CN114456497B - Preparation method of antistatic high-strength PP material - Google Patents
Preparation method of antistatic high-strength PP material Download PDFInfo
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- CN114456497B CN114456497B CN202210286051.XA CN202210286051A CN114456497B CN 114456497 B CN114456497 B CN 114456497B CN 202210286051 A CN202210286051 A CN 202210286051A CN 114456497 B CN114456497 B CN 114456497B
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004743 Polypropylene Substances 0.000 claims abstract description 135
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 97
- 229920000570 polyether Polymers 0.000 claims abstract description 97
- 150000002148 esters Chemical class 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 67
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002216 antistatic agent Substances 0.000 claims abstract description 47
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 42
- -1 polypropylene Polymers 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 229920001155 polypropylene Polymers 0.000 claims abstract description 34
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 26
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 description 13
- 238000001746 injection moulding Methods 0.000 description 13
- 238000010008 shearing Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of PP materials, and discloses a preparation method of an antistatic high-strength PP material. The preparation method of the antistatic high-strength PP material comprises the following steps: (1) Taking N-methyldiethanolamine and gamma-chloropropyl trimethoxyl silane, putting the N-methyldiethanolamine and gamma-chloropropyl trimethoxyl silane into a reaction kettle, taking potassium iodide as a catalyst, taking isopropanol and methanol as polar organic solvents, heating to dissolve and uniformly mix the raw materials, transferring the raw materials into a microwave reaction device, cooling, standing and separating the liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt; (2) The high molecular antistatic agent polyether ester and the obtained organosilicon quaternary ammonium salt are firstly subjected to drying treatment, then are uniformly mixed with PP, and are subjected to melt blending and extrusion molding in a double-screw extruder to prepare the antistatic high-strength polypropylene composite material. According to the method, the high-molecular antistatic agent and the small-molecular antistatic agent are added, so that the antistatic performance is improved from the two aspects of the bulk phase and the surface layer of the polypropylene, and the defect of insufficient antistatic performance of the polypropylene material is overcome.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of an antistatic high-strength PP material.
Background
Polypropylene is a general plastic with excellent characteristics of light weight, corrosion resistance, high temperature resistance and the like, and is widely applied to the fields of electronic devices, medical treatment, automobile industry and the like. However, polypropylene has good insulativity, charges are easy to accumulate on the surface through friction, the accumulated static charges are easy to adsorb dust, the attractive appearance of the PP product is affected, even fire and explosion can be caused when the PP product is serious, and the rapid development of the PP product is greatly limited. In order to improve the usability of the PP material and further expand the application range of the PP material, a new antistatic high-strength PP product is needed to meet the market demand.
The antistatic agent is added into the PP material, and the surface hydrophilicity of the PP material is improved, and the polar groups on the surface of the antistatic agent absorb moisture in the air to form a conductive layer, so that the leakage of accumulated static charges can be quickened, the antistatic capability of the PP material is improved, and the antistatic PP material is one of preparation methods of the antistatic PP material. Chinese patent (application number 201811629424.9) discloses a long-acting anti-cancer agentThe patent obtains a permanent antistatic PP material by adding a polymer antistatic agent ethylene-acrylate copolymer into the PP material. However, the amount of antistatic agent used in the technique of this patent is large, and the surface resistivity of PP material reaches 5.05X10 when 50 parts of antistatic agent are added 8 The omega/sq is added with a large amount of antistatic, so that the production cost is increased, and the mechanical property of the PP material is affected.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a preparation method of an antistatic high-strength PP material. According to the method, the high-molecular antistatic agent and the small-molecular antistatic agent are added, so that the antistatic performance is improved from the two aspects of the bulk phase and the surface layer of the polypropylene, and the defect of insufficient antistatic performance of the polypropylene material is overcome.
Specifically, the invention firstly adopts a plurality of polyether ester type high molecular antistatic agents with different molecular weights to blend with polypropylene, and the high molecular antistatic agents form a network structure in a polypropylene matrix by regulating and controlling the parameters such as the fluidity, the polarity and the like of the high molecular antistatic agents, so that the antistatic performance of the polypropylene material can be improved, and meanwhile, the tensile strength and the impact strength of the polypropylene can be obviously improved due to stronger acting force among molecules of the high molecular antistatic agents. Because the antistatic effect of the macromolecular antistatic agent is inferior to that of the micromolecular antistatic agent, the micromolecular antistatic agent is further added into the polypropylene on the basis that the macromolecular antistatic agent forms a network structure in the polypropylene matrix, and the micromolecular antistatic agent tends to be distributed on the surface of the polypropylene material, so that the polypropylene has good surface antistatic performance. Thus, the antistatic high-strength polypropylene material is obtained by cooperatively using the macromolecular antistatic agent and the micromolecular antistatic agent.
In order to achieve the purpose of the invention, the preparation method of the antistatic high-strength PP material comprises the following steps:
(1) The method is characterized in that N-methyldiethanolamine and gamma-chloropropyl trimethoxysilane are used as raw materials to synthesize the organosilicon quaternary ammonium salt through quaternization, and the specific process is as follows:
more specifically, N-methyldiethanolamine and gamma-chloropropyl trimethoxyl silane are taken in a reaction kettle, potassium iodide is taken as a catalyst, a mixed solvent of isopropanol and methanol is taken as a polar organic solvent, the mixture is heated to enable the added raw materials to be dissolved and evenly mixed, and then the mixture is transferred into a microwave reaction device for reaction, and after the reaction is finished, cooling, standing, liquid separation and rotary evaporation are carried out to obtain the organosilicon quaternary ammonium salt;
(2) Drying the high-molecular antistatic polyether ester and the organosilicon quaternary ammonium salt obtained in the step (1), uniformly mixing the dried high-molecular antistatic polyether ester and the organosilicon quaternary ammonium salt with PP, and carrying out melt blending and extrusion molding in a double-screw extruder to obtain the antistatic high-strength polypropylene composite material.
Further, in some embodiments of the present invention, the ratio of the material ratios in the step (1) by the amount of the materials is n (γ -chloropropyl trimethoxysilane): n (N-methyldiethanolamine) =1.0-1.5: 1.0.
further, in some embodiments of the present invention, the solvent dosage ratio in the step (1) is m (solvent) according to the mass ratio of the substances: m (raw material) =0.5-1.0: 1.0.
further, in some embodiments of the present invention, the mass ratio of isopropyl alcohol to methanol in step (1) is 1.0 to 3.0:1.0.
further, in some embodiments of the invention, the reaction time in step (1) is 8 to 16 hours.
Further, in some embodiments of the invention, the reaction temperature in step (1) is 120-200 ℃.
Further, in some embodiments of the present invention, the microwave power in the step (1) is 500-1000W.
Further, in some embodiments of the present invention, the polyether ester in step (2) is a copolymer composed of a polyester and a polyether, the polyester is polybutylene terephthalate, and the polyether is a polymer of ethylene glycol.
Preferably, in some embodiments of the present invention, the polyetherester in step (2) has a molecular weight of 1000 to 50000. One or more of polyether esters with different molecular weights can be added in the step (2), wherein the preferable molecular weight is 1000 polyether ester, the molecular weight is 10000 polyether ester, the molecular weight is 50000 polyether ester mass ratio is 1-4:3-4:0-3, wherein the optimal proportion is that polyether ester with the molecular weight of 1000, polyether ester with the molecular weight of 10000, polyether ester with the molecular weight of 50000=1: 1:1.
further, in some embodiments of the present invention, the mass ratio of the polyether ester, the silicone quaternary ammonium salt and the PP in the step (2) is 4 to 12:0.8-5:86-96, preferably 9:5:86.
further, in some embodiments of the present invention, the drying temperature in the step (2) is 80-120 ℃ and the drying time is 1-5 hours.
Further, in some embodiments of the present invention, the twin screw extruder in step (2) has an extrusion temperature of 160-220 ℃, an extruder screw speed of 50-80r/min, and an injection temperature of 150-200 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The invention utilizes the synergistic effect of the high molecular antistatic agent and the small molecular antistatic agent to improve the antistatic property of the PP composite material, so that the PP composite material reaches the quality even superior to that of similar products.
(2) The polyether ester high molecular antistatic agent adopted by the invention forms a network structure in the polypropylene matrix, so that the mechanical property of the PP composite material is improved.
(3) The high-molecular antistatic agent used in the invention has low price, the synthesis process of the organosilicon quaternary ammonium salt is simple, the cost is low, and the preparation process of the antistatic high-strength PP composite material is simple, thereby being beneficial to industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.2: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then 8wt% of polyether ester (2 wt% of polyether ester with molecular weight of 1000, 3wt% of polyether ester with molecular weight of 10000 and 2wt% of polyether ester with molecular weight of 50000), 1wt% of organosilicon quaternary ammonium salt and 91wt% of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 2
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.2: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =1.0:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 5wt percent (1 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000, 1wt percent of polyether ester with the molecular weight of 50000), the organosilicon quaternary ammonium salt with the mass fraction of 2wt percent and 93wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min, and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 3
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.0: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =1.0:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 6wt percent (1 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000, 2wt percent of polyether ester with the molecular weight of 50000), the organosilicon quaternary ammonium salt with the mass fraction of 2wt percent and 92wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min, and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 4
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.0: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then 8wt% of polyether ester (4 wt% of polyether ester with molecular weight of 1000 and 4wt% of polyether ester with molecular weight of 10000), 1wt% of organosilicon quaternary ammonium salt and 91wt% of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 5
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.5: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =1.0:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 7wt percent (1 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000, 3wt percent of polyether ester with the molecular weight of 50000), the organosilicon quaternary ammonium salt with the mass fraction of 2wt percent and 91wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min, and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 6
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.5: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then 10wt% of polyether ester (3 wt% of polyether ester with molecular weight of 1000, 4wt% of polyether ester with molecular weight of 10000, 3wt% of polyether ester with molecular weight of 50000), 1wt% of organosilicon quaternary ammonium salt and 89wt% of PP are mixed for 30 minutes in a high-speed mixer with rotating speed of 800r/min, and then are placed in a double-screw extruder with the temperature of 170-210 ℃ and the rotating speed of 60 r/min. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 7
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.3: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =1.0:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 9wt percent (3 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000, 3wt percent of polyether ester with the molecular weight of 50000), the organosilicon quaternary ammonium salt with the mass fraction of 1wt percent and 90wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 8
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.3: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 9wt percent (3 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000, 3wt percent of polyether ester with the molecular weight of 50000), the organosilicon quaternary ammonium salt with the mass fraction of 5wt percent and 86wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 9
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.4: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =1.0:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organosilicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then 4wt% of polyether ester (1 wt% of polyether ester with molecular weight of 1000, 2wt% of polyether ester with molecular weight of 10000 and 1wt% of polyether ester with molecular weight of 50000), 4wt% of organosilicon quaternary ammonium salt and 92wt% of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Example 10
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.4: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: polyether ester and organic silicon quaternary ammonium salt are firstly treated for 3 hours in a baking oven at 100 ℃, and then the polyether ester with the mass fraction of 8wt percent (2 wt percent of polyether ester with the molecular weight of 1000, 3wt percent of polyether ester with the molecular weight of 10000 and 2wt percent of polyether ester with the molecular weight of 50000), the organic silicon quaternary ammonium salt with the mass fraction of 3wt percent and 89wt percent of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min and then are placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP, the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt are further subjected to melt reaction, and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Comparative example 1
PP is placed in a double-screw extruder with the temperature of 170-210 ℃ and the rotating speed of 60 r/min. And under the shearing and heating actions of the screw, PP is further subjected to melt reaction and is conveyed to an extruder head, and PP material granules are obtained after extrusion, cooling, drying and granulating. The PP material is put into an injection molding machine at 170-200 ℃ to obtain the required sample strip.
Comparative example 2
(1) Synthesis of organosilicon quaternary ammonium salt: a certain amount of N-methyldiethanolamine and γ -chloropropyltrimethoxysilane [ N (γ -chloropropyltrimethoxysilane): N (N-methyldiethanolamine) =1.2: 1.0] adding the mixture into a high-pressure reaction kettle, adding a mixed solvent of isopropanol and methanol with potassium iodide serving as a catalyst, wherein the solvent dosage is m (solvent), the raw material is m (raw material) =0.8:1.0, the raw material is m (isopropanol) =1.0:1.0, and the mixture is heated to dissolve and uniformly mix the added raw materials, transferring the mixture into a microwave reaction device, setting the microwave power to be 800W, the reaction time to be 12h, the reaction temperature to be 170 ℃, cooling, standing, separating liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of antistatic high-strength polypropylene material: the organosilicon quaternary ammonium salt is firstly treated for 3 hours in a baking oven at 100 ℃, then the organosilicon quaternary ammonium salt with the mass fraction of 1wt% and 99wt% of PP are mixed for 30 minutes in a high-speed mixer with the rotating speed of 800r/min, and then the mixture is placed in a double-screw extruder with the rotating speed of 60r/min at 170-210 ℃. Under the shearing and heating actions of the screw, the PP and the organosilicon quaternary ammonium salt are further subjected to melt reaction and are conveyed to an extruder head, and after extrusion, cooling, drying and granulating, the antistatic high-strength PP composite material granules are obtained. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Comparative example 3
Preparation of antistatic high-strength polypropylene material: polyether ester is firstly treated in a 100 ℃ oven for 3 hours, and then 8wt% of polyether ester (2 wt% of polyether ester with molecular weight of 1000, 3wt% of polyether ester with molecular weight of 10000 and 2wt% of polyether ester with molecular weight of 50000) and 92wt% of PP are mixed in a high-speed mixer with rotating speed of 800r/min for 30 minutes, and then the mixture is placed in a double-screw extruder with the temperature of 170-210 ℃ and the rotating speed of 60 r/min. Under the shearing and heating actions of the screw, the PP and the high-molecular antistatic agent polyether ester are further subjected to melt reaction and are conveyed to an extruder head, and the antistatic high-strength PP composite material granules are obtained after extrusion, cooling, drying and granulating. And (3) obtaining the required sample strip from the antistatic high-strength PP composite material in an injection molding machine at 170-200 ℃.
Performance testing
The tensile strength of the material is carried out according to GB/T1040.1-2006, and the speed is 50mm/min; notch impact strength is carried out according to GB/T1043.1-2008, and V-shaped notch is formed; the surface resistivity is according to GB/T1410-2006 standard, the PP surface resistivity test sample strip is processed in a constant temperature and humidity box for 48 hours, the relative humidity is 65+/-0.2%, and the temperature is 23+/-0.2 ℃.
TABLE 1 Material Properties Table for examples 1-10 and comparative examples 1-3
| Detection item | Surface resistivity (Ω/sq) | Tensile Strength (MPa) | Notched impact strength at ambient temperature (kJ/m) 2 ) |
| Example 1 | 8.21×10 9 | 55.8 | 12.3 |
| Example 2 | 5.39×10 8 | 49.4 | 10.8 |
| Example 3 | 3.56×10 8 | 42.9 | 9.2 |
| Example 4 | 9.37×10 9 | 47.6 | 9.9 |
| Example 5 | 1.26×10 8 | 43.6 | 9.5 |
| Example 6 | 9.39×10 8 | 51.7 | 10.4 |
| Example 7 | 3.59×10 9 | 50.6 | 10.6 |
| Example 8 | 1.07×10 7 | 56.5 | 13.5 |
| Example 9 | 3.34×10 7 | 52.3 | 11.1 |
| Example 10 | 8.96×10 7 | 50.3 | 11.7 |
| Comparative example 1 | 3.06×10 16 | 28.1 | 3.5 |
| Comparative example 2 | 4.29×10 10 | 29.7 | 6.9 |
| Comparative example 3 | 6.16×10 12 | 41.9 | 9.1 |
According to the embodiment and the comparative example, the surface resistivity of the PP composite material is reduced by using the high-molecular antistatic agent and the small-molecular antistatic agent, the antistatic performance of the PP composite material is improved, and meanwhile, the mechanical property of the PP composite material is also improved. The composite use of the high-molecular antistatic agent and the small-molecular antistatic agent can greatly improve the tensile strength and the notch impact strength of the PA66 compared with the single use of the high-molecular antistatic agent and the small-molecular antistatic agent, and the high-molecular antistatic agent is mainly characterized in that the high-molecular antistatic agent forms a network structure in a polypropylene matrix, the small-molecular antistatic agent tends to be distributed on the surface of a polypropylene material, and the polypropylene material is endowed with good surface antistatic performance and is cooperatively used, so that the antistatic high-strength PP composite material is obtained.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. The preparation method of the antistatic high-strength PP material is characterized by comprising the following steps of:
(1) The method is characterized in that N-methyldiethanolamine and gamma-chloropropyl trimethoxysilane are used as raw materials to synthesize organic silicon quaternary ammonium salt through quaternization;
(2) Firstly, drying the high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt obtained in the step (1), then uniformly mixing the dried high-molecular antistatic agent polyether ester and the organosilicon quaternary ammonium salt with PP, and carrying out melt blending and extrusion molding in a double-screw extruder to obtain an antistatic high-strength polypropylene composite material;
the polyether ester in the step (2) is a copolymer composed of polyester and polyether, wherein the polyester is polybutylene terephthalate, and the polyether is a polymer of ethylene glycol; the molecular weight of the polyether ester in the step (2) is 1000-50000, the molecular weight of the polyether ester is 1000, the molecular weight of the polyether ester is 10000, the molecular weight of the polyether ester is 50000, and the mass ratio of the polyether ester is 1-4:3-4:0-3;
in the step (2), the mass ratio of the polyether ester, the organosilicon quaternary ammonium salt and the PP is 4-12:0.8-5:86-96.
2. The method for preparing the antistatic high-strength PP material according to claim 1, wherein in the step (1), N-methyldiethanolamine and gamma-chloropropyl trimethoxysilane are taken in a reaction kettle, potassium iodide is taken as a catalyst, a mixed solvent of isopropanol and methanol is taken as a polar organic solvent, the mixture is heated to dissolve and uniformly mix the added raw materials, the mixture is transferred to a microwave reaction device for reaction, and after the reaction is finished, the mixture is cooled, kept stand for liquid separation and rotary evaporation, so that the organosilicon quaternary ammonium salt is obtained.
3. The method for preparing the antistatic high-strength PP material according to claim 1 or 2, wherein the material ratio in the step (1) is n (γ -chloropropyl trimethoxysilane) in terms of the mass ratio: n (N-methyldiethanolamine) =1.0-1.5: 1.0.
4. the method for preparing an antistatic high-strength PP material according to claim 2, wherein the solvent dosage ratio in the step (1) is m (solvent) according to mass ratio of substances: m (raw material) =0.5-1.0: 1.0.
5. the method for preparing an antistatic high-strength PP material according to claim 2, wherein the mass ratio of isopropyl alcohol to methanol in the step (1) is 1.0-3.0:1.0.
6. the method for preparing an antistatic high-strength PP material according to claim 2, wherein the reaction time in the step (1) is 8-16 h; the reaction temperature in the step (1) is 120-200 ℃; the microwave power in the step (1) is 500-1000W.
7. The method for preparing the antistatic high-strength PP material according to claim 1, wherein the molecular weight is 1000 polyether ester, the molecular weight is 10000 polyether ester, the molecular weight is 50000 polyether ester=1: 1:1.
8. the method for preparing the antistatic high-strength PP material according to claim 1, wherein the mass ratio of the polyether ester, the organosilicon quaternary ammonium salt and the PP in the step (2) is 4-9:3-5:86-92.
9. The method for preparing the antistatic high-strength PP material according to claim 1, wherein the mass ratio of the polyether ester, the organosilicon quaternary ammonium salt and the PP in the step (2) is 9:5:86.
10. the method for preparing an antistatic high-strength PP material according to claim 1, wherein the drying temperature in the step (2) is 80-120 ℃ and the drying time is 1-5h.
11. The method for preparing an antistatic high-strength PP material according to claim 1, wherein the extrusion temperature of the twin-screw extruder in the step (2) is 160-220 ℃, and the screw speed of the extruder is 50-80r/min.
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