CN111138792A - Composite material containing waste lead-acid storage battery shell and application thereof - Google Patents
Composite material containing waste lead-acid storage battery shell and application thereof Download PDFInfo
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- CN111138792A CN111138792A CN201911337637.9A CN201911337637A CN111138792A CN 111138792 A CN111138792 A CN 111138792A CN 201911337637 A CN201911337637 A CN 201911337637A CN 111138792 A CN111138792 A CN 111138792A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three 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
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2207/20—Recycled plastic
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a composite material containing a waste lead-acid storage battery shell and application thereof. The composite material comprises: 80-96 parts of a storage battery shell; 0.5-2 parts of molecular chain repairing agent; a toughening agent: 2-10 parts; 2-10 parts of low temperature resistant agent and 0.2-0.7 part of antioxidant; the polypropylene shell composite material has the characteristics of good toughness, excellent long-term thermal aging stability and easiness in heat-seal welding; the composite material solves the problem that the polypropylene shell of the waste storage battery cannot be directly recycled, realizes the closed recycling from the storage battery shell to the storage battery shell, and avoids the problems of environmental pollution and resource waste of the waste storage battery shell.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a composite material containing a waste lead-acid storage battery shell, and a sheet or a profiled bar prepared from the composite material.
Technical Field
Lead acid batteries were invented in 1859 by the French Press (Plante) and have been in history for over a hundred years to date. The lead-acid storage battery has absolute advantages in chemical power supply since the invention is self-evident. The composite material has the advantages of low price, easily obtained raw materials, safe and reliable use process, wide application environment temperature range and the like, and has important application in traffic, communication, electric power, military affairs, navigation and aviation. Over the last decade, there has been a compounded growth at a rate of over 20% per year. Of course, lead-acid batteries also have their own drawbacks: low specific energy (i.e. electric energy stored in a storage battery per kilogram), short service life and frequent routine maintenance, the service life of a common storage battery is generally 2-3 years, and the height of the electrolyte needs to be checked regularly and distilled water needs to be added. Therefore, a large amount of waste lead-acid storage batteries are generated every day, and due to the high pollution of the lead-acid storage batteries, if the waste lead-acid storage batteries cannot be effectively recycled, the waste lead-acid storage batteries are destructively attacked to the surrounding environment, so that the country mainly supports and constructs a plurality of circular parks to effectively recycle the high-added-value and high-pollution lead, but no reasonable recycling way is found for low-value plastic shells with large volume ratio, serious performance degradation and pollution. Therefore, not only is resource waste and white pollution caused, but also some simple physical recycling is carried out, the mechanical property is poor, and lead contained in the plastic shell can cause pollution of other materials.
The chinese invention patent CN 101217205a discloses a method for pretreating and separating waste lead-acid storage batteries, which is used for separating various components of waste lead-acid storage batteries during lead recycling. The patent discloses that turning over of a hydraulic six-clack grab crane is carried out to separate solid and liquid primarily, then the solid is subjected to electromagnetic iron removal, magnetic metal detection, crushing and screening, lead plaster is effectively recovered, and a plastic shell is separated, but subsequent cleaning, sorting, purifying and modifying of the plastic shell are not involved.
The Chinese invention patent CN 105742745A discloses an energy-saving cleaning process for broken shells of waste lead-acid storage batteries, which can effectively separate plastic shells, obtain polypropylene plastic shell broken pieces with higher purity through water washing, flotation and purification, and effectively reduce the influence on the environment, but cannot provide a corresponding solution for recycling subsequent broken pieces and realizing high-value recovery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention mainly aims to provide a composite material containing a waste lead-acid storage battery shell, which can effectively recycle the waste storage battery shell and improve the performance by adopting multiple means, thereby realizing the high value-added recycling of the material.
The invention also aims to provide a preparation method of the composite material containing the waste lead-acid storage battery shell.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the composite material containing the waste lead-acid storage battery shell comprises the following components in parts by weight:
the storage battery shell is single-color or mixed-color broken pieces or plastic particles obtained by crushing, cleaning and sorting the waste lead-acid storage battery, and the content of polypropylene in the storage battery shell is more than or equal to 98% by mass;
according to the invention, the compound molecular chain repairing agent is added into the waste lead-acid storage battery shell, so that the partially broken molecular chains of the waste storage battery can be connected, meanwhile, the silane structure is grafted on the polypropylene main chain, the compatibility of the waste lead-acid storage battery shell with the toughening agent and the low temperature resistant agent is improved, the physical and mechanical properties of the material, especially the notch impact strength of a cantilever beam, are greatly improved, and the degradation caused by the combined action of heating, shearing and acid corrosion of the waste storage battery in the processing process is greatly reduced, so that the waste lead-acid storage battery shell reaches or even exceeds the level of a new material.
According to the invention, researches show that when the adding amount of the molecular chain repairing agent is excessive, although the toughness of the material can meet the requirement, the excessive molecular chain repairing agent causes the heat resistance of the material to be reduced and can not meet the heat resistance requirement of the material; when the addition amount of the molecular chain repairing agent is too low, the molecular chain repairing is insufficient, the toughness of the material is insufficient, and the toughness requirement of the material cannot be met. Therefore, the addition amount of the molecular chain repairing agent is preferably 0.5-2 parts.
Preferably, the molecular chain repairing agent is a compound of vinyltrimethoxysilane and styrene according to a volume ratio of 5-15:1, and the preferred volume ratio is 8-10: 1.
according to the invention, the low temperature resistant agent is added into the waste lead-acid storage battery shell, so that the defect of poor toughness of the material at low temperature is overcome, the impact strength of the cantilever beam notch at-30 ℃ is greatly improved, and the requirement of the storage battery shell on the material can be completely met.
Preferably, the low temperature resistant agent is high density polyethylene with the density of 0.94g/cm3-0.95g/cm3The melt flow rate MFR is 15g/10min-24g/10min at 190 ℃ under a load of 5 kg.
Preferably, the toughening agent is an ethylene-octene copolymer, and the melt flow rate MFR is 1g/10min-3g/10min under the conditions of 190 ℃ and 2.16Kg load.
In order to further improve the performance of the composite material, the composite material containing the waste lead-acid storage battery shell also comprises 0-1 part of color seeds in parts by weight.
The composite material containing the waste lead-acid storage battery shell can greatly improve the long-term thermal aging performance of the material by adding the compound antioxidant, so that the material is improved from 150 ℃ to 50 ℃ for 500 hours without aging, and the requirement of the storage battery shell on the long-term thermal aging resistance of the material is exceeded.
Preferably, the antioxidant is a compound of a hindered phenol antioxidant, a phosphite antioxidant and a thioester antioxidant in a mass ratio of 1:1:2-1:2: 2.
Preferably, the color seeds are black seeds with the weight content of carbon black of 20-55%.
The invention also provides a preparation method of the composite material containing the waste lead-acid storage battery shell, which comprises the following steps:
(1) weighing the components in proportion, mixing the storage battery shell, the toughening agent and the low temperature resistant agent in a high-speed mixer for 0.1-2 minutes, adding the molecular chain repairing agent, mixing for 1-2 minutes, adding the antioxidant, and mixing for 1-3 minutes at the rotation speed of 500 plus materials of 2000 revolutions per minute to obtain a premix;
(2) the premix is melted and extruded by a double-screw extruder, the temperature of each zone of the screw is 180-220 ℃, and the composite material containing the waste lead-acid storage battery shell is prepared by granulation.
The invention also provides a profiled bar or sheet prepared from the composite material containing the waste lead-acid storage battery shell, and the composite material containing the waste lead-acid storage battery shell can be formed into a lead-acid storage battery shell, a cover, a shell part containing an embedded part and the like through injection molding.
Compared with the prior art, the invention has the following beneficial effects:
the composite material containing the waste lead-acid storage battery shell prepared by the invention has the advantages of good toughness, excellent long-term thermal aging stability and easiness in heat-seal welding; the composite material solves the problem that the waste storage battery shell cannot be directly recycled, realizes the closed recycling from the storage battery shell to the storage battery shell, and avoids the problems of environmental pollution and resource waste of the waste storage battery shell.
The specific implementation mode is as follows:
the following examples are given to illustrate the present invention and it should be noted that the following examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that the modification and modification of the present invention by those of ordinary skill in the art are not essential to the present invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
battery case 1: crushing the white storage battery shell, wherein the mass content of polypropylene is 98%;
the battery case 2: crushing a black storage battery shell, wherein the mass content of polypropylene is 99%;
battery case 3: broken pieces of the variegated storage battery shell, wherein the mass content of polypropylene is 99.5 percent;
the battery case 4: black storage battery shell particles, wherein the mass content of polypropylene is 99%;
battery case 5: the battery shell particle with the variegated color comprises 100 percent of polypropylene by mass;
molecular chain repair agent 1: the mixed liquid is obtained by uniformly mixing vinyl trimethoxy silane and styrene according to the volume ratio of 5: 1.
Molecular chain repair agent 2: the vinyltrimethoxysilane and the styrene are uniformly mixed according to the volume ratio of 9:1 to obtain the mixed liquid.
Molecular chain repair agent 3: the mixed liquid is obtained by uniformly mixing vinyltrimethoxysilane and styrene according to the volume ratio of 18: 1.
Molecular chain repair agent 4: the mixed liquid is obtained by uniformly mixing vinyl trimethoxy silane and styrene according to the volume ratio of 2: 1.
A toughening agent: the ethylene-octene copolymer had a melt flow rate MFR of 2.0g/10min at 190 ℃ under a load of 2.16 Kg.
Low temperature resistant agent: high density polyethylene with density of 0.95g/cm3The melt flow rate MFR was 19g/10min at 190 ℃ under a load of 5 kg.
Antioxidant: the antioxidant is a compound of a hindered phenol antioxidant 1010, a phosphite antioxidant 168 and a thioester antioxidant DSTDP in a mass ratio of 1:2: 2.
Color variety: black seed 3025A, 45% carbon black by weight.
Examples 1-8, comparative examples 1-7:
weighing the components according to the weight parts shown in table 1, firstly mixing the storage battery shell, the toughening agent and the low temperature resistant agent in a high-speed mixer for 2 minutes, then adding the molecular chain repairing agent and mixing for 1 minute at the rotating speed of 2000 r/min, then adding the antioxidant and the color seeds, and mixing for 2 minutes at the rotating speed of 2000 r/min to obtain a premix; and melting and extruding the premix by a double-screw extruder, maintaining the temperature of each zone of a screw at 180-220 ℃, and performing vacuum granulation to obtain the composite material of the waste lead-acid storage battery shell.
TABLE 1 compositions of polypropylene composites in examples and comparative examples
Continuing with Table 1:
the samples of examples 1-8 and comparative examples 1-7 were injection molded into national standard bars according to a uniform process, and tested for mechanical properties and thermal aging resistance according to the test standards and conditions listed in Table 2, with the test data shown in Table 3 below.
Table 2: performance test criteria and conditions for composite materials
| Test items | Unit of | Test method |
| Tensile strength | MPa | GB/T 1040 |
| Notched Izod impact Strength (23 ℃ C.) | KJ/m2 | GB/T 1843 |
| Notched Izod impact Strength (-30 ℃ C.) | KJ/m2 | GB/T 1843 |
| Melt index | g/10min | GB/T 3682 |
| Bending strength | MPa | GB/T 9341 |
| Flexural modulus | MPa | GB/T 9341 |
| Thermal aging Properties | 150℃，500h |
Table 3: results of Performance test of each of the composites in examples 1 to 8 and comparative examples 1 to 7
As can be seen from the data in Table 3, the composite materials containing the waste lead-acid storage battery shells in examples 1 to 8 have good normal temperature and low temperature toughness, and the normal temperature cantilever notch impact is 40KJ/m2Above, the impact at low temperature (-30 ℃) is more than 3.8KJ/m2The toughness is better than that of a new material (K3003) traditionally adopted in the storage battery industry, particularly the low-temperature toughness is better and excellent, and the notch impact of the cantilever beam of the new material (K8003) at low temperature is only 2.5KJ/m2Left and right; on the other hand, the composite material is added with the compound antioxidant, and meanwhile, the long-term thermal aging performance is greatly improved under the action of the molecular chain repairing agent, the long-term aging time can reach more than 500 hours, and the new material (K8003) begins to be pulverized after the thermal aging time is about 80 hours, so that the composite material can prolong the service life of a storage battery and meet the requirement of a charging and discharging process on the thermal aging resistance of the material.
Comparative example 1 is a result of granulation of crushed pieces of crushed battery case, material contaminated during use and deteriorated performance during processing, cantilever beam defectThe impact strength of the mouth is only 11KJ/m2The low-temperature toughness is obviously reduced, and the material can only be used for degrading in products without requirements on the toughness of the material; in the comparative example 2, no molecular chain repairing agent is added, the molecular chain is seriously degraded, the toughness of the composite material is insufficient, and the requirement of a high-performance product is difficult to meet; in the comparative example 3, a system of compound antioxidant is not added, the long-term thermal aging performance of the material is very poor, and the material starts to be pulverized at 150 ℃ for 80 hours; the compound ratio of the two components in the molecular chain repairing agent added in the comparative examples 4 and 5 is not in a proper range, although the total addition amount meets the requirement, the toughness of the composite material can not be effectively improved, and the requirement on high toughness can not be met; compared with the prior art, the addition amount of the molecular chain repairing agent in the comparative example 6 is too high, and although the toughness of the material can meet the requirement, the heat resistance of the material is reduced due to the excessive molecular chain repairing agent and the heat resistance requirement of the material cannot be met; in comparative example 7, the addition amount of the molecular chain repairing agent is too low, the molecular chain repairing is insufficient, the toughness of the material is insufficient, and the toughness requirement of the material cannot be met.
The data analysis of the embodiment shows that the composite material containing the waste lead-acid storage battery shell can effectively recycle broken pieces of the waste storage battery shell, saves resources, greatly improves the comprehensive performance of the material, can be used for producing the storage battery shell, and can also be used for producing high-end products such as extruded pipes, building templates, high-toughness turnover baskets, grids and the like.
Claims (9)
1. The composite material containing the waste lead-acid storage battery shell is characterized by comprising the following components in parts by weight:
80-96 parts of a storage battery shell;
0.5-2 parts of molecular chain repairing agent;
2-10 parts of a toughening agent;
2-10 parts of low temperature resistant agent;
0.2 to 0.7 portion of antioxidant;
the storage battery shell is a single-color or mixed-color crushed piece or plastic particle obtained by crushing, cleaning and sorting the waste lead-acid storage battery, and the content of polypropylene in the storage battery shell is more than or equal to 98% by mass;
the molecular chain repairing agent is a compound of vinyltrimethoxysilane and styrene according to the volume ratio of 5-15: 1.
2. The composite material containing waste lead-acid storage battery shells as claimed in claim 1, wherein the molecular chain repairing agent is vinyltrimethoxysilane and styrene according to a volume ratio of 8-10: 1.
3. The composite material containing waste lead-acid battery cases according to claim 1, characterized in that the low temperature resistant agent is high density polyethylene with a density of 0.94g/cm3-0.95g/cm3The melt flow rate MFR is 15g/10min-24g/10min at 190 ℃ under a load of 5 kg.
4. The composite material containing waste lead-acid storage battery shells as claimed in claim 1, wherein the toughening agent is an ethylene-octene copolymer, and the melt flow rate MFR is 1g/10min-3g/10min under the conditions of 190 ℃ and 2.16Kg load.
5. The composite material containing the waste lead-acid storage battery shell as claimed in claim 1, wherein the antioxidant is a compound of hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant in a mass ratio of 1:1:2 to 1:2: 2.
6. The composite material containing waste lead-acid storage battery shells as claimed in claim 1, further comprising 0-1 part of a color seed by weight parts based on the whole composite material.
7. The composite material containing waste lead-acid battery shells as claimed in claim 5, wherein said color species is a black species with a carbon black content of 20-55% by weight.
8. The process for the preparation of a composite material containing casings of waste lead-acid batteries according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1) weighing the components in proportion, mixing the storage battery shell, the toughening agent and the low temperature resistant agent in a high-speed mixer for 0.1-2 minutes, adding the molecular chain repairing agent, mixing for 1-2 minutes, adding the antioxidant, and mixing for 1-3 minutes at the rotation speed of 500 plus materials of 2000 revolutions per minute to obtain a premix;
(2) the premix is melted and extruded by a double-screw extruder, the temperature of each zone of the screw is 180-220 ℃, and the composite material containing the waste lead-acid storage battery shell is prepared by granulation.
9. A profile or sheet prepared from the composite material containing a spent lead-acid battery casing according to any one of claims 1 to 7.
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