CN106633299B - A kind of polyethylene/montmorillonite carried titanium dioxide composite material and preparation method - Google Patents
A kind of polyethylene/montmorillonite carried titanium dioxide composite material and preparation method Download PDFInfo
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- CN106633299B CN106633299B CN201611177380.1A CN201611177380A CN106633299B CN 106633299 B CN106633299 B CN 106633299B CN 201611177380 A CN201611177380 A CN 201611177380A CN 106633299 B CN106633299 B CN 106633299B
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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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- 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
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Abstract
The invention discloses a kind of polyethylene/montmorillonite carried titanium dioxide composite material and preparation methods, are mixed by the raw material of following parts by weight: 100 parts of high density polyethylene (HDPE), 5~10 parts of montmorillonite load titanium dioxide, 1~5 part of compatilizer.Montmorillonite load titania powder is placed in high-speed mixer with high density polyethylene (HDPE), mixes 7-10min under 200-500r/min revolving speed, and adds the compatilizer of formula rate simultaneously；And obtained blend is added in screw extruder and carries out extruding pelletization, extrusion temperature is 120-150 DEG C, and then cooling, pelletizing obtains polyethylene/montmorillonite carried titanium dioxide composite material.The tensile strength that polyethylene/montmorillonite carried titanium dioxide composite material produced by the present invention has improves 47.2%~84.6%, and impact strength improves 30.4%~93.7%, and preparation method is simple, can substitute common polythene material, reduces material cost.
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 technique
Polymer/nano particle composite material is due to having the mechanical performance, the hot property, electrical property, photosensitiveness that attract people's attention
Energy is equal, it has also become one of the research hotspot of composite material research field at present.Polythene PE is to gather using ethylene as monomer through being catalyzed
It closes, a kind of thermoplastic resin prepared by granulation, odorless, nontoxic, feel ceraceous is (minimum with excellent resistance to low temperature
Use reachable -100~-70 DEG C of temperature) and chemical stability it is good, be resistant to the erosion of most of soda acids (intolerant to oxidizing property
Acid).However there is also certain deficiencies for the material, and if low temperature buffer performance is poor, more easy to aging, post-production formed heat-resistant
Difference, the disadvantages such as tensile strength is low, significantly limits it in the development and application of high-end engineering field.
Montmorillonite MMT is a kind of natural minerals of silicate, is the essential mineral component of bentonite ore, is one kind by nanometer
The electronegative silicate lamella in the surface of thickness, the earthy mineral of composition are packed together by the electrostatic interaction of interlayer,
Structure cell in crystal structure is made of one layer of alumina octahedral of folder among two layers of oxygen-octahedron.With unique one-dimensional stratiform
Nanostructure and cationic exchangeability characteristic.Modified montmorillonite has very strong adsorption capacity, and good dispersion performance can
High molecular material industry is widely applied as the additive of nanometer polymer high molecular material, shock resistance, antifatigue, ruler are improved
Very little stability and gas barrier property etc. to play the role of enhancing polymer comprehensive physical performance, while improving material and adding
Work performance.Nano-titanium dioxide, also known as titanium dioxide, diameter is at 100 nanometers hereinafter, product appearance is fluffy white powder.Have
The performances such as good uvioresistant, antibacterial, self-cleaning, anti-aging, can be widely used for cosmetics, functional fibre, plastics, ink,
The fields such as fine ceramics, but since its specific surface area is very big, and be inorganic matter, it is difficult, pole compatible with common organic polymer
The earth limits it in the application of field of polymer composite material.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of polyethylene/montmorillonite carried titanium dioxide composite materials
And preparation method thereof, solution polyethylene low temperature buffer performance is poor, and more easy to aging, post-production formed heat-resistant is poor, tensile strength
Low disadvantage.
In order to solve the above technical problems, the present invention adopts the following technical scheme: a kind of polyethylene/montmorillonite loads titanium dioxide
Titanium composite material is mixed by the raw material of following parts by weight: 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 parts by weight: 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 parts by weight: 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 parts by weight: 100 parts of high density polyethylene (HDPE), montmorillonite load dioxy
Change 10 parts of titanium, 5 parts of compatilizer.
Preferably, the compatilizer is Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene glycol oxide POE, polycthylene grafted ring
One of oxygen.
The present invention also provides a kind of preparation methods of polyethylene/montmorillonite carried titanium dioxide composite material, 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
It in suspension, is stirred under room temperature, vacuum drying, obtains the montmorillonite of surface cladding poly-dopamine；
(2) montmorillonite of surface cladding poly-dopamine is added in hydrogen chloride and acetic acid mixed solution under stirring at normal temperature, so
It is slowly added to TiO 2 precursor at 30 DEG C -90 DEG C afterwards, lasting to stir, 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/
7-10min is mixed under min revolving speed, and adds the compatilizer of formula rate simultaneously；
(4) blend that step (3) obtains is added in screw extruder and carries out extruding pelletization, extrusion temperature 120-
150 DEG C, then cooling, pelletizing obtains polyethylene/montmorillonite carried titanium dioxide composite material.
Preferably, montmorillonite is added in the buffer solution that pH value is 6.5 under room temperature, ultrasonic disperse in step (1)
Then dopamine is added in montmorillonite suspension liquid by 2min, stir 4h under room temperature.
Preferably, room temperature is vigorously stirred the lower montmorillonite by surface cladding poly-dopamine and is added in step (2)
In 0.2% hydrogen chloride and 0.2% acetic acid solution, it then is slowly added to TiO 2 precursor at 60 DEG C, it is lasting to stir
12h。
Preferably, the TiO 2 precursor in step (2) is iso-butyl titanate, titanium propanolate, titanium tetrachloride, metatitanic acid
One of tetra-ethyl ester is any two or more.
The present invention is combined montmorillonite and titanium dioxide nano-particle by organic poly-dopamine ingredient, is allowed to
Fine dispersion in polythene material matrix, and then improve the mechanical property of material.Polyethylene/montmorillonite obtained through the invention
Carried titanium dioxide composite material 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 material is mixed in the raw material by following parts by weight: high density
100 parts of polyethylene, 5~10 parts of montmorillonite load titanium dioxide, 1~5 part of compatilizer.
Wherein, montmorillonite load titanium dioxide the preparation method comprises the following steps:
(1) montmorillonite is added in buffer solution under room temperature, then poly-dopamine is added to montmorillonite by ultrasonic disperse
It in suspension, is stirred under room temperature, vacuum drying, obtains the montmorillonite of surface cladding poly-dopamine；
The mass percent that montmorillonite accounts for buffer solution is 10%~30%, to form good dispersion effect.
The additional amount of dopamine and molar ratio 1:1~1:5 of montmorillonite, the poly- DOPA that dopamine is formed in buffer solution
Amine has surface modified function, can enhance montmorillonite and polymer interface binding force.
(2) montmorillonite of surface cladding poly-dopamine is added in hydrogen chloride and acetic acid mixed solution under stirring at normal temperature, so
It is slowly added to TiO 2 precursor at 30 DEG C -90 DEG C afterwards, lasting to stir, vacuum drying obtains montmorillonite load titanium dioxide
Titanium powder.
Molar ratio between TiO 2 precursor and the montmorillonite of surface cladding poly-dopamine is 1:1~1:3, hydrogen chloride
With acetic acid solution 1:2 in molar ratio.TiO 2 precursor hydrolyzes to form nano-titanium dioxide by acid.
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, stirs 4h under room temperature.The optimum condition of dopamine polymerization is ph=6.5, acid
Under too strong or alkaline condition, dopamine can not form polymer, to be difficult to be modified montmorillonite.
In step (2), room temperature is vigorously stirred the hydrogen chloride that the lower montmorillonite by surface cladding poly-dopamine is added to 0.2%
(mass concentration) and 0.2% acetic acid (mass concentration) solution in, be then slowly added to TiO 2 precursor at 60 DEG C, hold
Continuous stirring 12h.60 DEG C are optimum temperatures that titanium dioxide is formed, and the titanium dioxide granule of the excessively high formation of temperature is too big, too low, instead
Answer rate too slow.
The present invention is described in further detail below by embodiment, but the present invention is not limited solely to following embodiment.
Embodiment 1
A kind of preparation method of polyethylene/montmorillonite carried titanium dioxide composite material of the present invention, comprises the following steps:
(1) 250g montmorillonite is 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 cladding poly-dopamine
De- soil.
(2) room temperature is vigorously stirred the hydrogen chloride and 0.2% that the lower montmorillonite by surface cladding poly-dopamine is added to 0.2%
Acetic acid solution in, 250g iso-butyl titanate is then slowly added at 60 DEG C, persistently stirs 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE) are placed in high-speed mixer, in 200r/
7min is mixed under min revolving speed, and adds 100g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizer simultaneously.
(4) blend that step (3) obtains is added in double screw extruder and carries out extruding pelletization, extrusion temperature is
120 DEG C, then by 40 DEG C of sink coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite material.
Polyethylene/montmorillonite carried titanium dioxide composite property made from this example is as follows: tensile strength reaches
27.7MPa, impact strength reach 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 material of the present invention, comprises the following steps:
(1) 300g montmorillonite is 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 cladding poly-dopamine
De- soil.
(2) room temperature is vigorously stirred the hydrogen chloride and 0.2% that the lower montmorillonite by surface cladding poly-dopamine is added to 0.2%
Acetic acid solution in, 300g iso-butyl titanate is then slowly added at 60 DEG C, persistently stirs 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE) are placed in high-speed mixer, in 300r/
8min is mixed under min revolving speed, and adds 150g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizer simultaneously.
(4) blend that step (3) obtains is added in double screw extruder and carries out extruding pelletization, extrusion temperature is
130 DEG C, then by 35 DEG C of sink coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite material.
Polyethylene/montmorillonite carried titanium dioxide composite property made from this example is as follows: tensile strength reaches
23.1MPa, impact strength reach 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 material of the present invention, comprises the following steps:
(1) 500g montmorillonite is 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 cladding poly-dopamine
De- soil.
(2) room temperature is vigorously stirred the hydrogen chloride and 0.2% that the lower montmorillonite by surface cladding poly-dopamine is added to 0.2%
Acetic acid solution in, 500g iso-butyl titanate is then slowly added at 60 DEG C, persistently stirs 12h, vacuum drying obtains covering de-
Native carried titanium dioxide powder.
(3) montmorillonite load titania powder and 10kg high density polyethylene (HDPE) are placed in high-speed mixer, in 500r/
10min is mixed under min revolving speed, and adds 500g Research of Grafting Malaic Anhydride Onto Polyethylene compatilizer simultaneously.
(4) blend that step (3) obtains is added in double screw extruder and carries out extruding pelletization, extrusion temperature is
150 DEG C, then by 35 DEG C of sink coolings, pelletizings, obtain polyethylene/montmorillonite carried titanium dioxide composite material.
Polyethylene/montmorillonite carried titanium dioxide composite property made from this example is as follows: tensile strength reaches
26.4MPa, impact strength reach 5.1KJ/m2, tensile strength improves 76.3%, and impact strength improves 59.3%.
Claims (7)
1. a kind of polyethylene/montmorillonite carried titanium dioxide composite material, it is characterised in that mixed by the raw material of following parts by weight
Form: 100 parts of high density polyethylene (HDPE), 5 ~ 10 parts of montmorillonite load titanium dioxide, 1 ~ 5 part of compatilizer, the polyethylene/montmorillonite is negative
The preparation method of carrying of titanium dioxide composite material includes the following steps:
(1) montmorillonite is added in buffer solution under room temperature, ultrasonic disperse, poly-dopamine is then added to montmorillonite and is suspended
It in liquid, is stirred under room temperature, vacuum drying, obtains the montmorillonite of surface cladding poly-dopamine；
(2) montmorillonite of surface cladding poly-dopamine is added in hydrogen chloride and acetic acid mixed solution under stirring at normal temperature, is then existed
It is slowly added to TiO 2 precursor at 30 DEG C -90 DEG C, lasting to stir, 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
7-10min is mixed under revolving speed, and adds the compatilizer of formula rate simultaneously；
(4) blend that step (3) obtains is added in screw extruder and carries out extruding pelletization, extrusion temperature 120-150
DEG C, then cooling, pelletizing obtains polyethylene/montmorillonite carried titanium dioxide composite material.
2. a kind of polyethylene/montmorillonite carried titanium dioxide composite material according to claim 1, it is characterised in that: by
The raw material of following parts by weight mixes: 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 material according to claim 1, it is characterised in that: by
The raw material of following parts by weight mixes: 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 material according to claim 1, it is characterised in that: by
The raw material of following parts by weight mixes: 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 material according to claim 1, it is characterised in that: institute
The compatilizer stated is one of Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene glycol oxide POE, polycthylene grafted epoxy.
6. a kind of polyethylene/montmorillonite carried titanium dioxide composite material according to claim 1, it is characterised in that: step
Suddenly in (2), room temperature is vigorously stirred the second that the lower montmorillonite by surface cladding poly-dopamine is added to 0.2% hydrogen chloride and 0.2%
In acid solution, it is then slowly added to TiO 2 precursor at 60 DEG C, persistently stirs 12h.
7. a kind of polyethylene/montmorillonite carried titanium dioxide composite material according to claim 1, it is characterised in that: step
Suddenly the TiO 2 precursor in (2) be one of iso-butyl titanate, titanium propanolate, titanium tetrachloride, tetraethyl titanate or
It is any two or more.
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| 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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