CN110616057A - Preparation and use methods of sealant for assembly line storage battery - Google Patents

Preparation and use methods of sealant for assembly line storage battery Download PDF

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Publication number
CN110616057A
CN110616057A CN201910912570.0A CN201910912570A CN110616057A CN 110616057 A CN110616057 A CN 110616057A CN 201910912570 A CN201910912570 A CN 201910912570A CN 110616057 A CN110616057 A CN 110616057A
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China
Prior art keywords
sealant
parts
storage battery
component
line storage
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CN201910912570.0A
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CN110616057B (en
Inventor
蒋寅
顾志伟
庄雪峰
陈吉琴
顾铖
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Pulitai Electronic Materials Jiangsu Co ltd
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Yixing City Pulitai Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Epoxy Resins (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention relates to the technical field of sealants, in particular to a preparation method and a use method of a sealant for an assembly line storage battery. The sealant for the assembly line storage battery comprises A, B two components, wherein the mass ratio of the A, B component is A: b is 2: 1; A. the component B comprises the following components in parts by weight: the component A comprises: 70-80 parts of bisphenol A epoxy resin, 10-15 parts of bisphenol F epoxy resin, 3-5 parts of butyl glycidyl ether, 8-12 parts of o-cresol glycidyl ether, 5-8 parts of polyurethane, 0.1 part of coupling agent and 0.1 part of defoaming agent; and B component: 420-480 parts of Mannich modified curing agent, 300-350 parts of benzyl alcohol, 2 parts of antioxidant, 20-35 parts of accelerator, 5-10 parts of thixotropic agent and 60 parts of nonyl phenol. The sealant prepared by the invention has the excellent performances of acid resistance, good sealing property, good toughness and strong bonding strength with lead, and meanwhile, the preparation process is simple and convenient to use, can meet the requirement of fast production of a production line, and is beneficial to improving the production efficiency of storage batteries.

Description

Preparation and use methods of sealant for assembly line storage battery
Technical Field
The invention belongs to the technical field of sealants, and particularly relates to a preparation method and a use method of a sealant for an assembly line storage battery.
Background
The sealing adhesive is called sealing glue for short, and is a multipurpose functional material with both bonding and sealing performances. It can prevent internal gas or liquid from leaking, prevent external dust, moisture, water, dirt and chemicals from invading inwards, and prevent mechanical vibration and impact damage or achieve the effect of sound and heat insulation. Therefore, the sealant is an indispensable important material for solving the problems of leakage, overflow, dripping and leakage in the lead-acid storage battery, and plays an important role in modern science and technology and national economy.
The lead storage battery is an industrial product which has wide application and huge demand. In the production process, the connection and wiring parts of the tank cover of the storage battery must be sealed and acid-blocked by an adhesive. The epoxy adhesive has the advantages of strong adhesion, low shrinkage, good electrical insulation performance, good mechanical property and the like, and is the most common sealing material in the lead storage battery. However, the prior sealant is difficult to take into consideration the technical indexes such as temperature resistance, toughness, acid resistance and sealing property, has the problems of high viscosity, poor toughness and acid resistance, cannot meet the requirement of rapid production of a production line, and brings inconvenience to pouring and using of the sealant.
Disclosure of Invention
In order to solve the problems, the invention provides a sealant for an assembly line storage battery in a first aspect, which comprises A, B two components, wherein the mass ratio of the A, B component is A: b is 2: 1; A. the component B comprises the following components in parts by weight:
the component A comprises:
and B component:
as a preferable technical scheme, the preparation raw material of the polyurethane comprises high-resilience polyether.
As a preferable technical scheme, the preparation raw material of the polyurethane also comprises hydroquinone-di (beta-hydroxyethyl) p-cresol ether.
As a preferable technical scheme, the coupling agent is any one of a silane coupling agent and a titanate coupling agent; the defoaming agent is any one of organic silicon and polyacrylate.
As a preferable technical scheme, the raw materials for preparing the Mannich modified curing agent comprise phenol, isophorone diamine, diaminodiphenylmethane and polyformaldehyde.
As a preferred technical scheme, the mole ratio of isophorone diamine to diaminodiphenylmethane is (2-4): 1.
as a preferable technical scheme, the mannich modified curing agent also comprises cardanol as a preparation raw material.
As a preferable technical solution, the molar ratio between cardanol and phenol is 1: (3-5).
As a preferable technical scheme, the raw material for preparing the component B also comprises hyperbranched p-phenylenediamine polymer.
As a preferred technical solution, the weight ratio of the hyperbranched p-phenylenediamine polymer to the mannich modified curing agent is 1: (2-3).
As a preferable technical scheme, the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, phenyl-alpha-naphthylamine, dialkyl diphenylamine, butyl octyl diphenylamine, 3, 5-di-tert-butyl-4-hydroxyphenyl acetate and benzoic acid.
As a preferable technical scheme, the accelerant is one or more of malic acid, succinic acid, maleic acid, fumaric acid, lactic acid, salicylic acid, malonic acid, oxalic acid, glycolic acid, glutaric acid and adipic acid.
As a preferred technical scheme, the thixotropic agent is a BYK thixotropic agent.
The invention provides a use method of the sealant for the storage battery in the production line, which comprises the following steps: and injecting the sealant into a cavity around the lead-acid storage battery pole, adding the colored epoxy resin identification glue on the upper part of the lead-acid storage battery pole, heating and curing the lead-acid storage battery, taking out the lead-acid storage battery, and naturally cooling and curing the lead-acid storage battery.
Has the advantages that: according to the invention, through modification of the curing agent and change of the raw material components, the curing temperature of the sealant is reduced, so that the sealant can be cured at a lower temperature, and the bonding strength of the sealant is enhanced. Simultaneously, the sealant has good fluidity before curing, can be quickly and automatically leveled after being injected into a plastic shell groove, greatly improves the working efficiency, and ensures the sealing effect because the fluidity is good and bubbles are not easy to generate. In addition, the sealant also has good acid resistance, and the quality of the encapsulated product is ensured. Therefore, the sealant disclosed by the invention has the excellent performances of good toughness, high gelling speed, excellent acid resistance and strong bonding strength with lead, and meanwhile, the sealant is simple in preparation process, convenient to use and reliable in operation, can meet the requirement of fast production on a production line, and is beneficial to improving the production efficiency of storage batteries.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "including". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase will render the claim closed except for the materials described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein in the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received by modifying or otherwise modifying such quantity without substantially changing the basic function to which it is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
Aiming at the technical problems, the invention provides a sealant for an assembly line storage battery in a first aspect, which comprises A, B two components, wherein the mass ratio of the A, B component is A: b is 2: 1; A. the component B comprises the following components in parts by weight:
the component A comprises:
and B component:
aiming at the technical problems, the invention provides a sealant for an assembly line storage battery in a first aspect, which comprises A, B two components, wherein the mass ratio of the A, B component is A: b is 2: 1; A. the component B comprises the following components in parts by weight:
the component A comprises:
and B component:
bisphenol A epoxy resin
The bisphenol A epoxy resin has strong adhesion to metal, high mechanical strength, good electrical insulation, corrosion resistance and the like. Furthermore, epoxy resins can be cured over a relatively wide temperature range and have a reduced volume shrinkage upon curing. Therefore, the method is widely applied to the fields of coating, adhesive, glass fiber reinforced plastic, laminated board, electronic casting, encapsulating and the like.
In the examples bisphenol A epoxy resin was purchased from Nantong star-Star synthetic materials, Inc. under the model of NPEL-128, and had an epoxy value of 0.52mol/100 g.
Bisphenol F epoxy resin
The bisphenol F epoxy resin is also called bisphenol F diglycidyl ether, BPF for short, and has the characteristic of low viscosity which is less than 1/3 of the viscosity of bisphenol A epoxy resin. The bisphenol F epoxy resin can be applied to the fields of solvent-free solid coatings, casting and casting molding materials, laminated materials and the like which require low liquid viscosity. The bisphenol F epoxy resin or the bisphenol F and bisphenol A blended epoxy resin has good heat resistance, water resistance and electrical properties, and can be used in the fields of casting and encapsulating materials of transformers and the like, sealing materials for semiconductors, conductive adhesives for semiconductors and the like.
In the examples, bisphenol F epoxy resin was purchased from Nantong star-Star synthetic materials, Inc., model No. NPEF-170, and had an epoxy value of 0.53mol/100 g.
Butyl glycidyl ether
The molecular formula of the butyl glycidyl ether is C7H14O2And colorless transparent liquid. Can be used as active diluent of bisphenol A epoxy resin, has toughening effect, and can improve the properties of cured resin, such as impact strength.
Examples butyl glycidyl ether was purchased from Hubei Green homeland materials technology GmbH, CAS: 2426-08-6.
O-cresol glycidyl ether
The molecular formula of the o-cresol glycidyl ether is C10H12O2A transparent yellowish liquid. Also named as linear o-cresol formaldehyde polyglycidyl ether, yellow to amber solid, can be dissolved in acetone, toluene and the like; good chemical resistance, especially acid resistance; good physical properties, low volatility and moisture resistance, and is an effective diluent of high-viscosity epoxy resin.
Examples o-cresol glycidyl ether was purchased from Hubei Green homeland materials technology GmbH, CAS: 2210-79-9.
Polyurethane
The polyurethane is named polyurethane, is a novel high-molecular synthetic material between rubber and plastic, and has the high strength of the plastic and the high elasticity of the rubber. Has excellent wear resistance and toughness, and is known as wear-resistant rubber; has high strength and elasticity. Under the same hardness, the rubber has higher bearing capacity than other elastomers, high impact resistance, good fatigue resistance and shock resistance, and excellent tear resistance, aging resistance, grease resistance and chemical resistance. The main raw materials of the polyurethane comprise diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and polypropylene glycol (PPG).
In one embodiment, the polyurethane is prepared from a starting material comprising a high resilience polyether.
In a preferred embodiment, the hydroxyl value of the high resilience polyether is 32-36 mg KOH.
In a preferred embodiment, the high resilience polyether has a viscosity of 800 to 1000 mPas.
In a preferred embodiment, the high resilience polyether has a weight average molecular weight of 4500-5500.
In a preferred embodiment, the polyurethane is prepared from starting materials that further include hydroquinone-bis (. beta. -hydroxyethyl) p-cresol ether.
In a preferred embodiment, the preparation of the polyurethane comprises the following steps:
adding 2-4 parts of high-resilience polyether and 6-10 parts of polyethylene glycol into a reaction kettle, drying at 100-140 ℃, then cooling to 60-70 ℃, adding N, N-dimethylformamide, stirring for dissolving, adding 0.08-0.12 part of dibutyltin laurate, and adding the N, N-dimethylformamide into the reaction kettle2Adding 2.2-2.8 parts of isocyanate into a reaction kettle for reaction under protection, controlling the reaction temperature at 70-80 ℃ for 2-3 h, then adding 0.6-1.0 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 0.5-1 h, and discharging to obtain the product.
In a more preferred embodiment, the preparation of the polyurethane comprises the steps of:
adding 3 parts of high resilience polyether and 8 parts of polyethylene glycol into a reaction kettle, performing vacuum dehydration and drying treatment at 120 ℃, then cooling to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 10-15 min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of isocyanate into a reaction kettle for reaction under protection, controlling the reaction temperature at 75 ℃ for 2-3 h, then adding 0.8 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 0.5-1 h, and discharging to obtain the product.
The inventor finds that the toughness of the sealant can be improved to a certain extent by adding a proper amount of polyurethane into the sealant A component. When the polyurethane prepared by the method is adopted, unexpected findings can be found that the performances such as adhesive strength, sealing property, acid resistance and the like can be obviously improved while the toughness of the sealant is improved, and especially the performances are obviously improved when the dosage of hydroquinone-di (beta-hydroxyethyl) p-cresol ether is about 0.8 part. Probably, on the premise of the use amount, the prepared polyurethane has reasonable molecular weight, and the molecular chain end contains a large amount of hydroquinone-di (beta-hydroxyethyl) p-cresol ether structure, so that the affinity and the spreading of the sealant to the surface of an adhered object are increased, the adhesion is improved, and a more compact space network is formed on the surface of the adhered object by the sealant, so that the performances of the sealant, the mechanical strength and the like are improved.
In the embodiment, the high-resilience polyether is purchased from Hubei green home materials technology corporation, and the model is EP-330N; polyethylene glycol was purchased from federal fine chemicals limited in Guangdong and specified as PE G600; dibutyl tin laurate (CAS: 77-58-7) and isocyanate (CAS: 75-13-8) were purchased from Ryozhou Ricken chemical Co., Ltd; hydroquinone-bis (β -hydroxyethyl) p-cresol ether was purchased from green home materials technologies, inc, north huo, CAS: 104-38-1.
Coupling agent
The coupling agent of the invention is a plastic additive for improving the interfacial properties of synthetic resin and inorganic filler or reinforcing material. Also known as surface modifiers. The device consists of two parts: a part is an inorganic group which can act with an inorganic filler or a reinforcing material; the other part is an organophilic group which can interact with the synthetic resin. It can reduce the viscosity of synthetic resin melt in the course of plastic processing, and can improve the dispersity of filling agent to raise processing property, so that it can make the product obtain good surface quality and mechanical, thermal and electric properties. The silane coupling agent is not particularly limited in the present invention.
In a preferred embodiment, the coupling agent is any one of a silane coupling agent and a titanate coupling agent.
In a more preferred embodiment, the coupling agent is a silane coupling agent.
The silane coupling agent in the examples was purchased from Nanjing Pining coupling agent Co., Ltd and was of the type: silane coupling agent KH560, CAS: 2530-83-8.
Defoaming agent
The defoaming agent of the present invention is also called defoaming agent. Most of the defoaming agents are liquid compound products which are mainly divided into three types: mineral oils, silicones, polyethers. The organic silicon defoamer has the characteristics of high defoaming speed, good foam inhibition and the like at normal temperature. The defoaming agent of the present invention is not particularly limited.
In a preferred embodiment, the defoaming agent is any one of silicones and polyacrylates.
In a more preferred embodiment, the defoamer is a silicone-based defoamer.
The silicone-based defoamer in the examples was purchased from Changzhou Shunhua chemical Co., Ltd, model number XPJ-E1100.
Mannich modified curing agent
The Mannich modified curing agent is a novel curing agent. The Mannich modification reaction is a relatively simple and effective method, and is modified by utilizing the condensation reaction of phenol, aldehyde and amine, and the product has the advantage of curing epoxy under low-temperature and humid conditions.
The amine can provide active hydrogen, and the active hydrogen and the phenolic hydroxyl cooperate to greatly enhance the reaction activity, improve the curing speed of amino and epoxy groups, and simultaneously have a phenolic aldehyde skeleton structure which can further improve the thermal deformation temperature and improve the heat resistance and the corrosion resistance of the cured epoxy resin. The amine is not limited strictly, and may be one or more selected from ethylenediamine, diethylenetriamine, hexamethylenediamine, urea, m-phenylenediamine, xylylenediamine methylamine, ethylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, p-hydroxydiphenylamine, diphenylethylamine, dibenzylamine, aniline, cyclohexylamine, and isobutylamine.
In one embodiment, the mannich modified curing agent is prepared from raw materials including phenol, isophorone diamine, diaminodiphenylmethane, and polyoxymethylene.
In one embodiment, the mole ratio of isophorone diamine and diaminodiphenylmethane is (2-4): 1.
the inventor finds that when aniline is used as a curing agent in the sealant, the sealant has low activity, high curing temperature and long curing time, so that the requirements of conventional drying tunnel heating and curing at low temperature cannot be met well, and the cured sealant has poor toughness and is easy to crack. The inventor effectively improves the activity of the curing agent and reduces the curing temperature of the epoxy resin sealant by performing Mannich modification on the compound isophorone diamine and diaminodiphenylmethane, so that the sealant can be cured and formed more quickly at a lower temperature. Probably, after the Mannich catalytic modification is carried out on the isophorone diamine and the diamino diphenyl methane by using the phenol and the polyformaldehyde, the Mannich catalytic modification is favorable for improving the electron cloud density on an amino nitrogen atom in a curing agent molecule to a certain extent, enhancing the acting force between the curing agent and an epoxy structure forming an intermolecular hydrogen bond, and accelerating the speed of forming a trimolecular transition state between the curing agent and an epoxy group, thereby being favorable for accelerating the curing of the epoxy resin sealant at a lower temperature and meeting the requirement of the fast production of an assembly line.
In addition, the inventors found that when isophorone diamine or diaminodiphenylmethane is used alone as the curing agent, the sealing property, curing property, toughness, and the like of the obtained epoxy resin sealant cannot be improved comprehensively, and that when isophorone diamine and diaminodiphenylmethane (2 to 4): 1 when the compound mixture is used as a curing agent, the comprehensive performance of the sealant can be improved to a great extent.
In one embodiment, the mannich modified curing agent is prepared from raw materials which also comprise cardanol.
In one embodiment, the molar ratio between cardanol and phenol is 1: (3-5).
In a preferred embodiment, the molar ratio between cardanol and phenol is 1: 4.
the inventor finds that a certain amount of cardanol is added in the preparation of the Mannich modified curing agent, so that the adhesion of the sealant to a lead pole can be obviously improved, the sealant can be rapidly cured at a lower temperature to obtain a sealing layer with good sealing performance and higher adhesion strength, and the sealing layer can be applied to high-temperature, humid and other environments. Probably, the combination of the benzene ring and the long alkyl chain in the cardanol can destroy the ordered arrangement of all the components in the component B, so that the viscosity of the curing agent component can be reduced, the cardanol can be better dispersed in the epoxy resin component in the component A, the reaction activation energy is reduced, and the curing reaction speed is accelerated. And due to the hydrophobicity of the nonpolar long alkyl chain in the cardanol structure and the hydrophilicity of the polar phenol structure, the solvation effect between the curing agent and the active diluent and the winding and dispersion between the epoxy resin are improved, so that the mixed epoxy resin sealant can be better attached to a storage battery to form a sealing structure, and the cohesiveness and the stability of the cured epoxy resin in a special environment are improved.
In one embodiment, the method of preparing the mannich-modified curing agent comprises the steps of:
adding 8 parts of phenol, 3 parts of isofluorodiketodiamine, 2 parts of diaminodiphenylmethane, 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and starting dropwise adding 4 parts of polyformaldehyde in batches when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Examples phenol (CAS: 108-95-2), polyoxymethylene (CAS: 30525-89-4), cardanol (CAS: 501-24-6), isophoronediamine (CAS: 2855-13-2), diaminodiphenylmethane (CAS: 19430-83-2) were purchased from Wanhua chemical group, Inc.
Antioxidant agent
The antioxidants of the present invention are chemical substances which, when present in the polymer system in only small amounts, retard or inhibit the progress of the oxidation process of the polymer, thereby preventing the aging of the polymer and extending its useful life, also known as "age resistors". The antioxidant of the present invention is not strictly limited.
In a preferred embodiment, the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, phenyl-alpha-naphthylamine, dialkyl diphenylamine, butyl octyl diphenylamine, 3, 5-di-tert-butyl-4-hydroxyphenyl acetate and benzoic acid.
In a more preferred embodiment, the antioxidant is benzoic acid (CAS: 65-85-0).
Accelerator
The accelerator of the present invention, when used in combination with a fixing agent, provides a relatively small amount of material that enhances the reaction rate. The accelerator is not strictly limited in the present invention.
In a preferred embodiment, the accelerator is one or more of malic acid, succinic acid, maleic acid, fumaric acid, lactic acid, salicylic acid, malonic acid, oxalic acid, glycolic acid, glutaric acid, adipic acid.
In a more preferred embodiment, the accelerator is salicylic acid.
In the examples salicylic acid was purchased from Shandong Longong trust group, Inc., CAS: 69-72-7.
Thixotropic agent
The thixotropic agent is also called an anti-sagging agent. A large specific surface area material capable of forming hydrogen bonds or some other structure with the polymer. The mixture becomes thin under stress and becomes thick after standing. After the adhesive is added with the thixotropic agent, when the adhesive is stirred and coated, the adhesive liquid becomes thin under the shearing action; when the operation is finished, the mixture becomes thick again and does not flow. The construction method is mainly used for construction on a vertical plane.
In one embodiment, the thixotropic agent is a BYK thixotropic agent.
In a preferred embodiment, the thixotropic agent is BYK-410.
BYK-410 according to the invention is a low molecular weight urea/carbamate functional group containing polymer solution, the thixotropy of which is achieved by precipitation of crystals forming a three-dimensional network.
In the examples BYK-410 was purchased from Hangzhou Rick chemical Co., Ltd.
Nonyl phenol
The nonyl phenol is an important fine chemical raw material and an intermediate, and is colorless or light yellow liquid at normal temperature. The method is mainly used for producing nonionic surfactants, lubricating oil additives, oil-soluble phenolic resin and insulating materials, and is also used in the fields of antioxidants, textile printing and dyeing auxiliaries, lubricating oil additives, pesticide emulsifiers, resin modifiers, resins, rubber stabilizers and the like.
In the examples nonylphenols were purchased from Shandong Longong trust group, Inc., CAS: 25154-52-3.
Hyperbranched p-phenylenediamine polymer
In one embodiment, the raw materials for preparing the B component further comprise hyperbranched p-phenylenediamine polymer.
In one embodiment, the weight ratio of the hyperbranched p-phenylenediamine polymer to the mannich-modified curing agent is 1: (2-3).
In one embodiment, the method for preparing the hyperbranched p-phenylenediamine polymer comprises the following steps:
dissolving p-phenylenediamine in water, adding pyridine, stirring and dissolving, and reserving for later use; adding cyanuric chloride into pyridine for dissolving, then adding aqueous solution of p-phenylenediamine in batches, reacting for 3-6 h at normal temperature under the condition of introducing inert gas, then filtering, washing with water and acetone, and drying in vacuum to obtain the cyanuric chloride.
In a preferred embodiment, the preparation method of the hyperbranched p-phenylenediamine polymer comprises the following steps:
dissolving 3.02g of p-phenylenediamine in 15mL of water, adding 0.72mL of pyridine, stirring and dissolving (heating if necessary) for later use; adding 2.76g of cyanuric chloride into a reaction bottle, adding a solvent for dissolving, adding an aqueous solution of p-phenylenediamine in batches, reacting at normal temperature for 3-6 h under the condition of introducing inert gas, filtering, washing with deionized water and acetone, and drying in vacuum to obtain the cyanuric chloride.
The inventor finds that the adhesive property and the acid resistance of the sealant to the lead pole can be obviously improved by adding a certain amount of hyperbranched p-phenylenediamine polymer into the sealant B component for the linear storage battery. Probably, the hyperbranched p-phenylenediamine polymer prepared by the method contains a large amount of terminal amino groups, so that the contact probability between the polymer and epoxy groups in epoxy resin is improved, and the curing reaction speed between the A component and the B component is accelerated. And moreover, due to a large number of branched structures in the hyperbranched p-phenylenediamine polymer, the viscosity of the component B is favorably reduced, the dispersion of the component B in the component A is further accelerated and uniform due to the branched structures, and meanwhile, the mixed component A and the mixed component B have lower surface tension, can be better spread on a shell cover, a pole and the like of a storage battery and can be better attached to a lead storage battery, so that the adhesiveness of the sealant and the lead storage battery is favorably improved. And a large number of hyperbranched structures of the hyperbranched p-phenylenediamine are beneficial to coating polar groups such as hydrophilic ether bonds and the like which are easily influenced by an acid environment during curing and molding, so that the polar groups are prevented from directly contacting the acid environment, and the acid resistance of the hyperbranched p-phenylenediamine is improved to a certain extent.
However, the inventors have found that not all hyperbranched amines in the present invention improve the adhesion of the sealant, and even when other hyperbranched polymers are used, the overall properties of the sealant, such as toughness, sealability, mechanical properties, etc., are severely affected due to the occurrence of significant phase separation. Probably, due to the different structures of the hyperbranched polymers, the reactivity between the hyperbranched polymers and epoxy resin is greatly different from that of components such as the Mannich modified curing agent, so that the sealant has strong selectivity in the curing process to form an obvious two-phase structure, and the non-uniformity of the cured adhesive layer seriously influences the response capability of the cured adhesive layer to external stimulation and influences the comprehensive performance of the cured adhesive layer.
Examples p-phenylenediamine (CAS: 106-50-3), cyanuric chloride (CAS: 108-77-0) were purchased from Vanhua chemical group, Inc.
The inventor finds that when a preparation raw material of the Mannich modified curing agent contains a specific amount of cardanol, the cardanol and the hyperbranched p-phenylenediamine polymer are mixed in a ratio of (2-3): when the adhesive is mixed with the proportion of 1 as a curing agent component of the sealant for the production line storage battery, the curing time of the sealant can be greatly reduced, the adhesion of the sealant to the surfaces of batteries such as lead poles and the like can be improved, and even the toughness of the sealant can be obviously improved without reducing the mechanical properties such as tensile strength and the like. Probably because in the molecular structure of the Mannich modified curing agent, the random structure formed by diaminodiphenylmethane and isofluorodiketone diamine can prevent the Mannich modified curing agent from generating high intermolecular force and high viscosity due to ordered arrangement, and the dispersibility of the curing agent in the component A is applied. While the curing agent has a random structure, the surface tension of the component B can be effectively reduced with the help of the amphiphilic structure of cardanol, the compatibility among A, B components, the spreading and permeability of the sealant to the sealing surface of the battery are improved, and the improvement of the cohesiveness of the sealant to the adhered surface is facilitated. Meanwhile, a stronger pi-pi conjugated system can be formed between a benzene ring structure in the molecular structure of the hyperbranched p-phenylenediamine polymer and a benzene ring structure in the Mannich modified curing agent, and then the component A and the component B in the sealant have basically similar curing activity under the dispersion and winding of a long alkyl chain of cardanol and a large number of hyperbranched structures in the hyperbranched p-phenylenediamine polymer, so that the sealant can be uniformly cured and formed to obtain a uniform and compact three-dimensional network structure, the permeation of acid liquor and the like in the environment to the inside of a glue layer is avoided, and the performances of toughness, sealing property, acid resistance and the like of the sealant are improved.
The invention provides a use method of the sealant for the storage battery in the production line, which comprises the following steps: and injecting the sealant into a cavity around the lead-acid storage battery pole, adding the colored epoxy resin identification glue on the upper part of the lead-acid storage battery pole, heating and curing the lead-acid storage battery, taking out the lead-acid storage battery, and naturally cooling and curing the lead-acid storage battery.
In a preferred embodiment, the method for using the sealant for the in-line storage battery comprises the following steps:
1) a sponge pad is placed on the pole, and the sponge pad is used for preventing glue leakage when a sealing glue (bottom glue) is injected after the battery cover is sealed;
2) after the battery cover is injected with the sealant and sealed and cured, the sealing ring on the correction pole post is integrated by the sealant (slot cover glue), so that the sealing effect of the sealing structure is good, and the phenomenon of cracking caused by the influence of vibration is not easy to occur;
3) the sealant is injected rapidly according to the predetermined addition amount, the contact height of the sealant and the pole is not less than 2/3 of the effective space height inside the pole hole, and the height is controlled to prevent the sealant from leaking due to the fact that most of 'acid leakage' phenomena occur at the negative electrode of the battery and acid leakage of acid liquid inside the battery along the gap between the contact surface of the pole and the sealant of the battery. Then placing the lead-acid storage battery in an oven for heating and curing at the temperature of 60-90 ℃ for 2-4 h, taking out, placing at room temperature, and naturally cooling and curing;
4) after the battery primer is cured, colored epoxy resin identification glue is added on the upper part of the battery primer.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The embodiment 1 provides a sealant for an assembly line storage battery, which comprises A, B two components, wherein the mass ratio of the A, B component is A: b is 2: 1; A. the component B comprises the following components in parts by weight:
the component A comprises:
and B component:
the bisphenol A epoxy resin is NPEL-128.
The bisphenol F epoxy resin is NPEF-170 in model number.
The preparation of the polyurethane comprises the following steps:
adding 3 parts of high resilience polyether and 8 parts of polyethylene glycol into a reaction kettle, performing vacuum dehydration and drying treatment at 120 ℃, then reducing the temperature to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 12min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of diphenylmethane diisocyanate into a reaction kettle for reaction under the protection, controlling the reaction temperature at 75 ℃ for 2.5 hours, then adding 0.8 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 45min, and discharging to obtain the product.
The preparation method of the Mannich modified curing agent comprises the following steps:
adding 8 parts of phenol, 3 parts of isofluorodiketodiamine, 1 part of diaminodiphenylmethane 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and dropwise adding 4 parts of polyformaldehyde in batches when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
The preparation method of the hyperbranched p-phenylenediamine polymer comprises the following steps:
dissolving 3.02g of p-phenylenediamine in 15mL of water, adding 0.72mL of pyridine, stirring and dissolving (heating if necessary) for later use; adding 2.76g of cyanuric chloride into a reaction bottle, adding a solvent for dissolving, adding an aqueous solution of p-phenylenediamine in batches, reacting at normal temperature for 4.5h under the condition of introducing inert gas, filtering, washing with deionized water and acetone, and drying in vacuum to obtain the cyanuric chloride.
The application method of the sealant for the storage battery in the production line comprises the following steps:
1) a sponge pad is placed on the pole, and the sponge pad is used for preventing glue leakage when a sealing glue (bottom glue) is injected after the battery cover is sealed; the vast majority of the "acid creep" phenomenon occurs at the negative electrode of the battery; the acid solution in the battery climbs along the gap between the contact surfaces of the battery pole and the sealant;
2) and (4) injecting a sealant into the battery cover, sealing and curing, and correcting the sealing ring on the pole. The sealing structure integrated by the sealant (slot cover glue) has good sealing effect and is not easy to crack under the influence of vibration;
3) the sealant is injected rapidly according to the predetermined addition amount, the contact height of the sealant and the pole is not less than 2/3 of the effective space height inside the pole hole, and the height is controlled to prevent the sealant from leaking due to the fact that most of 'acid leakage' phenomena occur at the negative electrode of the battery and acid leakage of acid liquid inside the battery along the gap between the contact surface of the pole and the sealant of the battery. Then placing the lead-acid storage battery in an oven for heating and curing at 75 ℃ for 3h, taking out and placing at room temperature for natural cooling and curing;
4) after the battery primer is cured, colored epoxy resin identification glue is added on the upper part of the battery primer.
Example 2
Example 2 is essentially the same as example 1, except that: the A, B component comprises the following components in parts by weight:
the component A comprises:
and B component:
example 3
Example 3 is essentially the same as example 1, except that: the A, B component comprises the following components in parts by weight:
the component A comprises:
and B component:
example 4
Example 4 is essentially the same as example 1, except that: the polyurethane is of the type PU601T and is purchased from the Nippon Feihua New Material science and technology Co.
Comparative example 1
Comparative example 1 is essentially the same as example 1 except that: the preparation of the polyurethane comprises the following steps: adding 8 parts of polyethylene glycol into a reaction kettle, carrying out vacuum dehydration and drying treatment at 120 ℃, then reducing the temperature to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 12min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of diphenylmethane diisocyanate into a reaction kettle for reaction under the protection, controlling the reaction temperature at 75 ℃ for 2.5 hours, then adding 0.8 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 45min, and discharging to obtain the product.
Comparative example 2
Comparative example 2 withExample 1 is essentially the same except that: the preparation of the polyurethane comprises the following steps: adding 3 parts of propylene glycol block polyether and 8 parts of polyethylene glycol into a reaction kettle, performing vacuum dehydration and drying treatment at 120 ℃, then reducing the temperature to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 12min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of diphenylmethane diisocyanate into a reaction kettle for reaction under the protection, controlling the reaction temperature at 75 ℃ for 2.5 hours, then adding 0.8 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 45min, and discharging to obtain the product.
The propylene glycol block polyether is L-35, and is purchased from Federal Fine chemical Co., Ltd in Guangdong.
Comparative example 3
Comparative example 3 is essentially the same as example 1 except that: the preparation of the polyurethane comprises the following steps: adding 3 parts of high resilience polyether and 8 parts of polyethylene glycol into a reaction kettle, performing vacuum dehydration and drying treatment at 120 ℃, then reducing the temperature to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 12min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of diphenylmethane diisocyanate into a reaction kettle for reaction under the protection, controlling the reaction temperature at 75 ℃ for 2.5 hours, then adding 0.4 part of hydroquinone-di (beta-hydroxyethyl) p-cresol ether, mixing and stirring, reacting for 45min, and discharging to obtain the product.
Comparative example 4
Comparative example 4 is essentially the same as example 1 except that: the preparation of the polyurethane comprises the following steps: adding 3 parts of high resilience polyether and 8 parts of polyethylene glycol into a reaction kettle, performing vacuum dehydration and drying treatment at 120 ℃, then reducing the temperature to 65 ℃, adding 25mL of N, N-dimethylformamide, stirring and dissolving for 12min, adding 0.1 part of dibutyltin laurate, and dissolving in N2Adding 2.4 parts of diphenylmethane diisocyanate into a reaction kettle for reaction under the protection, controlling the reaction temperature at 75 ℃ for 2.5h, then adding 0.8 part of propylene glycol, mixing and stirring, reacting for 45min, and discharging to obtain the product.
Comparative example 5
Comparative example 5 is essentially the same as example 1, except that: the component B comprises the following components in parts by weight:
comparative example 6
Comparative example 6 is essentially the same as example 1, except that: the preparation method of the Mannich modified curing agent comprises the following steps: adding 8 parts of phenol, 3 parts of isofluorodione diamine, 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and beginning to drop 4 parts of polyformaldehyde in batches when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Comparative example 7
Comparative example 7 is essentially the same as example 1 except that: the preparation method of the Mannich modified curing agent comprises the following steps: adding 8 parts of phenol, 1 part of diaminodiphenylmethane, 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and starting dropwise adding 4 parts of polyformaldehyde when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Comparative example 8
Comparative example 8 is essentially the same as example 1 except that: the preparation method of the Mannich modified curing agent comprises the following steps: adding 8 parts of phenol, 10 parts of isofluorodiketodiamine, 1 part of diaminodiphenylmethane, 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and starting dropwise adding 4 parts of polyformaldehyde in batches when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Comparative example 9
Comparative example 9 is essentially the same as example 1 except that: the preparation method of the Mannich modified curing agent comprises the following steps: adding 8 parts of phenol, 1 part of isofluorodione diamine, 6 parts of diaminodiphenylmethane, 0.3 part of ethylenediamine, 0.5 part of m-phenylenediamine and 2 parts of cardanol into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and starting dropwise adding 4 parts of polyformaldehyde in batches when the temperature is raised to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Comparative example 10
Comparative example 10 is essentially the same as example 1 except that: the preparation method of the Mannich modified curing agent comprises the following steps: adding 8 parts of phenol, 3 parts of isofluorodiketodiamine, 1 part of diaminodiphenylmethane, 0.3 part of ethylenediamine and 0.5 part of m-phenylenediamine into a reactor with a reflux condenser, a stirrer, a thermometer and a dropping device, stirring while heating, and dropwise adding 4 parts of polyformaldehyde in batches when the temperature is increased to 85 ℃; and then carrying out reflux reaction for 3h at 105 ℃, carrying out vacuum dehydration, connecting the reaction kettle to a vacuum distillation device, and stopping distillation until the liquid phase temperature is 120 ℃ to obtain the product.
Comparative example 11
Comparative example 11 is essentially the same as example 1, except that: the component B comprises the following components in parts by weight:
comparative example 12
Comparative example 12 is essentially the same as example 1 except that: the component B comprises the following components in parts by weight:
hyperbranched polyamide HyPer N102.
The hyperbranched polyamide HyPer N102 was purchased from Wuhan hyperbranched resins technology, Inc.
Comparative example 13
Comparative example 13 is essentially the same as example 1, except that: the component B comprises the following components in parts by weight:
comparative example 14
Comparative example 14 is essentially the same as example 1 except that: the component B comprises the following components in parts by weight:
evaluation of Performance
(1) Acid resistance (acid absorption): and (3) pouring the adhesive into a cylindrical sample block with the diameter of 40mm and the height of 9mm by using a mold. Placing the sample block at a density of 1.340g/cm3Soaking in sulfuric acid (25 deg.C) at 80 + -2 deg.C for 48 h. And taking out the sample block, cleaning the sample block with clear water, wiping the sample block with filter paper, weighing the mass of the sample block and calculating the mass growth rate.
(2) Sealing property: and (3) pouring the adhesive into a cylindrical sample block with the diameter of 40mm and the height of 9mm by using a mold. And placing one lead pole which is cast in 24 hours in the adhesive before casting, wherein a part of the lead pole is exposed out of the adhesive when the lead pole is placed. Placing the sample block at a density of 1.340g/cm3Soaking in sulfuric acid (25 deg.C) at 80 + -2 deg.C for 48 h. And taking out the sample block, washing with clear water, drying, forcibly separating the adhesive from the lead pole, and observing the condition of the contact surface of the lead pole and the adhesive. The soaking time can be prolonged according to the experimental requirements.
(3) Bonding strength: the adhesive is evenly coated on two lead strips with the thickness of 100mm multiplied by 10mm multiplied by 3mm, the coating area is about 10mm multiplied by 10mm, and the lead strips are fixed by iron clamps. After curing, the material is tested by a servo control material testing machine, the stretching speed is 20mm/min, and the testing temperature is 25 +/-2 ℃.
(4) Toughness (tensile strength): the adhesive was cast into 200mm × 10mm × 3mm dumbbell-shaped specimens using a mold, and tested using a servo-controlled material tester at a tensile rate of 20mm/min and a test temperature of 25 ± 2 ℃.
(5) The glass transition temperature is measured by a DSC differential scanning calorimeter at a temperature rise rate of 20 ℃/min and in a temperature range of 20-150 ℃.
The results of the experiment are shown in the following table:
table 1: acid resistance and sealability test data for the sealants obtained in example 1
Table 2: data for performance testing of sealants obtained in examples and comparative examples
As can be seen from the table, the sealant prepared by the invention has the advantages of low acid absorption rate, good acid resistance, strong bonding strength with lead, high tensile strength, good toughness, vitrification temperature of the primer after curing 93 ℃, bright lead pole and rich metallic luster after soaking in acid liquor for 120 hours for 5 times of cold and hot circulation, and excellent sealing property.
The sealant prepared in example 1 is a yellowish transparent viscous liquid with the viscosity of 1200-2800 and the curing condition of 2 hours at 60 ℃. The hardness after solidification is more than or equal to 80D, and the ABS splicing strength is more than or equal to 4 MPa.

Claims (10)

1. The sealant for the storage battery in the production line is characterized by comprising A, B two components, wherein the mass ratio of the A, B components is A: b is 2: 1; A. the component B comprises the following components in parts by weight:
the component A comprises:
and B component:
2. the sealant for the in-line storage battery of claim 1, wherein the raw material for preparing the polyurethane comprises high resilience polyether.
3. The sealant for the in-line storage battery according to claim 1 or 2, wherein the raw material for preparing the polyurethane further comprises hydroquinone-di (β -hydroxyethyl) p-cresol ether.
4. The sealant for the assembly line storage battery of claim 1, wherein the mannich modified curing agent is prepared from raw materials comprising phenol, isophorone diamine, diaminodiphenylmethane and polyoxymethylene.
5. The sealant for the assembly line storage battery according to claim 4, wherein the molar ratio of isophorone diamine to diaminodiphenylmethane is (2-4): 1.
6. the sealant for the in-line storage battery of claim 4, wherein the mannich modified curing agent is prepared from raw materials which also comprise cardanol.
7. The sealant for the production line storage battery as claimed in claim 4 or 6, wherein the molar ratio of the cardanol to the phenol is 1: (3-5).
8. The sealant for the in-line storage battery of claim 1, wherein the raw materials for preparing the component B further comprise hyperbranched p-phenylenediamine polymer.
9. The sealant for the production line storage battery of claim 1 or 8, wherein the weight ratio of the hyperbranched p-phenylenediamine polymer to the Mannich modified curing agent is 1: (2-3).
10. The use method of the sealant for the production line storage battery according to any one of claims 1 to 9, characterized in that the sealant is injected into a cavity around a lead-acid storage battery pole, a colored epoxy resin identification glue is added on the upper part of the sealant, then the lead-acid storage battery is heated and solidified, and the lead-acid storage battery is taken out and naturally cooled and solidified to obtain the sealant.
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