CN109575440A - A kind of anti-static polyolefin composite material and preparation method can be used for 3D printing - Google Patents
A kind of anti-static polyolefin composite material and preparation method can be used for 3D printing Download PDFInfo
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- CN109575440A CN109575440A CN201811516666.7A CN201811516666A CN109575440A CN 109575440 A CN109575440 A CN 109575440A CN 201811516666 A CN201811516666 A CN 201811516666A CN 109575440 A CN109575440 A CN 109575440A
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- composite material
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- polyolefin
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- polyolefin composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
Abstract
The invention discloses a kind of anti-static polyolefin composite material and preparation method that can be used for 3D printing, which includes following components and weight fraction: 70-95 parts of polyolefin；15-40 parts of polylactic acid；0-20 parts of expanding material；0.5-2 parts of antistatic agent；0.2-2 parts of heat stabilizer；0.2-2 parts of processing aid；Antistatic agent is that carbon nano-composite material or at least one are covalent linkage with boron element and are constituted the covalent organic structure polymer-based material of 2D.3D printing material provided by the invention has compared with antistatic property, can be widely applied to the dust-proof antistatic more demanding field of some pairs of materials.
Description
Technical field
The invention belongs to polymeric material field, be related to a kind of anti-static polyolefin composite material that can be used for 3D printing and
Preparation method.
Background technique
Rapid shaping technique is also referred to as 3D printing technique, is born in the late 1980s, is based on material stacking method
A kind of high-new manufacturing technology.It is a kind of revolutionary technology for overturning classical production process, be known as after steam engine, computer and
Another big invention after internet.One important branch of 3D printing is derived from the personal printing risen for 2008 or so.Absolutely
Most of individual's 3D printer is printed as using FDM (Deformation In The Fdm Process Fused Deposition Modeling) completion
Type.The basic principle of the technology be by thermal plastic high polymer long filament (at present the matching diameter of the printer of mainstream be 1.75mm and
High temperature hot end 3mm) is transmitted to by macromolecule melting using gear and continuously extrusion melts macromolecule, and is passed through under accurate positioning
The method building three-dimension object successively accumulated.
The current 3D printing macromolecule most common on the market has ABS and two kinds of polylactic acid PLA.Polylactic acid has good
Bright property has certain biodegradable performance without unpleasant peculiar smell when melting.But since the polarity of polylactic acid is higher, cause
Polylactic acid is hygroscopic, to influence its dimensional stability and electrical property, while heat resistance is poor.These features, which greatly suppress, beats
Print the use scope of object.Polyolefin is a kind of most widely used general-purpose plastics, it has at low cost, good mechanical performance, resistance to
Chemical property is good, and with insulating properties, heat resistance and the high grade of transparency, water absorption rate is low.For the application field for widening 3D printing product, knot
Reactive compatibilization technology is closed, by polylactic acid and polyolefin by the method for blending and modifying, can be obtained in conjunction with the advantages of the two
To low water absorption, polyolefin/polylactic acid composition of shape and size high stability.
Summary of the invention
The purpose of the present invention is exactly to provide a kind of antistatic polyene that can be used for 3D printing to solve the above-mentioned problems
Hydrocarbon composite material and preparation method, composite polyolefine material of the invention have compared with antistatic property, can be widely applied to pair
The dust-proof antistatic more demanding field of material.
The object of the present invention is achieved like this:
A kind of anti-static polyolefin composite material can be used for 3D printing of the invention includes following components and weight fraction:
Antistatic agent be carbon nano-composite material or it is at least one with boron element be to be covalently attached and to be constituted 2D covalently organic
Topology convergence species material.
Polyolefin is acrylic resin in a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing.
The preparation side of carbon nano-composite material in a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing
Method is as follows: the lotion magneton of polypropylene tetramer benzene sulfonic acid sodium salt, deionized water and toluene composition being stirred 60min, then carboxyl fossil
Black alkene, which is dispersed in the above lotion ultrasonic disperse 30min and is uniformly mixed, to be placed in ice bath, is separately added into 5g thiophene and chlorine later
Change copper and continue magneton and stir 12h, mixture is filtered totally three with being washed with acetone, methanol and deionized water respectively after the reaction was completed
It is secondary, it then will filter obtained product and be placed in 12h in 60 DEG C of vacuum drying ovens and obtain the carbon of polythiophene coated copper Nanoparticle Modified
Nanotube.
The preparation side of carbon nano-composite material in a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing
Method is as follows: obtained nitrine polyacrylic acid solution in the n,N-dimethylacetamide for being first dissolved in polyacrylic acid, and polymerization degree n=
20；It disperses the graphene oxide with carboxyl in nitrine polyacrylic acid solution, and ultrasonic disperse 30min, then mixes at room temperature
It closes stirring 60min to be placed in 200 DEG C of oil baths, magnetic agitation reacts 2h, and product is cooled to room temperature, and filters, and washs three times, most
Place the product in dryings in 60 DEG C of vacuum drying ovens afterwards for 24 hours.
Polyolefin and/or polylactic acid are 230 in a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing
DEG C, the melt flow rate (MFR) under the conditions of 2.16kg be 1~100g/10min.
Expanding material is that maleic anhydride grafting is poly- in a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing
Alkene, and maleic anhydride grafting ratio is 0.2~5%.Preferably, maleic anhydride stem grafting polyolefin includes following components and weight point
Number:
100 parts of polyolefin；
2~5 parts of maleic anhydride；
1~2 part of cumyl peroxide.
In a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing heat stabilizer be selected from phenols, amine,
At least one of phosphorous acid esters, half Hinered phenols, the compound of acryloyl group functional group and monothioester and calixarenes.
In a kind of above-mentioned anti-static polyolefin composite material that can be used for 3D printing processing aid be selected from low molecule esters,
At least one of the compound esters of metal soap, stearic acid and amides.
The present invention also provides a kind of preparation method of anti-static polyolefin composite material that can be used for 3D printing, including it is following
Step:
(1) prepare raw material by following components and weight fraction:
(2) antistatic agent and expanding material are first mixed, obtains the mixture of antistatic agent and expanding material, then again will
The mixture of antistatic agent and expanding material, polyolefin, polylactic acid, heat stabilizer, processing aid successively put into mixing machine and mix
Uniformly, 400~600 revs/min of speed, 15~30 DEG C of temperature, it is spare to obtain pre-composition for incorporation time 3~5 minutes；
It (3) is double screw extruder temperature of each section in the double screw extruder of 40~45:1 by pre-composition investment draw ratio
190~240 DEG C are set as, melting mixing is dispersed and extruding pelletization.
The present invention principle different with compatibility using the polarity of each component.In shear-mixed, by antistatic agent and increase
Hold agent maleic anhydride stem grafting polyolefin to be pre-mixed, the expanding material and polylactic acid blend of antistatic agent will be mixed with, the present invention uses
Polylactic acid molecule chain on there are also carboxyl, therefore it is anti-in processing interface can to occur with the maleic anhydride stem grafting polyolefin in system
It answers, realizes In Situ Compatibilization.3D printing material provided by the invention has compared with antistatic property, can be widely applied to some pairs of materials
Dust-proof antistatic more demanding field.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
Polyolefin selects the Z30S in Zhenghai, melting means 30g/10min；
The EP548R, melting means 30g/10min of polypropylene selection CSPC；
Polylactic acid selects polylactic acid 6, the production of Shanghai celluloid factory；
Antistatic agent 1 is the carbon nanomaterial that laboratory independently prepares, and preparation method is to remove polypropylene tetramer benzene sulfonic acid sodium salt
The lotion magneton of ionized water and toluene composition stirs 60min, then carboxylated graphene dispersion ultrasonic disperse in the above lotion
30min is uniformly mixed and is placed in ice bath, and a certain amount of thiophene is added later and copper chloride continues magneton stirring 12h；It has reacted
Mixture is washed into suction filtration three times with acetone, methanol and deionized water respectively after, graphene is then placed in 60 DEG C of vacuum
12h obtains the carbon nanotube (rGO-PTs-Cu) of polythiophene coated copper Nanoparticle Modified in baking oven；
Antistatic agent 2 is the carbon nanomaterial that laboratory independently prepares, the preparation method is as follows: being first dissolved in polyacrylic acid
N,N-dimethylacetamide (DMF) in be made nitrine polyacrylic acid (polymerization degree n=20) DMF solution；It again will be with carboxyl
Graphene oxide is scattered in DMF, and ultrasonic disperse 30min.60min is mixed in the two at room temperature, then flask is placed in 200
In DEG C oil bath, magnetic agitation reacts 2h；Product is cooled to room temperature, is filtered, washing is three times.Sample is finally placed in 60 DEG C of vacuum
The dry product that black can be obtained for 24 hours in baking oven；
Antistatic agent 3 is the one or several kinds of the covalent organic structure polymer of 2D (2D COFs) class material, with boron element
(B) it is constituted to be covalently attached；
Maleic anhydride stem grafting polyolefin is laboratory self-control, grafting rate 0.88%；
Phosphite ester type thermal stabilizing agent selects refined precious 1010；
Phenolic thermostabilizers select refined precious 168；
Processing aid selects refined treasured EBS.
The preparation method of comparative example 1~3 and Examples 1 to 6, by the proportion polyolefin in table 1, polylactic acid 6, maleic anhydride
Graft polyolefin, carbon nanotube, phenolic thermostabilizers 1010, phosphite ester type thermal stabilizing agent 168, processing aid EBS are in major diameter
Than being granulated after melting mixing in the double screw extruder for 1:40.It is thick to be molded 1mm, diameter 100mm disk, according to GB1410-78
Standard testing volume resistivity.It is molded into standard batten test tensile strength detailed construction simultaneously and is shown in Table 1.
The preparation method of comparative example 4 and embodiment 7~9, by the proportion in table 1 by polypropylene, polylactic acid, antistatic agent,
Heat stabilizer and processing aid first mix 5-10min in a high speed mixer, then the material mixed is added to twin-screw and is squeezed
Reactive extrursion in machine out, each section of temperature are respectively as follows: 170-190 DEG C of area's temperature, two 190-230 DEG C of area's temperature, three Qu Wendu
230-240 DEG C, four 230-240 DEG C of area's temperature, five 230-240 DEG C of area's temperature, six 230-240 DEG C of area's temperature, seven area temperature 240-
250 DEG C, eight 240-250 DEG C of area's temperature, nine 230-240 DEG C of area's temperature, screw speed is 50-80 revs/min.Extruded stock is granulated
And dried at 80 DEG C, finally obtain product of the invention.It is thick to be molded 1mm, diameter 100mm disk, according to GB1410-78 standard
Test volume resistivity, test result are shown in Table 1.
1 comparative example 1~4 of table and Examples 1 to 9 with when the performance test results
Above embodiments are used for illustrative purposes only, rather than limitation of the present invention, the technology people in relation to technical field
Member, without departing from the spirit and scope of the present invention, can also make various transformation or modification, therefore all equivalent
Technical solution also should belong to scope of the invention, should be limited by each claim.
Claims (10)
1. a kind of anti-static polyolefin composite material that can be used for 3D printing, which is characterized in that including following components and weight point
Number:
The antistatic agent be carbon nano-composite material or it is at least one with boron element be to be covalently attached and to be constituted 2D covalently organic
Topology convergence species material.
2. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
Polyolefin is acrylic resin.
3. a kind of anti-static polyolefin composite material that can be used for 3D printing as claimed in claim 2, which is characterized in that described
Carbon nano-composite material the preparation method is as follows: by polypropylene tetramer benzene sulfonic acid sodium salt, deionized water and toluene form lotion magneton
60min is stirred, then carboxylated graphene dispersion ultrasonic disperse 30min in the above lotion, which is uniformly mixed, is placed in ice bath,
It is separately added into 5g thiophene later and copper chloride continues magneton stirring 12h, mixture is used into acetone, methanol respectively after the reaction was completed
It is filtered altogether three times with deionized water washing, the product for then obtaining yield is placed in 12h in 60 DEG C of vacuum drying ovens and obtains polythiophene
The carbon nanotube of coated copper Nanoparticle Modified.
4. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
Carbon nano-composite material gathers the preparation method is as follows: nitrine will be made in n,N-dimethylacetamide that polyacrylic acid is dissolved in first
Acrylic acid solution, polymerization degree n=20；It disperses the graphene oxide with carboxyl in the nitrine polyacrylic acid solution, and surpasses
Sound disperses 30min, and 60min is then mixed at room temperature and is placed in 200 DEG C of oil baths, magnetic agitation reacts 2h, and product is cold
But it to room temperature, filters, three times, finally place the product in dryings in 60 DEG C of vacuum drying ovens for 24 hours for washing.
5. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
The melt flow rate (MFR) of polyolefin and/or polylactic acid under the conditions of 230 DEG C, 2.16kg is 1~100g/10min.
6. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
Expanding material is maleic anhydride stem grafting polyolefin, and the maleic anhydride grafting ratio is 0.2~5%.
7. a kind of anti-static polyolefin composite material that can be used for 3D printing as claimed in claim 6, which is characterized in that described
Maleic anhydride stem grafting polyolefin includes following components and weight fraction:
100 parts of polyolefin；
2~5 parts of maleic anhydride；
1~2 part of cumyl peroxide.
8. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
Heat stabilizer be selected from phenols, amine, phosphorous acid esters, half Hinered phenols, acryloyl group functional group and monothioester compound and
At least one of calixarenes.
9. a kind of anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, which is characterized in that described
Processing aid is selected from least one of low molecule esters, metal soap, the compound esters of stearic acid and amides.
10. a kind of preparation method for the anti-static polyolefin composite material that can be used for 3D printing as described in claim 1, special
Sign is, comprising the following steps:
(1) prepare raw material by following components and weight fraction:
(2) antistatic agent and expanding material are first mixed, obtains the mixture of antistatic agent and expanding material, then will resisted again quiet
The mixture of electric agent and expanding material, polyolefin, polylactic acid, heat stabilizer, processing aid successively put into mixing machine and are uniformly mixed,
Incorporation time 3~5 minutes, 400~600 revs/min of speed, 15~30 DEG C of temperature, it is spare to obtain pre-composition；
It (3) is double screw extruder temperature of each section setting in the double screw extruder of 40~45:1 by pre-composition investment draw ratio
It is 190~240 DEG C, melting mixing dispersion and extruding pelletization.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811516666.7A CN109575440A (en) | 2018-12-12 | 2018-12-12 | A kind of anti-static polyolefin composite material and preparation method can be used for 3D printing |
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| CN201811516666.7A CN109575440A (en) | 2018-12-12 | 2018-12-12 | A kind of anti-static polyolefin composite material and preparation method can be used for 3D printing |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429752A (en) * | 2021-06-29 | 2021-09-24 | 邦凯控股集团有限公司 | High-temperature-resistant film and preparation method thereof |
| CN113583349A (en) * | 2021-05-18 | 2021-11-02 | 会通新材料股份有限公司 | Environment-friendly polypropylene composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061648A (en) * | 2015-07-17 | 2015-11-18 | 北京化工大学 | Preparation method of polystyrene ultrafine powder by use of acryloyl chloride-phenethylene copolymer azide modified carbon nano tube as antistatic agent |
| CN105482394A (en) * | 2015-12-24 | 2016-04-13 | 江苏道勤新材料科技有限公司 | High-conductivity 3D printing consumable capable of being degraded and preparation method thereof |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
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2018
- 2018-12-12 CN CN201811516666.7A patent/CN109575440A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061648A (en) * | 2015-07-17 | 2015-11-18 | 北京化工大学 | Preparation method of polystyrene ultrafine powder by use of acryloyl chloride-phenethylene copolymer azide modified carbon nano tube as antistatic agent |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
| CN105482394A (en) * | 2015-12-24 | 2016-04-13 | 江苏道勤新材料科技有限公司 | High-conductivity 3D printing consumable capable of being degraded and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583349A (en) * | 2021-05-18 | 2021-11-02 | 会通新材料股份有限公司 | Environment-friendly polypropylene composite material and preparation method and application thereof |
| CN113429752A (en) * | 2021-06-29 | 2021-09-24 | 邦凯控股集团有限公司 | High-temperature-resistant film and preparation method thereof |
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