CN104725761A - Preparation method of novel ABS resin based material - Google Patents
Preparation method of novel ABS resin based material Download PDFInfo
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Abstract
The invention provides a preparation method of a novel ABS resin based material. The preparation method comprises the following steps: (1) adding montmorillonite into deionized water to obtain a suspended montmorillonite aqueous solution, adding a phosphoric acid solution of octadecyl trimethyl ammonium chloride, heating and stirring to obtain organic montmorillonite; (2) magnetically stirring the organic montmorillonite, polyaniline and hydrochloric acid solution together, dropwise adding an ammonium persulfate solution to obtain a green mixed solution, taking out, washing, drying and grinding to obtain a polyaniline-montmorillonite composite material; (3) hydrolyzing a coupling agent into an aqueous solution of acetone, adding tetrapod-like zinc oxide whiskers, ultrasonically stirring to obtain modified zinc oxide whiskers; (4) mixing ABS resin, a compatilizer, the polyaniline-montmorillonite composite material to obtain a premix; and (5) extruding and granulating the premix to obtain a granular material and drying to obtain the ABS resin based material.
Description
Technical field:
The present invention relates to a kind of material of construction, particularly relate to a kind of preparation method of ABS resin sill.
Background technology:
ABS resin is vinyl cyanide, 1,3-butadiene, cinnamic terpolymer, its English Acrylonitrile butadiene Styrene copolymers by name, therefore is called for short ABS.ABS resin maintains cinnamic excellent electrical properties and easy processing forming, turn increase elasticity, intensity (characteristic of divinyl), heat-resisting and erosion resistance (premium properties of vinyl cyanide), and surface hardness is high, chemical resistant properties is good, by changing the ratio of above-mentioned three kinds of components, the various performances of ABS can be changed, therefore ABS resin has extensive use, be mainly used in machinery, building, electrically, weaving, the field such as automobile and shipbuilding.
Such as, the Chinese patent that publication number is CN102746606B, publication date is 2014.06.18, application people is Shenzhen Keju New Material Co., Ltd. discloses " filling-modified ABS material of a kind of hollow glass microbead and preparation method thereof ", this material is made up of following component by weight percentage: ABS resin 50-80%, compatilizer 3-5%, toughner 5-1%, coupling agent 3-5%, strengthening agent 1-3%, hollow glass microbead 5-30%, plastic processing additives 1-3%.This invention take ABS resin as matrix resin, hollow glass microbead is filler, adopt the auxiliary agent of suitable species and proportioning, process under appropriate processing condition, make the filling-modified ABS material of hollow glass microbead of preparation with low cost, in tensile strength, flexural strength, modulus in flexure, shock strength, the aspects such as fluidity index are all more excellent, can be widely used in instrument, family expenses nitrogen, toy and amusement article and building trade, but the surface resistivity of this material is higher, at mine, petrochemical complex, Electronic Components Manufacturing workshop etc. needs the environment avoiding electrostatic to produce not to be suitable for, limit its scope of application.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of preparation method of ABS resin sill, and the matrix material prepared has good antistatic property, can be applicable to the environment needing to avoid electrostatic to produce.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A preparation method for new A BS resin-based materials, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, heated and stirred left standstill 10 hours after 1 hour, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and drip ammonium persulfate solution, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) coupling agent is hydrolyzed in the aqueous solution of acetone, after 1 hour, adds four acicular type zinc oxide crystal whisker, and be placed in water bath with thermostatic control ultrasonic agitation 40 minutes, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) the modified zinc oxide whisker that polyaniline montmorillonite Composite material ABS resin, compatilizer, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, obtain ABS resin sill by after pellet drying.
Preferably, in step of the present invention (1), the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1.
Preferably, in step of the present invention (1), Heating temperature during heated and stirred is 90 DEG C.
Preferably, in step of the present invention (2), the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3.
Preferably, in step of the present invention (2), the massfraction of hydrochloric acid soln, ammonium persulfate solution is 10%.
Preferably, in step of the present invention (3), coupling agent is silane coupling A 174.
Preferably, in step of the present invention (3), the temperature of water bath with thermostatic control is 75 DEG C.
Preferably, in step of the present invention (4), by weight, ABS resin 70-80 part, compatilizer 5-9 part, polyaniline montmorillonite Composite material 6-15 part, modified zinc oxide whisker 4-7 part.
Preferably, in step of the present invention (4), compatilizer is maleic anhydride grafted ethene-vinyl acetate between to for plastic.
Preferably, in step of the present invention (5), the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, and feeding rotating speed is 300r/min.
Compared with prior art, the present invention has following beneficial effect:
1. polyaniline is the excellent conductive polymers of a kind of conductivity, its specific conductivity is higher, polynite is the inorganic mineral with laminated structure, it obtains effective raising with the consistency of polyaniline after organically-modified, the organic group of aniline monomer molecule and montmorillonite layer has carried out effective exchange insertion reaction, define regularity and conduct electricity segment and conductive path preferably, therefore the specific conductivity of polyaniline montmorillonite Composite material is higher, it is compatible that it defines good interface by compatilizer and ABS resin matrix, effectively can improve specific conductivity and the antistatic property of integral material.
2. four acicular type zinc oxide crystal whisker is a kind of crystal whisker materials with semiconducting behavior, it has special regular three-D space structure, the needle-like portion in its 4 directions reaches some tens of pm, effectively can contact with the needle-like portion of adjacent whisker and form good three-dimensional conductive network, only need add than other conductive particles, electro-conductive fiber, the less amount of conductive sheet materials can obtain good conductivity, and there are not other conductive filler materials and can form oxide film and problem that the conductivity that causes declines in surface after long-term use, therefore its conductivity is more lasting, after the surface modification of coupling agent, four acicular type zinc oxide crystal whisker can be dispersed and form effective three-dimensional conductive network chain in ABS resin, thus effectively reduce the resistivity of integral material, its antistatic property of further raising and persistence thereof.
Embodiment:
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 7 parts that 14 parts, polyaniline montmorillonite Composite material ABS resin 70 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 6 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
Embodiment 2
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 5 parts that 15 parts, polyaniline montmorillonite Composite material ABS resin 75 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 9 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
Embodiment 3
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 6 parts that 10 parts, polyaniline montmorillonite Composite material ABS resin 72 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 5 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
Embodiment 4
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 4 parts that 12 parts, polyaniline montmorillonite Composite material ABS resin 80 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 7 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
Embodiment 5
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 4.5 parts that 6 parts, polyaniline montmorillonite Composite material ABS resin 74 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 8 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
Embodiment 6
A preparation method for ABS resin sill, its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1,10 hours are left standstill after 1 hour at heated and stirred 90 DEG C, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, massfraction be 10% hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and dripped the ammoniumsulphate soln that massfraction is 10%, the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) be hydrolyzed in the aqueous solution of acetone by silane coupling A 174, add four acicular type zinc oxide crystal whisker after 1 hour, and be placed in the water bath with thermostatic control ultrasonic agitation 40 minutes of 75 DEG C, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) by weight, the modified zinc oxide whisker 5.5 parts that 8 parts, polyaniline montmorillonite Composite material ABS resin 76 parts, maleic anhydride grafted ethene-vinyl acetate between to for plastic 7.5 parts, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, feeding rotating speed is 300r/min, obtains ABS resin sill by after pellet drying.
The material obtained by embodiment 1-6 and the surface resistivity of comparative example are tested by ASTM D257, and result is as shown in the table, wherein, and the Chinese patent of comparative example to be publication number be CN102746606B.
As seen from the above table, the surface resistivity of the material that the present invention obtains is starkly lower than comparative example, shows good antistatic property.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a preparation method for new A BS resin-based materials, is characterized in that: its step is as follows:
(1) polynite is added deionized water for stirring after 1 hour leave standstill within 10 hours, obtain polynite aqueous suspension, the phosphoric acid solution of octadecyl trimethyl ammonium chloride is added in polynite aqueous suspension, heated and stirred left standstill 10 hours after 1 hour, taking-up, filtration final vacuum are dried to constant weight, are placed in after ball mill is pulverized and obtain organo montmorillonite;
(2) organo montmorillonite step (1) obtained, polyaniline, hydrochloric acid soln add magnetic agitation in three mouthfuls of reactors together, and drip ammonium persulfate solution, green mixed solution is obtained after 2 hours, be colourless with deionized water wash to filtrate after taking-up, filter cake is dried at 80 DEG C and within 6 hours, is placed on grinding machine for grinding, obtain polyaniline montmorillonite Composite material;
(3) coupling agent is hydrolyzed in the aqueous solution of acetone, after 1 hour, adds four acicular type zinc oxide crystal whisker, and be placed in water bath with thermostatic control ultrasonic agitation 40 minutes, taking-up, suction filtration, drying, obtain modified zinc oxide whisker;
(4) the modified zinc oxide whisker that polyaniline montmorillonite Composite material ABS resin, compatilizer, step (2) obtained, step (3) obtain to add in mixing roll mixing 10 minutes together, obtains Preblend;
(5) Preblend that step (4) obtains is added extruding pelletization in twin screw extruder, obtain pellet, obtain ABS resin sill by after pellet drying.
2. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (1), the mass ratio of polynite and octadecyl trimethyl ammonium chloride is 6:1.
3. the preparation method of a kind of new A BS resin-based materials according to claim 1, it is characterized in that: in described step (1), Heating temperature during heated and stirred is 90 DEG C.
4. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (2), the mass ratio of organo montmorillonite, polyaniline, hydrochloric acid, ammonium persulphate is 20:18:1:3.
5. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (2), the massfraction of hydrochloric acid soln, ammonium persulfate solution is 10%.
6. the preparation method of a kind of new A BS resin-based materials according to claim 1, it is characterized in that: in described step (3), coupling agent is silane coupling A 174.
7. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (3), the temperature of water bath with thermostatic control is 75 DEG C.
8. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (4), by weight, ABS resin 70-80 part, compatilizer 5-9 part, polyaniline montmorillonite Composite material 6-15 part, modified zinc oxide whisker 4-7 part.
9. the preparation method of a kind of new A BS resin-based materials according to claim 1, it is characterized in that: in described step (4), compatilizer is maleic anhydride grafted ethene-vinyl acetate between to for plastic.
10. the preparation method of a kind of new A BS resin-based materials according to claim 1, is characterized in that: in described step (5), the temperature of twin screw extruder is 170-205 DEG C, and engine speed is 1100r/min, and feeding rotating speed is 300r/min.
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| CN108578124A (en) * | 2018-05-03 | 2018-09-28 | 常州市第人民医院 | A kind of Multifunctional hand pad |
| DE102020105849A1 (en) | 2020-03-04 | 2021-09-09 | Christian-Albrechts-Universität Zu Kiel | Polymer composite and manufacturing process for it |
| DE102020105848A1 (en) | 2020-03-04 | 2021-09-09 | Christian-Albrechts-Universität Zu Kiel | Thermoplastic extrusion and / or 2-component polymer additive as well as manufacturing process for this and additive use therefor |
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