WO2017075855A1 - 一种聚丙烯专用高效无卤阻燃剂母粒及其制备方法和应用 - Google Patents

一种聚丙烯专用高效无卤阻燃剂母粒及其制备方法和应用 Download PDF

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WO2017075855A1
WO2017075855A1 PCT/CN2015/095879 CN2015095879W WO2017075855A1 WO 2017075855 A1 WO2017075855 A1 WO 2017075855A1 CN 2015095879 W CN2015095879 W CN 2015095879W WO 2017075855 A1 WO2017075855 A1 WO 2017075855A1
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polypropylene
flame retardant
antioxidant
free flame
retardant masterbatch
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PCT/CN2015/095879
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English (en)
French (fr)
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袁海兵
郝建鑫
黄泽彬
吴磊
邓爵安
侯智谋
范木良
郝源增
任萍
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广州市聚赛龙工程塑料有限公司
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Priority to US15/518,766 priority Critical patent/US10400088B2/en
Publication of WO2017075855A1 publication Critical patent/WO2017075855A1/zh

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
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    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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    • 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
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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    • C08K5/3492—Triazines
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    • C08L2201/00—Properties
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    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the invention belongs to the field of preparation of flame-retardant masterbatch materials, and more particularly to a high-efficiency halogen-free flame retardant masterbatch for polypropylene and a preparation method and application thereof.
  • Flame retardant masterbatch is also called flame retardant masterbatch and fireproof masterbatch. It is called "concentrate” in foreign countries, which means the concentration of flame retardant. Flame-retardant masterbatch has been produced for decades. It was mainly used to solve the problem of uneven dispersion and dust pollution during the use of flame retardant powder. After years of development, a large number of scientific methods and new technologies have been applied. The research on flame retardant masterbatch has not only limited the conventional problems of dispersion and prevention of pollution. It has formed an independent discipline and developed into an independent industry. A large number of technical research and applications make the flame retardant masterbatch a high-tech, high-tech product.
  • the existing flame retardant technology all imparts flame retardant properties to polyolefins by directly adding a flame retardant.
  • the commonly used halogen-free flame retardants mainly include inorganic flame retardants and phosphorus-nitrogen intumescent flame retardants, while inorganic flame retardants have poor compatibility with polyolefin resins, and the flame retarding efficiency is low, only when a large amount of filling is used. It has a certain flame retardant effect, which will seriously damage the mechanical properties and processing properties of polyolefin.
  • a phosphorus-nitrogen halogen-free flame retardant having a high flame retardant efficiency is generally used in the polyolefin resin, and the surface of the flame retardant can form a heat when heated.
  • the layer of dense foamed carbon layer plays a role in heat insulation, oxygen barrier, smoke suppression, and prevention of droplets. It has good flame retardant properties and is halogen-free, low-toxic and non-corrosive when burned. The system is burning, so it develops very quickly.
  • the phosphorus-nitrogen flame retardant is generally powder, and its fineness is generally above 400 mesh, it is easy to generate a large amount of dust pollution during weighing, mixing, and granulation, which deteriorates the production environment and causes human health. It is very harmful and causes a certain degree of wear and tear on the processing equipment.
  • the phosphorus-nitrogen flame retardants have the problems of strong hygroscopicity, low thermal stability, and poor compatibility with polyolefin resin, resulting in the flame retardant material being sensitive to moisture, easy to foam and degrade, and flame retardant.
  • the agent has poor dispersibility in the resin and to some extent impairs the processing properties and physical and mechanical properties of the material.
  • the invention provides a special high-efficiency halogen-free flame retardant masterbatch for polypropylene according to the deficiencies in the current flame retardant masterbatch materials.
  • Another object of the present invention is to provide a method and an application for preparing the above-mentioned polypropylene-specific high-efficiency halogen-free flame-retardant masterbatch.
  • the invention adopts the environmentally-friendly, high-efficiency halogen-free flame retardant and the high-pitch-crush-extrusion continuous production process, so that the obtained halogen-free flame-retardant masterbatch has the advantages of dust-free, easy dispersion, high flame-retardant efficiency and low cost.
  • the processing adaptability is strong, which can reduce dust pollution and improve the production environment.
  • the invention provides a high-efficiency halogen-free flame retardant masterbatch for polypropylene, the masterbatch comprising the following raw material composition by weight percentage:
  • the microporous polypropylene has a size of 3 to 5 mm, and the cell surface has a cell size of 10 to 100 ⁇ m and a cell density of more than 10 5 /cm 3 .
  • the microporous polypropylene is used as a liquid flame retardant (bisphenol A bis(diphenyl phosphate)) adsorbent, and the carrier of the flame retardant masterbatch, the main function is to bisphenol A bis(diphenylphosphoric acid)
  • the ester is adsorbed into the micropores, and the phosphorus-nitrogen halogen-free flame retardant powder is bonded to obtain a particulate halogen-free flame retardant master batch.
  • Ammonium polyphosphate, pentaerythritol phosphate and melamine are respectively used as an acid source, a carbon source and a gas source to form an intumescent flame retardant system, and the three synergistically achieve the purpose of high efficiency flame retardant.
  • Bisphenol A bis(diphenyl phosphate) is a high-efficiency phosphorus-based flame retardant that can synergistically flame retardant with melamine.
  • Pentaerythritol stearate acts as a low melting point lubricant which acts to reduce the abrasion between the material and the equipment on the one hand and to improve the dispersion of the halogen-free flame retardant in the carrier on the other hand.
  • the role of the antioxidant 1010 and the antioxidant 168 is to improve the heat processing stability of the material and the ability to resist aging of the heat.
  • the raw material composition is as follows by weight percent:
  • the microporous polypropylene is prepared by the following preparation method:
  • the high-melt strength copolymerized polypropylene, the foaming agent, the antioxidant 1010, the antioxidant 168 and the calcium stearate are stirred, melt blended and extruded, pelletized, and dried to obtain the microporous polypropylene.
  • microporous polypropylene comprises the following composition of raw materials in percentage by weight:
  • the ammonium polyphosphate has an average particle diameter of 8 to 10 ⁇ m.
  • ammonium polyphosphate is purchased from HT-208 of Jinan Taixing Fine Chemical Co., Ltd. or APP high molecular weight ammonium polyphosphate (n>1000) of Shandong Shi'an Chemical Co., Ltd.
  • the pentaerythritol phosphate has a purity of more than 99%, a water content of less than 0.2%, and an average particle diameter of 5 to 8 ⁇ m.
  • the pentaerythritol phosphate is purchased from pentaerythritol phosphate (PEPA) of Jiangsu Vicotri Chemical Co., Ltd.
  • the melamine has a purity greater than 99%.
  • the melamine is purchased from the superior product melamine of Chengdu Yulong Chemical Co., Ltd. or the Tianfu brand melamine (purity greater than 99.8%) of Chuanhua Co., Ltd.
  • the bisphenol A bis(diphenyl phosphate) has a viscosity of from 1800 to 2600 mPa ⁇ s at 40 ° C and a color tone of less than 80.
  • the bisphenol A bis(diphenyl phosphate) is purchased from WSFR-BDP of Zhejiang Wansheng Co., Ltd.
  • the invention also provides a preparation method of the special high-efficiency halogen-free flame retardant masterbatch for polypropylene, comprising the following steps:
  • microporous polypropylene high melt strength copolymerized polypropylene, foaming agent, antioxidant 1010, antioxidant 168 and calcium stearate are stirred, melt blended and extruded, pelletized, dried, ie The microporous polypropylene is obtained;
  • the microporous polypropylene prepared by the S1 has a size of 3 to 5 mm, and the cell surface has a cell size of 10 to 100 ⁇ m and a cell density of more than 10 5 /cm 3 .
  • the extruder has an aspect ratio of 20 to 40; the barrel temperature of the extruder is 150 to 180 ° C; and the main engine speed of the extruder is 300 to 700 r/min.
  • the high-efficiency halogen-free flame retardant masterbatch for polypropylene prepared by the invention has the characteristics of easy dispersibility, easy processing, high flame retardant efficiency and low production cost, and can be widely applied to flame-retardant polypropylene materials for extrusion, injection molding and blown film. Production.
  • the present invention has the following beneficial effects:
  • the remarkable effect of the invention is that the self-made microporous polypropylene is used as the carrier of the adsorbent and the masterbatch, and the liquid flame retardant (bisphenol A bis(diphenyl phosphate)) is all adsorbed into the micropores, thereby Avoid the problems of processing difficulties, uneven dispersion, and loss due to the direct addition of liquid flame retardants.
  • the liquid flame retardant bisphenol A bis(diphenyl phosphate)
  • the invention combines optimized ammonium phosphate, pentaerythritol phosphate and melamine to form a highly efficient phosphorus-nitrogen halogen-free expansion flame retardant system, thereby producing a synergistic flame retardant effect, thereby reducing the addition amount of the flame retardant and reducing the physical properties of the flame retardant to the material.
  • the invention adopts a liquid high-efficiency flame retardant (bisphenol A bis(diphenyl phosphate)) to be compounded with a solid intumescent flame retardant system, on the one hand, can produce a synergistic flame retardant effect, reduce the addition amount of the flame retardant, and On the one hand, it is possible to effectively avoid the difficulty of coating the carrier due to the large amount of the flame retardant powder, thereby improving the processing efficiency.
  • a liquid high-efficiency flame retardant bisphenol A bis(diphenyl phosphate)
  • the high-efficiency halogen-free flame retardant masterbatch for polypropylene prepared by the invention is granular, and the particle size of the base resin is substantially the same, so the material is uniformly mixed, and the uneven mixing of the powder and the pellet is effectively avoided, resulting in unstable material quality. Case.
  • reagents, methods, and devices employed in the present invention are routine reagents, methods, and devices in the art.
  • microporous polypropylenes described in the following examples and comparative examples were prepared by the following procedures:
  • high melt strength copolymer polypropylene brand: PP-WFW4, Japan Mitsubishi Chemical Corporation
  • foaming agent brand: MJ Addifoam 43TM, Beijing Plastics Trading Co., Ltd.
  • antioxidant model: SONOX 1010, Shandong Linyi Sanfeng Chemical Co., Ltd.
  • antioxidant model: SONOX 168, Shandong Linyi Sanfeng Chemical Co., Ltd.
  • lubricant calcium stearate 3818, Zhongshan Huamingtai Chemical Co., Ltd.
  • the temperature of each section of the single-screw extruder from the hopper to the die is: 180 ° C, 190 ° C, 200 ° C, 190 ° C, 190 ° C, 200 ° C, 210 ° C, 220 ° C, the host
  • the screw speed is 450r/min
  • the frequency of the main hopper feed screw is 13H Z
  • the material is blended and melted and extruded
  • the pellets from the die of the single screw extruder are granulated and dried by water ring to obtain micro Hole polypropylene.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 32% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 17% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 22% (excellent product, Chengdu Yulong Chemical Co., Ltd.) Production), bisphenol A bis(diphenyl phosphate) 8% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 19.8% (homemade, preparation method as above), pentaerythritol stearate 0.5% ( P(ETS), Longsha Chemical Company, USA, antioxidant 1010: 0.5% (Model: SONOX 1010, Linyi Sanfeng Chemical Co., Ltd., Shandong Province), antioxidant 168: 0.2% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 5 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 35.7% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 15% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 20% (Chuanhua Co., Ltd.), double Phenol A bis(diphenyl phosphate) 8% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 20% (homemade, preparation method as above), pentaerythritol stearate 0.6% ( P(ETS), Longsha Chemical Company, USA, antioxidant 1010: 0.4% (Model: SONOX 1010, Linyi Sanfeng Chemical Co., Ltd., Shandong Province), antioxidant 168: 0.3% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 5 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 38% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 16.5% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 20% (excellent product, Chengdu Yulong Chemical Co., Ltd.) Production), bisphenol A bis(diphenyl phosphate) 9% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 15% (homemade, preparation method as above), pentaerythritol stearate 0.8% ( P(ETS), Longsha Chemical Company, USA, 1010:0.3% antioxidant (Model: SONOX 1010, Sanfeng Chemical Co., Ltd., Linyi City, Shandong Province), antioxidant 168: 0.4% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 6 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 32.3% (APP high molecular weight ammonium polyphosphate (n>1000), Shandong Shi'an Chemical Co., Ltd.), pentaerythritol phosphate 13% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 18% (Chuanhua shares) Ltd.), bisphenol A bis(diphenyl phosphate) 10% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 25% (homemade, preparation method as above), pentaerythritol stearic acid Ester 1% ( P(ETS), Longsha Chemical Company, USA, antioxidant 1010: 0.2% (Model: SONOX 1010, Linyi Sanfeng Chemical Co., Ltd., Shandong Province), antioxidant 168: 0.5% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 7 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 45% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 25% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 4.5% (excellent product, Chengdu Yulong Chemical Co., Ltd.) Production), bisphenol A bis(diphenyl phosphate) 9% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 15% (homemade, preparation method as above), pentaerythritol stearate 0.8% ( P(ETS), Longsha Chemical Company, USA, 1010:0.3% antioxidant (Model: SONOX 1010, Sanfeng Chemical Co., Ltd., Linyi City, Shandong Province), antioxidant 168: 0.4% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 6 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 32.3% (APP high molecular weight ammonium polyphosphate (n>1000), Shandong Shi'an Chemical Co., Ltd.), pentaerythritol phosphate 13% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 18% (Chuanhua shares) Ltd.), bisphenol A bis(diphenyl phosphate) 10% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), copolymerized polypropylene 25% (brand: EP548R, Zhonghai Shell Petrochemical Co., Ltd.), Pentaerythritol stearate 1% ( P(ETS), Longsha Chemical Company, USA, antioxidant 1010: 0.2% (Model: SONOX 1010, Linyi Sanfeng Chemical Co., Ltd., Shandong Province), antioxidant 168: 0.5% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • each component in the above formulation was accurately weighed, and then bisphenol A bis(diphenyl phosphate) and microporous polypropylene were uniformly mixed and allowed to stand for 7 hours.
  • the blend, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are then added to a pressurized inversion mixer to control the temperature in the mixing chamber to 160 ° C and the rotor speed to be 50 r/min.
  • the mixing time is 6 min.
  • ammonium polyphosphate, pentaerythritol phosphate and melamine powder are added to the internal mixer twice, each time of feeding is 4 min; after all the materials are added, it is further mixed for 8 min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentage components:
  • Ammonium polyphosphate 38% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 16.5% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 20% (excellent product, Chengdu Yulong Chemical Co., Ltd.) Production), microporous polypropylene 24% (homemade, preparation method as above), pentaerythritol stearate 0.8% ( P(ETS), Longsha Chemical Company, USA, 1010:0.3% antioxidant (Model: SONOX 1010, Sanfeng Chemical Co., Ltd., Linyi City, Shandong Province), antioxidant 168: 0.4% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • the components in the above formula are accurately weighed, and then the microporous polypropylene, pentaerythritol stearate, antioxidant 1010, and antioxidant 168 are added to a pressurized inversion mixer to control the mixing chamber.
  • the temperature is 160 ° C
  • the rotor speed is 50 r / min
  • the mixing time is 6 min
  • the ammonium polyphosphate, pentaerythritol phosphate, melamine powder is added to the internal mixer twice after the material is melted, and the feeding interval is 4 min. After all the materials were added, they were mixed for 8 minutes.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the ratio is based on the following mass percentages:
  • Ammonium polyphosphate 38% (brand: HT-208, Jinan Taixing Fine Chemical Co., Ltd.), pentaerythritol phosphate 16.5% (produced by Jiangsu Weike Terry Chemical Co., Ltd.), melamine 20% (excellent product, Chengdu Yulong Chemical Co., Ltd.) Production), bisphenol A bis(diphenyl phosphate) 9% (brand: WSFR-BDP, Zhejiang Wansheng Co., Ltd.), microporous polypropylene 15% (homemade, preparation method as above), pentaerythritol stearate 0.8% ( P(ETS), Longsha Chemical Company, USA, 1010:0.3% antioxidant (Model: SONOX 1010, Sanfeng Chemical Co., Ltd., Linyi City, Shandong Province), antioxidant 168: 0.4% (Model: SONOX 168, Shandong Linyi City Sanfeng Chemical Co., Ltd.).
  • the components in the above formula are accurately weighed, and then bisphenol A bis(diphenyl phosphate), microporous polypropylene, pentaerythritol stearate, antioxidant 1010, antioxidant 168 are added to the addition.
  • the temperature in the mixing chamber is controlled to 160 ° C
  • the rotor speed is 50 r / min
  • the mixing time is 6 min
  • the ammonium polyphosphate, pentaerythritol phosphate, melamine powder are divided into two parts after the material is melted.
  • each feeding interval is 4min; all materials are added and then mixed for 8min.
  • the above-mentioned mixed rubber head is conveyed to the hopper of the single-screw extruder through the conveyor belt, and the rubber head is cut into pieces by the cutter in the hopper, and the temperature of each section of the barrel is controlled to be 170 ° C, and the main engine speed is 500 r/min.
  • the single-screw melt-kneading extrusion is carried out, and then air-cooled and ground-faced to form a polypropylene-specific high-efficiency halogen-free flame retardant masterbatch.
  • the preparation method is the same as that of the third embodiment, except that the microporous polypropylene (brand: XP100, Shenzhen Plastic Trading Co., Ltd.) has an average cell diameter of 8 ⁇ m and a cell density of 10 4 /cm 3 .
  • the microporous polypropylene brand: XP100, Shenzhen Plastic Trading Co., Ltd.
  • the preparation method is the same as that of Example 3, except that the acid source used is melamine pyrophosphate (MPP) (produced by Shandong Shi'an Chemical Co., Ltd.).
  • MPP melamine pyrophosphate
  • the preparation method is the same as that of the third embodiment, except that the liquid flame retardant used is resorcinol bis(diphenyl phosphate) (produced by Zhejiang Wansheng Chemical Co., Ltd.).
  • the polypropylene high-efficiency halogen-free flame retardant masterbatch prepared by the invention is mixed with the polypropylene resin according to the formulation of Table 1 to prepare flame-retardant polypropylene, and Table 2 is the masterbatch prepared by comparing the preparation of the comparative examples 1 to 4.
  • the propylene resin was mixed according to the formulation of Table 2 to prepare a flame retardant polypropylene.
  • Table 3 The test results of the above flame retardant polypropylene performance are shown in Table 3:
  • the masterbatch prepared in Example 3 and the masterbatch prepared in Comparative Example 1 have a flame retardancy of the material after changing the ratio of the flame retardant ammonium polyphosphate, pentaerythritol phosphate, and melamine.
  • the reduction of 1.5mmV0 to 3.2mmV0 indicates that the synergistic effect between the flame retardants is reduced, resulting in a decrease in flame retardant performance.
  • the masterbatch prepared in Example 4 and the masterbatch prepared in Comparative Example 2 were compared with the conventional copolymerized polypropylene as a carrier, the flame retardancy of the material was lowered, and the physical and mechanical properties were also lowered.
  • the flame retardant masterbatch prepared by adding the liquid flame retardant bisphenol A bis(diphenyl phosphate) has a greatly reduced flame retardancy, which is reduced from 1.5 mm V0 to 3.2 mm V0.
  • the liquid flame retardant bisphenol A bis(diphenyl phosphate) used in the invention has the effect of flame retarding and synergistic effect with the ammonium polyphosphate, pentaerythritol phosphate and melamine solid flame retardant used in the invention.
  • Example 4 Comparative Example 4 Compared with Example 3, the liquid flame retardant was not adsorbed by the microporous polypropylene, but was added by direct addition, and the prepared masterbatch was reduced in flame retardancy, and the physical and mechanical properties of the material were also The decrease indicates that only the liquid flame retardant and the microporous polypropylene are pre-adsorbed, and then loaded with the solid flame retardant to obtain a better mixing effect.
  • Example 5 compared with Example 3, when the microporous polypropylene having a small cell diameter and cell density was used, the flame retardant masterbatch was prepared because of its reduced adsorption capacity to the liquid flame retardant. The burning effect is poor.

Abstract

本发明提供了一种聚丙烯专用高效无卤阻燃剂母粒，包括如下按重量百分比数计的原料组成：聚磷酸铵30～40％；季戊四醇磷酸酯10～20％；三聚氰胺15～25％；双酚A双(二苯基磷酸酯)5～15％；微孔聚丙烯10～30％；季戊四醇硬脂酸酯0.1～1％；抗氧剂10100.1～0.5％；抗氧剂1680.1～0.5％；所述的微孔聚丙烯尺寸为3～5mm的颗粒，颗粒表面的泡孔尺寸为10～100微米，泡孔密度大于105个/立方厘米。本发明制备的聚丙烯专用高效无卤阻燃剂母粒具有易分散、易加工、阻燃效率高、生产成本低的特点，可广泛应用于挤出、注塑、吹膜用阻燃聚丙烯材料的生产。

Description

一种聚丙烯专用高效无卤阻燃剂母粒及其制备方法和应用 技术领域
本发明属于阻燃母粒材料制备领域，更具体地，涉及一种聚丙烯专用高效无卤阻燃剂母粒及其制备方法和应用。
背景技术
阻燃母粒也称阻燃母料、防火母粒。在国外称其为“浓缩物”，意之阻燃剂的浓缩。阻燃母粒产生已经有几十年历史，其最初主要是解决阻燃剂粉料使用过程中分散不均，扬尘污染严重的问题，经过多年的发展，大量科学手段和新型技术的应用，人们对阻燃母粒的研究已经不仅仅局限与分散、防止污染这些常规问题上了。其已经形成一个独立学科并发展成为一个独立的行业。大量的技术研究和应用使阻燃母粒成为高科技、高技术型的产品。
现有的阻燃技术一都是通过直接添加阻燃剂赋予聚烯烃阻燃性能。目前，常用的无卤阻燃剂主要有无机阻燃剂和磷氮类膨胀型阻燃剂，而无机阻燃剂由于与聚烯烃树脂的相容性差，阻燃效率低，只有在大量填充时才具有一定的阻燃效果，而这样会严重损害聚烯烃的力学性能和加工性能。为了克服无机类阻燃剂阻燃效率太低这一缺点，通常在聚烯烃树脂中采用阻燃效率较高的磷氮类无卤阻燃剂，这类阻燃剂在受热时表面能形成一层致密泡沫炭层，起到隔热、隔氧、抑烟，又能防止熔滴，具有良好的阻燃性能，而且燃烧时无卤、低毒和无腐蚀性气体产生，属于环保型的阻燃体系，所以发展十分迅速。
由于这种磷氮类阻燃剂一般都为粉体，而且其细度一般在400目以上，在称量、混合、造粒过程中容易产生大量的粉尘污染，恶化生产环境，对人体健康造成很大危害，而且会对加工设备造成一定程度的磨损。而且磷氮类阻燃剂都具有吸湿性较强、热稳定性不高、与聚烯烃树脂的相容性较差的问题，导致阻燃材料对水分较敏感、易发泡和降解、阻燃剂在树脂中分散性较差和在一定程度上损害材料的加工性能和物理机械性能的缺点。
发明内容
本发明根据目前阻燃母粒材料中的不足，提供了一种聚丙烯专用高效无卤阻燃母粒。
本发明的另一目的在于提供上述聚丙烯专用高效无卤阻燃母粒的制备方法和应用。
本发明通过选用环保、高效的无卤阻燃剂和高搅-破碎-挤出的连续生产工艺，使制得的无卤阻燃母粒具有无尘、易分散、阻燃效率高、成本低、加工适应性强等特点，从而可以减少粉尘污染、改善生产环境。
本发明的技术目的通过以下技术方案实现：
本发明提供了一种聚丙烯专用高效无卤阻燃剂母粒，所述母粒包括如下按重量百分比数计的原料组成：
Figure PCTCN2015095879-appb-000001
Figure PCTCN2015095879-appb-000002
所述的微孔聚丙烯尺寸为3～5mm的颗粒，颗粒表面的泡孔尺寸为10～100微米，泡孔密度大于105个/立方厘米。
其中微孔聚丙烯是作为液体阻燃剂(双酚A双(二苯基磷酸酯))的吸附剂，以及该阻燃母粒的载体，主要作用是把双酚A双(二苯基磷酸酯)吸附到微孔中，以及把磷氮类无卤阻燃剂粉体粘合起来，以得到颗粒状的无卤阻燃剂母料。聚磷酸铵、季戊四醇磷酸酯、三聚氰胺三者分别作为酸源、碳源、气源组成膨胀型阻燃体系，三者相互协同起到高效阻燃的目的。双酚A双(二苯基磷酸酯)作为一种高效磷系阻燃剂，可与三聚氰胺起到磷氮协同阻燃的效果。季戊四醇硬脂酸酯作为一种低熔点的润滑剂，其作用一方面是减少物料与设备之间的磨损，另一方面是提高无卤阻燃剂在载体中的分散效果。抗氧剂1010和抗氧剂168的作用是提高材料的受热加工稳定性和耐热氧老化的能力。
优选地，如下按重量百分比数计的原料组成：
Figure PCTCN2015095879-appb-000003
优选地，所述微孔聚丙烯采用如下制备方法制得：
将高熔体强度共聚聚丙烯、发泡剂、抗氧剂1010，抗氧剂168和硬脂酸钙搅拌，熔融共混挤出，切粒、干燥，即得所述微孔聚丙烯。
更优选地，所述微孔聚丙烯包括如下按重量百分比数计的原料组成：
Figure PCTCN2015095879-appb-000004
Figure PCTCN2015095879-appb-000005
优选地，所述聚磷酸铵的平均粒径为8～10μm。
更优选地，所述聚磷酸铵购自济南泰星精细化工有限公司的HT-208或山东世安化工有限公司的APP高分子量多聚磷酸铵(n>1000)。
优选地，所述季戊四醇磷酸酯的纯度大于99％，含水率小于0.2％，平均粒径为5～8μm。
更优选地，所述季戊四醇磷酸酯购自江苏维科特瑞化工有限公司的季戊四醇磷酸酯(PEPA)。
优选地，所述三聚氰胺的纯度大于99％。
更优选地，所述三聚氰胺购自成都玉龙化工有限公司的优等品三聚氰胺或川化股份有限公司的天府牌三聚氰胺(纯度大于99.8％)。
优选地，所述的双酚A双(二苯基磷酸酯)的粘度在40℃下为1800-2600mPa·s，色泽小于80。
更优选地，所述双酚A双(二苯基磷酸酯)购自浙江万盛股份有限公司的WSFR-BDP。
本发明还提供所述的聚丙烯专用高效无卤阻燃剂母粒的制备方法，包括如下步骤：
S1.微孔聚丙烯的制备：将高熔体强度共聚聚丙烯、发泡剂、抗氧剂1010，抗氧剂168和硬脂酸钙搅拌，熔融共混挤出，切粒、干燥，即得所述微孔聚丙烯；
S2.将S1步骤中所得的微孔聚丙烯和双酚A双(二苯基磷酸酯)混匀，静置，待用；
S3.将季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168和S2步骤中所得的混合物进行熔融共混后，加入聚磷酸铵、季戊四醇磷酸酯和三聚氰胺共混，密炼，挤出，切粒即得所述聚丙烯专用高效无卤阻燃剂母粒。
优选地，所述S1制备得到的微孔聚丙烯尺寸为3～5mm的颗粒，颗粒表面的泡孔尺寸为10～100微米，泡孔密度大于105个/立方厘米。
优选地，所述挤出机的长径比为20～40；挤出机的机筒温度为150～180℃；挤出机的主机转速300～700r/min。
本发明制备的聚丙烯专用高效无卤阻燃剂母粒具有易分散、易加工、阻燃效率高、生产成本低的特点，可广泛应用于挤出、注塑、吹膜用阻燃聚丙烯材料的生产。
与现有技术相比，本发明具有以下有益效果：
本发明的显著效果在于采用自制的微孔聚丙烯同时作为吸附剂和母粒的载体，通过将液体阻燃剂(双酚A双(二苯基磷酸酯))全部吸附到微孔中，从而避免直接添加液体阻燃剂造成的加工困难、分散不均、易损耗等问题。
本发明通过优化的聚磷酸铵、季戊四醇磷酸酯、三聚氰胺组成高效的磷氮类无卤膨胀阻燃体系，产生协同阻燃效果，从而可以减少阻燃剂的添加量，降低阻燃剂对材料物理力学性能的影响。
本发明采用液体高效阻燃剂(双酚A双(二苯基磷酸酯))与固体的膨胀阻燃体系进行复配，一方面可以产生协同阻燃效果，降低阻燃剂的添加量，另一方面，可有效避免因阻燃剂粉体较多而带来的载体包覆困难，从而提升加工效率。
本发明制备的聚丙烯专用高效无卤阻燃剂母粒由于是颗粒状，和基础树脂的颗粒尺寸基本一致，所以物料混合均匀，有效避免了粉体和粒料混合不均匀导致材料质量不稳定的情况。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，但不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
以下实施例和对比例中所述的微孔聚丙烯是通过如下步骤制备得到：
按以下质量百分比组成进行配比：高熔体强度共聚聚丙烯(牌号：PP-WFW4，日本三菱化学公司)89％，发泡剂(牌号：MJ Addifoam 43TM，北京市塑化贸易有限公司)10％，抗氧剂(型号：SONOX 1010，山东省临沂市三丰化工有限公司)为0.2％，抗氧剂(型号：SONOX 168，山东省临沂市三丰化工有限公司)为0.3％，润滑剂(硬脂酸钙3818，中山华明泰化工股份有限公司)0.5％，将上述物料称量完毕后搅拌均匀，然后加入到长径比为40:1的单螺杆挤出机的主喂料料斗中，设定单螺杆挤出机从料斗到模头的各段温度分别为：180℃、190℃、200℃、190℃、190℃、190℃、200℃、210℃、220℃，主机的螺杆转速为450r/min，主料斗进料螺杆的频率为13HZ，将物料共混熔融挤出；将从单螺杆挤出机口模出来的粒条经过水环切粒、干燥，即得到微孔聚丙烯。
实施例1：
按以下质量百分比组成进行配比：
聚磷酸铵32％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷 酸酯17％(江苏维科特瑞化工有限公司生产)，三聚氰胺22％(优等品，成都玉龙化工有限公司生产)，双酚A双(二苯基磷酸酯)8％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯19.8％(自制，制备方法如上)，季戊四醇硬脂酸酯0.5％(
Figure PCTCN2015095879-appb-000006
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.5％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.2％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置5小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
实施例2
按以下质量百分比组成进行配比：
聚磷酸铵35.7％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷酸酯15％(江苏维科特瑞化工有限公司生产)，三聚氰胺20％(川化股份有限公司)，双酚A双(二苯基磷酸酯)8％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯20％(自制，制备方法如上)，季戊四醇硬脂酸酯0.6％(
Figure PCTCN2015095879-appb-000007
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.4％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.3％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置5小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
实施例3
按以下质量百分比组成进行配比：
聚磷酸铵38％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷 酸酯16.5％(江苏维科特瑞化工有限公司生产)，三聚氰胺20％(优等品，成都玉龙化工有限公司生产)，双酚A双(二苯基磷酸酯)9％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯15％(自制，制备方法如上)，季戊四醇硬脂酸酯0.8％(
Figure PCTCN2015095879-appb-000008
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.3％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.4％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置6小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
实施例4
按以下质量百分比组成进行配比：
聚磷酸铵32.3％(APP高分子量多聚磷酸铵(n>1000)，山东世安化工有限公司)，季戊四醇磷酸酯13％(江苏维科特瑞化工有限公司生产)，三聚氰胺18％(川化股份有限公司)，双酚A双(二苯基磷酸酯)10％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯25％(自制，制备方法如上)，季戊四醇硬脂酸酯1％(
Figure PCTCN2015095879-appb-000009
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.2％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.5％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置7小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
对比例1
按以下质量百分比组成进行配比：
聚磷酸铵45％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷 酸酯25％(江苏维科特瑞化工有限公司生产)，三聚氰胺4.5％(优等品，成都玉龙化工有限公司生产)，双酚A双(二苯基磷酸酯)9％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯15％(自制，制备方法如上)，季戊四醇硬脂酸酯0.8％(
Figure PCTCN2015095879-appb-000010
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.3％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.4％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置6小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
对比例2
按以下质量百分比组成进行配比：
聚磷酸铵32.3％(APP高分子量多聚磷酸铵(n>1000)，山东世安化工有限公司)，季戊四醇磷酸酯13％(江苏维科特瑞化工有限公司生产)，三聚氰胺18％(川化股份有限公司)，双酚A双(二苯基磷酸酯)10％(牌号：WSFR-BDP，浙江万盛股份有限公司)，共聚聚丙烯25％(牌号：EP548R，中海壳牌石油化工有限公司)，季戊四醇硬脂酸酯1％(
Figure PCTCN2015095879-appb-000011
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.2％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.5％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)和微孔聚丙烯掺混均匀，静置7小时。然后将此掺混物、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
对比例3：
按照以下质量百分比组成进行配比：
聚磷酸铵38％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷 酸酯16.5％(江苏维科特瑞化工有限公司生产)，三聚氰胺20％(优等品，成都玉龙化工有限公司生产)，微孔聚丙烯24％(自制，制备方法如上)，季戊四醇硬脂酸酯0.8％(
Figure PCTCN2015095879-appb-000012
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.3％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.4％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将微孔聚丙烯、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
对比例4：
按以下质量百分比组成进行配比：
聚磷酸铵38％(牌号：HT-208，济南泰星精细化工有限公司)，季戊四醇磷酸酯16.5％(江苏维科特瑞化工有限公司生产)，三聚氰胺20％(优等品，成都玉龙化工有限公司生产)，双酚A双(二苯基磷酸酯)9％(牌号：WSFR-BDP，浙江万盛股份有限公司)，微孔聚丙烯15％(自制，制备方法如上)，季戊四醇硬脂酸酯0.8％(
Figure PCTCN2015095879-appb-000013
P(ETS)，美国龙沙化工公司)，抗氧剂1010:0.3％(型号：SONOX 1010，山东省临沂市三丰化工有限公司)，抗氧剂168：0.4％(型号：SONOX 168，山东省临沂市三丰化工有限公司)。
将上述配方中的各组分进行准确称量，然后将双酚A双(二苯基磷酸酯)、微孔聚丙烯、季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168加入到加压式翻转密炼机中，控制密炼室内的温度为160℃，转子转速为50r/min，密炼时间为6min，待物料熔融后分两次将聚磷酸铵、季戊四醇磷酸酯、三聚氰胺粉体加入到密炼机中，每次投料间隔4min；物料全部加入后再密炼8min。
上述密炼后的胶头经传输带输送到单螺杆挤出机的料斗里，经料斗内的切刀将胶头切成碎块，控制机筒各段温度为170℃，主机转速500r/min，经单螺杆熔融混炼挤出，然后经风冷磨面切粒制成聚丙烯专用高效无卤阻燃剂母粒。
对比例5：
制备方法同实施例3，不同的是采用的微孔聚丙烯(牌号：XP100，深圳市塑德贸易有限公司)的泡孔平均直径为8微米，泡孔密度为104个/立方厘米。
对比例6：
制备方法同实施例3，不同的是采用的酸源为蜜胺焦磷酸盐(MPP)(山东世安化工有限公司生产)。
对比例7：
制备方法同实施例3，不同的是采用的液体阻燃剂为间苯二酚双(二苯基磷酸酯)(浙江万盛化工有限公司生产)。
将本发明制备的聚丙烯专用高效无卤阻燃剂母粒与聚丙烯树脂按照表1的配方混合，制备成阻燃聚丙烯，表2为将对比例1～4制备得到的母粒与聚丙烯树脂按照表2的配方混合，制备成阻燃聚丙烯，针对上述阻燃聚丙烯性能测试结果如表3所示：
对本发明制备的聚丙烯专用高效无卤阻燃剂母粒的效果进行以下实验：
表1实施例配方
Figure PCTCN2015095879-appb-000014
表2对比例配方
Figure PCTCN2015095879-appb-000015
表3阻燃PP材料性能的测试结果
Figure PCTCN2015095879-appb-000016
从以上数据可以看出，由实施例3制备的母粒和由对比例1制备的母粒对比，改变阻燃剂聚磷酸铵、季戊四醇磷酸酯、三聚氰胺的配比后，材料的阻燃性由1.5mmV0降为3.2mmV0，说明阻燃剂之间的协同效果下降，导致了阻燃性能的降低。由实施例4制备的母粒和由对比例2制备的母粒对比，改用普通的共聚聚丙烯做载体进行加工时，材料的阻燃性下降，而且物理力学性能也有所降低。
而对比例3和实施例3对比，不添加液体阻燃剂双酚A双(二苯基磷酸酯)制备的阻燃母粒，其阻燃性大大降低，由1.5mmV0降低为3.2mmV0，说明本发明采用的液体阻燃剂双酚A双(二苯基磷酸酯)与本发明采用的聚磷酸铵、季戊四醇磷酸酯、三聚氰胺固体阻燃剂产生了阻燃增效的作用。
对比例4与实施例3相比，液体阻燃剂未被微孔聚丙烯吸附，而是采用直接添加的方式进行加入，其制备得到的母粒阻燃效果降低，而且材料的物理力学性能也有所下降，说明只有将液体阻燃剂与微孔聚丙烯进行预先吸附后，再与固体阻燃剂进行负载，才能获得较好的混合效果。
对比例5和实施例3相比，改用泡孔直径和泡孔密度都较小的微孔聚丙烯时，由于其对液体阻燃剂的吸附能力下降，因此其制备的阻燃母粒阻燃效果较差。
对比例6和对比例7，与对比例3相比，分别将酸源阻燃剂改为蜜胺焦磷酸盐，将液体阻燃剂改为间苯二酚双(二苯基磷酸酯)后，由于阻燃剂种类的不同，阻燃剂之间的协同阻燃效果降低，阻燃母粒的阻燃效率大大降低。通过表3中相应数据可以表明的是，只有在采用本发明固体阻燃剂聚磷酸铵、季戊四醇磷酸酯、三聚氰胺和液体阻燃剂双酚A双(二苯基磷酸酯)，并在本发明自制的微孔聚丙烯进行吸附和负载后，才能在不影响材料加工性能和物理机械性能的前提下，获得 最佳的阻燃性能。

Claims (10)

  1. 一种聚丙烯专用高效无卤阻燃剂母粒，其特征在于，包括如下按重量百分比数计的原料组成：
    Figure PCTCN2015095879-appb-100001
    所述的微孔聚丙烯直径为3～5mm的颗粒，颗粒表面的泡孔直径为10～100微米，泡孔密度大于105个/立方厘米。
  2. 根据权利要求1所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，包括如下按重量百分比数计的原料组成：
    Figure PCTCN2015095879-appb-100002
  3. 根据权利要求1或2所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，所述微孔聚丙烯采用如下制备方法制得：
    将高熔体强度共聚聚丙烯、发泡剂、抗氧剂1010，抗氧剂168和硬脂酸钙搅拌，熔融共混挤出，切粒、干燥，即得所述微孔聚丙烯。
  4. 根据权利要求3所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，所述微孔聚丙烯包括如下按重量百分比数计的原料组成：
    Figure PCTCN2015095879-appb-100003
    Figure PCTCN2015095879-appb-100004
  5. 根据权利要求1或2所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，所述聚磷酸铵的平均粒径为8～10μm。
  6. 根据权利要求1或2所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，所述季戊四醇磷酸酯的平均粒径为5～8μm。
  7. 根据权利要求1或2所述的聚丙烯专用高效无卤阻燃剂母粒，其特征在于，所述的双酚A双(二苯基磷酸酯)的粘度在40℃下为1800-2600mPa·s，色泽小于80。
  8. 一种权利要求1所述的聚丙烯专用高效无卤阻燃剂母粒的制备方法，其特征在于，包括如下步骤：
    S1.微孔聚丙烯的制备：将高熔体强度共聚聚丙烯、发泡剂、抗氧剂1010，抗氧剂168和硬脂酸钙搅拌，熔融共混挤出，切粒、干燥，即得所述微孔聚丙烯；
    S2.将S1步骤中所得的微孔聚丙烯和双酚A双(二苯基磷酸酯)混匀，静置，待用；
    S3.将季戊四醇硬脂酸酯、抗氧剂1010、抗氧剂168和S2步骤中所得的混合物进行熔融共混后，加入聚磷酸铵、季戊四醇磷酸酯和三聚氰胺共混，密炼，挤出，切粒即得所述聚丙烯专用高效无卤阻燃剂母粒。
  9. 根据权利要求8所述的制备方法，其特征在于，所述挤出机的长径比为20～40；挤出机的机筒温度为150～180℃；挤出机的主机转速300～700r/min。
  10. 一种微孔聚丙烯在制备聚丙烯专用高效无卤阻燃剂母粒中的应用，其特征在于，所述微孔聚丙烯采用如下制备方法制得：将高熔体强度共聚聚丙烯80～90％、发泡剂5～12％、抗氧剂10100.1～0.5％，抗氧剂1680.1～0.5％和硬脂酸钙0.5～1％搅拌，熔融共混挤出，切粒、干燥，即得所述微孔聚丙烯。
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