CN106554557A - Anti-static polyolefin compositionss and preparation method thereof - Google Patents
Anti-static polyolefin compositionss and preparation method thereof Download PDFInfo
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- CN106554557A CN106554557A CN201510641929.7A CN201510641929A CN106554557A CN 106554557 A CN106554557 A CN 106554557A CN 201510641929 A CN201510641929 A CN 201510641929A CN 106554557 A CN106554557 A CN 106554557A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- 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
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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
- 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
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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
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of polyolefin composition, and in particular to a kind of anti-static polyolefin compositionss and preparation method thereof.It is prepared from the following raw materials in parts by weight：Polyethylene A 10-70 parts, polyethylene B5-20 parts, antistatic additive 5-20 parts, conducting masterbatch 20-50 parts；Wherein：The comonomer of polyethylene A is 1- hexenes and ethylene, and the comonomer of polyethylene B is propylene or one kind and ethylene in butylene.The present composition has good surface resistivity, notch impact strength, processing characteristics, and the product obtained using polyethylene composition Jing blowings also has preferable surface resistivity.The present invention also provides its preparation method, rational technology.
Description
Technical field
The present invention relates to a kind of polyolefin composition, and in particular to a kind of anti-static polyolefin compositionss and preparation method thereof.
Background technology
Polyethylene has excellent mechanical property, chemical stability, electrical insulating property, processing characteristics and high sexual valence due to which
Than, range of application is extremely wide, but due to the excellent insulating properties of polyethylene, so after because being charged by friction, be difficult to eliminate, so as to
Electrostatic is produced, dust suction, electric shock can be caused, or even produce spark that blast occurs.In order to avoid such accident, mould in some occasions
The use of material products must make antistatic treatment.
Traditional polyethylene is antistatic modified will often to add more conductive filler, and blowing processing has inflation drawing to raw material
The effect stretched, declines can the antistatic effect of material, and now the addition of conductive filler also needs further to increase, although also can
Playing improves the anlistatig purpose of polyethylene, but the mechanical property of matrix material, processing characteristics can be had a negative impact.
Patent " CN20130655948 " discloses a kind of processing method of ultrahigh molecular weight polyethylene tubing, and the patent is in superelevation point
In sub- weight northylen add 2～4% carbon blacks, 1～1.5% antistatic additive, 1～2% graphite, 1～2% ethylene glycol Cortex cocois radiciss, 1～2%
Smoothing preparation, mainly for the improvement that the processing characteristics of ultra-high molecular weight polyethylene is made, the antistatic effect that material can reach has
Limit.
Patent " CN 200610040792 " discloses a kind of anti-static flame-retarding polyethylene composition and preparation method thereof, its conductive carbon black
Content up to 10～19%, and conductive carbon black content is higher, and on material mechanical performance, processing characteristics affects will be bigger.
Document " research of the Anti-static PP " resin based on PP, is prepared for three kinds of antistatic additive masterbatch, but its surface resistivity
It is minimum only to reduce by 4 orders of magnitude (to 1 × 1012Ω), antistatic effect is limited.
The content of the invention
It is an object of the invention to provide a kind of easy-formation heat-proof polythene compositionss, with good pressure performance, pliability and compared with
High crystallization temperature and crystalline rate, the present invention also provide its preparation method.
Anti-static polyolefin compositionss of the present invention, are prepared from the following raw materials in parts by weight：
Wherein：The comonomer of polyethylene A is 1- hexenes and ethylene, and the comonomer of polyethylene B is in propylene or butylene
Plant and ethylene.
Polyethylene A is：Melt mass flow rate is 8～12g/10min, and density is 0.945-0.955g/cm3, Mw molecular weight
(weight average molecular weight) is in 25-45 ten thousand.
Polyethylene B is：Melt mass flow rate is 1.7-2.5g/10min, and density is 0.950-0.955g/cm3, Mw molecules
In 40-60 ten thousand, comonomer is propylene or butylene to amount.
The comonomer of polyethylene A is 1- hexenes and ethylene, and 1- hexenes are 0.01-0.03 with the mol ratio of ethylene：1.
When the comonomer of polyethylene B is propylene and ethylene, propylene is 0.01-0.05 with the mol ratio of ethylene：1, when poly- second
When the comonomer of alkene B is butylene and ethylene, butylene is 0.003-0.005 with the mol ratio of ethylene：1.
Antistatic additive of the present invention is Polymer Antistatic Agent, and preferably Polyethylene oxide, Polyethylene Glycol/methacrylic acid be common
Polymers, Polyethylene Glycol/polyamide copolymer, Polyethylene Glycol/polyester-amide copolymer, ethylene oxide/propylene oxide copolymer contain
The Polymers of quaternary ammonium salt group.
Conducting masterbatch is 70 by polyethylene A, conductive carbon black, dispersant, coupling agent in mass ratio：20：5：5 compositions.
Conductive carbon black is：Specific volume is regarded as 3.5～5.0cm3/ g, iodine absorption value are 500～700g/kg, and ash is less than 2.0%.
Dispersant is low-molecular weight polymer, preferably Tissuemat E or liquid paraffin.
Coupling agent is silane coupler.
The preparation method of anti-static polyolefin compositionss of the present invention, comprises the following steps：
(1) by conductive carbon black and dispersant, coupling agent in stirrer for mixing 3-10 minute, blender rotating speed 1500-2000
Rev/min, add polyethylene A mixing 3-5 minutes, 500-1000 rev/min of blender rotating speed；
(2) material of the mix homogeneously for obtaining step (1) is added in banbury carries out banburying 10-30 minutes, then adopts
Carried out extruding with single screw extrusion machine, pelletize, masterbatch is obtained, banburying, the maximum temperature of extruding pelletization are 200 DEG C；
(3) polyethylene A, polyethylene B and antistatic additive blending pelletize are subsequently adding, product is obtained.
The present invention compared with prior art, has the advantages that：
(1) compositionss of the present invention impart material more preferable while guaranteeing that material has good antistatic property
Impact property and processability, the blow-molded article surface for being produced are smooth, and antistatic property is splendid.
(2) present invention makes group using antistatic additive is with conductive carbon black compounding use and preferably polyethylene base resin forms compositionss
Compound has good surface resistivity, notch impact strength, processing characteristics, and is obtained using polyethylene composition Jing blowings
Product also have preferable surface resistivity.
Specific embodiment
With reference to embodiment, the present invention will be further described.
1st, raw material used in embodiment and comparative example is as follows：
Polyethylene A-1：Melt mass flow rate (21.6Kg) is 10g/10min, and density is 0.950g/cm3, Mw molecules
350,000, comonomer is 1- hexenes to amount, and 1- hexenes are 0.015 with the mol ratio of ethylene；
Polyethylene A-2：Melt mass flow rate (21.6Kg) is 12g/10min, and density is 0.952g/cm3, Mw molecules
310,000, comonomer is 1- hexenes to amount, and 1- hexenes are 0.013 with the mol ratio of ethylene；
Polyethylene A-3：Melt mass flow rate (21.6Kg) is 8g/10min, and density is 0.949g/cm3, Mw molecular weight
400,000, comonomer is 1- hexenes, and 1- hexenes are 0.016 with the mol ratio of ethylene；
Polyethylene B-1：Melt mass flow rate (21.6Kg) is 2.1g/10min, and density is 0.951g/cm3, Mw molecules
510,000, comonomer is butylene and ethylene to amount, and butylene is 0.004 with the mol ratio of ethylene；
Polyethylene B-2：Melt mass flow rate (21.6Kg) is 1.7g/10min, and density is 0.952g/cm3, Mw molecules
530,000, comonomer is propylene and ethylene to amount, and propylene is 0.035 with the mol ratio of ethylene；
Antistatic additive 1：Polyethylene Glycol/polyamide copolymer, it is commercially available；
Antistatic additive 2：Polyethylene oxide, it is commercially available；
Conducting masterbatch 1：Pressed by polyethylene A-1, conductive carbon black, polyethylene of dispersing agent wax and coupling agent Silane coupling agent KH550
Mass ratio is 70：20：5：5 compositions；Wherein：Conductive carbon black：Depending on specific volume 4.5cm3/ g, iodine absorption value 657g/kg, ash 1.0%；
Conducting masterbatch 2：Pressed by polyethylene A-2, conductive carbon black, dispersant liq paraffin and coupling agent Silane coupling agent KH550
Mass ratio is 70：20：5：5 compositions；Wherein：Conductive carbon black：Depending on specific volume 3.5cm3/ g, iodine absorption value 550g/kg, ash 1.0%；
Graphite：It is commercially available；
Ethylene glycol coconut monoethanolamide：It is commercially available.
2nd, embodiment and the test method used in comparative example：
The test condition of compression moulding of the table 1 used in embodiment and comparative example.
The test condition of the compression moulding used in 1 embodiment of table and comparative example
The test condition of blowing is as follows：
25L buckets, bucket weight 1.7kg, 220 DEG C of blow temperatures, molding cycle 90 seconds are blown using blow moulding machine.
Melt mass flow rate：Tested by GB/T 3682, condition be 180 DEG C of temperature, load 21.6kg.
Simply supported beam notch impact strength：Tested according to GB/T 1043,23 DEG C of test temperature.
Stretching yield stress：Test by the regulations of GB/T 1040, draw speed 50mm/min.
Surface resistivity：Test according to the regulations of GB/T 1414.
Embodiment 1-18
A kind of anti-static polyolefin compositionss, its preparation method are comprised the following steps：
(1) by conductive carbon black and dispersant, coupling agent in stirrer for mixing 5 minutes, 1500 revs/min of blender rotating speed, then
Polyethylene A is added to mix 4 minutes, 800 revs/min of blender rotating speed；
(2) material of the mix homogeneously for obtaining step (1) is added in banbury carries out banburying 20 minutes, then using list
Screw extruder carries out extruding, pelletize, and masterbatch is obtained, and banburying, the maximum temperature of extruding pelletization are 200 DEG C.
(3) polyethylene A, polyethylene B and antistatic additive blending pelletize are subsequently adding, product is obtained.
Embodiment 1-18 adopts above-mentioned preparation method, the concrete component of embodiment 1-18 to be shown in Table 2-4, and embodiment 1-18 is prepared into
To the performance test results of product be shown in Table 2-4.
The performance test results of 2 embodiment 1-6 constituent content of table and products thereof
The performance test results of 3 embodiment 7-12 constituent content of table and products thereof
The performance test results of 4 embodiment 13-18 constituent content of table and products thereof
Note：It is blank in table to represent without addition.
Preparation method used by comparative example 1-10 is identical with embodiment 1-18, and concrete component is shown in Table 5-6, and comparative example 1-10 is prepared into
To the performance test results of product be shown in Table 5-6.
The performance test results of 5 comparative example 1-5 constituent content of table and products thereof
Note：It is blank in table to represent without addition.
The performance test results of 6 comparative example 6-10 constituent content of table and products thereof
Note：It is blank in table to represent without addition.
Claims (10)
1. a kind of anti-static polyolefin compositionss, it is characterised in that：It is prepared from the following raw materials in parts by weight：
Wherein：The comonomer of polyethylene A is 1- hexenes and ethylene, and the comonomer of polyethylene B is in propylene or butylene
Plant and ethylene.
2. anti-static polyolefin compositionss according to claim 1, it is characterised in that：Polyethylene A is：Melt quality
Flow rate is 8～12g/10min, and density is 0.945-0.955g/cm3, Mw molecular weight is in 25-45 ten thousand.
3. anti-static polyolefin compositionss according to claim 1, it is characterised in that：Polyethylene B is：Melt quality
Flow rate is 1.7-2.5g/10min, and density is 0.950-0.955g/cm3, Mw molecular weight is in 40-60 ten thousand.
4. anti-static polyolefin compositionss according to claim 1, it is characterised in that：The comonomer of polyethylene A is
1- hexenes and ethylene, 1- hexenes are 0.01-0.03 with the mol ratio of ethylene：1.
5. anti-static polyolefin compositionss according to claim 1, it is characterised in that：When the comonomer of polyethylene B
During for propylene with ethylene, propylene is 0.01-0.05 with the mol ratio of ethylene：1, when the comonomer of polyethylene B is butylene and second
During alkene, butylene is 0.003-0.005 with the mol ratio of ethylene：1.
6. anti-static polyolefin compositionss according to claim 1, it is characterised in that：Antistatic additive is Polyethylene oxide, gathers
Ethylene glycol/methacrylic acid copolymer, Polyethylene Glycol/polyamide copolymer, Polyethylene Glycol/polyester-amide copolymer, oxirane
/ epoxy propane copolymer or the Polymers containing quaternary ammonium salt group.
7. anti-static polyolefin compositionss according to claim 1, it is characterised in that：Conducting masterbatch by polyethylene A, lead
Electrical carbon is black, dispersant, coupling agent are 70 in mass ratio：20：5：5 compositions.
8. anti-static polyolefin compositionss according to claim 7, it is characterised in that：Conductive carbon black is：Regard specific volume as
3.5～5.0cm3/ g, iodine absorption value are 500～700g/kg, and ash is less than 2.0%.
9. anti-static polyolefin compositionss according to claim 7, it is characterised in that：Dispersant is Tissuemat E or liquid
Paraffin；Coupling agent is silane coupler.
10. the preparation method of the arbitrary described anti-static polyolefin compositionss of a kind of claim 1-9, it is characterised in that：Including
Following steps：
(1) by conductive carbon black and dispersant, coupling agent in stirrer for mixing 3-10 minute, blender rotating speed 1500-2000
Rev/min, add polyethylene A mixing 3-5 minutes, 500-1000 rev/min of blender rotating speed；
(2) material of the mix homogeneously for obtaining step (1) is added in banbury carries out banburying 10-30 minutes, then adopts
Carried out extruding with single screw extrusion machine, pelletize, masterbatch is obtained, banburying, the maximum temperature of extruding pelletization are 200 DEG C；
(3) polyethylene A, polyethylene B and antistatic additive blending pelletize are subsequently adding, product is obtained.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724325A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Flame-retardant antistatic rotational molding polyolefin composition and preparation method thereof |
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| CN103709493A (en) * | 2013-12-25 | 2014-04-09 | 常州普莱克红梅色母料有限公司 | High-concentration anti-static master batch for polyolefin and preparation method thereof |
| CN104558747A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Quickly molded high density polyethylene composition and preparation method thereof |
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2015
- 2015-09-30 CN CN201510641929.7A patent/CN106554557B/en active Active
Patent Citations (4)
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| WO2009003627A1 (en) * | 2007-07-05 | 2009-01-08 | Basell Polyolefine Gmbh | Pe molding composition for blow-molding of small low-density blow moldings |
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| CN104558747A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Quickly molded high density polyethylene composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724325A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Flame-retardant antistatic rotational molding polyolefin composition and preparation method thereof |
| CN110724325B (en) * | 2018-07-16 | 2022-04-08 | 中国石油化工股份有限公司 | Flame-retardant antistatic rotational molding polyolefin composition and preparation method thereof |
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