CN116102880A - Long carbon chain polyamide composition for battery sealing ring and preparation method thereof - Google Patents
Long carbon chain polyamide composition for battery sealing ring and preparation method thereof Download PDFInfo
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- CN116102880A CN116102880A CN202211585914.XA CN202211585914A CN116102880A CN 116102880 A CN116102880 A CN 116102880A CN 202211585914 A CN202211585914 A CN 202211585914A CN 116102880 A CN116102880 A CN 116102880A
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- 238000007789 sealing Methods 0.000 title claims abstract description 50
- 239000004952 Polyamide Substances 0.000 title claims abstract description 42
- 229920002647 polyamide Polymers 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- 229920006396 polyamide 1012 Polymers 0.000 claims abstract description 25
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000000806 elastomer Substances 0.000 claims abstract description 24
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 12
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 12
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 11
- 239000008116 calcium stearate Substances 0.000 claims description 11
- 235000013539 calcium stearate Nutrition 0.000 claims description 11
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- -1 carboxylic acid sodium salt Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- NWADXBLMWHFGGU-UHFFFAOYSA-N dodecanoic anhydride Chemical compound CCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCC NWADXBLMWHFGGU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920000572 Nylon 6/12 Polymers 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004677 Nylon Substances 0.000 abstract description 4
- 229920001778 nylon Polymers 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 230000009172 bursting Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 35
- 238000012360 testing method Methods 0.000 description 31
- 238000001746 injection moulding Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920006099 Vestamid® Polymers 0.000 description 9
- 239000002585 base Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention discloses a long carbon chain polyamide composition for a battery sealing ring and a preparation method thereof, belonging to the field of polymer composite materials, and comprising the following components in parts by weight: 65-90 parts of long carbon chain polyamide resin, 2-15 parts of polyamide elastomer, 6-15 parts of flame retardant, 0.1-2 parts of nucleating agent, 0.1-4 parts of antioxidant, 0-2 parts of lubricant and 0.01-0.1 part of dispersing agent. The invention provides a method for preparing an alkaline battery sealing ring by taking long carbon chain nylon PA1012 as matrix resin and adding a polyamide elastomer, a flame retardant, a nucleating agent, a lubricant and an antioxidant for modification, which is compared with the PA612 and PA66 battery sealing ring materials which are widely used in the market: the product has low water absorption, good flame retardance, good alkali liquid resistance and stable bursting pressure, can ensure that the alkaline battery is not leaked for a long time, and greatly improves the safety performance of the alkaline battery.
Description
Technical Field
The invention relates to the field of polymer composite materials, in particular to a long carbon chain polyamide composition for a battery sealing ring and a preparation method thereof.
Background
The current annual usage of alkaline batteries reaches over 200 hundred million, and each battery needs a sealing ring. At present, the alkaline battery sealing ring mainly uses PA66, PA610 and PA612 modified materials, wherein the water absorption rate of the materials is the lowest PA612 and the highest PA 66; the alkali resistance PA612 is the best and the PA66 is the worst; the current battery sealing ring using PA612 on the market is installed in an alkaline battery, and when the battery sealing ring is stored at 90 ℃ and 90% humidity, the leakage phenomenon can occur within 30 days, so that the battery sealing ring cannot be used in a humid environment; therefore, a long carbon chain polyamide composition for an alkaline battery sealing ring, which is little influenced by environmental humidity and can keep alkali resistance for a long time, and a preparation method thereof are provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a long carbon chain polyamide composition for an alkaline battery sealing ring, which is little influenced by environmental humidity and can keep alkali resistance for a long time, and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the long carbon chain polyamide composition for the battery sealing ring comprises the following components in parts by mass:
65-90 parts of long carbon chain polyamide resin, 2-15 parts of polyamide elastomer, 6-15 parts of flame retardant, 0.1-2 parts of nucleating agent, 0.1-4 parts of antioxidant, 0-2 parts of lubricant and 0.01-0.1 part of dispersing agent.
Further, the long carbon chain polyamide resin in the composition is PA1012 with low water absorption and good alkali resistance, namely polydecanediamine dodecanoyl anhydride, which is used as a base material for toughening, flame retarding, lubricating and dispersing modification, and is used for the application of an alkaline battery sealing ring.
Further, the polyamide elastomer is a copolymer with one of polyamide 11, polyamide 12, polyamide 1012 and polyamide 6 as hard segments and polyether or polyester as soft segments.
Further, the flame retardant is melamine cyanurate MCA.
Further, the nucleating agent is long-chain linear saturated carboxylic acid sodium salt taking carbon chain length C28-C32 as a main component; such as, for example, clariant NAV-101, germany.
Further, the antioxidant is one or a mixture of more than two of antioxidant 1098, antioxidant 245 and antioxidant 168.
Further, the lubricant is one or a mixture of two or more of PETS, calcium stearate, zinc stearate and silicone master batch.
Further, the dispersing agent is aminosilane; the aminosilane is at least one of monoaminosilane and bisaminosilane;
wherein the monoaminosilane is one or a mixture of more than two of 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl trimethoxy silane and 3-aminopropyl triethoxy silane;
wherein the bisaminosilane is one or a mixture of more than two of N-2-aminoethyl-3-aminopropyl methyl diethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, N-2-aminoethyl-3-aminopropyl triethoxy silane and N-2-aminoethyl-3-aminopropyl trimethoxy silane.
The application also provides a preparation method of the long carbon chain polyamide composition for the battery sealing ring, which comprises the following steps:
uniformly mixing long carbon chain polyamide resin, polyamide elastomer, nucleating agent, antioxidant, lubricant and dispersing agent by a high-speed mixer to obtain a material A; in the preparation process of the material A, firstly, mixing all granular materials for 3-5 minutes by using a high-speed mixer, and then adding a dispersing agent to mix for 3-5 minutes;
adding the material A into a main hopper of an extruder, and discharging the material A into the main hopper through a metering scale; adding the flame retardant or the flame retardant master batch into an auxiliary hopper of an extruder, and carrying out side feeding and granulation by a metering scale; the temperature of the extruder is 200-270 ℃; the temperature of one area of the extruder is 160-220 ℃, and the temperature of other areas and the temperature of a machine head are 220-260 ℃; the rotating speed of the extruder is 50-1000r/min.
The invention has the beneficial effects that:
according to the composition, the PA1012 is used as the modified base material of the sealing ring of the alkaline battery, so that the water absorption rate of the material is greatly reduced compared with that of the existing PA66, PA610 and PA612, the influence of temperature and humidity in the service environment of the battery after the composition is installed in the alkaline battery is ensured to be small, the sealing ring cannot generate liquid leakage due to large dimensional change after absorption, and the service life of the battery is greatly prolonged; meanwhile, the alkali corrosion resistance of the alkaline-resistant battery of the PA1012 is greatly improved compared with that of the existing PA66, PA610 and PA612, and the storage and service life of the battery are directly improved;
according to the invention, flame retardant modification is carried out on the PA1012, so that the nylon sealing ring material cannot catch fire when the battery is damaged by impact and the like in the use process, and the use safety performance is greatly improved; the nylon elastomer is used for toughening the material, so that the nylon elastomer has good compatibility with PA1012, improves the toughness of the material, and does not influence the flame retardant property of the material; the invention adopts the scheme of combining the nucleating agent and the lubricant, greatly improves the mold release property of the material during injection molding processing, and reduces the molding period.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The long carbon chain polyamide composition for the battery sealing ring comprises the following components in parts by mass:
65-90 parts of long carbon chain polyamide resin, 2-15 parts of polyamide elastomer, 6-15 parts of flame retardant, 0.1-2 parts of nucleating agent, 0.1-4 parts of antioxidant, 0-2 parts of lubricant and 0.01-0.1 part of dispersing agent.
Further, the long carbon chain polyamide resin in the composition is PA1012 with low water absorption and good alkali resistance, namely polydecanediamine dodecanoyl anhydride, which is used as a base material for toughening, flame retarding, lubricating and dispersing modification, and is used for the application of an alkaline battery sealing ring.
Further, the polyamide elastomer is a copolymer with one of polyamide 11, polyamide 12, polyamide 1012 and polyamide 6 as hard segments and polyether and polyester as soft segments.
Further, the flame retardant is melamine cyanurate MCA.
Further, the nucleating agent is long-chain linear saturated carboxylic acid sodium salt taking carbon chain length C28-C32 as a main component; such as, for example, clariant NAV-101, germany.
Further, the antioxidant is one or a mixture of more than two of antioxidant 1098, antioxidant 245 and antioxidant 168.
Further, the lubricant is one or a mixture of two or more of PETS, calcium stearate, zinc stearate and silicone master batch.
Further, the dispersing agent is aminosilane; the aminosilane comprises monoaminosilane and bisaminosilane;
wherein the monoaminosilane comprises: 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane;
wherein the bisaminosilane comprises: n-2-aminoethyl-3-aminopropyl methyl diethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, N-2-aminoethyl-3-aminopropyl triethoxy silane, N-2-aminoethyl-3-aminopropyl trimethoxy silane.
The application also provides a preparation method of the long carbon chain polyamide composition for the battery sealing ring, which comprises the following steps:
uniformly mixing long carbon chain polyamide resin, polyamide elastomer, nucleating agent, antioxidant, lubricant and dispersing agent by a high-speed mixer to obtain a material A; in the preparation process of the material A, firstly, mixing all granular materials for 3-5 minutes by using a high-speed mixer, and then adding a dispersing agent to mix for 3-5 minutes;
adding the material A into a main hopper of an extruder, and discharging the material A into the main hopper through a metering scale; adding the flame retardant or the flame retardant master batch into an auxiliary hopper of an extruder, and carrying out side feeding and granulation by a metering scale; the temperature of the extruder is 200-270 ℃; the temperature of one area of the extruder is 160-220 ℃, and the temperature of other areas and the temperature of a machine head are 220-260 ℃; the rotating speed of the extruder is 50-1000r/min.
To further illustrate the present invention, the following is a detailed description of the long carbon chain polyamide composition for alkaline cell seal rings provided herein in connection with the examples. The raw materials in each of the following examples are commercially available.
Example 1
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, dongruisen, shandong, 10Kg of polyamide elastomer, germany Yingchang specialty Chemie, VESTAMID E, 0.2Kg of NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate, 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyldimethoxysilane are weighed out. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Example 2
80.78Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, shandong, 5Kg of polyamide elastomer, germany, yingchan, specialty Chemie, VESTAMID E, 2Kg of Kelaien NAV-101,0.1Kg of antioxidant 245,0.1Kg of lubricant PETS,0.02 Kg of 3-aminopropyl triethoxysilane were weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 12Kg of PA1012 master batch (50% content) of the flame retardant MCA, and feeding into a side feeding barrel of a double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Example 3
90.25Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new Shandong Chenrisen material and 2Kg of polyamide elastomer French Acomax were weighed
1.2Kg of Germany Clariant NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.2Kg of lubricant PETS,0.5 Kg of calcium stearate and 0.05 Kg of 3-aminopropyl trimethoxysilane. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 6Kg of flame retardant BASF Melapur MC25, and feeding the flame retardant BASF Melapur MC25 into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Example 4
67.7Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new Shandong Chenrisen material, 9Kg of polyamide elastomer, german Yingchang specialty Chemie company VESTAMID E, 0.1Kg of German Kelaien NAV-101,0.3Kg of antioxidant 1098,0.2Kg of antioxidant 168,0.6Kg of lubricant PETS, 2Kg of Dow Corning silicone master batch MB50-002,0.1 Kg of N-2-aminoethyl-3-aminopropyl methyl diethoxysilane are weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, 20Kg of PA1012 master batch (50% content) of flame retardant MCA is weighed and fed into a side feeding barrel of a double-screw extruder by a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Example 5
75.75Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new Shandong Chenrisen material and 10Kg of polyamide elastomer French Acomax were weighed
0.2Kg of Germany Corean NAV-101,0.4Kg of antioxidant 1098,0.2Kg of antioxidant 168,0.4Kg of lubricant PETS, 1Kg of Dow Corning silicone masterbatch MB50-002,0.05 Kg of N-2-aminoethyl-3-aminopropyl triethoxysilane. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 12Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Example 6
64.39Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, shandong, 15Kg of polyamide elastomer, germany Yingzhuang specialty Chemie VESTAMID E, 0.5Kg of Germany Kelaien NAV-101,2Kg of antioxidant 1098,2Kg of antioxidant 168,1Kg of lubricant PETS,0.1 Kg of Dow Corning silicone master batch MB50-002,0.01 Kg of N-2-aminoethyl-3-aminopropyl trimethoxysilane are weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, 15Kg of flame retardant BASF Melapur MC25 is weighed, and is fed into a side feeding machine barrel of the double-screw extruder by a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 1
78.15Kg of medium-viscosity polyamide 612 (relative viscosity 2.7) of new material from Chemie, shandong, dengchenruisen, 10Kg of polyamide elastomer, VESTAMID E, 0.2Kg of NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate, and 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyldimethoxysilane were weighed out. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 2
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, dongruisen, shandong, 10Kg of polyamide elastomer, germany Yingchang specialty Chemie, VESTAMID E, 0.2Kg of NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate, 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyldimethoxysilane are weighed out. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 3
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7), 10Kg of toughening agent maleic anhydride grafted POE (POE-MA), 0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate and 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyl dimethoxy silane are weighed out. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 4
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7), 10Kg of toughening agent maleic anhydride graft hydrogenated styrene-butadiene-styrene block copolymer (SEBS-MA), 0.2Kg of Germany Clay NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate and 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyldimethoxysilane are weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 5
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, shandong, was weighed out, 10Kg of polyamide elastomer, germany, yingchuang specialty Chemie, VESTAMID E, 0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.05 Kg of 3-aminopropyl methyldimethoxysilane. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 6
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, shandong, chengruisen, 10Kg of polyamide elastomer, VESTAMID E, 0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate, and 0.5Kg of Dow Corning silicone master batch MB50-002,0.05 Kg of 3-aminopropyl methyldimethoxysilane were weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
Comparative example 7
78.15Kg of medium-viscosity polyamide 1012 (relative viscosity 2.7) of new material from Chemie, shandong, dengchenruisen, 10Kg of polyamide elastomer, VESTAMID E, 0.2Kg of NAV-101,0.2Kg of antioxidant 1098,0.1Kg of antioxidant 168,0.3Kg of lubricant PETS,0.5 Kg of calcium stearate, and 0.5Kg of silicone masterbatch MB50-002 from Corning Germany were weighed. Then according to the preparation method, after uniformly mixing various materials by using a high-speed mixer, feeding the materials into a main hopper of a double-screw extruder by using a weighing scale; in addition, weighing 10Kg of flame retardant BASF Melapur MC25, and feeding into a side feeding machine barrel of the double-screw extruder by using a weighing scale; granulating by a double screw extruder, drying injection molding sample bars, testing mechanical properties, comparing the mold release of injection molding sealing rings, and installing the sealing rings into a battery for temperature and humidity testing.
The materials obtained in examples 1 to 6 and the products of comparative examples 1 to 7 were tested for mechanical properties (GB 1040 tensile test, 1A-shaped bars), mold release (injection seal), flame resistance (UL 94,1.6 mm), burst pressure fluidity (100 seals were taken to test burst pressure respectively), temperature and humidity resistance (seals were mounted in alkaline cells and stored at 90 ℃,90% humidity until leakage occurred), and the following tables were obtained after the test:
TABLE 1 results of mechanical, mold release, flame retardancy, burst pressure fluctuation test and temperature and humidity resistance test
From the results in table 1, it can be seen that:
1. comparative example 1 using PA612, which is currently in common use in the market, as a resin base material, it can be seen that the leakage failure time is increased from less than 30 days to more than 100 days when PA1012 is used (example 1) in accelerated temperature and humidity test.
2. In comparative example 2, the material was not flame retardant since no flame retardant was added.
3. Both comparative example 3 and comparative example 4 are not flame retardant due to the addition of the maleic anhydride grafted toughening agent.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The long carbon chain polyamide composition for the battery sealing ring is characterized by comprising the following components in parts by weight:
65-90 parts of long carbon chain polyamide resin, 2-15 parts of polyamide elastomer, 6-15 parts of flame retardant, 0.1-2 parts of nucleating agent, 0.1-4 parts of antioxidant, 0-2 parts of lubricant and 0.01-0.1 part of dispersing agent.
2. The long carbon chain polyamide composition for battery seal ring of claim 1 wherein the long carbon chain polyamide resin is polydecanediamine dodecanoyl anhydride.
3. The long carbon chain polyamide composition for battery seal ring according to claim 2, wherein the polyamide elastomer is a copolymer having one of polyamide 11, polyamide 12, polyamide 1012, and polyamide 6 as a hard segment and polyether or polyester as a soft segment.
4. The long carbon chain polyamide composition for battery seal ring of claim 1 wherein said flame retardant is melamine cyanurate.
5. The long carbon chain polyamide composition for battery seal ring of claim 1 wherein said nucleating agent is a long chain linear saturated carboxylic acid sodium salt having a carbon chain length of C28-C32.
6. The long carbon chain polyamide composition for battery seal ring of claim 1, wherein the antioxidant is one or a mixture of two or more of antioxidant 1098, antioxidant 245, antioxidant 168.
7. The long carbon chain polyamide composition for battery seal ring of claim 1, wherein the lubricant is one or a mixture of two or more of PETS, calcium stearate, zinc stearate, silicone master batch.
8. The long carbon chain polyamide composition for battery seal ring of claim 1, wherein said dispersant is an aminosilane; the aminosilane is at least one of monoaminosilane and bisaminosilane;
wherein the monoaminosilane is one or a mixture of more than two of 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl trimethoxy silane and 3-aminopropyl triethoxy silane;
wherein the bisaminosilane is one or a mixture of more than two of N-2-aminoethyl-3-aminopropyl methyl diethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, N-2-aminoethyl-3-aminopropyl triethoxy silane and N-2-aminoethyl-3-aminopropyl trimethoxy silane.
9. A process for the preparation of a long carbon chain polyamide composition for battery sealing rings as claimed in any one of claims 1 to 8, comprising the steps of:
uniformly mixing long carbon chain polyamide resin, polyamide elastomer, nucleating agent, antioxidant, lubricant and dispersing agent by a high-speed mixer to obtain a material A;
adding the material A into a main hopper of an extruder, and discharging the material A into the main hopper through a metering scale; adding the flame retardant or the flame retardant master batch into an auxiliary hopper of an extruder, and carrying out side feeding and granulation by a metering scale.
10. The method according to claim 9, wherein the extruder has a zone temperature of 160-220 ℃ and other zones and heads at 220-260 ℃; the rotating speed of the extruder is 50-1000r/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285096A (en) * | 2003-03-19 | 2004-10-14 | Daicel Degussa Ltd | Polyamide resin composition and bond magnet |
| CN102604373A (en) * | 2012-02-23 | 2012-07-25 | 无锡殷达尼龙有限公司 | Formula of nylon hose |
| CN114381117A (en) * | 2022-03-02 | 2022-04-22 | 广东圆融新材料有限公司 | Halogen-free flame-retardant antistatic bio-based polyamide composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285096A (en) * | 2003-03-19 | 2004-10-14 | Daicel Degussa Ltd | Polyamide resin composition and bond magnet |
| CN102604373A (en) * | 2012-02-23 | 2012-07-25 | 无锡殷达尼龙有限公司 | Formula of nylon hose |
| CN114381117A (en) * | 2022-03-02 | 2022-04-22 | 广东圆融新材料有限公司 | Halogen-free flame-retardant antistatic bio-based polyamide composition and preparation method thereof |
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