, additive level is about the 2-50 weight % of mixture total weight amount in the enriched material form, better is about 3-40 weight %.After adding in this mixture, the nanoclay of embedding forms flaking because of adding compatilizer well known by persons skilled in the art.In preferred embodiment, compatilizer is a kind of grafted maleic anhydride, and as U.S. Patent No. 5,717,500 (Karande etc.) disclose.In U.S. Patent No. 6,632,868 (Qian etc.) also disclose the purposes of compatilizer.But " nano-complex " that uses this paper to define replaced any inconsistent intension of middle words such as Qian.
Preparation need be used the mixing equipment of extruding well known by persons skilled in the art during nano-complex, those equipment that disclose as the patent of Qian etc.But the present invention is different from conventional.Usually, enriched material is by mixing TPO and nanoclay, and the polypropylene (PP-g-MAH) of optional compatible dispersion agent such as maleinization prepares.
Among the present invention, TPO is not used in and forms this enriched material.But TPO component (that is, PP and elastomerics, particularly polyolefin elastomer) is separated to add at the different positions of forcing machine.More specifically, polyolefin elastomer adds in the downstream of other component, and nanoclay and its optional dispersion agent can both for more time and still less be dispersed in the polypropylene carrier intrusively fully.This method of the present invention can be used for preparing the nano-complex enriched material of any weight ratio and the mixture of nano-complex, comprises those disclosed such as Qian.
Preferably, the weight ratio that the inventive method can be used for preparing nanoclay and compatible dispersion agent is greater than 3.1: 1, and less than 10: 1 enriched material and extrusion grade mixture.Preferably, weight ratio is about 3.1: 1 to 5: 1.
Preferably, the weight ratio that the inventive method can be used for preparing nanoclay and compatible dispersion agent is less than 2.2: 1, and greater than 1: 1.9 mixture.Preferably, described weight ratio is about 1.5: 1 to 1: 1, be about 1.33: 1 better, improving the dispersion of nanoclay in this mixture (before forcing machine import downstream adds optional polyolefin elastomer), and improve the brightness and the rigidity of mixture by enabling to be dispersed in nanoclay amount maximum in this mixture.
Preferably, mixing equipment is the twin screw extruder that corotation changes, and can buy from Werner-Pfleiderer.The screw speed of this forcing machine should be at about 50-2, the 000rpm scope.Temperature distribution scope from 2 horn bodies to die head should be from the fusing point of thermoplasticity matrix polymer to about 270 ℃, should be about 200 ℃ to this nanometer enriched material.Nano-complex can carry out granulation, uses in order to the back.
If the weight ratio of nanoclay and compatible dispersion agent is greater than 3.1: 1 and less than 10: 1, then this particle is fit to be used for making resultant articles in the dilution of shaping operation after a while or " dispersion " with enriched material.Preferably, the enriched material particle adds in the import of last former.Perhaps, to the specific goods of extruding, described particle can use by mixture, and must dilution.Find that unexpectedly the equilibrium of the various mechanical propertiess that end article is required can promptly, reach compatible dispersant dosage minimum by the ratio of nanoclay and compatible dispersion agent.Therefore, according to the present invention, described weight ratio is within the scope of nano-complex enriched material, but mixture that can nano-complex uses.If the weight ratio of nanoclay and compatible dispersion agent was less than 2.2: 1, and greater than 1: 1.9, then described particle was suitable as the final mixture that can be shaped or extrude into end article.
Owing to above-mentioned separately blended reason, among the present invention, optional polyolefin elastomer or the rubber of using substitutes the TPO of blending.Can use any suitable polyolefin elastomer.For example, can use polybutadiene rubber, ethylene-propylene-elastoprene (EPDM), ethylene-octene copolymer and other elastomerics.Final elastomeric non-limitative example has, from many companies such as Bayer, and Dupont-Dow Elstomers, Uniroyal Chemical, those elastomericss are buied by ExxonMobil and other company.ENGAGE
TM8180, ENGAGE
TM8842 and other ENGAGE
TMPolyolefin elastomer is particularly preferred ethylene-octene copolymer, can be from DuPontDow Elastomers LLC, and Wilmington, DE buys, and the function of this multipolymer is as the impact modifying agent to nano-complex of the present invention.
Nano-complex enriched material particle of the present invention can mix with TPO, forms goods, balanced well rigidity and toughness by adding nanoclay therein.The nano-complex enriched material can dilute or " dispersion " according to any ratio that those skilled in the art require to reach final nanoclay concentration in goods.
A kind of mode of diluting is with the twin screw extruder in any source or from the continuous mixing device of Farrel.Further data about this hybrid technology can be found on www.nanocor.com/tech_sheets/P806.pdf, has described nanometer enriched material commonly used is distributed among the TPO.
The another kind of mode of diluting is to mix the particle of nano-complex enriched material when the shaping end article.The former of any kind be mixed into stomatopod so that enriched material of the present invention is distributed among the TPO.According to the requirement of the running cost of raw material catalogue, this is that expensive enriched material is joined a kind of effective means in the final shaping prod, because this enriched material can punctual (just-in-time) obtain.
A kind of TPO mixing machine is in TPO produces and do not require the necessary enriched material additive that uses, and this mixing machine can add all raw materials in the ingress of forcing machine, except polyolefin elastomer.After nanoclay and compatible dispersion agent have mixed fully mutually and be distributed to the TPO matrix polymer, add polyolefin elastomer in the downstream part.In this manner, if the time of forcing machine position postponed in the middle of this mixing machine was routinely added to polyolefin elastomer, and mix nanoclay and compatible dispersion agent ingress, the brightness that this mixing machine can make TPO have to be provided by wherein nanoclay and the benefit of all processing of inflexible and performance to forcing machine.
Other optional components
The technician who mixes the field of TPO recognizes and need add optional component in nano-complex of the present invention.These optional components comprise tinting material (dyestuff or pigment), nucleator, whipping agent, the activator that can reduce the activation temperature of whipping agent, tensio-active agent, softening agent, stablizer, fire retardant, UV absorption agent, filler, perfume compound, demolding aids, processing aid, biocides, anti static additive, biocide, lubricant, and their combination.Should add effectively but the optional additives of the amount of not wasting according to the particular process or the performance objective of these additives in the nano-complex of the present invention.Do not need through unsuitable experiment, those skilled in the art just can determine the minimal effective dose and the maximum not wastage of every kind of desired additives.
Purposes of the present invention
Because nanoclay has improved brightness and rigidity, has also kept flexibility simultaneously, the moulded product of being made by TPO has higher value.This moulded product can manufacture different shape, and parts of trolley part, big apparatus etc. are arranged.
Further specify the present invention by the following examples.
Embodiment
Embodiment 1-17 and Comparative examples A-C
The condition preparation of listing according to the described prescription of table 1 and commercial source and table 2 contains the mixture of nanoclay.It is constant that nanoclay and dispersant concentration keep, the concentration difference of polyolefin copolymer rubber.
| Table 1 | ||||||
| The enriched material prescription that is used for TPO | ||||||
| Component, weight % | 1 | 2 | 3 | 4 | ||
| Nanoclay | 40 | 40 | 40 | 40 | ||
| PP-g-MAH | 10 | 10 | 10 | 10 | ||
| The EO copolymer rubber | 15 | 10 | 5 | 0 | ||
| PP | 35 | 40 | 45 | 50 | ||
| Commercial source | ||||||
| Component and purposes | The source | Trade mark | ||||
| Nanoclay improves rigidity | Nanocor | 144P | ||||
| Ethylene-octene copolymer improves impact | DuPont-Dow | EG8180 | ||||
| PP-g-MAH (maleinization polypropylene), the dispersing nanometer clay | Crompton | PolyBond PBX5104 | ||||
| PP (polypropylene) is as the enriched material carrier | ||||||
| TPO (TPO) | Basell | CA387:Adflex KS311P; With Pro-Fax SG702 | ||||
The weight ratio of nanoclay and compatible dispersion agent is 4: 1, is suitable for to make the nano-complex enriched material.
| Table 2 | ||||
| The enriched material preparation condition | ||||
| Embodiment | 1 | 2 | 3 | 4 |
| The enriched material mixing equipment | Werner ﹠ Pfleiderer ZSK 25 corotations change twin screw extruder | |||
| The enriched material mixing temperature | 200℃ | |||
| The enriched material mixing velocity | 1100rpm | |||
| The interpolation order | Except that ethylene-octene copolymer, all components adds together, and the downstream adds the EO multipolymer, promptly thoroughly disperses the back to add in carrier at nanoclay and dispersion agent | |||
After making enriched material 1-4, they are sneaked into three kinds of different TPO, add the nano-complex enriched material before the useful article to simulate TPO to be configured as shortly.
Table 3 is listed amount of dilution, is also referred to as dispersion amount, and the rigidity of end article and toughness.
| Table 3 | ||||
| The TPO mixture | ||||
| Embodiment | Enriched material | Weight % | TPO | Weight % |
| Comparative examples A | -- | -- | CA387P | 100 |
| 5 | 1 | 20 | CA387P | 80 |
| 6 | 2 | 20 | CA387P | 80 |
| 7 | 3 | 20 | CA387P | 80 |
| 8 | 4 | 20 | CA387P | 80 |
| Comparative example B | -- | -- | Pro-Fax SG702 | 100 |
| 9 | 1 | 20 | Pro-Fax SG702 | 80 |
| 10 | 2 | 20 | Pro-Fax SG702 | 80 |
| 11 | 3 | 20 | Pro-Fax SG702 | 80 |
| 12 | 4 | 20 | Pro-Fax SG702 | 80 |
| Comparative example C | -- | -- | Adflex KS311P | 100 |
| 13 | 1 | 20 | Adflex KS311P | 80 |
| 14 | 2 | 20 | Adflex KS311P | 80 |
| 15 | 3 | 20 | Adflex KS311P | 80 |
| 16 | 4 | 20 | Adflex KS311P | 80 |
| 17 | 2 | 10 | Adflex KS311P | 90 |
| Embodiment | ASTM D790(PSI) | ASTM D3837 (joule) | ||||||
| Young's modulus | Yielding stress | Instrument impacts under the room temperature | 0 ℃ of instrument impacts | -30 ℃ of instruments impact | ||||
| Peak value | Peak value | Peak value | Total amount | Peak value | Total amount | |||
| Comparative examples A | 120000 | 3380 | 16.7 | 30.7 | 24.9 | 45 | ||
| 5 | 149000 | 3540 | 16.8 | 30.5 | 24.6 | 39.3 | ||
| 6 | 157000 | 3740 | 16.6 | 30.2 | 22.6 | 27 | ||
| 7 | 158000 | 3850 | 16.6 | 29.7 | 13.8 | 14.4 | ||
| 8 | 179000 | 4110 | 16.5 | 28.7 | 3.9 | 4.9 | ||
| Comparative example B | 155000 | 4770 | 18.8 | 33.8 | 22.4 | 41.3 | ||
| 9 | 233000 | 5530 | 20.1 | 31.1 | 24.1 | 37.4 | ||
| 10 | 239000 | 5650 | 21.1 | 30.3 | 18.5 | 22.5 | ||
| 11 | 244000 | 5720 | 20.6 | 28.5 | ||||
| 12 | 258000 | 5980 | 20.6 | 24.3 | 11.5 | 12.1 | ||
| Comparative example C | 78400 | 2530 | 13.8 | 25 | ||||
| 13 | 123000 | 3040 | 16.1 | 26.9 | ||||
| 14 | 130000 | 3220 | 15.7 | 26.4 | ||||
| 15 | 133000 | 3330 | 15.1 | 26.2 | ||||
| 16 | 149000 | 3540 | 15.4 | 25.4 | ||||
| 17 | 109000 | 3010 | 15.2 | 26.4 | ||||
Table 3 shows that embodiment 5-8,9-12 and 13-16 (respectively containing 8 weight % nanoclays) surpass Comparative examples A, B and C respectively aspect Young's modulus and yielding stress.Because each comparative example is that (A is rigidity TPO to dissimilar TPO; B is the impingement multipolymer; C is flexible TPO), complicated to the evaluation of instrument impact property.By comparing instrument impact peak value and the ballistic total amount of instrument, all embodiment 5-16 show ductility.Descend with polyolefin copolymer content, the instrument impact property under the different operating temperature also descends.Therefore, reach rigidity and flexible equilibrium preferably at embodiment 5,9 and 13.
Embodiment 14 and 17 has compared the nanoclay amount in the TPO mixture of same component, and embodiment 14 contains 8% nanoclay, and embodiment 17 contains 4%.With comparative example C, again to the Trendline of 8 weight %, rigidity increases along this line from 0 weight % to 4 weight % in foundation.
Embodiment 18-34 and Comparative Example D-F
Carry out second group of test, further specifying the present invention can be by will directly being added to the scope that directly prepares final mixture in the forcing machine as each component of raw material.Table 4 has been listed component and commercial source thereof.Table 5 is listed based on the 7 kinds of different ingredients (A-G) under three kinds of different preparations and the different mixing conditions in forcing machine.Table 6 is listed performance (the embodiment 18-34 and the Comparative Example D-F) of 20 kinds of different extrudates and formation.To at these all embodiment, the weight ratio of nanoclay and compatible dispersion agent is 12: 9 or 1.33: 1.
| Table 4 | ||
| Commercial source | ||
| Component and purposes | The source | Trade mark |
| Nanoclay improves rigidity | Nanocor | 144P |
| Ethylene-octene copolymer improves impact | DuPont-Dow | EG8180 |
| PP-g-MAH (maleinization polypropylene), the dispersing nanometer clay | Crompton | PolyBond PBX5104 |
| Polypropylene (melt flow index 12) | Basell | Pro-Fax 6323 |
| The blend of Irganox 1010 and Irgafos 168 processing stabilizers | Ciba | B-225 |
| PP (melt flow index 60) | Various | PP 60MFI |
| Table 5 | ||||||||||||||
| Mixing equipment | Werner﹠Pfleiderer ZSK 25 corotations change twin screw extruder | |||||||||||||
| Mixing temperature | 200℃ | |||||||||||||
| Prescription and interpolation order | ||||||||||||||
| Prescription A | Prescription B | Prescription C | Prescription D | Prescription E | Prescription F (contrast) | Prescription G | ||||||||
| Component | Weight % | Component | Weight % | Component | Weight % | Component | Weight % | Component | Weight % | Component | Weight % | Component | Weight % | |
| I.44P Nanomer | 12 | I.44P Nanomer | 12 | I.44P Nanomer | 12 | I.44P Nanomer | 12 | I.44P Nanomer | 12 | I.44P Nanomer | 12 | 1.44P Nanomer | 12 | |
| Ingress's feeder 1 | ||||||||||||||
| B-255 | 0.3 | B-255 | 0.3 | B-255 | 0.3 | B-255 | 0.3 | B-255 | 0.3 | B-255 | 0.3 | B-255 | 0.3 | |
| PBX5104 | 9 | PBX5104 | 9 | PBX5104 | 9 | PBX5104 | 9 | PBX5104 | 9 | PBX5104 | 9 | PBX5104 | 9 | |
| Profax6323 | 18.7 | Profax6323 | 9.35 | Profax6323 | 0 | Profax6323 | 38.7 | Profax6323 | 20 | Profax6323 | 58.7 | Profax6323 | 8.7 | |
| PP 60MFI | 0 | PP 60MFI | 9.35 | PP 60MFI | 18.7 | PP 60MFI | 0 | PP 60MFI | 18.7 | Engage8180 | 20 | PP 60MFI | 0 | |
| At lateral parts fed downstream device 2 | ||||||||||||||
| Engage8180 | 20 | Engage8180 | 20 | Engage8180 | 20 | Engage8180 | 20 | Engage8180 | 20 | Engage8180 | 20 | |||
| Profax6323 | 40 | Profax6323 | 40 | Profax6323 | 40 | Profax6323 | 20 | Profax6323 | 20 | Profax6323 | 50 | |||
| Table 6 | |||||||||||||||
| Ratio | Modulus in flexure (± standard deviation) | Modulus (± standard deviation) | Stress (± standard deviation) | Elongation % (± standard deviation) | The Izod impact machine (Notched Izod) (± standard deviation) of otch is arranged if having, fracture | ||||||||||
| Embodiment | Prescription | Ratio * | Mixing velocity (rpm) | Input speed (Lbs/hr) | ASTM D790 (psi *1000) | ASTM D638 (psi *1000) | ASTM D638 (psi) | ASTM D638 (inch/inch) | ASTM D256 (ft-lb/inch) | ||||||
| 18 | A | 40/60 | 500 | 40 | 302 | ±10 | 388 | ±21 | 4600 | ±200 | 7.2 | ±0.2 | 5.3 | ±0.5 | Part |
| 19 | A | 40/60 | 1000 | 40 | 266 | ±2 | 355 | ±3 | 4330 | ±12 | 9.0 | ±0.1 | 10.3 | ±0.2 | Part |
| 20 | A | 40/60 | 1000 | 80 | 263 | ±8 | 349 | ±5 | 4170 | ±22 | 7.8 | ±0.1 | 6.3 | ±0.5 | Part |
| 21 | A | 40/60 | 500 | 80 | 228 | ±1 | 304 | ±5 | 3610 | ±29 | 7.3 | ±0.1 | 3.7 | ±0.2 | Part |
| 22 | B | 40/60 | 500 | 80 | 272 | ±1 | 360 | ±7 | 4250 | ±8 | 8.3 | ±0.1 | 8.3 | ±0.4 | Part |
| 23 | B | 40/60 | 1000 | 80 | 255 | ±4 | 347 | ±16 | 3809 | ±29 | 8.0 | ±0.3 | 6.9 | ±0.4 | Part |
| 24 | B | 40/60 | 1000 | 40 | 232 | ±3 | 355 | ±12 | 4080 | ±2 | 8.1 | ±0.1 | 2.2 | ±0.2 | Part |
| 25 | B | 40/60 | 500 | 40 | 254 | ±1 | 306 | ±7 | 3690 | ±6 | 7.8 | ±0.1 | 5.8 | ±0.1 | Part |
| 26 | C | 40/60 | 1000 | 40 | 246 | ±2 | 344 | ±5 | 3870 | ±45 | 9.0 | ±0.3 | 12.0 | ±0.9 | Non-cracking |
| 27 | C | 40/60 | 500 | 80 | 231 | ±2 | 309 | ±12 | 3480 | ±61 | 7.2 | ±0.1 | 6.7 | ±0.4 | Part |
| 28 | D | 60/40 | 500 | 40 | 280 | ±4 | 366 | ±12 | 4480 | ±30 | 7.8 | ±0.1 | 5.9 | ±0.4 | Part |
| 29 | D | 60/40 | 1000 | 40 | 266 | ±4 | 346 | ±5 | 4300 | ±6 | 8.9 | ±0.1 | 6.9 | ±0.2 | Part |
| 30 | D | 60/40 | 1000 | 80 | 241 | ±1 | 319 | ±7 | 3870 | ±15 | 8.3 | ±0.2 | 6.1 | ±0.3 | Part |
| 31 | D | 60/40 | 500 | 80 | 222 | ±2 | 284 | ±6 | 3480 | ±7 | 7.8 | ±0.1 | 4.3 | ±0.3 | Part |
| 32 | E | 60/40 | 1000 | 80 | 289 | ±3 | 378 | ±8 | 4480 | ±19 | 6.7 | ±0.1 | 4.5 | ±0.3 | Part |
| 33 | E | 60/40 | 1000 | 40 | 257 | ±1 | 332 | ±5 | 3970 | ±9 | 7.8 | ±0.1 | 6.6 | ±0.3 | Part |
| Comparative Example D | F | 100/0 | 500 | 40 | 292 | ±2 | 383 | ±8 | 4500 | ±5 | 7.8 | ±0.2 | 7.0 | ±0.5 | Part |
| Comparative Example E | F | 100/0 | 1000 | 40 | 243 | ±2 | 321 | ±9 | 3810 | ±13 | 9.6 | ±0.1 | 7.5 | ±0.4 | Part |
| Comparative Example F | F | 100/0 | 1000 | 80 | 237 | ±1 | 313 | ±3 | 3720 | ±13 | 9.4 | ±0.2 | 6.7 | ±0.3 | Part |
| 34 | G | 30/70 | 1000 | 80 | 298 | ±1 | 390 | ±10 | 4470 | ±20 | 7.6 | ±0.1 | 7.2 | ±0.4 | Part |
Table 6 is presented at the lateral parts downstream and adds polyolefin elastomer, can obtain the polyacrylic homogeneous dispersion of nanoclay, polypropylene and maleinization in forcing machine, can will have the TPO of premium properties to make particle, supplies shaping subsequently or extrudes usefulness.The modulus in flexure of TPO is at least 222,000 pounds/inch
2The direct comparison of carrying out (Comparative Example D and embodiment 18 and 28 compare), (Comparative Example E and embodiment 19 and 29 compare), (Comparative Example F and embodiment 20,30 and 34 compare) shows, postponing to add elastomerics and postponing to add a part of thermoplasticity matrix polymer to have higher modulus in flexure, improves the ability at forcing machine upstream portion dispersing nanometer clay.
Embodiment 35
This embodiment shows that nanoclay and the weight ratio with compatible dispersion agent of superperformance characteristic are 4: 1, does not need the extrusion grade TPO is further diluted.Table 7 has been listed these preparations.Table 8 has been listed the mechanical property of mixture.
| Table 7 | |||||
| The preparation of embodiment 35 | |||||
| Component and purposes | Weight % | Trade mark | The source | ||
| Nanoclay improves rigidity | 12 | 144P | Nanocor | ||
| Propylene copolymer | 84.2 | Inspire 114 | Dow | ||
| PP-g-MAH (maleinization polypropylene), the dispersing nanometer clay | 3 | PolyBond PBX5104 | Crompton | ||
| Distearyl-sulfo--dipropionate | 0.5 | DSTDP | Various | ||
| The blend of Irganox 1010 and Irgafos 168 processing stabilizers | 0.3 | B-225 | Ciba | ||
| Table 8 | |||||
| Additional parameter | Ratio | 40/60 | |||
| Mixing velocity (rpm) | 1000 | ||||
| Input speed (Pounds Per Hour) | 80 | ||||
| Modulus in flexure (± standard deviation) | ASTM D790(psi *1000) | 323±1 | |||
| Modulus (± standard deviation) | ASTM D638(psi *1000) | 401±7 | |||
| Stress (± standard deviation) | ASTM D638(psi *) | 4790±14 | |||
| Elongation % (± standard deviation) | ASTM D638 (inch/inch) | 8.4±0.2 | |||
| The Izod impact machine (± standard deviation) that otch is arranged, if having, fracture | ASTM D256 (ft-lb/inch) | 5.9 ± 0.3, the part fracture | |||
The invention is not restricted to above-mentioned embodiment.Claims are as follows.
Claims (12)
1. mixture, it comprises:
A kind of nano-complex, this mixture is selected from:
(a) thermoplasticity matrix polymer, nanoclay and compatible dispersion agent, the weight ratio of nanoclay and compatible dispersion agent be less than 2.2: 1, and greater than 1: 1.9,
(b) thermoplasticity matrix polymer, nanoclay and compatible dispersion agent, the weight ratio of nanoclay and compatible dispersion agent be greater than 3.1: 1, and less than 10: 1.
2. mixture as claimed in claim 1 is characterized in that described nano-complex also comprises polyolefin elastomer.
3. mixture as claimed in claim 1 or 2, it is characterized in that, described nano-complex also comprises and is selected from following component: tinting material, nucleator, whipping agent, the activator that can reduce the whipping agent activation temperature, tensio-active agent, softening agent, stablizer, fire retardant, UV absorption agent, filler, perfume compound, demolding aids, processing aid, biocides, anti static additive, biocide, lubricant, and their combination.
4. as claim 1,2 or 3 described mixtures, it is characterized in that described nanoclay comprises the nano-complex of at least 9 weight %.
5. as each described mixture among the claim 1-4, it is characterized in that described mixture also comprises and nano-complex blended TPO.
6. goods are by making as each described mixture among the claim 1-5.
7. a use is as the method for mixture as described in the claim 5, and this method comprises carries out the blended step with each described nano-complex and TPO among the claim 1-4 in the shaping or the extrusion step of final thermoplastic article.
8. method as claimed in claim 7 is characterized in that, described mixing step is with about 4: 1 mixed TPO and nano-complex.
9. method of using mixture as claimed in claim 4, this method comprises carries out granulation with further processing steps with described nano-complex.
10. method as claimed in claim 9 is characterized in that, described further processing is that described nano-complex is molded or extrude and be shape of products.
11. as preparation process of mixture as described in each among the claim 2-4, this method may further comprise the steps:
(a) thermoplasticity matrix polymer, nanoclay and nanoclay dispersion agent are added to forcing machine;
(b) add polyolefin elastomer in the downstream that adds thermoplasticity matrix polymer, nanoclay and nanoclay dispersion agent.
12. method as claimed in claim 11, it is characterized in that, described step (a) comprises that also adding is selected from following component: tinting material, nucleator, whipping agent, the activator that can reduce the whipping agent activation temperature, tensio-active agent, softening agent, stablizer, fire retardant, UV absorption agent, filler, perfume compound, demolding aids, processing aid, biocides, anti static additive, biocide, lubricant, and their combination.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50967903P | 2003-10-08 | 2003-10-08 | |
| US60/509,679 | 2003-10-08 | ||
| US60/538,534 | 2004-01-22 | ||
| US60/539,250 | 2004-01-26 |
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| Publication Number | Publication Date |
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| CN1918227A true CN1918227A (en) | 2007-02-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480029263 Pending CN1918227A (en) | 2003-10-08 | 2004-10-01 | Nanoclay-containing composites and methods of making them |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108779388A (en) * | 2016-03-22 | 2018-11-09 | 沙特***石油公司 | The in-situ preparation of nanoclay drilling fluid |
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2004
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108779388A (en) * | 2016-03-22 | 2018-11-09 | 沙特***石油公司 | The in-situ preparation of nanoclay drilling fluid |
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Assignee: POLYONE POLYMER (SHANGHAI) CO., LTD. Assignor: PolyOne polymer Ltd. Contract fulfillment period: 2007.01.01 to 2019.05.19 Contract record no.: 2007990000060 Denomination of invention: Composite containing nano clay and preparation method thereof Granted publication date: unauthorized License type: General permission, cross licensing Record date: 20071008 Assignee: Puliwan polymer (Shenzhen) Co., Ltd. Assignor: PolyOne polymer Ltd. Contract fulfillment period: 2007.01.01 to 2019.05.19 Contract record no.: 2007990000061 Denomination of invention: Composite containing nano clay and preparation method thereof Granted publication date: unauthorized License type: General permission, cross licensing Record date: 20071008 Assignee: Polyone Polymer (Suzhou) Ltd. Assignor: PolyOne polymer Ltd. Contract fulfillment period: 2007.01.01 to 2019.05.19 Contract record no.: 2007990000062 Denomination of invention: Composite containing nano clay and preparation method thereof Granted publication date: unauthorized License type: General permission, cross licensing Record date: 20071008 |
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Free format text: COMMON LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.1 TO 2019.5.19 Name of requester: PLIVAN POLYMER ( SHENZHEN ) CO., LTD. Effective date: 20071008 Free format text: COMMON LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.1 TO 2019.5.19 Name of requester: PLIVAN POLYMER ( SHANGHAI ) CO., LTD. Effective date: 20071008 Free format text: COMMON LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.1 TO 2019.5.19 Name of requester: PLIVAN POLYMER ( SUZHOU) CO., LTD. Effective date: 20071008 |
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