CN103849056A - PE (polyethylene) flame retardant modified antistatic toughening masterbatch and preparation method thereof - Google Patents

PE (polyethylene) flame retardant modified antistatic toughening masterbatch and preparation method thereof Download PDF

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Publication number
CN103849056A
CN103849056A CN201210594672.0A CN201210594672A CN103849056A CN 103849056 A CN103849056 A CN 103849056A CN 201210594672 A CN201210594672 A CN 201210594672A CN 103849056 A CN103849056 A CN 103849056A
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flame
retardant modified
mother particle
modified antistatic
antistatic
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CN201210594672.0A
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Inventor
张明亮
王学成
夏伟光
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Qingdao Sanli Zhongdemei Water Equipment Co Ltd
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Qingdao Sanli Zhongdemei Water Equipment Co Ltd
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Priority to CN201210594672.0A priority Critical patent/CN103849056A/en
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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
    • C08L23/06—Polyethene
    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three 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)

Abstract

This invention discloses PE (polyethylene) flame retardant modified antistatic toughening masterbatch and a preparation method thereof. The PE flame retardant modified antistatic toughening masterbatch is composed of the following components in mass percentage: 10%-15% of a PE carrier, 25%-40% of a halogen-free flame retardant, 10%-30% of micron calcium carbonate, 10%-30% of a grafted elastomer, 5%-15% of an antistatic agent, 1%-3% of a lubricant dispersant, 0.5%-2% of a coupling agent, 0.5%-1.5% of an antioxidant, and 0.5%-1% of a stabilizer. The PE flame retardant modified antistatic toughening masterbatch has the characteristics of high concentration, multiple functionality, low cost, convenience in use and the like when applied to polyethylene. Moreover, the grafted elastomer can be used for obviously improving the toughness, the micron calcium carbonate can be used for greatly improving the toughness, rigidity and heat resistance and also keeping good impact strength, the halogen-free flame retardant has high flame-retardant properties of safety, smoke suppression, no-toxicity, and environmental friendliness, and the antistatic agent can be used for reducing the surface resistivity to a range of 10<8>-10<10> omega. cm while ensuring the antistatic property.

Description

Flame-retardant modified antistatic plasticizing mother particle of PE and preparation method thereof
Technical field
The present invention relates to a kind of technical field of polymer materials, specifically flame-retardant modified antistatic plasticizing mother particle of a kind of PE and preparation method thereof.
Background technology
Polyethylene (PE) be a kind of light weight nontoxic, there is good electrical insulation capability and the thermoplastics of resistance to chemical corrosion, its intensity is higher, winter hardiness is good, and forming process is convenient, is widely used in the industries such as building, communications and transportation, electric wire, chemical machinery.The shortcomings such as but PE plastics exist, and shock strength is poor, toughness is low, easy firing and static resistance deficiency, are all restricted in a lot of Application Areass.Therefore PE plastics conventionally need to be to being just employed after its modification, the common modification that comprises toughness reinforcing enhancing, the aspect such as fire-retardant, antistatic.Research in the past shows, elasticity physical efficiency is effectively toughness reinforcing, but causes intensity, rigidity to decline by a relatively large margin; Mineral filler can strengthen effectively, obviously declines but often impact toughness; After elastomerics, mineral filler are mixed with PE and additive, extrude, intensity and the toughness of granulation to material has good modified effect, elastomerics, both blend of mineral filler have become the important effective means of current toughness reinforcing enhancing to PE modification.But, in PE plastics, directly adding auxiliary agent (as fire retardant, static inhibitor etc.) carries out physically modified and but has a lot of unsatisfactory parts, and the auxiliary agent of existing technique great majority are powder, easily cause in process of production powder to fly upward and be unfavorable for cleaner production, also can cause complex production process, inefficiency etc. simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of high density, multi-functional, low cost and flame-retardant modified antistatic plasticizing mother particle of PE easy to use and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: the flame-retardant modified antistatic plasticizing mother particle of PE, its component by mass percent proportioning is: PE carrier 10%～15%, halogen-free flame retardants 25%～40%, micro-calcium carbonate 10%～30%, grafting elastomerics 10%～30%, static inhibitor 5%～15%, lubrication dispersing agent 1%～3%, coupling agent 0.5%～2%, oxidation inhibitor 0.5%～1.5%, stablizer 0.5%～1%.
Described PE carrier is polyvinyl resin.
Described halogen-free flame retardants is the one in phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant and organophosphorated salt fire retardant.
The median size of described micro-calcium carbonate is between 0.1 μ m～10 μ m.
Described grafting elastomerics is terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH), maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH), maleic anhydride graft styrene-butadiene-styrene (SBS-g-MAH), terpolymer EP rubber-glycidyl methacrylate graft thing (EPDM-g-GMA), styrene-butadiene-styrene-glycidyl methacrylate copolymer (SBS-g-GMA), one in ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA).
Described static inhibitor is the one in two (2-hydroxyethyl) octyl group methyl biconjugate ammonium tosylates, quaternary ammonium compound, alkylsulfonate, stearic acid monoglycerides (GMS), polyether ester, Nanometer-sized Antimony-doped stannic oxide (ATO).
Described lubrication dispersing agent is one or more the mixture in polysiloxane, polyethylene wax, Poly Propylene Wax, EVA wax, OP wax, ethylene bis stearic amide.
Described coupling agent is silane coupling agent or calcium stearate coupling agent.
Described oxidation inhibitor is the compound of hindered phenol antioxygen 1076 and phosphite antioxidant 168.
Described stablizer is one or more the compound in triacetonamine stablizer, benzotriazole stablizer, benzophenone stablizer, hindered amine stabilizer.
The preparation method of the above-mentioned flame-retardant modified antistatic plasticizing mother particle of PE, comprises the following steps:
(1) each component is weighed up stand-by by weight ratio;
(2) PE carrier and halogen-free flame retardants, micro-calcium carbonate, grafting elastomerics, static inhibitor, lubrication dispersing agent, coupling agent, oxidation inhibitor, stablizer are added in high-speed mixer, fully mix 3～15 minutes, discharging is stand-by;
(3) said mixture added to twin screw extruder is extruded, after granulation, drying, pack and obtain the flame-retardant modified antistatic plasticizing mother particle of PE.
The invention has the beneficial effects as follows, compared with prior art, flame-retardant modified antistatic plasticizing mother particle of the present invention is applied to polyethylene (PE) and has high density, multi-functional, low cost and the feature such as easy to use, and grafting elastomerics has the toughness of significantly improving, consistency is good simultaneously, micro-calcium carbonate can significantly improve toughness, rigidity, thermotolerance and maintenance good impact strength, halogen-free flame retardants has safety, presses down the high flame resistance of cigarette, nontoxic, environmental protection, and static inhibitor makes surface resistivity be reduced to 10 in ensureing antistatic property 8～10 10between Ω cm, therefore, use this master batch to polyethylene toughening flame-proof and improve antistatic property to there is good modified effect, and technique is simple, easy to use, cost is low, avoid environmental pollution simultaneously and be conducive to cleaner production etc., thering are good economic results in society.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1:
The flame-retardant modified antistatic plasticizing mother particle of a kind of PE, its component by mass percent proportioning is: compound 1%, the triacetonamine stablizer 0.5% of polyvinyl resin 15%, phosphate flame retardant 30%, micro-calcium carbonate 20%, terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH) 20%, two (2-hydroxyethyl) octyl group methyl biconjugate ammonium tosylate 10%, polysiloxane 2%, silane coupling agent 1.5%, hindered phenol antioxygen 1076 and phosphite antioxidant 168, wherein, the median size of micro-calcium carbonate is between 0.1 μ m～10 μ m.
Preparation method: (1) weighs up stand-by by each component by weight ratio; (2) polyvinyl resin and phosphate flame retardant, micro-calcium carbonate, terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH), two (2-hydroxyethyl) octyl group methyl biconjugate ammonium tosylate, polysiloxane, silane coupling agent, hindered phenol antioxygen 1076 are added in high-speed mixer with compound, the triacetonamine stablizer of phosphite antioxidant 168, fully mix 3～15 minutes, discharging is stand-by; (3) said mixture added to twin screw extruder is extruded, after granulation, drying, pack and obtain the flame-retardant modified antistatic plasticizing mother particle of PE.
Embodiment 2:
The flame-retardant modified antistatic plasticizing mother particle of a kind of PE, its component by mass percent proportioning is: compound 0.5%, the benzotriazole stablizer 0.5% of polyvinyl resin 12%, phosphorous acid ester fire retardant 40%, micro-calcium carbonate 20%, maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH) 10%, stearic acid monoglycerides (GMS) 15%, polyethylene wax 1%, calcium stearate coupling agent 1%, hindered phenol antioxygen 1076 and phosphite antioxidant 168, wherein, the median size of micro-calcium carbonate is between 0.1 μ m～10 μ m.
Preparation method: (1) weighs up stand-by by each component by weight ratio; (2) polyvinyl resin and phosphorous acid ester fire retardant, micro-calcium carbonate, maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH), stearic acid monoglycerides (GMS), polyethylene wax, calcium stearate coupling agent, hindered phenol antioxygen 1076 are added in high-speed mixer with compound, the benzotriazole stablizer of phosphite antioxidant 168, fully mix 3～15 minutes, discharging is stand-by; (3) said mixture added to twin screw extruder is extruded, after granulation, drying, pack and obtain the flame-retardant modified antistatic plasticizing mother particle of PE.
Embodiment 3:
The flame-retardant modified antistatic plasticizing mother particle of a kind of PE, its component by mass percent proportioning is: compound 1%, the hindered amine stabilizer 0.5% of polyvinyl resin 12%, phosphonate fire retardant 25%, micro-calcium carbonate 25%, ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA) 25%, Nanometer-sized Antimony-doped stannic oxide (ATO) 8%, OP wax 1.5%, calcium stearate coupling agent 2%, hindered phenol antioxygen 1076 and phosphite antioxidant 168, wherein, the median size of micro-calcium carbonate is between 0.1 μ m～10 μ m.
Preparation method: (1) weighs up stand-by by each component by weight ratio; (2) polyvinyl resin and phosphonate fire retardant, micro-calcium carbonate, ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA), Nanometer-sized Antimony-doped stannic oxide (ATO), OP wax, calcium stearate coupling agent, hindered phenol antioxygen 1076 are added in high-speed mixer with compound, the hindered amine stabilizer of phosphite antioxidant 168, fully mix 3～15 minutes, discharging is stand-by; (3) said mixture added to twin screw extruder is extruded, after granulation, drying, pack and obtain the flame-retardant modified antistatic plasticizing mother particle of PE.

Claims (10)

1. the flame-retardant modified antistatic plasticizing mother particle of PE, it is characterized in that, its component by mass percent proportioning is: PE carrier 10%～15%, halogen-free flame retardants 25%～40%, micro-calcium carbonate 10%～30%, grafting elastomerics 10%～30%, static inhibitor 5%～15%, lubrication dispersing agent 1%～3%, coupling agent 0.5%～2%, oxidation inhibitor 0.5%～1.5%, stablizer 0.5%～1%.
2. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, described halogen-free flame retardants is the one in phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant and organophosphorated salt fire retardant.
3. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, the median size of described micro-calcium carbonate is between 0.1 μ m～10 μ m.
4. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, it is characterized in that, described grafting elastomerics is terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH), maleic anhydride extension bar ethylene-octene copolymer (POE-g-MAH), maleic anhydride graft styrene-butadiene-styrene (SBS-g-MAH), terpolymer EP rubber-glycidyl methacrylate graft thing (EPDM-g-GMA), styrene-butadiene-styrene-glycidyl methacrylate copolymer (SBS-g-GMA), one in ethylene-methyl acrylate-glyceryl methacrylate terpolymer (E-MA-GMA).
5. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, it is characterized in that, described static inhibitor is the one in two (2-hydroxyethyl) octyl group methyl biconjugate ammonium tosylates, quaternary ammonium compound, alkylsulfonate, stearic acid monoglycerides (GMS), polyether ester, Nanometer-sized Antimony-doped stannic oxide (ATO).
6. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, described lubrication dispersing agent is one or more the mixture in polysiloxane, polyethylene wax, Poly Propylene Wax, EVA wax, OP wax, ethylene bis stearic amide.
7. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, described coupling agent is silane coupling agent or calcium stearate coupling agent.
8. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, described oxidation inhibitor is the compound of hindered phenol antioxygen 1076 and phosphite antioxidant 168.
9. the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, described stablizer is one or more the compound in triacetonamine stablizer, benzotriazole stablizer, benzophenone stablizer, hindered amine stabilizer.
10. the preparation method of the flame-retardant modified antistatic plasticizing mother particle of PE according to claim 1, is characterized in that, comprises the following steps:
(1) each component is weighed up stand-by by weight ratio;
(2) PE carrier and halogen-free flame retardants, micro-calcium carbonate, grafting elastomerics, static inhibitor, lubrication dispersing agent, coupling agent, oxidation inhibitor, stablizer are added in high-speed mixer, fully mix 3～15 minutes, discharging is stand-by;
(3) said mixture added to twin screw extruder is extruded, after granulation, drying, pack and obtain the flame-retardant modified antistatic plasticizing mother particle of PE.
CN201210594672.0A 2012-12-04 2012-12-04 PE (polyethylene) flame retardant modified antistatic toughening masterbatch and preparation method thereof Pending CN103849056A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497401A (en) * 2014-12-16 2015-04-08 上海邦中新材料有限公司 Toughening master batch for aluminium-plastic composite material and preparation method thereof
CN108219257A (en) * 2017-12-26 2018-06-29 上海普利特复合材料股份有限公司 A kind of high filling antistatic master granule and its preparation method and application
CN112111123A (en) * 2020-08-04 2020-12-22 河北鸿翔电讯器材有限公司 Impact-resistant polyethylene plastic pipe and preparation method thereof
CN113698633A (en) * 2021-08-16 2021-11-26 见喜纳米材料技术研发(河南)有限公司 Flame-retardant master batch composition with improved fluidity and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497401A (en) * 2014-12-16 2015-04-08 上海邦中新材料有限公司 Toughening master batch for aluminium-plastic composite material and preparation method thereof
CN108219257A (en) * 2017-12-26 2018-06-29 上海普利特复合材料股份有限公司 A kind of high filling antistatic master granule and its preparation method and application
CN112111123A (en) * 2020-08-04 2020-12-22 河北鸿翔电讯器材有限公司 Impact-resistant polyethylene plastic pipe and preparation method thereof
CN112111123B (en) * 2020-08-04 2022-05-24 河北鸿翔电讯器材有限公司 Impact-resistant polyethylene plastic pipe and preparation method thereof
CN113698633A (en) * 2021-08-16 2021-11-26 见喜纳米材料技术研发(河南)有限公司 Flame-retardant master batch composition with improved fluidity and preparation method thereof

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Application publication date: 20140611