CN106479166B - Antistatic low VOC polyamide 6 composite material of one kind and preparation method thereof - Google Patents
Antistatic low VOC polyamide 6 composite material of one kind and preparation method thereof Download PDFInfo
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 68
- -1 polypropylene Polymers 0.000 claims abstract description 66
- 239000004743 Polypropylene Substances 0.000 claims abstract description 64
- 229920001155 polypropylene Polymers 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 239000010445 mica Substances 0.000 claims abstract description 24
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- XRRONFCBYFZWTM-UHFFFAOYSA-N octadecanoic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCC(O)=O XRRONFCBYFZWTM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to a kind of antistatic low VOC polyamide 6 composite materials, are made of the components of following parts: PA6 is 60 parts -80 parts;Adsorbing master batch is 1 part -5 parts;Antioxidant is 0.1 part -0.5 part;Lubricant is 0.4 part -0.8 part;Dilute treated graphite oxide is 16 parts -24 parts;The absorption master batch includes polypropylene and mica.For the technical program using the oxygen-containing functional group on the surface of graphene oxide, in the suitable long chain alkane of surface grafting by way of chemical bonding, long chain alkane can effectively stop the reunion of graphene, and graphene can be better dispersed in PA6 composite material;The addition of absorption master batch can be effectively removed the various volatile small molecules generated in process and organic compound, reduce VOC numerical value.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of antistatic low VOC polyamide 6 composite material and
Preparation method.
Background technique
Polyamide 6 (PA6) is a kind of important thermoplastic polymer, and good stability of the dimension, insulating properties is good, oil resistant, extensively
Applied to fields such as household electrical appliance, mechanical fitting, office appliance and Communication Equipments.As the improvement of people's living standards, to making
Material has increasingly higher demands, in some special fields, such as automotive material, to the antistatic property of PA6
There is a degree of requirement with VOC (volatile organic compounds) performance.
PA6 composite material VOC performance difference is following aspect: firstly, PA6 raw material are in the synthesis process, there are more small
Molecular impurity, this will lead to increasing for VOC numerical value;Secondly, PA6 composite material is in process, various phases are often added
Hold agent, these compatilizers are often converted into small-molecule substance when heating to some extent, lead to increasing for VOC numerical value.
Summary of the invention
The object of the present invention is to provide a kind of antistatic low VOC polyamide 6 composite materials and preparation method thereof, existing to solve
The problem of the VOC high of the PA6 composite material of technology.
The present invention is achieved by the following technical solutions:
A kind of antistatic low VOC polyamide 6 composite material, is made of the components of following parts:
The absorption master batch includes polypropylene and mica.
The mass ratio of the polypropylene and mica is 40-60:6-10.
The antioxidant is three (2,4- di-t-butyl) phenyl-phosphites, four [β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid] one of pentaerythritol ester or 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene or more
Kind.
The lubricant is the combination of one or both of calcium stearate or stearic acid sodium.
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 40-60:6-10;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
The mass ratio of the normal heptane and polypropylene pre-expanded particles is 50-90:60-80.
Treated the dilute preparation method of graphite oxide, comprising the following steps:
1) dilute water-soluble of graphite oxide is formed to the dilute middle addition deionized water of graphite oxide, after ultrasonic reaction 20-30 minutes
Liquid;
2) cetylamine and dehydrated alcohol are weighed, is added in the dilute aqueous solution of graphite oxide, in 100-120 DEG C of oil bath pan
Under environment, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hours up to after handling
Graphite oxide it is dilute;
The graphene oxide and the mass ratio of the deionized water are 60-80:20-30;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 10-30:5-11:70-
90。
The preparation method of the antistatic low VOC polyamide 6 composite material of any of the above-described, comprising the following steps:
1) weigh parts by weight be 60 parts -80 parts of PA6,1 part -5 parts of absorption master batch, 0.1 part -0.5 part of antioxidant and
0.4 part -0.8 part of lubricant, 16 parts -24 parts treated that graphene oxide is mixed and stirred for uniformly, obtaining mixture;
2) by mixture extruding pelletization obtained in step 1) to get arrive PA6 composite material.
Above-mentioned steps 1) in each raw material before mixing respectively dry 5 hours at 100 DEG C.
The step 2) specifically:
Mixture obtained in step 1) is put into extruding pelletization in the hopper of double screw extruder, wherein described double
Screw extruder includes six humidity provinces sequentially arranged, and the temperature of the first humidity province is 180 DEG C~220 DEG C, second temperature area
Temperature be 250 DEG C~290 DEG C, the temperature of third humidity province is 250 DEG C~290 DEG C, the temperature of the 4th humidity province is 250 DEG C~
290 DEG C, the temperature of the 5th humidity province is 250 DEG C~290 DEG C, and the temperature of the 6th humidity province is 250 DEG C~290 DEG C, double spiral shells
The head temperature of bar extruder is 250 DEG C~290 DEG C, and screw speed is 120r/min~300r/min.
The beneficial effects of the present invention are:
The technical program is connect by way of chemical bonding on surface using the oxygen-containing functional group on the surface of graphene oxide
Branch suitable long chain alkane, long chain alkane can effectively stop the reunion of graphene, and graphene can be better dispersed in
In PA6 composite material.
The addition of graphene can promote the antistatic property in PA6 composite material, and the surface resistivity of material can reach
108。
The addition of absorption master batch can be effectively removed the various volatile small molecules generated in process and organise
Object is closed, VOC numerical value is reduced.
Specific embodiment
Carry out the technical solution that the present invention will be described in detail by the following examples, embodiment below is merely exemplary, only
It can be used to explanation and illustration technical solution of the present invention, and be not to be construed as the limitation to technical solution of the present invention.
Raw material used in present embodiments and supplier are as follows:
PA6 (model B3EG6), German BASF;PP (model Z30S), Daqing Refinery;Antioxidant (model
Irganox1010, Irganox168, Irganox1330), Switzerland's Ciba;Calcium stearate expects chemical industry in Hubei;Stearic acid
Sodium, the emerging milky way chemical industry in Hubei;Graphene oxide, Changsha Ross science and technology;Mica (2500 mesh), the sharp mining industry of Chuzhou lattice.
Test equipment used in the present invention is as follows:
ZSK30 type double screw extruder, German W&P company;JL-1000 type tensile testing machine, the wide just experiment instrument in Guangzhou
The production of device company;HTL900-T-5B type injection (mo(u)lding) machine, the production of Hai Tai plastics machinery Co., Ltd;XCJ-500 type shock-testing
Machine, the production of Chengde testing machine factory;QT-1196 type tester for elongation, Dongguan City Gao Tai detecting instrument Co., Ltd;QD-GJS-
B12K type high-speed mixer, Beijing perseverance Order instrument and meter Co., Ltd.
Adsorb the preparation of master batch:
Preparation example 1
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 40:6;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 50:60;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 2
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 40:10;
2) using normal heptane as foaming agent, the polypropylene pre-expanded particles that step 1) obtains are foamed, foaming poly- third is made
Alkene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 50:80;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 3
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 40:8;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 50:70;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 4
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 60:6;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 90:60;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 5
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 60:10;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 90:80;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 6
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 60:8;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 90:70;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 7
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 50:6;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 70:60;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
Preparation example 8
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;
The mass ratio of the polypropylene and mica is 50:10;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, it is poly- that foaming is made
Propylene;The mass ratio of the normal heptane and polypropylene pre-expanded particles is 60:80;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch.
The dilute preparation of graphite oxide after processing:
Preparation example 9
Treated the dilute preparation method of graphite oxide, comprising the following steps:
1) dilute water-soluble of graphite oxide is formed to the dilute middle addition deionized water of graphite oxide, after ultrasonic reaction 20-30 minutes
Liquid;
2) cetylamine and dehydrated alcohol are weighed, is added in the dilute aqueous solution of graphite oxide, in 100-120 DEG C of oil bath pan
Under environment, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hours up to after handling
Graphite oxide it is dilute;
The graphene oxide and the mass ratio of the deionized water are 60:20;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 10:5:70.
Preparation example 10
Treated the dilute preparation method of graphite oxide, comprising the following steps:
1) dilute water-soluble of graphite oxide is formed to the dilute middle addition deionized water of graphite oxide, after ultrasonic reaction 20-30 minutes
Liquid;
2) cetylamine and dehydrated alcohol are weighed, is added in the dilute aqueous solution of graphite oxide, in 100-120 DEG C of oil bath pan
Under environment, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hours up to after handling
Graphite oxide it is dilute;
The graphene oxide and the mass ratio of the deionized water are 80:30;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 30:11:90.
Preparation example 11
Treated the dilute preparation method of graphite oxide, comprising the following steps:
1) dilute water-soluble of graphite oxide is formed to the dilute middle addition deionized water of graphite oxide, after ultrasonic reaction 20-30 minutes
Liquid;
2) cetylamine and dehydrated alcohol are weighed, is added in the dilute aqueous solution of graphite oxide, in 100-120 DEG C of oil bath pan
Under environment, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hours up to after handling
Graphite oxide it is dilute;
The graphene oxide and the mass ratio of the deionized water are 70:25;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 20:8:80.
Preparation example 12
Treated the dilute preparation method of graphite oxide, comprising the following steps:
1) dilute water-soluble of graphite oxide is formed to the dilute middle addition deionized water of graphite oxide, after ultrasonic reaction 20-30 minutes
Liquid;
2) cetylamine and dehydrated alcohol are weighed, is added in the dilute aqueous solution of graphite oxide, in 100-120 DEG C of oil bath pan
Under environment, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hours up to after handling
Graphite oxide it is dilute;
The graphene oxide and the mass ratio of the deionized water are 75:28;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 22:9:75.
Embodiment 1
1) weigh parts by weight be 60 parts of PA6,1 part of preparation example 1 into preparation example 8 made from any preparation example absorption master batch,
16 parts of preparation examples 9 treated graphene oxide made from any preparation example, 0.1 part of Irganox1330 into preparation example 12
It is mixed and stirred for uniformly, obtaining mixture with 0.4 part of stearic acid sodium;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material P1, wherein the temperature of the first humidity province of double screw extruder is 180 DEG C, and the temperature in second temperature area is 250
DEG C, the temperature of third humidity province is 250 DEG C, and the temperature of the 4th humidity province is 250 DEG C, and the temperature of the 5th humidity province is 250 DEG C, the
The temperature of six humidity provinces is 250 DEG C, and the head temperature of the double screw extruder is 250 DEG C, screw speed 120r/min.
Embodiment 2
1) weigh parts by weight be 80 parts of PA6,5 parts of preparation examples 1 into preparation example 8 made from any preparation example absorption master batch,
24 parts of preparation examples 9 into preparation example 12 treated graphene oxide made from any preparation example, 0.2 part of Irganox1330,
0.1 part of Irganox1010,0.2 part of Irganox168 and 0.8 part of calcium stearate are mixed and stirred for uniformly, obtaining mixture;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material P2, wherein the temperature of the first humidity province of double screw extruder is 220 DEG C, and the temperature in second temperature area is 290
DEG C, the temperature of third humidity province is 290 DEG C, and the temperature of the 4th humidity province is 290 DEG C, and the temperature of the 5th humidity province is 290 DEG C, the
The temperature of six humidity provinces is 290 DEG C, and the head temperature of the double screw extruder is 290 DEG C, screw speed 300r/min.
Embodiment 3
1) weigh parts by weight be 70 parts of PA6,3 parts of preparation examples 1 into preparation example 8 made from any preparation example absorption master batch,
20 parts of preparation examples 9 into preparation example 12 treated graphene oxide made from any preparation example, 0.2 part of Irganox1330,
0.1 part of Irganox168,0.3 part of calcium stearate and 0.3 part of stearic acid sodium are mixed and stirred for uniformly, obtaining mixture;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material P3, wherein the temperature of the first humidity province of double screw extruder is 200 DEG C, and the temperature in second temperature area is 270
DEG C, the temperature of third humidity province is 270 DEG C, and the temperature of the 4th humidity province is 270 DEG C, and the temperature of the 5th humidity province is 270 DEG C, the
The temperature of six humidity provinces is 270 DEG C, and the head temperature of the double screw extruder is 270 DEG C, screw speed 210r/min.
Embodiment 4
1) weigh parts by weight be 75 parts of PA6,4 parts of preparation examples 1 into preparation example 8 made from any preparation example absorption master batch,
23 parts of preparation examples 9 into preparation example 12 treated graphene oxide made from any preparation example, 0.2 part of Irganox1010,
0.1 part of Irganox168,0.5 part of stearic acid sodium are mixed and stirred for uniformly, obtaining mixture;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material P4, wherein the temperature of the first humidity province of double screw extruder is 210 DEG C, and the temperature in second temperature area is 280
DEG C, the temperature of third humidity province is 280 DEG C, and the temperature of the 4th humidity province is 280 DEG C, and the temperature of the 5th humidity province is 280 DEG C, the
The temperature of six humidity provinces is 280 DEG C, and the head temperature of the double screw extruder is 280 DEG C, screw speed 240r/min.
Embodiment 5
1) weigh parts by weight be 75 parts of PA6,3 parts of preparation examples 1 into preparation example 8 made from any preparation example absorption master batch,
19 parts of preparation examples 9 into preparation example 12 treated graphene oxide made from any preparation example, 0.2 part of Irganox1010,
0.1 calcium stearate and 0.5 part of stearic acid sodium are mixed and stirred for uniformly, obtaining mixture;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material P5, wherein the temperature of the first humidity province of double screw extruder is 200 DEG C, and the temperature in second temperature area is 285
DEG C, the temperature of third humidity province is 285 DEG C, and the temperature of the 4th humidity province is 285 DEG C, and the temperature of the 5th humidity province is 285 DEG C, the
The temperature of six humidity provinces is 285 DEG C, and the head temperature of the double screw extruder is 285 DEG C, screw speed 250r/min.
Comparative example 1
1) parts by weight are weighed as 75 parts of PA6,0.2 part of Irganox1010,0.1 calcium stearate and 0.5 part of stearic acid sodium mixing
And stir evenly, obtain mixture;
2) mixture obtained in step 1) is put into the hopper of double screw extruder extruding pelletization to get to PA6
Composite material D1, wherein the temperature of the first humidity province of double screw extruder is 190 DEG C, and the temperature in second temperature area is 280
DEG C, the temperature of third humidity province is 280 DEG C, and the temperature of the 4th humidity province is 280 DEG C, and the temperature of the 5th humidity province is 280 DEG C, the
The temperature of six humidity provinces is 280 DEG C, and the head temperature of the double screw extruder is 280 DEG C, screw speed 250r/min.
Batten test is made with injection molding machine in PA6 composite material prepared by above-described embodiment 1-5 and comparative example 1, tests number
According to being as follows:
It can be seen that PA6 composite material produced by the present invention is compared compared with PA6 in comparative example, is not only resisted quiet by the comparison of upper table
Electrical property is greatly improved, and VOC performance has also obtained largely improving, this greatly expands PA6 composite wood
The application field of material has very real meaning.
The above is only the descriptions of the preferred embodiment of the present invention, it is noted that due to the finiteness of literal expression, and
Objectively there is unlimited specific structure, for those skilled in the art, is not departing from the principle of the invention
Under the premise of, several improvements and modifications can also be made, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (7)
1. a kind of antistatic low VOC polyamide 6 composite material, which is characterized in that be made of the components of following parts:
60 parts -80 parts of PA6;
1 part -5 parts of master batch of absorption;
0.1 part -0.5 part of antioxidant;
0.4 part -0.8 part of lubricant;
Treated 16 parts -24 parts of graphene oxide;
The preparation method of the absorption master batch, comprising the following steps:
1) polypropylene and mica are adequately mixed according to the ratio, polypropylene pre-expanded particles is squeezed out in extruder;It is described
The mass ratio of polypropylene and mica is 40-60:6-10;
2) using normal heptane as foaming agent, polypropylene pre-expanded particles made from step 1) are foamed, expanded polypropylene is made;
3) expanded polypropylene and water are mixed 5-10 minutes in super mixer, is prepared into absorption master batch;
The preparation method of treated the graphene oxide, comprising the following steps:
1) deionized water is added into graphene oxide, forms the aqueous solution of graphene oxide after ultrasonic reaction 20-30 minutes;
2) cetylamine and dehydrated alcohol are weighed, is added in the aqueous solution of graphene oxide, in 100-120 DEG C of oil bath pan environment
Under, back flow reaction 20-24 hours;
3) product in step 2) is filtered, is placed in 60-80 DEG C of vacuum tank dry 20-24 hour up to the oxygen that arrives that treated
Graphite alkene;
The graphene oxide and the mass ratio of the deionized water are 60-80:20-30;
The mass ratio of the cetylamine, the dehydrated alcohol and the graphene oxide water solution is 10-30:5-11:70-90.
2. antistatic low VOC polyamide 6 composite material according to claim 1, which is characterized in that the antioxidant is three
(2,4- di-t-butyl) phenyl-phosphite, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters or 1,3,
One of 5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene is a variety of.
3. antistatic low VOC polyamide 6 composite material according to claim 1, which is characterized in that the lubricant is hard
The combination of one or both of resin acid calcium or odium stearate.
4. antistatic low VOC polyamide 6 composite material according to claim 1, which is characterized in that the normal heptane and poly-
The mass ratio of propylene pre-expanded particles is 50-90:60-80.
5. the preparation method of the antistatic low VOC polyamide 6 composite material of any one of the claims 1 to 4, feature exist
In, comprising the following steps:
1) weighing parts by weight is 60 parts -80 parts of PA6,1 part -5 parts of absorption master batch, 0.1 part -0.5 part of antioxidant and 0.4
Part -0.8 part of lubricant, 16 parts -24 parts treated that graphene oxide is mixed and stirred for uniformly, obtaining mixture;
2) by mixture extruding pelletization obtained in step 1) to get arrive PA6 composite material.
6. the preparation method of antistatic low VOC polyamide 6 composite material according to claim 5, which is characterized in that above-mentioned
Each raw material in step 1) is 5 hours dry at 100 DEG C respectively before mixing.
7. the preparation method of antistatic low VOC polyamide 6 composite material according to claim 5, which is characterized in that described
Step 2) specifically:
Mixture obtained in step 1) is put into extruding pelletization in the hopper of double screw extruder, wherein the twin-screw
Extruder includes six humidity provinces sequentially arranged, and the temperature of the first humidity province is 180 DEG C~220 DEG C, the temperature in second temperature area
Degree is 250 DEG C~290 DEG C, and the temperature of third humidity province is 250 DEG C~290 DEG C, and the temperature of the 4th humidity province is 250 DEG C~290
DEG C, the temperature of the 5th humidity province is 250 DEG C~290 DEG C, and the temperature of the 6th humidity province is 250 DEG C~290 DEG C, and the twin-screw squeezes
The head temperature of machine is 250 DEG C~290 DEG C out, and screw speed is 120r/min~300r/min.
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CN107723830B (en) * | 2017-11-03 | 2020-07-07 | 中科纺织研究院(青岛)有限公司 | Preparation method and application of high-strength graphene oxide grafted polyamide fiber |
CN107987400A (en) * | 2017-12-15 | 2018-05-04 | 会通新材料股份有限公司 | A kind of graphene modified polypropene micro foaming composite material and preparation method thereof |
CN109021483A (en) * | 2018-06-20 | 2018-12-18 | 安徽江淮汽车集团股份有限公司 | A kind of AES-PET composite material and preparation method of low VOC |
CN108795031B (en) * | 2018-08-28 | 2020-12-01 | 安徽江淮汽车集团股份有限公司 | High-performance PA6 composite material and preparation method thereof |
CN109679331A (en) * | 2018-11-12 | 2019-04-26 | 任素飞 | A kind of 6 composite material of static resistant polyamide |
CN110117393A (en) * | 2019-04-26 | 2019-08-13 | 集美大学 | A kind of graphene Masterbatch material and preparation method thereof with antistatic property |
CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102675883A (en) * | 2012-05-10 | 2012-09-19 | 北京科技大学 | Surface modified graphene polymer-based piezoresistive composite material and preparation method thereof |
CN103013105A (en) * | 2012-12-28 | 2013-04-03 | 常州大学 | Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof |
CN103724799A (en) * | 2013-12-09 | 2014-04-16 | 天津金发新材料有限公司 | Polypropylene combination with low smell and diffusion and preparation method thereof |
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CN102675883A (en) * | 2012-05-10 | 2012-09-19 | 北京科技大学 | Surface modified graphene polymer-based piezoresistive composite material and preparation method thereof |
CN103013105A (en) * | 2012-12-28 | 2013-04-03 | 常州大学 | Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof |
CN103724799A (en) * | 2013-12-09 | 2014-04-16 | 天津金发新材料有限公司 | Polypropylene combination with low smell and diffusion and preparation method thereof |
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