CN101492568A - Nylon for battery seal ring and method of producing the same - Google Patents
Nylon for battery seal ring and method of producing the same Download PDFInfo
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- CN101492568A CN101492568A CNA2009101111443A CN200910111144A CN101492568A CN 101492568 A CN101492568 A CN 101492568A CN A2009101111443 A CNA2009101111443 A CN A2009101111443A CN 200910111144 A CN200910111144 A CN 200910111144A CN 101492568 A CN101492568 A CN 101492568A
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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
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Abstract
The invention discloses a nylon used for a battery sealing ring, which is prepared by the following raw materials according to the percentage by weight: 66.80 percent of nylon, 17 percent of toughener, 1 percent of antioxidant, 1 percent of antistatic agent, and 1 percent of lubricant. The preparation method comprises the following steps: firstly, according to the percentage by weight: the raw materials are put into a stirrer for blending and stirring; after that, the stirred raw materials are put into a hopper and is heated up to be within 270 DEG C to 275 DEG C for preheating; and then hot materials are squeezed out from a machine head by a double screw; and then the extruded materials are put into a water tank for cooling and sent into a pelleter; and finally, the nylon used for the battery sealing ring is prepared by granulating, cooling, bagging and packaging. The nylon reduces the water absorbing capability of materials, increases the dimension stability of products, can effectively control bursting pressure and is convenient for demoulding of the products.
Description
Technical field
The present invention relates to nylon for battery seal ring and manufacture method thereof, is the battery seal ring proprietary material, mainly uses in the production of alkaline Mn cell.
Background technology
Nylon is as maximum most important kind in the engineering plastics, has very strong vitality, mainly be the high performance realized after its modification, following modification of nylon will develop to directions such as the high rigidity nylon of high strength, alloy nylon, nano-nylon, fire-retardant nylon, antistatic nylon, conduction nylon and magnetic nylon.
Nylon 66 is used for battery seal ring and originates in 20th century the seventies U.S., and the producer that early start is done battery seal ring with nylon is the Duracell of a largest battery manufacturer battery in the world.Domesticly there is part producer to begin to pay close attention to the experiment that nylon 66 is used for battery seal ring to last century Mo.There is part producer to bring into use nylon 66 to do battery seal ring gradually.Because at that time condition restriction, domestic battery producer not quite understands its production technique, and processing is difficulty relatively, often goes wrong in the production process, even blasts.Arrived earlier 2000s, many experts begin to pay close attention to, research battery seal ring problem of materials, and some scholar has proposed the possibility of production domesticization.But because the development of the development of domestic nylon and international nylon differs apart from bigger, and, inside battery gaseous tension maximum can reach 1.01-2.02MPa, sealing-ring is most important to alkaline Mn cell leak-proof anti-explosive safety performance, battery seal ring nylon material technology content own is quite high, so never realize production domesticization.
At present sealing-ring is produced material and mainly contained two kinds: a kind of is to be raw material with polypropylene PP, and another kind is to be raw material with the nylon PA66 after the modification.The PP ring structure is used on the low-grade battery owing to do not possess explosion-proof performance more.Explosion-proof ditch is arranged on the PA66 ring structure, and the discharge gas that can split automatically under the excessive situation of cell internal pressure has been avoided blast.At present to compare with the PP sealing-ring be 6: 4 structure to the consumption of PA66 sealing-ring, so the trend of World Battery development is to use the PA66 sealing-ring in alkaline Mn cell fully.
The quality of battery seal ring quality is directly connected to the safe in utilization of battery.Because the complex structure of battery seal ring, wall thickness little (less than 0.2 millimeter) requires to have certain high low-temperature flexibility, intensity and agent of low hygroscopicity again, so very high to its requirement of performance index of producing material.The complete dependence on import of cell sealing loop material for a long time.Maximum model that existing market is used is the inferior EPR27 in French sieve ground (producing in Korea S) and these two kinds of type products of the 101F of Du Pont (produced in USA).
The applicant dropped into research and development cell sealing loop material---modification of nylon (GASKET PA66-0518) since 2004, be the main raw of production mercury-free alkaline manganese dioxide battery sealing-ring, and primary study mainly is the following aspects:
1, water-intake rate.Because nylon is easy to suction, the nylon suction reaches 10% under the normal condition, because nylon one suction, all performances can sharply descend, do not reach the requirement of heavy-duty battery sealing-ring, so the present invention is to solve the sucking nylon water problems in the matter of utmost importance of modification at all.
2, dimensional stability.Because battery seal ring is a thin-gage goods, mainly seal, so dimensional stability is required quite strict.Generally to control within five.But nylon itself does not possess its performance, so will seek a kind of material and nylon mixing in the research process of the present invention, improves its dimensional stability.
3, burstpressures.Because burstpressures directly influences the safety performance of battery, so will control its burstpressures.If burstpressures is too low, battery can produce leakage, can not normally use.If pressure is too high, just in case improper use is short-circuited, produce a large amount of gases, the possibility of blasting is just arranged.Therefore to control certain limit.Present international material, tool is not adjusted the burstpressures function.Have only by adjusting mould to change its burstpressures, but the cell sealing ring mould is quite expensive, a mold at least 80 ten thousand is adjusted bad being easy to and is gone wrong, and a mold has just been scrapped, and cost is quite high.
4, release problems.Because the battery seal ring precision is quite high, all is to use imported materials and items at present, processing is again thin-gage goods, so require quite high to demolding performace, because in the middle of domestic many big factories production process, all be full automatic equipment, 8 hours needs of every production manually are coated with demoulding cream and keep release property.
Summary of the invention
The object of the present invention is to provide a kind of nylon for battery seal ring, and the manufacture method of this material, to reduce water-intake rate, improve product size stability, effective controlled blasting pressure, and make things convenient for product stripping.
In order to reach above-mentioned purpose, solution of the present invention is:
Nylon for battery seal ring is formed by the mixed by weight percentage system of following raw materials according:
Nylon 66 80%, toughner 17%, oxidation inhibitor 1%, static inhibitor 1%, lubricant 1%.
Wherein, described toughner is selected the maleic anhydride graft ultra-low density polyethylene for use.
Described oxidation inhibitor is selected oxidation inhibitor 1098 for use.
Described static inhibitor is selected a kind of in sulfonate, alkyl phosphate class, sulfonic group betaines or the alkylol amide for use.
Described lubricant selected fatty acid glyceryl ester.
The manufacture method of nylon for battery seal ring, its step is as follows:
At first, by weight percentage, with nylon 66 80%, toughner 17%, oxidation inhibitor 1%, static inhibitor 1%, lubricant 1% is put stirrer for mixing into, stirs;
Again the raw material that stirs is put in the hopper, be warming up to 270 ℃～275 ℃ and carry out preheating;
Then, the heat material is extruded from head through twin screw;
Then, the material of extruding is sent in the dicing machine after entering and cooling off in the tank;
At last, pelletizing, cooling, pack, the nylon for battery seal ring grain is promptly made in packing.
Because nylon breach and low temperature impact strength are lower, water-absorbent is big, and most of polyolefine has good high low-temperature flexibility, suction hardly, it is the minimum kind of water-absorbent in the macromolecular material, if both advantages can be united two into one, just might develop outstanding battery seal ring PP Pipe Compound.The key that polyolefine and nylon blending prepare tenacity increased nylon is the problem that will solve consistency difference between nonpolar polyolefine and the strong polar nylon.The method that adopts be earlier on polyolefinic molecular chain grafting can with the small molecules of nylon molecule chain end amido reaction, as maleic anhydride and vinylformic acid, then in the process that melt extrudes with nylon, modified polyolefin and nylon reaction, generate the in-situ copolymerization thing, strengthened the bonding force between phase interface, refinement dispersed phase size, enlarged the distribution range of disperse phase in external phase, make blend performance be improved significantly.Since vinylformic acid with polyolefine grafting process in easy autohemagglutination, therefore seldom use, adopt maleic anhydride (MAH) graft-modified polyolefin substantially.
Polyolefine principal item has high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density of polyethylene (LLDPE), polypropylene (PP), terpolymer EP rubber (EPDM) etc.Because the rigidity of HDPE, LDPE, LLDPE and PP itself is bigger, behind modified by maleic acid anhydride graft, though be greatly improved with the consistency of nylon, the adjusting of burstpressures is very difficult.EPDM is a kind of rubber commonly used, behind modified by maleic acid anhydride graft, descends with the rigidity of blend of nylon, and the adjusting of burstpressures is also than being easier to, but mobile very poor, the injection moulding thin-gage goods is difficulty very.
Ooze theory according to exceeding of Wu, lab scale, pilot experiment through 25mm and 50mm twin screw, again through careful screening, the present invention has finally selected the ultra-low density polyethylene (ULDPE) of metallocene catalysts to be the base-material of graft modification, select maleic anhydride (MAH) grafting ultra-low density polyethylene (ULDPE) for use, again nylon 66, ULDPE-MAH and examples of suitable lubricants are carried out second time blending reaction by twin screw and extrude and prepared the special-purpose PA66 of battery seal ring.
Ultra-low density polyethylene (ULDPE) has all advantages of EPDM, but has excellent flowability simultaneously, and the reaction mechanism of ULDPE-g-MAH and nylon is as follows:
The formation of ULDPE-g-nylon copolymer has greatly improved both consistencies, makes the dispersion particle diameter of ULDPE in nylon have only 1-2u.
The mechanism of ULDPE tenacity increased nylon is as follows:
1, the ULDPE elastic granule constitutes the stress concentration center in nylon matrix, brings out a large amount of crazings or shear zone.The generation and the development need of a large amount of crazings or shear zone consume lot of energy, thereby can significantly improve the impact resistance of nylon.
When 2, being subjected to external impacts, the ULDPE elastic granule not only can bring out crazing with the consumption striking energy, and the crazing that is developing is stopped, and makes it can not develop into destructive crackle.
3, shear zone also is the important factor that stops the crazing development.
4, the ULDPE elastic granule can also make developing crazing on its surface branching take place.The result of branching has on the one hand increased the quantity of crazing greatly, thereby has absorbed more striking energy, can reduce every forward position stress on the other hand and causes its termination.
Reduce absorptive mechanism:
Flowability by control ULDPE-MAH makes its flowability greater than nylon, can form the upper layer that is rich in ULDPE-MAH on injection-molded item, the nylon that absorbs water is easily shielded, thereby reduce water-absorbent.
Static inhibitor improves the mechanism of nylon processibility:
By contrasting domestic and international material, finding all has a common fault, is difficult for the demoulding.After deliberation, discovery is that exsiccant nylon material and metal pattern have very strong static, thereby causes being difficult for the demoulding.Therefore selected the static inhibitor of suitable molecule structure for use, existing good antistatic effect has good lubricity again, has improved the processibility of nylon greatly.
Welding mechanism:
The superoxide decomposes forms free radical
ROOR-2R·
The hydrogen atom that elementary free radical is captured ULDPE forms macromolecular radical
R+ULDPE ULDPE+RH
R+MAH MAH+RH
Disproportionation termination: molecular weight no change
-CH
2CH
2+H
2CCH
2--CH
2CH
3+CH
2＝CH
2-
Coupling termination
-CH
2CH
2+H
2CCH
2--CH
2CH
2-CH
2CH
2-
Cause molecular weight to increase or the formation gel, mobile decline
Grafting:
The present invention is a base-material with homemade PA66 specifically, with maleic anhydride graft ultra-low density polyethylene (ULDPE-MAH) is toughner, improve the toughness and the notched Izod impact strength 250J/M of product, improved dimensional stability, water-intake rate reduces one percentage point than imported product.By contrast, perforation can be split in the middle of existing external product (French sieve ground is inferior) was made the finished product sealing-ring, toughness inadequately, too crisp, thereby can cause that battery high-temperature examines leakage, there are not these problems and use product of the present invention to make sealing-ring, improve the stability and the quality of battery greatly.Change the toughner consumption, the intensity that can regulate PA66 continuously, thereby the burstpressures of adjusting sealing-ring.The sealing-ring production mould is all different to the product burstpressures of producing, and burstpressures is too high, can not split to the anti-riot ditch of certain pressure, does not have anti-riot effect, and danger is very big; The too low requirement of not satisfying product again.Existing external product (Asia, French sieve ground) can not be adjusted burstpressures and product of the present invention can be accomplished.With the glycerin fatty acid ester is lubricant, improves the flowability and the release property of product, and 270 ℃, the melting index that records PA66 under the 2.16KG is greater than 20g/10min, after the twin screw blending and modifying forms finished product.Existing external product (French sieve ground the is inferior) demoulding is bad, and 8 hours needs of every production manually are coated with demoulding cream, and product stripping of the present invention is fine, thereby can produce the protection equipment that plays continuously always, improves output and product percent of pass.
Embodiment
The concrete manufacturing of nylon for battery seal ring material of the present invention is as follows:
(1) raw material stirring:
1, check earlier whether stirrer can normally move, must confirm that compressed air pressure is normal, bleeder valve is in closing condition, can feed intake.
2, the PA66 that adds two bag 25kg earlier advances stirrer.
3, add batching again and advance stirrer, prepare burden consumption by weight percentage: nylon 66 80%, toughner 17%, oxidation inhibitor 1%, static inhibitor 1%, lubricant 1% is measured, toughner is selected the maleic anhydride graft ultra-low density polyethylene for use, oxidation inhibitor is selected oxidation inhibitor 1098 for use, and static inhibitor is selected a kind of in sulfonate, alkyl phosphate class, sulfonic group betaines or the alkylol amide, lubricant selected fatty acid glyceryl ester for use.
4, the PA66 that adds two bag 25kg again advances stirrer.
5, after the lid of fastening stirrer after preparing guarantees that the screw of stirrer is all tightened, just can start shooting and stir (churning time for setting-up time).
6, pack into after raw material stirring is finished in the bag, the raw material in the bag is put in the hopper.
(2) drive to operate:
1, pre-heating temperature elevation: open master switch, the switch of then opening a district, two districts, three districts, four districts, five districts, six districts, seven districts, eight districts, nine districts, head and water pump heats.Processing requirement is carried out parameter setting to each heating zone temperature control instrument according to heating.Each temperature of heating zone is as follows:
| Temperature value (℃) | One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Eight districts | Nine districts | Head | The material temperature |
| Set | 270 | 275 | 275 | 275 | 275 | 270 | 270 | 270 | 270 | 273 | 275 |
Attention: each is distinguished temperature and fluctuates up and down and be no more than 10 ℃.
2, check dicing machine:
1. whether aerated rod opens (switch is upwards opened) automatically.
2. whether the dicing machine master switch opens (master switch is on the dicing machine left side, and open mode is: the black downward red knob of knob upwards).
3. whether the dicing machine P cock opens (open mode: upwards).
Whether rotating speed regulates (being transferred to 350r/min).
4. whether the vacuum gas filling valve on the cutting machine opens (in the face of the dicing machine mouth, outwards being that qi of chong channel ascending adversely has pressure, is the no pressure of venting inwards).
3, start:
Each is distinguished temperature and reaches and open oil pump, hair dryer after stable; open all switches of dicing machine; the dicing machine rotating speed begins to be transferred to 350r/min; open the aerated rod switch of dicing machine; the cutting machine outlet connects (nylon that has just come out is not wanted) with sack; open the main frame current switch again, slowly allow screw rod start, open the feeding switch again, slowly carry out feeding.
4, process:
The heat material is extruded from head through twin screw, flows to tank, at this moment always wears your gloves, and carries out the nylon traction when feeding reaches 100r/min when engine speed reaches 250r/min.Slowly be drawn to first brandreth and dry up second brandreth through hair dryer; fill in the dicing machine mouth and get final product; slowly open big main frame electric current again after stable and feeding is opened big dicing machine rotating speed simultaneously; reach processing requirement at last; when the stable back of product color becomes the no stain of white; can take away the paper bag of dicing machine mouth, allow nylon granule fall into cooling (fall into the long nylon of cooling tank and should pick the place of putting into regulation, must not arbitrarily throw out without care) in the cooling tank.
Attention:
(1) engine speed is controlled at: 250r/min (25.2HZ)
Feeding is controlled at: 250r/min-350r/min (35HZ)
The main frame current control exists: between the 70A-85A
Material is pressed: below the 5.5Mpa
Should slowly start when (2) screw rod starts and reach processing requirement at last, feeding should slowly start too and reaches processing requirement at last.
(3) respectively distinguishing temperature does not reach to set and must not start screw rod when requiring in order to avoid screw rod can rupture.
5, pack, packing:
Material will just can gone into the bag packing with scoop before the pack after stirring in the cooling tank.Every bag of weight is: the 25KG/ bag, drain the air in the bag when sealing earlier, and mix up suitable temperature, seal again.
The present invention has mainly used for reference polyolefinic maleic anhydride graft technology and toughening nylon technology.Utilize the hydrophobicity (water-absorbent is less than 0.1%) and the high tenacity of ultra-low density polyethylene,, it can be reacted, play toughness reinforcing and the absorptive effect of reduction nylon with the end amido of nylon by grafted maleic anhydride.Utilize static inhibitor and nylon and polyolefinic uncompatibility, be penetrated into product surface easily, play the effect that improves mobile and demoulding ability.
Product performance of the present invention are more stable, and yield rate is higher, and security is better.Following table is a like product performance comparison table:
| Project | GASKET PA66-0518 of the present invention | France sieve inferior EPR27 in ground | Dupont 101F |
| Saturated water absorption | 5％ | 6％ | 8.7％ |
| Toughness | Good | Generally | Bad |
| Dimensional stability | Good | Good | Good |
| Hot and humid examination | Good, can deposit more than 60 days | Substantially reach | Can only deposit at most 15 days |
| Intermediolateral column perforation situation | Good (can not split) | Can split once in a while | Regular meeting |
| The bubble situation | Do not have | Have once in a while | Regular meeting has |
| Jiao Kou is in conjunction with situation | Good | Good | Problem is arranged once in a while |
Reliability of products of the present invention:
1, crosslinking technology: under the high temperature and strong shearing action of twin screw extruder, superoxide can produce free radical, capture the reactive hydrogen on the ULDPE molecule, thereby make the maleic anhydride graft that contains unsaturated double-bond to ULDPE, by grafting ULDPE is done infrared analysis, the characteristic peak of carbonyl has appearred in discovery at the 1750cm-1 place, show that maleic anhydride is grafted on the ULDPE.
2, reactively blending is extruded: under the high temperature and strong shearing action of twin screw extruder, the end amido of anhydride group on the ULDPE and nylon produces reaction, plays toughening effect.Find that by the formic acid dissolution experiment behind not grafting ULDPE and nylon blending, nylon can be dissolved in and form clear solution in the formic acid, grafting ULDPE does not then float over above the solution; Behind ULDPE-MAH and the nylon blending, can't obtain clear solution, but form opaque emulsion.
Claims (6)
1, nylon for battery seal ring is characterized in that: mixed to make forming by weight percentage by following raw materials according:
Nylon 6680%, toughner 17%, oxidation inhibitor 1%, static inhibitor 1%, lubricant 1%.
2, nylon for battery seal ring as claimed in claim 1 is characterized in that: toughner is selected the maleic anhydride graft ultra-low density polyethylene for use.
3, nylon for battery seal ring as claimed in claim 1 is characterized in that: oxidation inhibitor is selected oxidation inhibitor 1098 for use.
4, nylon for battery seal ring as claimed in claim 1 is characterized in that: static inhibitor is selected a kind of in sulfonate, alkyl phosphate class, sulfonic group betaines or the alkylol amide for use.
5, nylon for battery seal ring as claimed in claim 1 is characterized in that: lubricant selected fatty acid glyceryl ester.
6, the manufacture method of nylon for battery seal ring is characterized in that step is as follows:
At first, by weight percentage, with nylon 6680%, toughner 17%, oxidation inhibitor 1%, static inhibitor 1%, lubricant 1% is put stirrer for mixing into, stirs;
Again the raw material that stirs is put in the hopper, be warming up to 270 ℃～275 ℃ and carry out preheating;
Then, the heat material is extruded from head through twin screw;
Then, the material of extruding is sent in the dicing machine after entering and cooling off in the tank;
At last, pelletizing, cooling, pack, the nylon for battery seal ring grain is promptly made in packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101111443A CN101492568A (en) | 2009-02-27 | 2009-02-27 | Nylon for battery seal ring and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101111443A CN101492568A (en) | 2009-02-27 | 2009-02-27 | Nylon for battery seal ring and method of producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101492568A true CN101492568A (en) | 2009-07-29 |
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ID=40923366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101111443A Pending CN101492568A (en) | 2009-02-27 | 2009-02-27 | Nylon for battery seal ring and method of producing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140671A (en) * | 2014-06-26 | 2014-11-12 | 浙江野马电池有限公司 | Modified nylon 610 material special for alkaline zinc-manganese battery sealing ring |
| CN104419203A (en) * | 2013-08-29 | 2015-03-18 | 阿克马法国公司 | Battery gasket based on a polyamide composition |
| CN105542283A (en) * | 2016-01-25 | 2016-05-04 | 蚌埠市万达塑料制品有限公司 | Lateral sealing ring of plastic heat preservation bottle plug |
| CN107501929A (en) * | 2017-09-19 | 2017-12-22 | 无锡九宇宝新能源科技有限公司 | A kind of alkaline battery PA sealing rings of high thermal stability and preparation method thereof |
| CN107880814A (en) * | 2017-12-19 | 2018-04-06 | 广州市合诚化学有限公司 | A kind of adhering resin of resistance to compression groove excellent performance and preparation method and application |
| CN111423722A (en) * | 2020-05-23 | 2020-07-17 | 厦门市嘉能科技有限公司 | Modified nylon for battery sealing ring, preparation method of modified nylon and battery sealing ring |
| CN113563660A (en) * | 2021-09-23 | 2021-10-29 | 北京能之光科技有限公司 | Toughening agent for automobile engineering plastics |
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2009
- 2009-02-27 CN CNA2009101111443A patent/CN101492568A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419203A (en) * | 2013-08-29 | 2015-03-18 | 阿克马法国公司 | Battery gasket based on a polyamide composition |
| CN104419203B (en) * | 2013-08-29 | 2017-10-27 | 阿克马法国公司 | Cell gasket based on daiamid composition |
| CN104140671A (en) * | 2014-06-26 | 2014-11-12 | 浙江野马电池有限公司 | Modified nylon 610 material special for alkaline zinc-manganese battery sealing ring |
| CN105542283A (en) * | 2016-01-25 | 2016-05-04 | 蚌埠市万达塑料制品有限公司 | Lateral sealing ring of plastic heat preservation bottle plug |
| CN107501929A (en) * | 2017-09-19 | 2017-12-22 | 无锡九宇宝新能源科技有限公司 | A kind of alkaline battery PA sealing rings of high thermal stability and preparation method thereof |
| CN107880814A (en) * | 2017-12-19 | 2018-04-06 | 广州市合诚化学有限公司 | A kind of adhering resin of resistance to compression groove excellent performance and preparation method and application |
| CN107880814B (en) * | 2017-12-19 | 2019-11-19 | 广州市合诚化学有限公司 | A kind of adhering resin and the preparation method and application thereof that resistance to compression slot is had excellent performance |
| CN111423722A (en) * | 2020-05-23 | 2020-07-17 | 厦门市嘉能科技有限公司 | Modified nylon for battery sealing ring, preparation method of modified nylon and battery sealing ring |
| CN111423722B (en) * | 2020-05-23 | 2022-08-09 | 厦门市嘉能科技有限公司 | Modified nylon for battery sealing ring, preparation method of modified nylon and battery sealing ring |
| CN113563660A (en) * | 2021-09-23 | 2021-10-29 | 北京能之光科技有限公司 | Toughening agent for automobile engineering plastics |
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Open date: 20090729 |