CN109439252A - A kind of epoxy resin sealant and its preparation method and application - Google Patents

A kind of epoxy resin sealant and its preparation method and application Download PDF

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Publication number
CN109439252A
CN109439252A CN201811264609.4A CN201811264609A CN109439252A CN 109439252 A CN109439252 A CN 109439252A CN 201811264609 A CN201811264609 A CN 201811264609A CN 109439252 A CN109439252 A CN 109439252A
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component
parts
epoxy resin
bisphenol
promotor
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CN109439252B (en
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王贵平
陆璐侃
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Guangzhou Pochely New Material Technology Co Ltd
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Guangzhou Pochely New Material Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The invention discloses a kind of epoxy resin sealants and its preparation method and application.The sealant is made of component A and B component, and the component A includes following parts by weight of component: 75~80 parts of bisphenol f type epoxy resin, 7~10 parts of bisphenol A type epoxy resin, 1~1.2 part of silane coupling agent and 10~15 parts of diluent;The B component includes following parts by weight of component: 30~35 parts of curing agent, I 25~30 parts of promotor, II 20~25 parts of promotor and 12~17 parts of solvent.The present invention can effectively improve the adhesive property and acid-resistant corrosion of epoxy resin sealant by the component and proportion of preferred sealant, make it is suitable for seal polyphenylene oxide material lead-acid accumulator slot cover.

Description

A kind of epoxy resin sealant and its preparation method and application
Technical field
The present invention relates to epoxy resin sealant technical fields, and in particular to a kind of epoxy resin sealant and its preparation side Method and application.
Background technique
Polyphenylene oxide (Polyphenylene Oxide, PPO) is one of big general engineering plastic in the world five, big with rigidity, The advantages that heat resistance is high, fire retardant, intensity is higher, excellent electrical properties.In addition, PPO also has many advantages, such as wear-resisting, nontoxic, anti-pollution. The dielectric constant and dielectric loss of PPO is one of the smallest kind in engineering plastics, is hardly influenced by temperature, humidity, It can be used for basic, normal, high frequency electric field field.Therefore application of the PPO in lead-acid accumulator is more and more concerned.
The molded product of polyphenylene oxide and Noryl, extruded product, usually using solvent-based adhesive or adhesive What solution was bonded, when bonding as other plastics, it is necessary to completely remove the impurity on surface and pollution;And environmental protection height It is required that social environment under, solvent-based adhesive is increasingly restricted.
Lead-acid accumulator producer form is different currently on the market, but close about the epoxy middle cover for PPO material battery The relevant report of sealing is relatively fewer, and main cause is the lead-acid accumulator of PPO material, compared with traditional ABS material, bonding Difficulty is higher, and seal request is tightened up.According to epoxy resin storage battery middle cover glue general currently on the market as PPO material Lid sealant in the epoxy of battery, it may appear that the low problem of adhesive strength, adhesive strength are only 5MPa or so, and as storage The sealing of cell through lid, at least need to reach 6MPa or more just has certain guarantee to accumulator product quality.Therefore, it is necessary to open It is good to send out adhesive property a kind of, can be used for sealing the sealant of polyphenylene oxide material lead-acid accumulator slot cover.
Summary of the invention
It is an object of the invention to a kind of epoxy resin sealant and its system are provided in place of overcome the deficiencies in the prior art Preparation Method and application improve the adhesive property and acid-resistant corrosion of epoxy resin sealant, make it is suitable for seal polyphenylene oxide material Matter lead-acid accumulator slot cover.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of epoxy resin sealant, is made of component A and B component, and the component A includes following parts by weight of component: double 75~80 parts of phenol F type epoxy resin, 7~10 parts of bisphenol A type epoxy resin, 1~1.2 part of silane coupling agent and diluent 10~15 Part;The B component includes following parts by weight of component: 30~35 parts of curing agent, I 25~30 parts of promotor, promotor II 20~25 Part and 12~17 parts of solvent.
The present invention select bisphenol f type epoxy resin based on, viscosity is low, preferable wellability existing to the surface PPO and There is preferably corrosion resistance after solidification, the present invention effectively improves epoxy resin sealing by the component and proportion of preferred sealant The adhesive property and acid-resistant corrosion of glue, make it is suitable for seal polyphenylene oxide material lead-acid accumulator slot cover.
As the preferred embodiment of epoxy resin sealant of the present invention, the curing agent is polyetheramine.
As the preferred embodiment of epoxy resin sealant of the present invention, the promotor I is 2,4,6- tri- (two Methyaminomethyl) phenol.
As the preferred embodiment of epoxy resin sealant of the present invention, the promotor II is 2,4,6- tri- (dimethylamino methyl) phenolate.
As the preferred embodiment of epoxy resin sealant of the present invention, the sealant is by component A and B component Composition, the component A includes following parts by weight of component: 79.5 parts of bisphenol f type epoxy resin, 8.5 parts of bisphenol A type epoxy resin, 1 part and 11 parts of diluent of silane coupling agent;The B component includes following parts by weight of component: 30 parts of curing agent, I 28 parts of promotor, II 25 parts and 17 parts of solvent of promotor.
As the preferred embodiment of epoxy resin sealant of the present invention, the silane coupling agent is KH560, institute Stating diluent is difunctional epoxide diluent, and the solvent is benzyl alcohol.
The present invention selects difunctional epoxide diluent, both reduces viscosity, is easy to technological operation, and utmostly reduces dilute Release influence of the agent to adhesive property;The addition of coupling agent KH-560, auxiliary improve epoxy resin sealant and the caking property of PPO Energy;Curing agent uses polyetheramine, keeps comparable toughness after making solidification, ensure that the adhesive property of PPO to the greatest extent;Solidification 2,4,6- tri- (dimethylamino methyl) phenol of di-tertiary amine system promotor and 2,4,6- tri- (dimethylamino methyl) phenolates in system Collocation uses, and both improves curing rate, guarantees production efficiency, and maintain the operating time at room temperature, meets production requirement.
Preparation method as epoxy resin sealant of the present invention, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, diluent and silane coupling agent is then added, after dispersing 15~20min with the revolving speed of 1000~1200r/min, vacuum is de- Bubble, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: curing agent, promotor I, promotor II and solvent are proportionally added into mixing plant, stirred After mixing uniformly, B component is obtained.
The present invention also provides above-mentioned epoxy resin sealants for sealing polyphenylene oxide material lead-acid accumulator slot cover Purposes.
As the preferred embodiment of purposes of the present invention, by the component A and B component by weight 100:25~ 30 are added in mixing container after mixing evenly, carry out encapsulating to battery container cover, solidify 1 hour at 70 DEG C.
Compared with prior art, the invention has the benefit that
The present invention selects based on bisphenol f type epoxy resin, and compound bisphenol A type epoxy resin resin, viscosity is low, to the surface PPO There is preferably corrosion resistance after existing preferable wellability and solidification, and by the component and proportion of preferred sealant, effectively Improve epoxy resin sealant adhesive property and acid-resistant corrosion, make it is suitable for seal polyphenylene oxide material Plumbic acid accumulator container Lid.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention It further illustrates.It will be appreciated by those skilled in the art that described herein, specific examples are only used to explain the present invention, not For limiting the present invention.
In embodiment, used experimental method is conventional method unless otherwise specified, material used, reagent etc., It is commercially available unless otherwise specified.
Embodiment 1
As a kind of embodiment of epoxy resin sealant of the present invention, epoxy resin sealant packet described in the present embodiment It includes and is made of component A and B component, the component A includes following parts by weight of component: 79.5 parts of bisphenol f type epoxy resin, bisphenol-A 8.5 parts of type epoxy resin, 1 part of silane coupling agent KH-560 and 11 parts of difunctional epoxide diluent;The B component include with Lower parts by weight of component: 30 parts of polyetheramine, 2,4,6- tri- 28 parts of (dimethylamino methyl) phenol (DMP-30), 2,4,6- tri- (diformazans Amino methyl) 25 parts and 17 parts of benzyl alcohol of phenolate (DMP-30 salt).
The preparation method of epoxy resin sealant described in the present embodiment, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, difunctional epoxide diluent and KH-560 is then added, 15~20min is dispersed with the revolving speed of 1000~1200r/min Afterwards, vacuum defoamation, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: polyetheramine, DMP-30, DMP-30 salt and benzyl alcohol are proportionally added into mixing plant, are stirred After mixing uniformly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:25 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.
The test result of the sealant of the present embodiment is as shown in table 1:
Table 1
As seen from the results in Table 1, the PPO shear strength of the sealant of the present embodiment reaches 8MPa or more, has good viscous Performance and acid corrosion-resistant performance are connect, sealing polyphenylene oxide material lead-acid accumulator slot cover is suitable for.
Embodiment 2
As a kind of embodiment of epoxy resin sealant of the present invention, epoxy resin sealant packet described in the present embodiment It includes and is made of component A and B component, the component A includes following parts by weight of component: 78 parts of bisphenol f type epoxy resin, bisphenol A-type 8 parts of epoxy resin, 1.1 parts of silane coupling agent KH-560 and 12.9 parts of difunctional epoxide diluent;The B component include with Lower parts by weight of component: 35 parts of polyetheramine, DMP-3025 parts, 25 parts of DMP-30 salt and 15 parts of benzyl alcohol.
The preparation method of epoxy resin sealant described in the present embodiment, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, difunctional epoxide diluent and KH-560 is then added, 15~20min is dispersed with the revolving speed of 1000~1200r/min Afterwards, vacuum defoamation, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: polyetheramine, DMP-30, DMP-30 salt and benzyl alcohol are proportionally added into mixing plant, are stirred After mixing uniformly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:25 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.
The test result of the sealant of the present embodiment is as shown in table 2:
Table 2
Embodiment 3
As a kind of embodiment of epoxy resin sealant of the present invention, epoxy resin sealant packet described in the present embodiment It includes and is made of component A and B component, the component A includes following parts by weight of component: 77 parts of bisphenol f type epoxy resin, bisphenol A-type 7 parts of epoxy resin, 1 part of silane coupling agent KH-560 and 15 parts of difunctional epoxide diluent;The B component includes following heavy Measure part component: 33 parts of polyetheramine, 30 parts of DMP-30,20 parts of DMP-30 salt and 17 parts of benzyl alcohol.
The preparation method of epoxy resin sealant described in the present embodiment, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, difunctional epoxide diluent and KH-560 is then added, 15~20min is dispersed with the revolving speed of 1000~1200r/min Afterwards, vacuum defoamation, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: polyetheramine, DMP-30, DMP-30 salt and benzyl alcohol are proportionally added into mixing plant, are stirred After mixing uniformly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:28 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.
The test result of the sealant of the present embodiment is as shown in table 3:
Table 3
Embodiment 4
As a kind of embodiment of epoxy resin sealant of the present invention, epoxy resin sealant packet described in the present embodiment It includes and is made of component A and B component, the component A includes following parts by weight of component: 80 parts of bisphenol f type epoxy resin, bisphenol A-type 9 parts of epoxy resin, 1 part of silane coupling agent KH-560 and 10 parts of difunctional epoxide diluent;The B component includes following heavy Measure part component: 34 parts of polyetheramine, 28 parts of DMP-30,22 parts of DMP-30 salt and 16 parts of benzyl alcohol.
The preparation method of epoxy resin sealant described in the present embodiment, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, difunctional epoxide diluent and KH-560 is then added, 15~20min is dispersed with the revolving speed of 1000~1200r/min Afterwards, vacuum defoamation, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: polyetheramine, DMP-30, DMP-30 salt and benzyl alcohol are proportionally added into mixing plant, are stirred After mixing uniformly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:30 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.
The test result of the sealant of the present embodiment is as shown in table 4:
Table 4
Comparative example 1
Epoxy resin sealant described in this comparative example includes being made of component A and B component, and the component A includes following heavy Measure part component: 79.5 parts of bisphenol f type epoxy resin, 8.5 parts of bisphenol A type epoxy resin, 1 part of silane coupling agent KH-560 and double 11 parts of functional group's epoxide diluent;The B component includes following parts by weight of component: 30 parts of alicyclic ring amine curing agent, DMP-30 28 Part, 2,25 parts of dimethyl benzylamine and 17 parts of benzyl alcohol.
The preparation method of epoxy resin sealant described in this comparative example, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, difunctional epoxide diluent and KH-560 is then added, 15~20min is dispersed with the revolving speed of 1000~1200r/min Afterwards, vacuum defoamation, vacuum degree -0.098~-0.1MPa, 1~1.5h of deaeration obtain component A;
(2) preparation of B component: alicyclic ring amine curing agent, DMP-30, dimethyl benzylamine and benzyl alcohol are proportionally added into stirring In equipment, after mixing evenly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:25 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.
The test result of the sealant of this comparative example is as shown in table 5:
Table 5
Comparative example 2
Epoxy resin sealant described in this comparative example includes being made of component A and B component, and the component A includes following heavy Measure part component: 79.5 parts of bisphenol f type epoxy resin, 8.5 parts of bisphenol A type epoxy resin, 1 part of silane coupling agent KH-560 and double 11 parts of functional group's epoxide diluent;The B component includes following parts by weight of component: 40 parts of polyetheramine, 20 parts of DMP-30, DMP- 30 25 parts of salt and 15 parts of benzyl alcohol.
The preparation method of epoxy resin sealant described in this comparative example, comprising the following steps:
(1) preparation of component A: first bisphenol f type epoxy resin and bisphenol A type epoxy resin being added in stirred tank, stirring Uniformly, after difunctional epoxide diluent and KH-560,15~20min of high speed dispersion then being added, vacuum defoamation, vacuum degree- 0.098~-0.1MPa, 1~1.5h of deaeration, obtains component A;
(2) preparation of B component: polyetheramine, DMP-30, DMP-30 salt and benzyl alcohol are proportionally added into mixing plant, are stirred After mixing uniformly, B component is obtained;
(3) component A and B component are added in mixing container by weight 100:25 after mixing evenly, to battery Slot cover carries out encapsulating, solidifies 1 hour at 70 DEG C.The test result of the sealant of this comparative example is as shown in table 6:
Table 6
By the result of table 1~6 it is found that compared with comparative example, sealant of the invention passes through preferred ingredient and its content, tool There are preferable adhesive strength and acid corrosion-resistant performance, is more suitable for sealing polyphenylene oxide material lead-acid accumulator slot cover.Present invention choosing Based on bisphenol f type epoxy resin, viscosity is low, preferable wellability existing to the surface PPO, and has after solidifying preferably resistance to Corrosivity;Double official's diluents are selected, viscosity is both reduced, is easy to technological operation, and utmostly reduce diluent to adhesive property Influence;The addition of coupling agent KH-560, auxiliary improve epoxy resin sealant and the adhesive property of PPO;Curing agent uses Polyetheramine keeps comparable toughness after making solidification, ensure that the adhesive property of PPO to the greatest extent;Di-tertiary amine in curing system It is that promotor collocation uses, both improves curing rate, guarantee production efficiency, and maintain the operating time at room temperature, meet life Production demand.The present invention effectively improves the adhesive property of epoxy resin sealant and resistance to by the component and proportion of preferred sealant Sour corrosion, make it is suitable for seal polyphenylene oxide material lead-acid accumulator slot cover.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention And range.

Claims (9)

1. a kind of epoxy resin sealant, which is characterized in that be made of component A and B component, the component A includes following weight Part component: 75~80 parts of bisphenol f type epoxy resin, 7~10 parts of bisphenol A type epoxy resin, 1~1.2 part of silane coupling agent and dilute Release 10~15 parts of agent;The B component includes following parts by weight of component: 30~35 parts of curing agent, promotes I 25~30 parts of promotor II 20~25 parts and 12~17 parts of solvent of agent.
2. epoxy resin sealant according to claim 1, which is characterized in that the curing agent is polyetheramine.
3. epoxy resin sealant according to claim 2, which is characterized in that the promotor I is 2,4,6- tri- (diformazans Amino methyl) phenol.
4. epoxy resin sealant according to claim 3, which is characterized in that the promotor II is 2,4,6- tri- (two Methyaminomethyl) phenolate.
5. epoxy resin sealant according to claim 1, which is characterized in that be made of component A and B component, the A group Dividing includes following parts by weight of component: 79.5 parts of bisphenol f type epoxy resin, 8.5 parts of bisphenol A type epoxy resin, 1 part of silane coupling agent With 11 parts of diluent;The B component includes following parts by weight of component: 30 parts of curing agent, I 28 parts of promotor, II 25 parts of promotor With 17 parts of solvent.
6. epoxy resin sealant according to claim 1, which is characterized in that the silane coupling agent is KH560, described Diluent is difunctional epoxide diluent, and the solvent is benzyl alcohol.
7. the preparation method of described in any item epoxy resin sealants according to claim 1~6, which is characterized in that including with Lower step:
(1) bisphenol f type epoxy resin and bisphenol A type epoxy resin: being first added in stirred tank, stir evenly by the preparation of component A, Then diluent and silane coupling agent is added, after dispersing 15~20min with the revolving speed of 1000~1200r/min, vacuum defoamation, very Reciprocal of duty cycle -0.098~-0.1MPa, 1~1.5h of deaeration, obtains component A;
(2) preparation of B component: curing agent, promotor I, promotor II and solvent are proportionally added into mixing plant, and stirring is equal After even, B component is obtained.
8. described in any item epoxy resin sealants are for sealing polyphenylene oxide material lead-acid accumulator according to claim 1~6 The purposes of slot cover.
9. purposes according to claim 8, which is characterized in that by the component A and B component by weight 100:25~30 It is added in mixing container after mixing evenly, encapsulating is carried out to battery container cover, is solidified 1 hour at 70 DEG C.
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Publication number Priority date Publication date Assignee Title
CN112226188A (en) * 2020-10-20 2021-01-15 中国电力科学研究院有限公司 Composite adhesive and preparation method and use method thereof
CN114146604A (en) * 2021-12-01 2022-03-08 赵学利 Epoxy resin sealant and preparation method thereof

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