CN111286293B - PP plastic shell adhesive for storage battery and preparation method of PP plastic shell adhesive - Google Patents
PP plastic shell adhesive for storage battery and preparation method of PP plastic shell adhesive Download PDFInfo
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- CN111286293B CN111286293B CN202010278688.5A CN202010278688A CN111286293B CN 111286293 B CN111286293 B CN 111286293B CN 202010278688 A CN202010278688 A CN 202010278688A CN 111286293 B CN111286293 B CN 111286293B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a PP plastic shell adhesive for a storage battery and a preparation method thereof. The anti-aging material comprises 52-65 wt% of thermoplastic polyester elastomer, 9.5-13 wt% of polyethylene, 15-24 wt% of polypropylene, 4-6 wt% of polyisobutylene, 3-5 wt% of polystyrene and 0.5-1.5 wt% of anti-aging agent. The adhesive for the PP plastic shell of the storage battery has the advantages of strong acid and strong alkali resistance, high strength, high toughness and good temperature resistance, and is suitable for PP plastic shells of power storage batteries.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a PP plastic shell adhesive for a storage battery and a preparation method thereof.
Background
ABS material and PP material are two main materials for manufacturing the lead-acid storage battery shell. The ABS material has good strength and bright color, but has low molecular density, and water vapor can easily permeate the cell wall. If the battery is used for a long time, the battery is easily dehydrated, and the service life of the battery may be shortened. The battery adopting the ABS material is easy to age and poor in air tightness by adopting an epoxy glue sealing process. Furthermore, the glue sealing process is usually performed manually, and it is difficult to ensure the stability of the battery. Domestic batteries are basically made of ABS materials. The PP material is soft and flexible, and can not burst when bearing high pressure. The molecular density of the material is higher than that of ABS, the water vapor permeability of the material is about 1/10 of ABS material, and the battery is not easy to lose water after long-term use. The PP material has good hot melting property, is suitable for the heat sealing process of the battery and is difficult to glue and seal. And the sealing effect of the battery and the stability of the battery quality can be ensured by adopting machine heat sealing. The battery imported from abroad is basically made of PP material.
At present, the most popular is to use epoxy resin for sealing, and automobile batteries and partial motorcycle batteries basically remain the heat sealing process, and after all, the machine operation is realized, the automation degree is high, and no foreign substance is required to be added for assistance, so the ABS process using heat sealing is also tried, but the internal space of the VRLA battery is limited for a while, and the heat sealing technology is difficult to realize.
Chinese patent publication No.: CN107815280A discloses a formula of epoxy resin glue, which has the technical scheme that the formula comprises the following substances in parts by weight: epoxy resin: 260-275 parts; curing agent: 2-3 parts of a solvent; solvent: 25-35 parts; magnesium hydroxide: 45-55 parts of a solvent; silicon micropowder: 100-115 parts; coupling agent: 0.1-1.5 parts; curing agent accelerator: 0.05-0.20 part; in the patent, the curing agent of the epoxy resin adhesive comprises dicyandiamide, the curing agent accelerator comprises 2-methylimidazole, and an organic solvent is adopted, so that when the epoxy resin adhesive is used due to toxic irritant substances, the phenomenon of allergic dermatitis of operators is common.
Chinese patent publication No.: the patent of CN105385392B discloses a hot melt adhesive for bonding a steel material and a double-resistance PPR material and a preparation technology thereof, wherein the formula ratio of the used raw materials is as follows: 50-80 parts of PPR, 10-30 parts of POE (ethylene-octene copolymer), 1-5 parts of epoxy resin, 0.08-0.25 part of dicumyl peroxide (DCP), 1-3 parts of maleic anhydride, 0.5-2 parts of oligomeric silsesquioxane (POSS), 3-8 parts of petroleum resin and 5-10 parts of other auxiliary agents. The hot melt adhesive and PP plastic can not be well sintered, and the sealing effect of a PP plastic shell of the storage battery with the PP plastic shell can not be met.
Chinese patent publication No.: CN109777348A discloses a hot melt adhesive, its characterized in that: the hot melt adhesive comprises, by weight, 35-55 parts of thermoplastic resin, 5-15 parts of a viscosity regulator, 4-9 parts of paraffin, 15-0.35 part of organic silicon, 0-0.4 part of nitrate, 1.1-2.5 parts of N-phenyl-alpha-naphthylamine, 0.5-1.5 parts of an antioxidant and 0.6-1.8 parts of a softener, and the hot melt adhesive is prepared by heating materials in a kettle body in a steam heating manner and assisting a stirring device. The hot melt adhesive can not be well sintered with PP plastic, and the sealing effect of a PP plastic shell of the storage battery with the PP plastic shell can not be met.
Therefore, the development of the special adhesive for the PP plastic shell of the lead-acid storage battery, which is nontoxic in the preparation process and excellent in performance, has great social benefit.
Disclosure of Invention
The invention aims to provide a PP plastic shell adhesive for a storage battery, which is resistant to strong acid and strong alkali, high in strength, high in toughness and good in temperature resistance.
In order to achieve the purpose, the invention provides a PP plastic shell adhesive for a storage battery, which is characterized by comprising the following components:
further, the PP plastic shell adhesive for the storage battery is characterized by comprising the following components:
further, the thermoplastic polyester elastomer is a linear block copolymer containing polybutylene terephthalate hard segments and aliphatic polyester or polyether soft segments.
Further, the thermoplastic polyester elastomer was KP3363HR of korea crone.
Further, the polypropylene is one of homo-polypropylene and co-polypropylene or a combination of the homo-polypropylene and the co-polypropylene.
Further, the copolymerized polypropylene is PPB-M09 from Nominal petrochemical company.
Further, the anti-aging agent is one of a basf antioxidant 168, an antioxidant 285 and an antioxidant 1010.
The PP plastic shell adhesive for the storage battery is characterized by comprising the following steps of,
heating and dehumidifying: heating thermoplastic polyester elastomer, polyethylene, polypropylene, polyisobutylene, polystyrene and anti-aging agent by microwave to remove moisture at 80-90 deg.C for 2-3 hr;
mixing: then all the raw materials are mixed and evenly mixed by a stirrer for standby;
preparation: adding the uniformly stirred mixed material into a double-screw extruder, carrying out graft copolymerization at the temperature of 170-200 ℃, and carrying out blending extrusion granulation or casting to form blocks.
In the compositions of the invention, the thermoplastic polyester elastomer (TPEE) provides the compositions with flexural fatigue resistance, excellent high temperature performance at the moment, excellent impact resistance, especially at low temperatures (-40 ℃), good tear resistance and good abrasion resistance.
Meanwhile, the invention adopts the thermoplastic polyester elastomer (TPEE) to carry out blending modification on the polypropylene (PP), the solubility parameters of the TPEE and the PP are relatively close, the compatibility of a blending system is relatively good, and the toughness of the PP is improved.
The addition of the TPEE improves the crystallization rate of the PP, changes the crystallization size of the PP, improves the crystallization temperature of the PP, plays a role in heterogeneous nucleation on the blend, simultaneously hinders the movement of the PP chain segment and the discharge of the PP chain segment into ordered lattices, and ensures that the crystallinity of the blend is lower than that of pure PP, thereby improving the temperature resistance of the composition.
The polypropylene (PP) and the adhered PP plastic shell play roles in grafting, copolymerization and crosslinking. The polypropylene should be used in the composition of the present invention in an amount sufficient to provide the desired balance of processability and mechanical properties for the blended system. The inventor selects 52-65 wt% of thermoplastic polyester elastomer through experiments; 15-24 wt% of polypropylene. Preferably, 55-65 wt% of thermoplastic polyester elastomer; 15-24 wt% of polypropylene. The formula improves the toughness of a blending system and also improves the temperature resistance.
In the preferred formulation, the polypropylene copolymer improves the thermoplasticity, so that the material can be melted and cooled after being heated and then hardened and can be acted repeatedly, and simultaneously improves the surface rigidity and the scratch resistance.
The melting point of Polyethylene (PE) is 100 ℃ and 130 ℃, and the low-temperature resistance is excellent. The polyethylene can still maintain good mechanical property at minus 60 ℃, has excellent chemical stability, and improves the acid resistance and the temperature resistance.
In the invention, as Polystyrene (PS) molecular chains are rigid, the volume of phenyl is large, and the steric hindrance effect is strong, after the polystyrene is added, the large steric hindrance effect is generated, the cohesive force of the thermoplastic polyester elastomer is reduced, the wettability is increased, and the adhesive property of the thermoplastic polyester elastomer is improved.
The Polyisobutylene (PIB) has excellent air tightness, and due to the existence of two substituted methyl groups, molecular chain movement is slow and the free volume is small, so that low diffusion coefficient and gas permeability are generated, the dispersion of each component is promoted, and the performance is favorably improved.
The anti-aging agent prevents the PP from undergoing an auto-oxidation chain reaction process, i.e., the radicals R & ROO & generated in the oxidation process are changed into RH and ROOH or ROOH is changed into ROH by co-supplying hydrogen, thereby improving the oxidation resistance and the pyrolysis resistance of PP in processing and application and prolonging the service life of products.
Therefore, the storage battery PP plastic shell adhesive has excellent processing performance and mechanical performance by blending polyethylene, polyisobutylene, polystyrene and polypropylene, acting with the thermoplastic polyester elastomer and assisting with the anti-aging agent, and the components have combined action in the melt extrusion process, so that the acid resistance of the composition is improved, and the temperature resistance and the mechanical performance of the composition are improved.
By adopting the technical scheme, the adhesive for the PP plastic shell of the storage battery, which is prepared by the invention, has the characteristics of strong acid and strong alkali resistance, high strength, high toughness and good temperature resistance, and is suitable for the special adhesive for the PP plastic shell of the power storage battery.
The invention has the beneficial effects that:
1. the storage battery PP plastic shell adhesive is prepared from thermoplastic polyester elastomer, polyethylene, polypropylene, polyisobutylene, polystyrene, PP resin and an anti-aging agent as raw materials, and the agent used in the preparation process does not contain toxic and irritant substances.
2. The PP plastic shell adhesive for the storage battery has the advantages of strong acid and strong alkali resistance, high strength, high toughness and good temperature resistance.
3. The prepared PP plastic shell adhesive for the storage battery can be well sintered with PP plastic, and can meet the sealing effect of the PP plastic shell storage battery.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following experiments, the thermoplastic polyester elastomer was KP3363HR from Korea Kelon, and the polypropylene was PPB-M09 from Nominan petrochemical company. The anti-aging agent is one of Pasteur antioxidant 168, antioxidant 285 and antioxidant 1010.
Example 1: preparation of PP plastic shell adhesive for storage battery
Raw materials: see table 1.
The preparation method comprises the following steps:
(1) the raw materials are dehumidified and dried before production, firstly microwave heating is adopted for dehumidification, the temperature is 80-90 ℃, and the time is 2-3 hours;
(2) uniformly mixing the raw materials of the thermoplastic polyester elastomer, the polyethylene, the polypropylene, the polyisobutylene, the polystyrene and the anti-aging agent by using a stirrer for later use;
(3) and adding the uniformly stirred mixed material into a double-screw extruder, and performing blending extrusion granulation at the temperature of 170-200 ℃ to prepare the required hot melt adhesive particles, namely obtaining the PP plastic shell adhesive for the storage battery.
TABLE 1 dosage (wt%) of each example and comparative example is shown in Table
Example 2: preparation of PP plastic shell adhesive for storage battery
Raw materials: see table 1.
The preparation method comprises the following steps:
(1) before production, the raw materials are dehumidified and dried, firstly, a steam-containing or other heating dehumidification mode is adopted, the temperature is 80-90 ℃, and the time is 2-3 hours;
(2) uniformly mixing the raw materials of the thermoplastic polyester elastomer, the polyethylene, the polypropylene, the polyisobutylene, the polystyrene and the anti-aging agent by using a stirrer for later use;
(3) keeping the uniformly stirred mixed material in a reaction kettle at the temperature of 170-200 ℃ and stirring at a high speed for 10-30 min;
(4) and (3) casting the prepared PP hot melt adhesive in a forming die cavity for cooling and forming, thereby preparing the required shape of the hot melt adhesive. And obtaining the PP plastic shell adhesive for the storage battery.
Example 3: preparation of PP plastic shell adhesive for storage battery
Raw materials: see table 1.
The preparation method comprises the following steps: the same as in example 1.
Example 4: preparation of PP plastic shell adhesive for storage battery
Raw materials: see table 1.
The preparation method comprises the following steps: the same as in example 1.
Comparative example 1: preparation of adhesive
Raw materials: see table 1.
The preparation method comprises the following steps: the same as in example 1.
Comparative example 2: preparation of adhesive
Raw materials: see table 1.
The preparation method comprises the following steps: the same as in example 1.
Comparative example 3: preparation of adhesive
Raw materials: see table 1.
The preparation method comprises the following steps: the same as in example 1.
Example 5: effect testing experiment
The test results of each example and comparative example are shown in table 2.
TABLE 2 table of results of performance test of each example and comparative example
The test results in table 2 show that the peel strength of the PP plastic shell adhesive for the storage battery obtained in the embodiment of the invention to the polypropylene material is 3.3-3.6N/cm, which is much higher than that of the PP plastic shell adhesive in comparative example 1, comparative example 2 and comparative example 3. In comparative example 1, the ratio of the thermoplastic polyester elastomer to the polypropylene was too small, which resulted in a substantial decrease in the adhesive performance, with a peel strength of 2.1N/cm. In comparative example 2, the ratio of the thermoplastic polyester elastomer to the polypropylene was too large, and the adhesive performance was also reduced. In comparative example 3, the peel strength of the adhesive was also reduced due to the absence of the steric effect of polystyrene.
The adhesive for the PP plastic shell of the storage battery has high peeling strength and better toughness to a polypropylene material, can be well sintered with PP plastic, and has good sealing effect to the PP plastic shell of the storage battery. Meanwhile, the hardness of the test sample of the embodiment of the invention is 60-70, the tensile strength is 24-27MPa, and the performance of the test sample is superior to that of the comparative examples 1, 2 and 3. The adhesive for the PP plastic shell of the storage battery has good mechanical property, and meets the requirements of the processing property and the mechanical property of the PP plastic shell of the storage battery.
Experiments of the invention find that the polypropylene copolymer and the polypropylene homopolymer can achieve the same effect.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (8)
1. The PP plastic shell adhesive for the storage battery is characterized by comprising the following components:
2. the PP plastic shell adhesive for the storage battery of claim 1, which is characterized by comprising the following components:
3. the PP plastic shell adhesive for the storage battery of claim 1, wherein the thermoplastic polyester elastomer is a linear block copolymer containing polybutylene terephthalate hard segments and aliphatic polyester or polyether soft segments.
4. The battery PP plastic case adhesive according to claim 3, wherein the thermoplastic polyester elastomer is KP3363HR from Korea Kelong.
5. The PP plastic shell adhesive for the storage battery of claim 1, wherein the polypropylene is one of homo-polypropylene and co-polypropylene or a combination of the homo-polypropylene and the co-polypropylene.
6. The PP plastic shell adhesive for the storage battery of claim 5, wherein the co-polypropylene is PPB-M09 from Nominax petrochemical company.
7. The battery PP plastic case adhesive according to claim 1, wherein the anti-aging agent is one of a BASF antioxidant 168, an antioxidant 285 and an antioxidant 1010.
8. The PP plastic shell adhesive for the storage battery of claim 1 is prepared by the following steps,
heating and dehumidifying: heating thermoplastic polyester elastomer, polyethylene, polypropylene, polyisobutylene, polystyrene and anti-aging agent by microwave to remove moisture at 80-90 deg.C for 2-3 hr;
mixing: then all the raw materials are mixed and evenly mixed by a stirrer for standby;
preparation: adding the uniformly stirred mixed materials into a double-screw extruder, and performing blending extrusion granulation or casting to form blocks at the temperature of 170-200 ℃.
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