CN1197903C - Modifying laminated silicate, nano composite polyethylene-laminated silicate material and their prepn. - Google Patents
Modifying laminated silicate, nano composite polyethylene-laminated silicate material and their prepn. Download PDFInfo
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- CN1197903C CN1197903C CN 01124193 CN01124193A CN1197903C CN 1197903 C CN1197903 C CN 1197903C CN 01124193 CN01124193 CN 01124193 CN 01124193 A CN01124193 A CN 01124193A CN 1197903 C CN1197903 C CN 1197903C
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Abstract
The present invention discloses modified layer silicate, nanometer polyethylene prepared by compounding layer silicate and polyethylene and a preparation method thereof. The modified layer silicate is prepared by the way that 60 to 99 wt% of layer silicate is treated by 1 to 40 wt% of treating agent, so that an ion exchange reaction or a surface chemical reaction is carried out between the layer silicate and the treating agent, and polymers are inserted into the layers of the layer silicate so as to form a polyethylene-layer silicate nanometer composite material. The polyethylene-layer silicate nanometer composite material comprises 50 to 98 wt% of polyethylene, 1 to 40 wt% of modified layer silicate and 1 to 30 wt% of auxiliary agent. The modified layer silicate and the nanometer polyethylene obtained by compounding the polyethylene have the advantages of favorable strength and combination properties, and particularly have excellent high-temperature properties. Thus, the modified layer silicate and the nanometer polyethylene can replace crosslinked polyethylene to be used for making various pipes.
Description
Invention field
The present invention relates to a kind of modified layered silicate and nano-polyethylene, particularly a kind of modified layered silicate, polyethylene-laminated nm-silicate composite material and preparation method thereof.
Background technology
Polyolefine is the synthesizing polymeric material of output maximum in the world, has advantages such as inexpensive, easy to process.As general-purpose plastics, shortcoming is that intensity is lower, poor heat resistance.Poly shortcoming is just more outstanding, adopts traditional composite modifying method to be difficult to take into account the intensity and the toughness of matrix material.Though crosslinked polyethylene can improve the performance of material,, cause environmental pollution because this product can't recycle or utilization again.
Development along with nanotechnology, development in recent years a kind of polynite or other layered silicates embed the compound method for preparing nano material in the superpolymer, polynite is distributed in the polymkeric substance with the form of nano particle, the composite property that obtains improves a lot, see people's such as A.M.Dubios Mater.Sci.Eng.Rep, 2000 the 28th volumes, the 1-63 page or leaf.This method realized inorganic nano phase homodisperse, inorganic/organic interface in conjunction with, independently adorn and have a feature performance benefit incomparable than conventional polymer/inorganic filler composite material.But this method mainly is applicable to nylon, Resins, epoxy polar materials, and for non-polar material such as polypropylene, effect is relatively poor, sees people MacromolecuIes such as M..Kawasumi, 1997 the 30th volumes.Then do not appear in the newspapers for poly modification.
The reason that is difficult to prepare polyethylene one stratiform silicate nanometer composite material is that polyethylene is a non-polar polymer, and layered silicate and treatment agent thereof are polar materials, and the two intermiscibility is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of employing particular processing agent modified layered silicate, described layered silicate can be compound with polyethylene well, improves various poly performances comprehensively.
Another object of the present invention is to provide a kind of particular processing agent modified layered silicate and the compound polyethylene-laminated nm-silicate composite material that obtains of polyethylene-nano-polyethylene of adopting, described nano-polyethylene has excellent comprehensive performances, low cost of manufacture, product is pollution-free.
Another object of the present invention is to provide a kind of preparation method of nano-polyethylene, this method technology is simple, low cost of manufacture, nontoxic, pollution-free, good product performance.
To achieve these goals, the technical solution used in the present invention is: a kind of modified layered silicate comprises:
Layered silicate: 60-99wt%
Treatment agent: 1-40wt%
Described layered silicate can be one or more combination of the polynite of 60-400 purpose, talcum, lithium montmorillonite, zeolite, vermiculite, and is fit to other layered silicates of the present invention; Preferred polynite.Described treatment agent be dimethylaminoethyl acrylate methyl base amine ethyl ester to the chlorion Trimethoxy silane, its structural formula is as follows:
Percentage ratio involved in the present invention is weight percentage.
The loading capacity of described layered silicate is 40-200mmol/100g.
The preparation method of modified sheet silicate is: layered silicate is distributed in the liquid solvent, add treatment agent, make layered silicate and treatment agent generation ion exchange reaction or surface chemical reaction,, obtain the modified sheet silicate powder through filtration, dry, pulverizing.Described solvent can be water, ethanol, methyl alcohol, propyl alcohol, Virahol, THF (tetrahydrofuran (THF)) and be fit to other solvents of the present invention.Temperature of reaction is room temperature or reflux temperature, and described reflux temperature is the temperature of all kinds of SOLVENTS reflux just, i.e. boiling temperature.
Also can adopt the additive method of prior art to prepare treatment agent modified layered silicate of the present invention.
Nano-polyethylene of the present invention comprises:
Polyethylene: 50-98wt%
Modified sheet silicate: 1-40wt%
Auxiliary agent: 1-30wt%
Wherein said polyethylene can be low molecule, middle molecule, polymer or ultra high molecular polyethylene; Described auxiliary agent is the common oxidation inhibitor that adopts of prior art, anti ultraviolet agent, compound accelerant, coupler etc.; Described coupler is firsthand maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene.
The composition and the content of described auxiliary agent are preferably: oxidation inhibitor 0.2-0.3wt%, pro-oxidant 0.2-0.3wt% and maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene 0.5-30wt%.
Polyethylene-poly preparation method of modified sheet silicate composite Nano is: polyethylene, modified sheet silicate, auxiliary agent are mixed in proportion, through the twin screw extruder extruding pelletization.Also can adopt the additive method of prior art to prepare polyethylene of the present invention-modified sheet silicate composite Nano polyethylene.
Organic amine ion in the treatment agent of the present invention can displace Na+, Ca+, the Mg+ plasma in the layered silicate, and the interlamellar spacing in the layered silicate is increased, help polymkeric substance and insert stratiform silicate layer formation polyethylene-laminated nm-silicate composite material.After particularly nonpolar polyethylene inserts layered silicate among the present invention, can stronger physics and chemical action be arranged, form good binding, improve poly performance at inorganic/organic interface with treatment agent.
Adopt modified sheet silicate of the present invention and polyethylene compound, the nano-polyethylene that obtains, it is outstanding to have good intensity and over-all properties, particularly high-temperature behavior, nano-polyethylene of the present invention can replace crosslinked polyethylene be used to make various material of construction, cable sheath, as Building Cooling water pipe material.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, described embodiment is used to describe the present invention rather than restriction the present invention.
Embodiment 1
In the 500ml ethanolic soln of the 80-200 of 5wt% order polynite, add the 2.5g treatment agent, back flow reaction 4 hours is filtered, and is washed till no ion with ethanol, and vacuum-drying is ground to and obtains modified montmorillonoid to constant weight.
Embodiment 2
In the 100-250 of 10wt% order steatitic 500ml methyl alcohol, add the 0.5g treatment agent, back flow reaction 4 hours is filtered, and is washed till no ion with ethanol, and vacuum-drying is ground and is obtained modified montmorillonoid to constant weight.
Embodiment 3
In the 500ml aqueous solution of the 150-300 of 10wt% order lithium montmorillonite and polynite (weight ratio 1: 1), add the 20g treatment agent, room temperature reaction 4 hours filters, and is washed till no ion with ethanol, and vacuum-drying is ground and is obtained modified montmorillonoid to constant weight.
Embodiment 4
The described nano-polyethylene of present embodiment comprises:
Polyethylene (trade mark 6000M): 90wt%
Modified montmorillonoid: 5wt%
The composition of auxiliary agent and content are:
Antioxidant 1010: 0.2%
Pro-oxidant 7910:0.2%
Maleic anhydride inoculated polypropylene 4.6%
Wherein maleic anhydride inoculated polypropylene is directly purchased.
Qilu Petrochemical), modified montmorillonoid, auxiliary agent mix according to the above ratio, at 210 ℃ of extruding pelletizations Celsius, promptly obtains nano-polyethylene of the present invention through twin screw extruder with the trade mark is 6000M polyethylene (manufacturer:.
Embodiment 5
The described nano-polyethylene of present embodiment comprises:
Polyethylene (trade mark 2F0.3A) 85wt%
Modification talcum: 7wt%
The composition of auxiliary agent and content are:
Antioxidant 1010 0.3%
Pro-oxidant 7,910 0.2%
Maleic anhydride grafted polyethylene 7.5%.
Sinopec Shanghai branch office), modified montmorillonoid, auxiliary agent mix according to the above ratio, at 190 ℃ of extruding pelletizations Celsius, promptly obtains nano-polyethylene of the present invention through twin screw extruder with the trade mark is the polyethylene (manufacturer: of 2F0.3A.
Embodiment 6-9
| Form and content % | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Polyethylene (trade mark) | 50(6100M) | 60(2480) | 70(6000M) | 98(2F0.3A) |
| Layered silicate | 40 (lithium montmorillonites) | 20 (zeolites) | 1 (vermiculite) | 1 (mixing polynite) |
| Auxiliary agent | ||||
| Antioxidant 1010 | 0.3 | 0.2 | 0.3 | 1.2 |
| Pro-oxidant 7910 | 0.2 | 0.2 | 0.3 | 0.3 |
| Maleic anhydride grafted polyethylene | (9.5 modified poly ethylene) | (19.6 modified poly ethylene) | (28.4 modified poly ethylene) | (0.5 modified poly ethylene) |
Among the embodiment 6-9, used poly trade mark 6000M, 2480 (manufacturers: Qilu Petrochemical)
Comparative example
The described nano-polyethylene of present embodiment comprises:
Polyethylene (trade mark 6000M): 95wt%
Antioxidant 1010 0.2%
Pro-oxidant 7,910 0.22%
Maleic anhydride inoculated polypropylene 4.6%
With the 6000M polyethylene (manufacturer: Qilu Petrochemical), auxiliary agent mixes according to the above ratio, through twin screw extruder at 210 ℃ of extruding pelletizations Celsius.
The performance of the nano-polyethylene that embodiment 4-9 obtains sees Table 1.
Table 1
| Performance | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example | Standard GB |
| The Izod shock strength, Gpa, 23 ℃ | 154.2 | 85 | 98.1 | 150 | 133.2 | 132.5 | 126.7 | 1843-80 |
| Tensile yield strength, MPa | 33.4 | 32.9 | 30.2 | 34.1 | 32 | 32.1 | 31.96 | 1040-92 |
| Tension set, % | 55 | 63 | 45 | 50 | 40.8 | 30.6 | 22.48 | |
| Flexural strength, MPa | 26.4 | 26.4 | 24.8 | 25.5 | 23.9 | 23.9 | 23.42 | 1042-79 |
| Modulus in flexure, MPa | 922 | 878 | 756 | 898 | 823 | 689 | 642 | |
| Heat-drawn wire, ℃, 0.46MPa | 98 | 94.8 | 88.5 | 92.3 | 90.5 | 87.4 | 82.9 | 1634-79 |
Claims (8)
1. modified layered silicate is characterized in that comprising:
Layered silicate: 60-99wt%
Treatment agent: 1-40wt%;
Described layered silicate is one or more combination of polynite, talcum, lithium montmorillonite, zeolite, vermiculite; Described treatment agent be dimethylaminoethyl acrylate methyl base amine ethyl ester to the chlorion Trimethoxy silane, its structural formula is as follows:
2. the preparation method of the described modified layered silicate of claim 1, it is characterized in that layered silicate is distributed in the liquid solvent, add treatment agent, make layered silicate generation ion exchange reaction or surface chemical reaction, through filtration, drying, pulverize, obtain the modified sheet silicate powder.
3. the preparation method of modified layered silicate according to claim 2 is characterized in that described solvent can be water, ethanol, methyl alcohol, propyl alcohol, Virahol or tetrahydrofuran (THF).
4. the preparation method of modified layered silicate according to claim 3 is characterized in that temperature of reaction is room temperature or reflux temperature.
5. the described modified layered silicate of claim 1 and polyethylene compound polyethylene-laminated nm-silicate composite material comprise
Polyethylene: 50-98wt%
Modified sheet silicate: 1-40wt%
Auxiliary agent: 1-30wt%
Described auxiliary agent is one or more the combination in the oxidation inhibitor that usually adopts of prior art, anti ultraviolet agent, compound accelerant, the coupler;
Described coupler is maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene.
6. polyethylene-laminated nm-silicate composite material according to claim 5 comprises:
Polyethylene: 50-98wt%
Modified sheet silicate: 1-40wt%
The composition of auxiliary agent and content:
Oxidation inhibitor 0.2-0.3wt%
Pro-oxidant 0.2-0.3wt%
Maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene 0.5-30wt%.
7. polyethylene-laminated nm-silicate composite material according to claim 6, described nano-polyethylene preferably includes:
The trade mark is the polyethylene of 6000M: 90wt%
Modified montmorillonoid: 5wt%
The composition of auxiliary agent and content are:
Antioxidant 1010,0.2%
Pro-oxidant 7,910 0.2%
Maleic anhydride inoculated polypropylene 4.6%
8. the preparation method of the described modified polyethylene-laminated nm-silicate composite material of claim 5 is characterized in that polyethylene, modified sheet silicate, auxiliary agent are mixed in proportion, through the twin screw extruder extruding pelletization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01124193 CN1197903C (en) | 2001-08-22 | 2001-08-22 | Modifying laminated silicate, nano composite polyethylene-laminated silicate material and their prepn. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01124193 CN1197903C (en) | 2001-08-22 | 2001-08-22 | Modifying laminated silicate, nano composite polyethylene-laminated silicate material and their prepn. |
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| CN1389501A CN1389501A (en) | 2003-01-08 |
| CN1197903C true CN1197903C (en) | 2005-04-20 |
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| CN 01124193 Expired - Fee Related CN1197903C (en) | 2001-08-22 | 2001-08-22 | Modifying laminated silicate, nano composite polyethylene-laminated silicate material and their prepn. |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300234C (en) * | 2004-03-02 | 2007-02-14 | 北京同众塑料制品有限公司 | High performance and high molecular polyethylene/sheet silicate nano composite materials |
| CN1318498C (en) * | 2005-04-30 | 2007-05-30 | 浙江大学 | Nano composite material of polyethylene/montorillonite clay in high density and preparation method thereof |
| CN100375761C (en) * | 2005-12-22 | 2008-03-19 | 武汉理工大学 | Resin/clay nano composite material and preparation process thereof |
| KR102344177B1 (en) * | 2014-01-31 | 2021-12-29 | 킴벌리-클라크 월드와이드, 인크. | Thin nanocomposite film for use in an absorbent article |
| CN108559168A (en) * | 2018-05-02 | 2018-09-21 | 苏州聚慧邦新材料科技有限公司 | A kind of organo montmorillonite dispersion liquid and its application in winding film |
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