CN109721855A - Antistatic PP/HDPE plastic for automotive interior parts and preparation method thereof - Google Patents
Antistatic PP/HDPE plastic for automotive interior parts and preparation method thereof Download PDFInfo
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- CN109721855A CN109721855A CN201910010729.XA CN201910010729A CN109721855A CN 109721855 A CN109721855 A CN 109721855A CN 201910010729 A CN201910010729 A CN 201910010729A CN 109721855 A CN109721855 A CN 109721855A
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- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 45
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 31
- 239000004033 plastic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 20
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000002048 multi walled nanotube Substances 0.000 claims description 87
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 81
- 238000007306 functionalization reaction Methods 0.000 claims description 41
- 229920000178 Acrylic resin Polymers 0.000 claims description 33
- 239000004925 Acrylic resin Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 25
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 19
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 230000008901 benefit Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 25
- 238000002156 mixing Methods 0.000 abstract description 3
- -1 polypropylene Polymers 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 150000002148 esters Chemical class 0.000 description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 208000036487 Arthropathies Diseases 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012857 repacking Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides antistatic PP/HDPE plastic for automotive upholsteries and a preparation method thereof, which have excellent mechanical properties and antistatic properties and are suitable for automotive upholsteries. The invention adopts a double-screw extruder, polypropylene resin and high-density polyethylene resin are fed into a main feeding port, and the functional composite material treated by isobutyl triethoxysilane is fed into a side feeding port, and the resin material can be modified by double-screw extrusion at the rotating speed of 300-400 rpm and the temperature of 230-240 ℃. The functional composite material treated by the isobutyl triethoxy silane can be wound by itself when the rotating speed or the temperature is too low or too high, so that the mixing uniformity of the functional composite material and resin components is influenced, and the mechanical property and the antistatic property of a product are further influenced. The functionalized composite material is beneficial to improving the mechanical property and the antistatic property of the product, and the mechanical property and the antistatic property of the product can be further improved after the functionalized composite material is treated by the isobutyl triethoxy silane.
Description
Technical field
The present invention relates to plastics arts, particularly, be related to a kind of automotive upholstery Anti-static PP/HDPE plastic and
Preparation method.
Background technique
Polypropylene, abbreviation PP have good heat resistance, belong to non-polar polymer, have excellent dielectricity and electricity
Insulating properties, electrical property are not influenced substantially by ambient humidity and electric field frequency, and in the working range of permission, temperature increases meeting
Reduce electrical property, its arc resistance is higher.
High density polyethylene (HDPE), abbreviation HDPE are that a kind of crystallinity is high, nonpolar thermoplastic resin.Ortho states HDPE's is outer
Table is creamy white, and section presents a degree of translucent.
Compound gained PP/HDPE plastics have been widely used both at present, with good heat resistance and cold resistance,
Chemical stability is good, and still, antistatic effect is unsatisfactory.
Electrostatic is a kind of charging savings phenomenon for concentrating on insulating materials surface, derived from frictional electricity, the raw electricity of contact or sense
Ying Sheng electricity.For insulator, charging is local, but plastic products is made to bring a series of danger because of electrification
Evil, such as: phenomena such as being easy to dust suction, adsorbing foul, electric shock is generated to people in the process of processing and using, or even since electrostatic is put
Electricity generates spark and leads to the major accidents such as explosion.
Automotive upholstery is primarily referred to as the used automobile product of automotive interior repacking, is related to the gloves of automotive interior
Case, automobile instrument panel, central control board etc. are the important components of body of a motor car.Automotive upholstery is mainly by plastic part structure
At PP/HDPE plastics are a kind of ideal selections, but for automotive upholstery, anti-static effect is a Xiang Fei
Often important technical indicator, directly influences ride comfort.
Therefore, it is badly in need of a kind of PP/HDPE plastics with antistatic effect at present, in automotive upholstery.
Summary of the invention
It is an object of that present invention to provide a kind of automotive upholstery Anti-static PP/HDPE plastics and preparation method thereof, with solution
Certainly existing PP/HDPE plastics antistatic effect is not good enough, is not able to satisfy the technical problems such as the demand of automotive upholstery.
To achieve the above object, the present invention provides a kind of automotive upholstery Anti-static PP/HDPE plastic preparation sides
Method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.3~0.5, twin-screw is added
The main spout of extruder；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 300~400rpm, and temperature is 230~240 DEG C, and extrusion is made
Grain to obtain the final product.
Preferably, the specific method of step (1) is: acidification multi-walled carbon nanotube and Tin tetrachloride pentahydrate (SnCl4·
5H2O), zinc nitrate hexahydrate (Zn (NO3)2·6H2O it) reacts, generates multi-wall carbon nano-tube composite material.Tin is with the shape of chlorate
Formula introduces, and zinc is introduced in the form of zinc nitrate, found through repetition test, and salt of the invention is more advantageous to multi-walled carbon nanotube
Doping, compared with nitric acid tin, zinc chloride, the mechanical performance and antistatic property of products obtained therefrom are more excellent.
Still more preferably, the acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid
(65wt%) is uniformly mixed with the proportion of 1g:100mL, is reacted 6~12 hours at 140 DEG C, by obtained product through taking out
Filter is washed to neutrality, vacuum drying to get.
Still more preferably, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of multi-walled carbon nanotube4·5H2O), zinc nitrate hexahydrate (Zn is added
(NO3)2·6H2O), then be added concentrated hydrochloric acid (38w.t.%), be slowly added to later concentrated ammonia liquor (25w.t.%) adjust pH=7~
10, it is reacted 8~24 hours in 120~180 DEG C, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, it is acidified multi wall carbon
Nanotube, Tin tetrachloride pentahydrate, zinc nitrate hexahydrate (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:50
~60g:20~30g:15~20mL.
Still more preferably, the post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
Preferably, in step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, Ji Wusi
The ethanol solution of alcohol stearate, the mass volume ratio of three are 1g:5~10mL:2~3mL；Wherein, lauroyl diethanolamine
Aqueous dispersions in, the mass ratio of lauroyl diethanolamine and water is 1:15~20, the ethanol solution of pentaerythritol stearate
In, the mass ratio of pentaerythritol stearate and ethyl alcohol is 1:8~12.
Preferably, in step (2), it is stirred to react condition are as follows: 120~130 DEG C are stirred to react 2~3 hours.
Preferably, in step (2), benefit is washed with deionized 2~3 times, is then dried 20~30 hours for 50~60 DEG C.
Preferably, in step (3), the acrylic resin is acrylic resin copolymer.
Preferably, in step (3), acrylic resin and high-density polyethylene resin are with 2000~3000 revs/min of mixing 2
~5 minutes.The too high or too low mechanical performance that will affect product of revolving speed.
Preferably, in step (4), the dosage of functionalization composite material is the 0.5~0.8% of acrylic resin quality.Function
The dosage that composite material can be changed is very few, will affect the antistatic property of product；Dosage is excessive, will affect the mechanical performance of product.
Preferably, in step (4), functionalization composite material is added in the isobutyl triethoxy silane of 5~8 times of weight,
300~500 revs/min mixed processing 5~6 hours, by products therefrom from the side spout of double screw extruder be added.Using different
When butyl triethoxysilane handles functionalization composite material, revolving speed and processing the time it is very crucial, revolving speed it is excessively high or
The too low treatment effect that can all influence to functionalization composite material, and then the mechanical performance and antistatic property of product are influenced, place
Overlong time or the too short treatment effect that also will affect to functionalization composite material are managed, and then influences the mechanical performance of product and resists
Antistatic property.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
The invention has the following advantages:
PP/HDPE plastics are prepared by primary raw material of PP and HDPE in the present invention, with excellent mechanical performance and
Antistatic property is suitable for automotive upholstery, specific as follows:
1, using double screw extruder, main spout into acrylic resin and high-density polyethylene resin, side spout into
The functionalization composite material of isobutyl triethoxy silane processing, in 300~400rpm revolving speed and 230~240 DEG C of temperature conditions
Under, twin-screw extrusion is carried out, it can be achieved that modification to resin material.Revolving speed or temperature are too low, excessively high can cause isobutyl group three
The functionalization composite material wound upon themselves of Ethoxysilane processing influence the mixing uniformity with resin Composition, and then influence to produce
The mechanical performance and antistatic property of product.Functionalization composite material helps to improve the mechanical performance and antistatic property of product,
Functionalization composite material can further improve the mechanical performance and antistatic property of product after isobutyl triethoxy silane is handled
Energy.
2, functionalization composite material is using multi-wall carbon nano-tube composite material as raw material, using lauroyl diethanolamine and season
Penta tetrol stearate functionalization and obtain, multi-wall carbon nano-tube composite material itself has certain electric conductivity, and mechanical performance is good
It is good, after lauroyl diethanolamine and pentaerythritol stearate joint dysfunction, branch is carried out to multi-wall carbon nano-tube pipe surface
Modification is conductively connected, to obtain antistatic property with being formed with resin Composition；Meanwhile multi-walled carbon nanotube is repaired through collateralization
Promote sufficiently to merge with resin component after decorations, improves the mechanical performance of product.
3, multi-wall carbon nano-tube composite material is that multi-walled carbon nanotube is obtained through tin and zinc doping, with multi-walled carbon nanotube phase
Than after tin and zinc doping, electric conductivity is more excellent, and then obtains antistatic property more preferably product.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
The present invention is further detailed explanation below.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim
Multitude of different ways implement.
Embodiment 1:
A kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.3, double screw extruder is added
Main spout；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 300rpm, and temperature is 230 DEG C, and extruding pelletization to obtain the final product.
Wherein, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, multi-wall carbon nano-tube is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of pipe4·5H2O), zinc nitrate hexahydrate (Zn (NO is added3)2·6H2O),
Then concentrated hydrochloric acid (38w.t.%) is added, is slowly added to concentrated ammonia liquor (25w.t.%) later and adjusts pH=7, it is small in 120 DEG C of reactions 8
When, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six water are acidified
Close zinc nitrate (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:50g:20g:15mL.
The acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid (65wt%) matching with 1g:100mL
It than being uniformly mixed, is reacted 6 hours at 140 DEG C, obtained product is filtered, is washed to neutrality, is dried in vacuo, i.e.,
?.
Post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
In step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, pentaerythrite are stearic
The ethanol solution of acid esters, the mass volume ratio of three are 1g:5mL:2mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine,
The mass ratio of lauroyl diethanolamine and water is 1:15, in the ethanol solution of pentaerythritol stearate, pentaerythrite stearic acid
The mass ratio of ester and ethyl alcohol is 1:8.
In step (2), it is stirred to react condition are as follows: 120 DEG C are stirred to react 2 hours.
In step (2), benefit is washed with deionized 2 times, is then dried 20 hours for 50 DEG C.
In step (3), the acrylic resin is acrylic resin copolymer.
In step (3), acrylic resin and high-density polyethylene resin are mixed 2 minutes with 2000 revs/min.
In step (4), the dosage of functionalization composite material is the 0.5% of acrylic resin quality.
In step (4), functionalization composite material is added in the isobutyl triethoxy silane of 5 times of weight, and 300 revs/min
Mixed processing 5 hours, products therefrom is added from the side spout of double screw extruder.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
Embodiment 2:
A kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.5, double screw extruder is added
Main spout；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 400rpm, and temperature is 240 DEG C, and extruding pelletization to obtain the final product.
Wherein, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, multi-wall carbon nano-tube is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of pipe4·5H2O), zinc nitrate hexahydrate (Zn (NO is added3)2·6H2O),
Then concentrated hydrochloric acid (38w.t.%) is added, is slowly added to concentrated ammonia liquor (25w.t.%) later and adjusts pH=10, react 24 in 180 DEG C
Hour, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, acidification multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six
Nitric hydrate zinc (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:60g:30g:20mL.
The acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid (65wt%) matching with 1g:100mL
It than being uniformly mixed, is reacted 12 hours at 140 DEG C, obtained product is filtered, is washed to neutrality, is dried in vacuo, i.e.,
?.
Post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
In step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, pentaerythrite are stearic
The ethanol solution of acid esters, the mass volume ratio of three are 1g:10mL:3mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine,
The mass ratio of lauroyl diethanolamine and water is 1:20, in the ethanol solution of pentaerythritol stearate, pentaerythrite stearic acid
The mass ratio of ester and ethyl alcohol is 1:12.
In step (2), it is stirred to react condition are as follows: 130 DEG C are stirred to react 3 hours.
In step (2), benefit is washed with deionized 3 times, is then dried 30 hours for 60 DEG C.
In step (3), the acrylic resin is acrylic resin copolymer.
In step (3), acrylic resin and high-density polyethylene resin are mixed 5 minutes with 3000 revs/min.
In step (4), the dosage of functionalization composite material is the 0.8% of acrylic resin quality.
In step (4), functionalization composite material is added in the isobutyl triethoxy silane of 8 times of weight, and 500 revs/min
Mixed processing 6 hours, products therefrom is added from the side spout of double screw extruder.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
Embodiment 3:
A kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.3, double screw extruder is added
Main spout；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 400rpm, and temperature is 230 DEG C, and extruding pelletization to obtain the final product.
Wherein, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, multi-wall carbon nano-tube is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of pipe4·5H2O), zinc nitrate hexahydrate (Zn (NO is added3)2·6H2O),
Then concentrated hydrochloric acid (38w.t.%) is added, is slowly added to concentrated ammonia liquor (25w.t.%) later and adjusts pH=10, react 24 in 120 DEG C
Hour, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, acidification multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six
Nitric hydrate zinc (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:50g:30g:15mL.
The acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid (65wt%) matching with 1g:100mL
It than being uniformly mixed, is reacted 12 hours at 140 DEG C, obtained product is filtered, is washed to neutrality, is dried in vacuo, i.e.,
?.
Post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
In step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, pentaerythrite are stearic
The ethanol solution of acid esters, the mass volume ratio of three are 1g:5mL:3mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine,
The mass ratio of lauroyl diethanolamine and water is 1:15, in the ethanol solution of pentaerythritol stearate, pentaerythrite stearic acid
The mass ratio of ester and ethyl alcohol is 1:12.
In step (2), it is stirred to react condition are as follows: 120 DEG C are stirred to react 3 hours.
In step (2), benefit is washed with deionized 2 times, is then dried 20 hours for 60 DEG C.
In step (3), the acrylic resin is acrylic resin copolymer.
In step (3), acrylic resin and high-density polyethylene resin are mixed 2 minutes with 3000 revs/min.
In step (4), the dosage of functionalization composite material is the 0.8% of acrylic resin quality.
In step (4), functionalization composite material is added in the isobutyl triethoxy silane of 5 times of weight, and 500 revs/min
Mixed processing 5 hours, products therefrom is added from the side spout of double screw extruder.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
Embodiment 4:
A kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.5, double screw extruder is added
Main spout；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 300rpm, and temperature is 240 DEG C, and extruding pelletization to obtain the final product.
Wherein, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, multi-wall carbon nano-tube is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of pipe4·5H2O), zinc nitrate hexahydrate (Zn (NO is added3)2·6H2O),
Then concentrated hydrochloric acid (38w.t.%) is added, is slowly added to concentrated ammonia liquor (25w.t.%) later and adjusts pH=7, it is small in 180 DEG C of reactions 8
When, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six water are acidified
Close zinc nitrate (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:60g:20g:20mL.
The acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid (65wt%) matching with 1g:100mL
It than being uniformly mixed, is reacted 6 hours at 140 DEG C, obtained product is filtered, is washed to neutrality, is dried in vacuo, i.e.,
?.
Post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
In step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, pentaerythrite are stearic
The ethanol solution of acid esters, the mass volume ratio of three are 1g:10mL:2mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine,
The mass ratio of lauroyl diethanolamine and water is 1:20, in the ethanol solution of pentaerythritol stearate, pentaerythrite stearic acid
The mass ratio of ester and ethyl alcohol is 1:8.
In step (2), it is stirred to react condition are as follows: 130 DEG C are stirred to react 2 hours.
In step (2), benefit is washed with deionized 3 times, is then dried 30 hours for 50 DEG C.
In step (3), the acrylic resin is acrylic resin copolymer.
In step (3), acrylic resin and high-density polyethylene resin are mixed 5 minutes with 2000 revs/min.
In step (4), the dosage of functionalization composite material is the 0.5% of acrylic resin quality.
In step (4), functionalization composite material is added in the isobutyl triethoxy silane of 8 times of weight, and 300 revs/min
Mixed processing 6 hours, products therefrom is added from the side spout of double screw extruder.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
Embodiment 5:
A kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, the specific steps are as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, stirring
It mixes, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filter, wash, it is multiple to obtain functionalization for drying
Condensation material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.4, double screw extruder is added
Main spout；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from twin-screw extrusion
The side spout of machine is added, and the revolving speed for controlling double screw extruder is 300rpm, and temperature is 235 DEG C, and extruding pelletization to obtain the final product.
Wherein, the specific method of step (1) is: acidification multi-walled carbon nanotube being dispersed in water, multi-wall carbon nano-tube is obtained
Tin tetrachloride pentahydrate (SnCl is added in the dispersion liquid of pipe4·5H2O), zinc nitrate hexahydrate (Zn (NO is added3)2·6H2O),
Then concentrated hydrochloric acid (38w.t.%) is added, is slowly added to concentrated ammonia liquor (25w.t.%) later and adjusts pH=8, react 12 in 150 DEG C
Hour, it is post-treated up to multi-wall carbon nano-tube composite material；Wherein, acidification multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six
Nitric hydrate zinc (Zn (NO3)2·6H2O) and the mass volume ratio of concentrated hydrochloric acid is 1g:55g:25g:18mL.
The acidization tool of multi-walled carbon nanotube are as follows: by multi-walled carbon nanotube and concentrated nitric acid (65wt%) matching with 1g:100mL
It than being uniformly mixed, is reacted 10 hours at 140 DEG C, obtained product is filtered, is washed to neutrality, is dried in vacuo, i.e.,
?.
Post-processing step includes: centrifugation, and washing to neutrality, 60 DEG C are dried in vacuo 24 hours.
In step (2), multi-wall carbon nano-tube composite material, the aqueous dispersions of lauroyl diethanolamine, pentaerythrite are stearic
The ethanol solution of acid esters, the mass volume ratio of three are 1g:8mL:2mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine,
The mass ratio of lauroyl diethanolamine and water is 1:18, in the ethanol solution of pentaerythritol stearate, pentaerythrite stearic acid
The mass ratio of ester and ethyl alcohol is 1:10.
In step (2), it is stirred to react condition are as follows: 125 DEG C are stirred to react 2 hours.
In step (2), benefit is washed with deionized 3 times, is then dried 25 hours for 55 DEG C.
In step (3), the acrylic resin is acrylic resin copolymer.
In step (3), acrylic resin and high-density polyethylene resin are mixed 4 minutes with 2000 revs/min.
In step (4), the dosage of functionalization composite material is the 0.6% of acrylic resin quality.
In step (4), functionalization composite material is added in the isobutyl triethoxy silane of 7 times of weight, and 400 revs/min
Mixed processing 5 hours, products therefrom is added from the side spout of double screw extruder.
A kind of automotive upholstery Anti-static PP/HDPE plastic obtained using above-mentioned preparation method.
Comparative example 1
In step (1), multi-walled carbon nanotube is only through tin dope (namely omitting zinc), remaining is the same as embodiment 1.
Comparative example 2
In step (2), multi-wall carbon nano-tube composite material only carries out functionalization (namely by lauroyl diethanolamine
Omit the ethanol solution of pentaerythritol stearate), remaining is the same as embodiment 1.
Comparative example 3
In step (4), isobutyl triethoxy silane is omitted, remaining is the same as embodiment 1.
Comparative example 4
In step (4), the temperature of double screw extruder is 220 DEG C, remaining is the same as embodiment 2.
Comparative example 5
In step (4), the temperature of double screw extruder is 245 DEG C, remaining is the same as embodiment 2.
Comparative example 6
In step (4), the revolving speed of double screw extruder is 270rpm, remaining is the same as embodiment 2.
Comparative example 7
In step (4), the revolving speed of double screw extruder is 450rpm, remaining is the same as embodiment 2.
Comparative example 8
Step (1) is acidified multi-walled carbon nanotube, Tin tetrachloride pentahydrate, the mass body of zinc nitrate hexahydrate and concentrated hydrochloric acid
Product is than being 1g:40g:25g:18mL, remaining is the same as embodiment 5.
Comparative example 9
Step (1) is acidified multi-walled carbon nanotube, Tin tetrachloride pentahydrate, the mass body of zinc nitrate hexahydrate and concentrated hydrochloric acid
Product is than being 1g:70g:25g:18mL, remaining is the same as embodiment 5.
Test example
Surface resistivity test is carried out to the plastic products of Examples 1 to 5 and comparative example 1~9, with reference to GB/T 1410-
2006, it the results are shown in Table 1.
1. surface resistivity of table compares
| Surface resistivity (Ω) | |
| Embodiment 1 | 5.3×104 |
| Embodiment 2 | 5.5×104 |
| Embodiment 3 | 3.1×104 |
| Embodiment 4 | 2.8×104 |
| Embodiment 5 | 2.9×104 |
| Comparative example 1 | 2.4×106 |
| Comparative example 2 | 5.7×106 |
| Comparative example 3 | 3.1×107 |
| Comparative example 4 | 4.3×106 |
| Comparative example 5 | 3.7×106 |
| Comparative example 6 | 8.1×105 |
| Comparative example 7 | 9.3×105 |
| Comparative example 8 | 4.8×106 |
| Comparative example 9 | 5.7×106 |
As shown in Table 1, the surface of plastic products resistivity of Examples 1 to 5 is low, and antistatic property is excellent, 1 multi wall of comparative example
Only through tin dope, antistatic property is obviously deteriorated carbon nanotube；2 multi-wall carbon nano-tube composite material of comparative example is only by lauroyl two
Ethanol amine carries out functionalization, and the functionalization composite material of comparative example 3 is without butyl triethoxysilane processing, antistatic property
It can obviously be deteriorated.The temperature of the double screw extruder of comparative example 4.5 is respectively 220 DEG C and 245 DEG C, the twin-screw of comparative example 6.7
The revolving speed of extruder is respectively 270rpm and 450rpm, the Tin tetrachloride pentahydrate and acidification multi-walled carbon nanotube of comparative example 8.9
Relative scale have slight variations, negative effect also is caused to the antistatic property of product.
Measuring mechanical property is carried out to the plastic products of Examples 1 to 5 and comparative example 2~3, with reference to GB/T1040.1-
2006 test tensile strengths, GB/T9341-2008 tested for flexural modulus test cantilever beam notch with reference to GB/T1043.1-2008
Impact strength the results are shown in Table 2.
2. mechanical performance of table compares
As shown in Table 2, the plastic products of Examples 1 to 5 have excellent mechanical performance, 2 multi-walled carbon nanotube of comparative example
Composite material only carries out functionalization by lauroyl diethanolamine, and the functionalization composite material of comparative example 3 is without three second of butyl
Oxysilane processing, mechanical performance are obviously deteriorated.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of automotive upholstery Anti-static PP/HDPE plastic preparation method, which is characterized in that specific step is as follows:
(1) multi-walled carbon nanotube generates multi-wall carbon nano-tube composite material after tin and zinc doping；
(2) step (1) resultant multi-wall carbon nano tube compound material is added in the aqueous dispersions of lauroyl diethanolamine, and stirring is mixed
It is even, the ethanol solution of pentaerythritol stearate is then added, is stirred to react, filters, washs, it is compound to obtain functionalization for drying
Material；
(3) after acrylic resin and high-density polyethylene resin are mixed according to mass ratio 1:0.3~0.5, twin-screw extrusion is added
The main spout of machine；
(4) by functionalization composite material obtained by step (2) after isobutyl triethoxy silane is handled, from double screw extruder
Side spout is added, and the revolving speed for controlling double screw extruder is 300~400rpm, and temperature is 230~240 DEG C, and extruding pelletization is
?.
2. preparation method according to claim 1, which is characterized in that the specific method of step (1) is: acidification multi wall carbon is received
Mitron is reacted with Tin tetrachloride pentahydrate, zinc nitrate hexahydrate, generates multi-wall carbon nano-tube composite material.
3. preparation method according to claim 2, which is characterized in that the acidization tool of multi-walled carbon nanotube are as follows: by multi wall
Carbon nanotube and concentrated nitric acid are uniformly mixed with the proportion of 1g:100mL, are reacted 6~12 hours at 140 DEG C, by what is obtained
Product filtered, is washed to neutrality, vacuum drying to get.
4. preparation method according to claim 2, which is characterized in that the specific method of step (1) is: multi wall carbon will be acidified
Nanotube is dispersed in water, and obtains the dispersion liquid of multi-walled carbon nanotube, and Tin tetrachloride pentahydrate is added, adds six nitric hydrates
Zinc, is then added concentrated hydrochloric acid, is slowly added to concentrated ammonia liquor later and adjusts pH=7~10, reacts 8~24 hours in 120~180 DEG C,
Post-treated multi-wall carbon nano-tube composite material to obtain the final product；Wherein, multi-walled carbon nanotube, Tin tetrachloride pentahydrate, six hydrations are acidified
The mass volume ratio of zinc nitrate and concentrated hydrochloric acid is 1g:50~60g:20~30g:15~20mL.
5. preparation method according to claim 1, which is characterized in that in step (2), multi-wall carbon nano-tube composite material,
The ethanol solution of the aqueous dispersions of lauroyl diethanolamine, pentaerythritol stearate, the mass volume ratio of three be 1g:5~
10mL:2~3mL；Wherein, in the aqueous dispersions of lauroyl diethanolamine, the mass ratio of lauroyl diethanolamine and water is 1:15
~20, in the ethanol solution of pentaerythritol stearate, the mass ratio of pentaerythritol stearate and ethyl alcohol is 1:8~12.
6. preparation method according to claim 1, which is characterized in that in step (2), be stirred to react condition are as follows: 120~
130 DEG C are stirred to react 2~3 hours.
7. preparation method according to claim 1, which is characterized in that in step (2), benefit is washed with deionized 2~3
It is secondary, then dry 20~30 hours for 50~60 DEG C.
8. preparation method according to claim 1, which is characterized in that in step (3), acrylic resin and high-density polyethylene
Olefine resin is mixed 2~5 minutes with 2000~3000 revs/min.
9. preparation method according to claim 1, which is characterized in that in step (4), functionalization composite material is added 5~8
In the isobutyl triethoxy silane of times weight, 300~500 revs/min mixed processing 5~6 hours, by products therefrom from double spiral shells
The side spout of bar extruder is added.
10. a kind of automotive upholstery Anti-static PP obtained using preparation method described in any one of claim 1~9 /
HDPE plastic.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105338799A (en) * | 2015-12-03 | 2016-02-17 | 安徽理工大学 | Nanocomposite made of magnetic-metal-doped multiwalled carbon nanotubes/tin dioxide |
| CN107482196A (en) * | 2017-08-06 | 2017-12-15 | 长沙善道新材料科技有限公司 | A kind of lithium ion battery composite nano materials and preparation method thereof |
| CN108948537A (en) * | 2018-08-30 | 2018-12-07 | 佛山豆萁科技有限公司 | Automotive upholstery plastics with anti-static function |
-
2019
- 2019-01-07 CN CN201910010729.XA patent/CN109721855A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105338799A (en) * | 2015-12-03 | 2016-02-17 | 安徽理工大学 | Nanocomposite made of magnetic-metal-doped multiwalled carbon nanotubes/tin dioxide |
| CN107482196A (en) * | 2017-08-06 | 2017-12-15 | 长沙善道新材料科技有限公司 | A kind of lithium ion battery composite nano materials and preparation method thereof |
| CN108948537A (en) * | 2018-08-30 | 2018-12-07 | 佛山豆萁科技有限公司 | Automotive upholstery plastics with anti-static function |
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