WO2020173491A1 - 一种高极性阻燃聚丙烯组合物、制备方法及其应用 - Google Patents
一种高极性阻燃聚丙烯组合物、制备方法及其应用 Download PDFInfo
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- WO2020173491A1 WO2020173491A1 PCT/CN2020/077076 CN2020077076W WO2020173491A1 WO 2020173491 A1 WO2020173491 A1 WO 2020173491A1 CN 2020077076 W CN2020077076 W CN 2020077076W WO 2020173491 A1 WO2020173491 A1 WO 2020173491A1
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- polypropylene
- flame retardant
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- polarity
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the field of polymer materials, and specifically relates to a high-polarity flame-retardant polypropylene composition, a preparation method and its application in a plastic-sealed lead-acid battery casing.
- Lead-acid batteries are widely used in energy systems such as start-up, start-stop, traction, lighting, and communication.
- the shell materials are mainly ABS resin-based materials and polypropylene resin-based materials.
- lead-acid batteries for starting, starting and stopping, and some lead-acid batteries for communication use polypropylene resin-based materials, while others are mostly ABS resin-based materials, and some use AS resin, PC resin, PVC resin and PPE resin-based materials. Materials, but accounted for relatively little.
- the start-up, start-stop, and communication batteries used in European and American countries mostly use polypropylene resin-based materials.
- polypropylene is generally medium and high-impact injection molding grade special materials (for example, some domestic battery shell manufacturers use AY564, B3001
- the production cost is high, and most of them rely on imports, which consumes a lot of foreign exchange every year.
- the battery is often subjected to greater shock and vibration during use, and needs to face the test of the use of environmental temperature changes in the four seasons of the year, the impact performance of the shell material at room temperature and low temperature is relatively high; with the upgrading of products, the battery The flame retardancy requirements of shell materials are getting higher and higher.
- the existing co-polypropylene EPF30R (7% ethylene and? Copolymer) has good processing properties and rigidity, but its impact strength at room temperature and low temperature is low, and its flame retardancy cannot meet the requirements of the new standard.
- glue welding and hot plate welding are mainly used between the lead-acid battery cover and the tank.
- the shell material of the lead-acid battery using the glue welding process is thin, the internal stress introduced by welding is small, and the life cycle of the finished lead-acid battery
- the inner shell is not easy to crack; while the lead-acid battery shell material using the hot plate welding process is thick, and the internal stress introduced by welding is large.
- the finished lead-acid battery often has quality problems such as shell cracking during use, but the hot plate welding process Simple, efficient, and low cost.
- polypropylene-based materials are non-polar materials with low surface energy.
- hot plate welding is the main method. Therefore, it is necessary to develop a high-polarity flame-retardant polypropylene composition that can effectively improve its adhesion to glue while being highly effective.
- the purpose of the present invention is to provide a high-polarity flame-retardant polypropylene combination with good flame retardancy, excellent heat resistance, good material toughness, high melt strength, and easy glue welding in view of the deficiencies in the prior art Things.
- a highly polar flame-retardant polypropylene composition which includes the following components by weight:
- the adhesive force of the polypropylene composition welded by epoxy resin glue exceeds 40kgf.
- the polypropylene is copolymerized polypropylene or a mixture of copolymerized polypropylene and homopolymerized polypropylene
- the second monomer in the copolymerized polypropylene may be 1-butene, 1-pentene, 1-hexene 1-heptene
- the content of the second monomer is 3 ⁇ 5% of the weight of polypropylene; the melt flow rate of polypropylene is 0.3 ⁇ 3g/10mm; the choice of the polypropylene resin type gives the material good flexibility.
- the brominated flame retardant system is a compound system of brominated flame retardant and antimony trioxide.
- the brominated flame retardant is selected from the group consisting of decabromodiphenylethane, tetrabromobisphenol A, bis(2,3-dibromo One or more of propyl) ether, tetrabromobisphenol S, bis(2,3-dibromopropyl) ether or bromotriazine.
- the polarity modifier is selected from styrene maleimide copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted PP copolymer, maleic anhydride grafted POE copolymer, ethylene-acrylic acid One or more of butyl ester-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, and the like.
- the antioxidant is a compound of hindered phenolic antioxidant and thioester;
- the hindered phenolic antioxidant is tetrakis[(3-(3, 5 -di-tert-butyl-4-hydroxyphenyl) propylene Acid] pentaerythritol ester (trade name 1010) or (3-(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (trade name 1076), etc.
- the thioester is thio Dilaurate dipropionate (DLTDP), dioctadecyl thiodipropionate (trade name DSTDP), etc.
- DLTDP dioctadecyl thiodipropionate
- DSTDP dioctadecyl thiodipropionate
- the molecular weight of the light stabilizer is greater than 2000, such as poly- ⁇ [6-[(1, 1, 3, 3, -tetramethylbutyl) -imino] -1, 3, 5, -triazine-2, 4-Diyl][2- (2, 2, 6, 6, -tetramethylpiperidinyl)-nimino-hexamethylene-[4-(2, 2, 6, 6 -tetramethylpiperidine Pyridinyl)-nimino (trade name UV-944), poly(1-hydroxyethyl-2, 2, 6, 6, -tetramethyl-4-hydroxypiperidine) succinate (trade name UV- 622), etc.
- the addition of light stabilizers can improve the UV resistance of the material.
- the acid absorption assistant is selected from one or more of hydrotalcite, highly active magnesium oxide, zinc stearate, calcium stearate, and magnesium hydroxide.
- the addition of the acid absorbent can reduce the effect of the flame retardant on The role of forming equipment corrosion.
- the processing aid is one or more of polyethylene wax, calcium stearate, stearic acid, polyamide wax, etc.
- the addition of a lubricant can improve the processing performance.
- a method for preparing a highly polar flame-retardant polypropylene composition which includes the following steps:
- an application of a highly polar flame-retardant polypropylene composition in the preparation of a shell material for a glue-sealed lead-acid battery Further, the high-polarity flame-retardant polypropylene composition is applied to a lead-acid battery shell material welded by epoxy resin glue.
- the present invention has the following beneficial effects:
- the present invention uses copolymerized polypropylene or a mixture of copolymerized polypropylene and homopolymerized polypropylene to make the material have good flexibility; at the same time, organic bromine flame retardant is used as the main flame retardant, and antimony trioxide is used as the auxiliary barrier. Combustion agent, improve the flame retardant effect, the amount of flame retardant is small, and the impact on the toughness of the material is small; the use of hindered phenolic antioxidants and thioesters as the compound antioxidant system makes the material have good high temperature thermal oxygen aging , To ensure the stable thermal performance of the material under high temperature; the added acid absorption aid can greatly reduce the corrosion of the material to the mold.
- the polarity modifier used in the present invention can effectively improve the adhesion between the lead-acid battery shell material prepared from the polypropylene composition and the epoxy resin glue.
- the high-polarity flame-retardant polypropylene composition of the present invention prepares sample strips according to standards, and performs the performance tests listed in Table 1 below.
- the equipment used in the present invention includes:
- the twin-screw extruder used to prepare the highly polar flame-retardant polypropylene composition is SHJ-30 produced by Nanjing Ruiya High Polymer Equipment Co., Ltd.
- the injection molding machine used to prepare the test strips of the high-polarity flame-retardant polypropylene composition is the B-920 type produced by Zhejiang Haitian Injection Molding Machine Co., Ltd.
- the instrument used to test the melt flow rate is the ZR21452 melt flow rate meter produced by Meister Industrial Systems (China) Co., Ltd.
- the impact testing machine used to test the impact strength is the T92 type produced by Tinius Olsenis, USA.
- the universal testing machine for testing tensile strength and adhesion is H10K-S manufactured by Hounsfield Company.
- the UL-94 vertical combustion instrument used to test the combustion performance is the HVUL-2 type produced by ATLAS, USA.
- the provided raw materials can be purchased from the market.
- polypropylene is selected from CNOOC and Shell EP300M and HP840N;
- Decabromodiphenylethane is selected from Shandong Shouguang RDT-3K;
- Octabromoether is selected from Lianyungang Legend Flame Retardant Technology Co., Ltd. E-08N;
- Antimony trioxide is selected from S-05N of Yunnan Muli Antimony Industry;
- Polar modifier Kingfa Technology KF118, Planck BONDYRAM 1001CN;
- Test conditions The sample thickness is 0.8mm, 150 ° C, the number of air changes is 5-20 times/hour, and the sample has no cracking and powdering phenomenon within 400 hours.
- Test conditions The thickness of the sample strip is 0.8mm, 150 ° C, the number of air changes is 5-20 times/hour, oven,
- Example 2 The sample has no cracking and powdering phenomenon within 400 hours.
- Example 2 The sample has no cracking and powdering phenomenon within 400 hours.
- Test conditions 150 ° C, oven with 5-20 air changes/hour, sample thickness of 0.8mm, no cracking and powdering of the sample within 400 hours.
- Test conditions 150 ° C, oven with 5-20 air changes per hour, sample thickness of 0.8mm, no cracking and powdering of samples within hours.
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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)
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CN201910149559.3A CN109880236A (zh) | 2019-02-28 | 2019-02-28 | 一种高极性阻燃聚丙烯组合物、制备方法及其应用 |
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CN114672099A (zh) * | 2022-02-22 | 2022-06-28 | 金发科技股份有限公司 | 一种氢氧化镁母粒及其制备方法和应用 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN113012768B (zh) * | 2021-03-03 | 2023-03-17 | 上海大学 | 一种高分子阻燃复合材料基因库的构建方法及应用 |
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