CN106633299A - Polyethylene/montmorillonoid-supported titanium dioxide composite material and preparation method thereof - Google Patents
Polyethylene/montmorillonoid-supported titanium dioxide composite material and preparation method thereof Download PDFInfo
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- CN106633299A CN106633299A CN201611177380.1A CN201611177380A CN106633299A CN 106633299 A CN106633299 A CN 106633299A CN 201611177380 A CN201611177380 A CN 201611177380A CN 106633299 A CN106633299 A CN 106633299A
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- montmorillonite
- titanium dioxide
- polyethylene
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- dioxide composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses a polyethylene/montmorillonoid-supported titanium dioxide composite material and a preparation method thereof. The polyethylene/montmorillonoid-supported titanium dioxide composite material is prepared by mixing the following raw materials in parts by weight: 100 parts of high-density polyethylene, 5 to 10 parts of montmorillonoid-supported titanium dioxide and 1 to 5 parts of a compatilizer. The polyethylene/montmorillonoid-supported titanium dioxide composite material is prepared by placing montmorillonoid-supported titanium dioxide powder and the high-density polyethylene in a high-speed mixer; mixing for 7 to 10 minutes at the rotating speed of 200 to 500 r/min, and simultaneously, adding the compatilizer in a formula proportion; adding the obtained blend into a screw extruder for extruding and pelletizing, wherein the extruding temperature is 120 to 150 DEG C; then cooling and pelletizing. According to the polyethylene/montmorillonoid-supported titanium dioxide composite material prepared by the invention, the tensile strength is improved to 47.2% to 84.6%; the impact strength is improved to 30.4% to 93.7%; the preparation method is simple and feasible; the polyethylene/montmorillonoid-supported titanium dioxide composite material can replace a common polyethylene material; the material cost is reduced.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to polyethylene and montmorillonite load titanium dioxide composite wood
Material and preparation method thereof.
Background technology
Polymer/nano particle composite material is due to mechanical performance, hot property, electrical property, the photosensitiveness for attracting people's attention
Can wait, it has also become one of study hotspot of current composite research field.Polythene PE is that, with ethylene as monomer, Jing catalysis is poly-
Close, pelletize and a kind of obtained thermoplastic resin, its odorless is nontoxic, and feel ceraceous is (minimum with excellent resistance to low temperature
It is reachable -100～-70 DEG C using temperature) and chemical stability is good, is resistant to the erosion of most of soda acids (intolerant to oxidizing property
Acid).But the material there is also certain deficiency, such as low temperature buffer poor performance is easier to aging, post-production formed heat-resistant
Difference, the low shortcoming of tensile strength significantly limit its development and application in high-end engineering field.
Montmorillonite MMT is a kind of natural minerals of silicate, is the essential mineral component of bentonite ore, is a class by nanometer
The electronegative silicate lamella in surface of thickness, the earthy mineral of composition are packed together by the electrostatic interaction of interlayer, its
Structure cell in crystal structure is made up of one layer of alumina octahedral of folder in the middle of two-layer silicon-oxy tetrahedron.With unique one-dimensional stratiform
Nanostructured and cation exchange characteristic.Modified montmorillonite has very strong absorbability, and good dispersive property can
Extensively to apply macromolecular material industry as the additive of nanometer polymer macromolecular material, shock resistance, resisting fatigue, chi are improved
Very little stability and gas barrier property etc., so as to play a part of to strengthen polymer comprehensive physical performance, while improve material adding
Work performance.Nano titanium oxide, also known as titanium dioxide, below 100 nanometers, product appearance is fluffy white powder to diameter.Have
The performances such as good uvioresistant, antibacterial, self-cleaning, aging resistance, can be widely used for cosmetics, functional fibre, plastics, ink,
The fields such as fine ceramics, but due to its specific surface area it is very big, and for inorganic matters, it is difficult to, pole compatible with common organic polymer
The earth limits its application in field of polymer composite material.
The content of the invention
The technical problem to be solved is just to provide a kind of polyethylene/montmorillonite carried titanium dioxide composite
And preparation method thereof, polyethylene low temperature buffer poor performance is solved, it is easier to aging, post-production formed heat-resistant is poor, tensile strength
Low shortcoming.
To solve above-mentioned technical problem, the present invention is adopted the following technical scheme that：A kind of polyethylene/montmorillonite loads titanium dioxide
Titanium composite material, is mixed by the raw material of following weight portion：100 parts of high density polyethylene (HDPE), montmorillonite load titanium dioxide 5～
10 parts, 1～5 part of compatilizer.
Preferably, being mixed by the raw material of following weight portion：100 parts of high density polyethylene (HDPE), montmorillonite load dioxy
Change 8 parts of titanium, 3 parts of compatilizer.
Preferably, being mixed by the raw material of following weight portion：100 parts of high density polyethylene (HDPE), montmorillonite load dioxy
Change 5 parts of titanium, 2 parts of compatilizer.
Preferably, being mixed by the raw material of following weight portion：100 parts of high density polyethylene (HDPE), montmorillonite load dioxy
Change 10 parts of titanium, 5 parts of compatilizer.
Preferably, described compatilizer is Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene glycol oxide POE, polycthylene grafted ring
One kind in oxygen.
Present invention also offers a kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite, including such as
Lower step：
(1) montmorillonite is added in buffer solution under room temperature, then poly-dopamine is added to montmorillonite by ultrasonic disperse
In suspension, stir under room temperature, vacuum drying obtains the montmorillonite of Surface coating poly-dopamine；
(2) montmorillonite of Surface coating poly-dopamine is added in hydrogen chloride and acetic acid mixed solution, so under stirring at normal temperature
Afterwards TiO 2 precursor is slowly added at 30 DEG C -90 DEG C, is persistently stirred, vacuum drying obtains montmorillonite load titanium dioxide
Titanium powder；
(3) montmorillonite load titania powder and high density polyethylene (HDPE) are placed in high-speed mixer, in 200-500r/
Mix 7-10min under min rotating speeds, and while add the compatilizer of formula proportion；
(4) blend that step (3) is obtained is added in screw extruder carries out extruding pelletization, and extrusion temperature is 120-
150 DEG C, then cooling, pelletizing, obtain polyethylene/montmorillonite carried titanium dioxide composite.
Preferably, in step (1), montmorillonite is added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse
2min, is then added to dopamine in montmorillonite suspension liquid, and under room temperature 4h is stirred.
Preferably, in step (2), room temperature is stirred vigorously the lower montmorillonite by Surface coating poly-dopamine and is added to
In 0.2% hydrogen chloride and 0.2% acetic acid solution, then TiO 2 precursor is slowly added at 60 DEG C, is persistently stirred
12h。
Preferably, the TiO 2 precursor in step (2) is iso-butyl titanate, titanium propanolate, titanium tetrachloride, metatitanic acid
It is one or any two or more in tetra-ethyl ester.
The present invention is combined montmorillonite with titanium dioxide nano-particle by organic poly-dopamine composition, is allowed to
Fine dispersion in polythene material matrix, and then improve the mechanical property of material.By polyethylene/montmorillonite obtained in the present invention
Carried titanium dioxide composite have tensile strength improve 47.2%～84.6%, impact strength improve 30.4%～
93.7%, and preparation method is simple, can substitute common polythene material, reduces material cost.
Specific embodiment
Polyethylene/montmorillonite carried titanium dioxide composite by the raw material of following weight portion in being mixed：High density
100 parts of polyethylene, 5～10 parts of montmorillonite load titanium dioxide, 1～5 part of compatilizer.
Wherein, the preparation method of montmorillonite load titanium dioxide is：
(1) montmorillonite is added in buffer solution under room temperature, then poly-dopamine is added to montmorillonite by ultrasonic disperse
In suspension, stir under room temperature, vacuum drying obtains the montmorillonite of Surface coating poly-dopamine；
It is 10%～30% that montmorillonite accounts for the mass percent of buffer solution, to form good dispersion effect.
The addition of dopamine and the mol ratio 1 of montmorillonite:1～1:5, the poly- DOPA that dopamine is formed in buffer solution
Amine has surface modified function, can strengthen montmorillonite and polymer interface adhesion.
(2) montmorillonite of Surface coating poly-dopamine is added in hydrogen chloride and acetic acid mixed solution, so under stirring at normal temperature
Afterwards TiO 2 precursor is slowly added at 30 DEG C -90 DEG C, is persistently stirred, vacuum drying obtains montmorillonite load titanium dioxide
Titanium powder.
Mol ratio between the montmorillonite of TiO 2 precursor and Surface coating poly-dopamine is 1:1～1:3, hydrogen chloride
With acetic acid solution in molar ratio 1:2.TiO 2 precursor forms nano titanium oxide by acid hydrolysis.
In step (1), montmorillonite is added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse 2min, then
Dopamine is added in montmorillonite suspension liquid, under room temperature 4h is stirred.The optimum condition of dopamine polymerization is ph=6.5, acid
Under too strong or alkalescence condition, dopamine cannot form polymer, so as to be difficult to that montmorillonite is modified.
In step (2), room temperature is stirred vigorously the hydrogen chloride that the lower montmorillonite by Surface coating poly-dopamine is added to 0.2%
In (mass concentration) and 0.2% acetic acid (mass concentration) solution, then TiO 2 precursor is slowly added at 60 DEG C, is held
Continuous stirring 12h.60 DEG C is optimum temperature that titanium dioxide is formed, and the titanium dioxide granule of the too high formation of temperature is too big, too low, instead
Answer speed too slow.
The present invention is described in further detail below by embodiment, but the present invention is not limited solely to following examples.
Embodiment 1
A kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite of the present invention, comprises the steps of：
(1) 250g montmorillonites are added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse 2min, then will
10g dopamine is added in montmorillonite suspension liquid, and 4h is stirred under room temperature, and vacuum drying obtains the illiteracy of Surface coating poly-dopamine
De- soil.
(2) room temperature is stirred vigorously the hydrogen chloride and 0.2% that the lower montmorillonite by Surface coating poly-dopamine is added to 0.2%
Acetic acid solution in, 250g iso-butyl titanates are then slowly added at 60 DEG C, persistently stir 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE)s are placed in high-speed mixer, in 200r/
Mix 7min under min rotating speeds, and while add 100g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizers.
(4) blend that step (3) is obtained is added in double screw extruder carries out extruding pelletization, and extrusion temperature is
120 DEG C, then by 40 DEG C of tanks coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite.
Polyethylene/montmorillonite carried titanium dioxide composite property is as follows obtained in this example：Tensile strength reaches
27.7MPa, impact strength reaches 4.5KJ/m2, tensile strength improves 84.6%, and impact strength improves 40.6%.
Embodiment 2
A kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite of the present invention, comprises the steps of：
(1) 300g montmorillonites are added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse 2min, then will
15g dopamine is added in montmorillonite suspension liquid, and 4h is stirred under room temperature, and vacuum drying obtains the illiteracy of Surface coating poly-dopamine
De- soil.
(2) room temperature is stirred vigorously the hydrogen chloride and 0.2% that the lower montmorillonite by Surface coating poly-dopamine is added to 0.2%
Acetic acid solution in, 300g iso-butyl titanates are then slowly added at 60 DEG C, persistently stir 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE)s are placed in high-speed mixer, in 300r/
Mix 8min under min rotating speeds, and while add 150g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizers.
(4) blend that step (3) is obtained is added in double screw extruder carries out extruding pelletization, and extrusion temperature is
130 DEG C, then by 35 DEG C of tanks coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite.
Polyethylene/montmorillonite carried titanium dioxide composite property is as follows obtained in this example：Tensile strength reaches
23.1MPa, impact strength reaches 6.2KJ/m2, tensile strength improves 54.6%, and impact strength improves 93.7%.
Embodiment 3
A kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite of the present invention, comprises the steps of：
(1) 500g montmorillonites are added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse 2min, then will
30g dopamine is added in montmorillonite suspension liquid, and 4h is stirred under room temperature, and vacuum drying obtains the illiteracy of Surface coating poly-dopamine
De- soil.
(2) room temperature is stirred vigorously the hydrogen chloride and 0.2% that the lower montmorillonite by Surface coating poly-dopamine is added to 0.2%
Acetic acid solution in, 500g iso-butyl titanates are then slowly added at 60 DEG C, persistently stir 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE)s are placed in high-speed mixer, in 500r/
Mix 10min under min rotating speeds, and while add 500g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizers.
(4) blend that step (3) is obtained is added in double screw extruder carries out extruding pelletization, and extrusion temperature is
150 DEG C, then by 35 DEG C of tanks coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite.
Polyethylene/montmorillonite carried titanium dioxide composite property is as follows obtained in this example：Tensile strength reaches
26.4MPa, impact strength reaches 5.1KJ/m2, tensile strength improves 76.3%, and impact strength improves 59.3%.
Claims (9)
1. a kind of polyethylene/montmorillonite carried titanium dioxide composite, it is characterised in that mixed by the raw material of following weight portion
Form：100 parts of high density polyethylene (HDPE), 5～10 parts of montmorillonite load titanium dioxide, 1～5 part of compatilizer.
2. a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 1, it is characterised in that：By
The raw material of following weight portion is mixed：100 parts of high density polyethylene (HDPE), 8 parts of montmorillonite load titanium dioxide, 3 parts of compatilizer.
3. a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 1, it is characterised in that：By
The raw material of following weight portion is mixed：100 parts of high density polyethylene (HDPE), 5 parts of montmorillonite load titanium dioxide, 2 parts of compatilizer.
4. a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 1, it is characterised in that：By
The raw material of following weight portion is mixed：100 parts of high density polyethylene (HDPE), 10 parts of montmorillonite load titanium dioxide, 5 parts of compatilizer.
5. a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 1, it is characterised in that：Institute
The compatilizer stated is the one kind in Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene glycol oxide POE, polycthylene grafted epoxy.
6. a kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite, it is characterised in that comprise the steps：
(1) montmorillonite is added in buffer solution under room temperature, ultrasonic disperse, then poly-dopamine is added to into montmorillonite and is suspended
In liquid, stir under room temperature, vacuum drying obtains the montmorillonite of Surface coating poly-dopamine；
(2) montmorillonite of Surface coating poly-dopamine is added in hydrogen chloride and acetic acid mixed solution under stirring at normal temperature, Ran Hou
TiO 2 precursor is slowly added at 30 DEG C -90 DEG C, is persistently stirred, vacuum drying obtains montmorillonite load titanium dioxide powder
End；
(3) montmorillonite load titania powder and high density polyethylene (HDPE) are placed in high-speed mixer, in 200-500r/min
Mix 7-10min under rotating speed, and while add the compatilizer of formula proportion；
(4) blend that step (3) is obtained is added in screw extruder carries out extruding pelletization, and extrusion temperature is 120-150
DEG C, then cooling, pelletizing, obtain polyethylene/montmorillonite carried titanium dioxide composite.
7. the preparation method of a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 6, it is special
Levy and be：In step (1), montmorillonite is added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse 2min, then
Dopamine is added in montmorillonite suspension liquid, under room temperature 4h is stirred.
8. the preparation method of a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 6, it is special
Levy and be：In step (2), room temperature is stirred vigorously the hydrogen chloride that the lower montmorillonite by Surface coating poly-dopamine is added to 0.2%
In 0.2% acetic acid solution, TiO 2 precursor is then slowly added at 60 DEG C, persistently stirs 12h.
9. the preparation method of a kind of polyethylene/montmorillonite carried titanium dioxide composite according to claim 6, it is special
Levy and be：TiO 2 precursor in step (2) is in iso-butyl titanate, titanium propanolate, titanium tetrachloride, tetraethyl titanate
It is one or any two or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225980A (en) * | 2020-11-05 | 2021-01-15 | 玉环德谷新材料科技有限公司 | High-density wear-resistant plastic and preparation method thereof |
| CN116230400A (en) * | 2023-03-31 | 2023-06-06 | 佛山市欣源电子股份有限公司 | Power capacitor |
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| CN1657267A (en) * | 2005-01-26 | 2005-08-24 | 四川大学 | Method of preparing polymer / inorganic nanometer particle compesite |
| CN1769338A (en) * | 2004-11-05 | 2006-05-10 | 中国科学院化学研究所 | Polyethylene /montmorillonite nanometer composite material and preparation method |
| CN104327243A (en) * | 2014-10-30 | 2015-02-04 | 河海大学 | Polyurethane foam loaded titanium dioxide and montmorillonite composite material and preparation method of composite material |
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2016
- 2016-12-19 CN CN201611177380.1A patent/CN106633299B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1338483A (en) * | 2001-09-27 | 2002-03-06 | 中国科学院长春应用化学研究所 | In-situ polymerization process for preparing nm-class compoiste polyolefin/inorganic component material |
| CN1769338A (en) * | 2004-11-05 | 2006-05-10 | 中国科学院化学研究所 | Polyethylene /montmorillonite nanometer composite material and preparation method |
| CN100410314C (en) * | 2004-11-05 | 2008-08-13 | 中国科学院化学研究所 | Polyethylene /montmorillonite nanometer composite material and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225980A (en) * | 2020-11-05 | 2021-01-15 | 玉环德谷新材料科技有限公司 | High-density wear-resistant plastic and preparation method thereof |
| CN116230400A (en) * | 2023-03-31 | 2023-06-06 | 佛山市欣源电子股份有限公司 | Power capacitor |
| CN116230400B (en) * | 2023-03-31 | 2023-09-05 | 佛山市欣源电子股份有限公司 | Power capacitor |
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