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CN108102213B - Flame-retardant polypropylene composition and preparation method and application thereof - Google Patents

Flame-retardant polypropylene composition and preparation method and application thereof Download PDF

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Publication number
CN108102213B
CN108102213B CN201711106143.0A CN201711106143A CN108102213B CN 108102213 B CN108102213 B CN 108102213B CN 201711106143 A CN201711106143 A CN 201711106143A CN 108102213 B CN108102213 B CN 108102213B
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flame
retardant
polypropylene composition
parts
antimony
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CN108102213A (en
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卢翔
黄险波
叶南飚
姜向新
杨友强
杨霄云
肖鹏
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Jiangsu Jinfa Renewable Resources Co ltd
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Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
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    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
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    • C08K3/2279Oxides; Hydroxides of metals of antimony
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/32Phosphorus-containing compounds
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    • C08K5/00Use of organic ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/06Ethers; Acetals; Ketals; Ortho-esters
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
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    • C08K5/1345Carboxylic esters of phenolcarboxylic acids
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    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/56Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57Organo-tin compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/328Phosphates of heavy metals
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/011Nanostructured additives

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Abstract

The invention discloses a flame-retardant polypropylene composition and a preparation method and application thereof, wherein the flame-retardant polypropylene composition comprises the following components: 60-80 parts of polypropylene resin; 10-25 parts of environment-friendly brominated flame retardant; 2-10 parts of flame-retardant synergist; 2-10 parts of a thermal stability modifier; the flame-retardant synergist is a compound of antimony flame-retardant synergist and inorganic powder, and the weight percentage of the antimony flame-retardant synergist is 45-55% based on the total weight of the flame-retardant synergist. According to the invention, the thermal stability modifier and the flame-retardant synergist are added into the flame-retardant polypropylene composition, and the flame-retardant polypropylene composition and the flame-retardant synergist have synergistic effect, so that the prepared flame-retardant polypropylene composition not only is remarkably improved in thermal stability, but also keeps good fluidity, and can be widely applied to various parts and products needing flame retardance and heat resistance, such as storage batteries, power supplies, extension plugs, lamp decorations, electric cookers, induction cookers and the like.

Description

Flame-retardant polypropylene composition and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant polypropylene composition, and a preparation method and application thereof.
Background
As is well known, polypropylene is a flammable substance because the oxygen index is only 17% -18%, and the flame retardant property is a precondition for the application of the polypropylene in the field of many small household appliances. But for some long-term heated, structurally complex products, such as: electric appliance housings or parts such as rice cookers, toilet covers, microwave ovens, wiring boards, induction cookers, and the like, require a material having high fluidity and high heat resistance in addition to flame retardant properties.
The flame retardant modification of polypropylene is mainly realized by adding a flame retardant into polypropylene resin to enable the polypropylene resin to generate specific physical and chemical reactions in the combustion process so as to achieve the purpose of flame retardance. The fire retardant suitable for polypropylene mainly comprises brominated fire retardant series and halogen-free fire retardant series. The bromine-series flame-retardant series mainly comprises octabromoether, octabromoS ether, decabromodiphenylethane, bromotriazine, poly (pentabromobenzyl) acrylate, brominated epoxy, brominated polystyrene and the like. The octabromo flame retardant mainly refers to octabromo ether and octabromo S ether, and can be widely applied to polypropylene flame retardant products due to the high-efficiency flame retardant property, and generally can meet the V-0 grade standard of a UL94 standard sample of 127mm multiplied by 12.7mm multiplied by 1.6 mm. Therefore, a material which is tested by the test method of UL94 to achieve V-0 grade flame retardant effect of a sample strip of 127mm multiplied by 12.7mm multiplied by 0.6mm is needed to meet the market demand. However, the octabromine flame retardant has a low self decomposition temperature, and bromine atoms on a molecular structure are easy to emit hydrogen bromide to eliminate reaction with adjacent hydrogen atoms in the processing process, and further catalyze the breakage of other carbon-bromine bonds, so that the thermal stability of the octabromine flame retardant is reduced, the polypropylene material added with the octabromine flame retardant is easy to degrade and discolor due to overheating in the processing process, and the application of the polypropylene material in the field needing certain heat resistance is severely limited.
In order to improve the thermal stability of octabromo flame-retardant polypropylene materials, patent CN100398503C discloses that the thermal decomposition temperature of octabromo ether is increased by adding an ionic emulsifier, a non-ionic emulsifier or an amphoteric surfactant, and sorbitol sugar, glycidyl isocyanurate, 1, 4-butanediol bis (β -aminocrotonic acid) ester during the preparation of octabromo ether. The university of fertilizer industry reports that the thermal decomposition temperature of octabromoether is increased by a method of coating octabromoether by amino resin prepolymer, wherein the initial decomposition temperature of the coated octabromoether is increased from 160 ℃ to over 240 ℃, at volume 32, phase 6, page 837-840. Patent CN102250382A discloses a method for improving the thermal stability of octabromoether by adding zinc stearate/barium stearate or zinc stearate/calcium stearate composite thermal stability auxiliary agent with specific proportion, composite antioxidant with specific dosage and specific proportion, and coupling agent of specific variety.
The method has different effects on improving the thermal stability of the octabromoether flame retardant, but the process is complex and the cost is high.
Disclosure of Invention
In order to solve the problem of poor thermal stability of the flame-retardant polypropylene composition, the invention aims to provide a flame-retardant polypropylene composition which not only has remarkably improved thermal stability, but also retains good fluidity.
The invention is realized by the following technical scheme:
the flame-retardant polypropylene composition comprises the following components in parts by weight:
60-80 parts of polypropylene resin;
10-25 parts of environment-friendly brominated flame retardant;
2-10 parts of flame-retardant synergist;
2-10 parts of a thermal stability modifier;
0.1 to 2 portions of composite antioxidant;
wherein the flame-retardant synergist is a compound of antimony flame-retardant synergist and inorganic powder, and is based on the total weight of the flame-retardant synergist,
the weight percentage of the antimony flame-retardant synergist is 45-55%. Because the antimony flame-retardant synergist can accelerate the decomposition of the environment-friendly brominated flame retardant and reduce the thermal decomposition temperature of the environment-friendly brominated flame retardant, the antimony flame-retardant synergist and other inorganic powder are compounded to form a flame-retardant synergistic system, the content of antimony trioxide is reduced, so that the damage to heat resistance is reduced, and the synergistic efficiency meeting the flame-retardant requirement can be ensured.
The polypropylene resin is homopolymerized polypropylene.
The antimony flame-retardant synergist is one or a mixture of more of antimony trioxide, sodium antimonate, antimony phosphate or antimony phosphite.
The inorganic powder is selected from montmorillonite, wollastonite, calcium carbonate, silica, glass microsphere, carbon nanotube or graphene
One or a mixture of several.
The environment-friendly bromine-series flame retardant is one or a mixture of more of eight bromine ether, eight bromine S ether, poly (pentabromobenzyl acrylate), decabromodiphenylethane or bromotriazine.
The heat stability modifier is one or a mixture of more of a calcium-zinc heat stabilizer, a barium-zinc heat stabilizer or an organic tin heat stabilizer, and preferably a compound of the organic tin heat stabilizer and the barium-zinc heat stabilizer in a weight ratio of 1: 1.
The composite antioxidant is a compound of a hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant in a weight ratio of 1:5-5: 1.
According to the actual performance requirements, the flame retardant polypropylene composition of the invention further comprises 0.1-1 part of lubricant by weight, wherein the lubricant is one or a mixture of more of stearamide lubricants, ester lubricants or white mineral oil. .
The invention also provides a preparation method of the flame-retardant polypropylene composition, which comprises the following steps:
(a) fully mixing the raw materials of the components in a high-speed mixer for 5-30 minutes according to the proportion;
(b) and (2) conveying the mixture into a double-screw extruder, controlling the temperature of each section of screw of the extruder between 160-220 ℃, controlling the feeding speed at 100-600 revolutions per minute, controlling the length-diameter ratio of the screw of the double-screw extruder at 25-40, and controlling the rotation speed of the screw at 200-600 revolutions per minute, fully melting, plasticizing and blending the materials under the shearing, mixing and conveying of the screw, and then extruding, granulating and drying to obtain the flame-retardant polypropylene composition.
The invention also provides the application of the flame-retardant polypropylene composition in power supplies, extension plugs, bathrooms, storage batteries, lamp decorations, electric cookers or electromagnetic ovens.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the flame-retardant synergist is added into the flame-retardant polypropylene composition, and the thermal stability modifier and the composite antioxidant are combined, so that the prepared flame-retardant polypropylene composition not only is remarkably improved in thermal stability, but also keeps good fluidity, and can be widely applied to various parts and products needing flame retardance and heat resistance, such as storage batteries, power supplies, extension plugs, lamp decorations, electric cookers, induction cookers and the like.
(2) The flame-retardant polypropylene composition with high fluidity and high thermal stability can be prepared by adopting a simple blending method, so that the complex process and method for preparing the flame-retardant polypropylene material by firstly preparing the octabromo flame retardant with higher thermal stability and then utilizing the octabromo flame retardant are avoided, the preparation flow is simplified, and the flame-retardant polypropylene composition has the characteristics of high preparation efficiency, simplicity in operation and the like.
Detailed Description
The following examples are given to specifically describe the present invention, but are not limited thereto.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
polypropylene resin: homo-polypropylene of Zhonghai Shell brand number PP HP 500N;
environmental-friendly brominated flame retardant: octabromo ether of the sea water chemical industry of lianyuankang, octabromo S ether of danxia chemical industry; decabromodiphenylethane of Bailexus chemical Co., Ltd, Israel chemical bromotriazine;
antimony-based synergistic flame retardant: antimony trioxide from Chanderchen antimony Limited liability company, antimony phosphate and antimony phosphite from Shenzhen Jingqiao technology Limited;
inorganic powder: montmorillonite of Jiangxi Weipu science and technology Limited, wollastonite of Dalian Yida fine mineral, calcium carbonate of Dongguan Melitai chemical industry Limited, silicon dioxide of Guangzhou Zongvana chemical industry Limited, glass beads of 3M (China) Limited, carbon nanotubes of Shenzhen special new material science and technology Limited, and graphene of Suzhou carbofeng graphene science and technology Limited;
thermal stability modifier: organotin heat stabilizers of chemical industry ltd of Benxing Hubei, barium-zinc heat stabilizers of Shanghai trade ltd of Aidicke;
lubricant: stearamide lubricants;
compound antioxidant: the Qiba refined hindered phenol type main antioxidant 168 and the phosphite ester type auxiliary antioxidant 1010 are mixed according to the mass ratio of 1: 2-1: 4.
The performance test method comprises the following steps:
melt index: a plastic melt flow rate tester is adopted, the test temperature is 230 ℃, and the weight is 2.16 kg.
Initial decomposition temperature: adopting a thermal weight loss analyzer, wherein the testing temperature range is 30-700 ℃, the heating rate is 10 ℃/min, and the temperature corresponding to 5wt% thermal weight loss is taken as the initial decomposition temperature.
Examples 1-8 and comparative examples 1-5:
weighing the components according to the weight parts shown in the table 1, and fully mixing the raw materials of the components in a high-speed mixer for 5-30 minutes according to the proportion; and (2) conveying the mixture into a double-screw extruder, controlling the temperature of each section of screw of the extruder between 160-220 ℃, controlling the feeding speed at 100-600 revolutions per minute, controlling the length-diameter ratio of the screw of the double-screw extruder at 25-40, and controlling the rotation speed of the screw at 200-600 revolutions per minute, fully melting, plasticizing and blending the materials under the shearing, mixing and conveying of the screw, and then extruding, granulating and drying to obtain the flame-retardant polypropylene composition. Corresponding test specimens were produced according to the standard and the properties were determined, the specific values being listed in Table 1.
TABLE 1 flame retardant Polypropylene composite composition and Properties
Figure DEST_PATH_IMAGE001
According to the test results of the examples and the comparative examples, the flame-retardant polypropylene composition prepared by adding the specific compounded flame-retardant synergist into the flame-retardant polypropylene composition and combining the thermal stability modifier and the composite antioxidant not only is remarkably improved in thermal stability, but also keeps good fluidity.

Claims (8)

1. The flame-retardant polypropylene composition is characterized by comprising the following components in parts by weight:
60-80 parts of polypropylene resin;
10-25 parts of environment-friendly brominated flame retardant;
2-10 parts of flame-retardant synergist;
2-10 parts of a thermal stability modifier;
0.1 to 2 portions of composite antioxidant;
the flame-retardant synergist is a compound of antimony flame-retardant synergist and inorganic powder, and the weight percentage of the antimony flame-retardant synergist is 45-55% based on the total weight of the flame-retardant synergist;
the inorganic powder is a mixture of at least four of montmorillonite, silica, glass beads, carbon nanotubes or graphene;
the thermal stability modifier is one or a mixture of more of a calcium-zinc heat stabilizer, a barium-zinc heat stabilizer or an organic tin heat stabilizer;
the composite antioxidant is a compound of a hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant in a weight ratio of 1:5-5: 1.
2. The flame retardant polypropylene composition according to claim 1, wherein the polypropylene resin is a homo-polypropylene.
3. The flame retardant polypropylene composition according to claim 1, wherein the antimony-based flame retardant synergist is one or more of antimony trioxide, sodium antimonate, antimony phosphate or antimony phosphite.
4. The flame retardant polypropylene composition according to claim 1, wherein the environmentally friendly bromine-based flame retardant is one or a mixture of eight bromine ethers, eight bromine S ethers, poly (pentabromobenzyl acrylate), decabromodiphenylethane or bromotriazine.
5. The flame retardant polypropylene composition according to claim 1, wherein the heat stability modifier is a compound of an organotin heat stabilizer and a barium zinc heat stabilizer in a weight ratio of 1: 1.
6. The flame retardant polypropylene composition according to any one of claims 1 to 5, further comprising 0.1 to 1 part by weight of a lubricant, wherein the lubricant is one or a mixture of stearylamine lubricant, ester lubricant or white mineral oil.
7. The process for the preparation of a flame retardant polypropylene composition according to any of claims 1 to 6, comprising the steps of:
(a) fully mixing the raw materials of the components in a high-speed mixer for 5-30 minutes according to the proportion;
(b) and (2) conveying the mixture into a double-screw extruder, controlling the temperature of each section of screw of the extruder between 160-220 ℃, controlling the feeding speed at 100-600 revolutions per minute, controlling the length-diameter ratio of the screw of the double-screw extruder at 25-40, and controlling the rotation speed of the screw at 200-600 revolutions per minute, fully melting, plasticizing and blending the materials under the shearing, mixing and conveying of the screw, and then extruding, granulating and drying to obtain the flame-retardant polypropylene composition.
8. Use of the flame retardant polypropylene composition according to any one of claims 1 to 6 in power supplies, extension plugs, bathrooms, storage batteries, lighting fixtures, electric cookers or electromagnetic ovens.
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CN109161094B (en) * 2018-07-09 2021-04-13 金发科技股份有限公司 Flame-retardant polypropylene material and preparation method and application thereof
CN109486041A (en) * 2018-11-01 2019-03-19 广东基地光电有限公司 A kind of fire-retardant PP diffuser plate and preparation method thereof
CN111484668A (en) * 2019-12-19 2020-08-04 会通新材料股份有限公司 Flame-retardant polypropylene composite material and preparation method thereof
CN111205553A (en) * 2020-01-09 2020-05-29 山东清河化工科技有限公司 Preparation method of ultrahigh molecular weight polypropylene material with high thermal-oxidative stability
CN112358687B (en) * 2020-11-10 2023-06-20 江苏金发科技新材料有限公司 Flame-retardant polypropylene composition and preparation method thereof
CN112480534A (en) * 2020-11-26 2021-03-12 上海明克包装制品有限公司 Heat-resistant flame-retardant paper-plastic composite bag and preparation method thereof
CN114085448B (en) * 2021-12-23 2022-11-18 南通科顺建筑新材料有限公司 High-temperature-resistant waterproof coiled material sizing material composition, high-temperature-resistant waterproof coiled material sizing material, and preparation method and application thereof
CN114835556A (en) * 2022-05-11 2022-08-02 常州巨德新材料有限公司 Bromine-containing norbornene derivative, preparation method thereof and flame-retardant polydicyclopentadiene material

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JP2003160705A (en) * 2001-11-28 2003-06-06 Suzuhiro Kagaku:Kk Flame-retardant polypropylene composition

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CN1696188A (en) * 2005-03-07 2005-11-16 广东顾地塑胶股份有限公司 Fire retardant composite material of polypropylene and application
CN101469095B (en) * 2007-12-28 2013-01-30 上海普利特复合材料股份有限公司 Environment protective and flame-retardant polypropelene composition
CN102250382B (en) * 2011-05-17 2012-10-31 山东兄弟科技股份有限公司 Preparation method of high thermostable eight bromo ether

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Publication number Priority date Publication date Assignee Title
JPH08113682A (en) * 1994-10-14 1996-05-07 Sumitomo Bakelite Co Ltd Flame-retardant polypropylene sheet
JP2003160705A (en) * 2001-11-28 2003-06-06 Suzuhiro Kagaku:Kk Flame-retardant polypropylene composition

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