阅读说明：本技术 一种耐深冲耐电解液树脂 (Deep-drawing-resistant electrolyte-resistant resin ) 是由 蔡栋宇 蔡炳照 顾嘉卫 周锦君 项尚林 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种耐深冲耐电解液树脂,由聚酯多元醇、聚烯烃、环氧树脂和酚醛树脂组成,其制备方法包括聚酯多元醇和树脂的制备,这种耐深冲耐电解液树脂的优点：该款产品用于CPP和铝箔的粘接,具备优异的剥离强度,复合制品耐冲压达800mm；粘合剂耐电池电解液性能卓越。这种制备方法的优点：制备工艺的参数易于控制,制备过程无排放,属于环境友好型生产方案。(The invention discloses a deep-drawing resistant electrolyte-resistant resin, which consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, wherein the preparation method comprises the preparation of the polyester polyol and the resin, and the deep-drawing resistant electrolyte-resistant resin has the advantages that: the product is used for bonding the CPP and the aluminum foil, has excellent peeling strength, and the stamping resistance of a composite product reaches 800 mm; the adhesive has excellent resistance to battery electrolyte. The preparation method has the advantages that: the parameters of the preparation process are easy to control, and the preparation process has no emission, and belongs to an environment-friendly production scheme.)

1. A deep drawing resistant electrolyte resistant resin is characterized in that: the polyester polyol epoxy resin is composed of polyester polyol, polyolefin, epoxy resin and phenolic resin, and the preparation steps are as follows:

first step, preparation of polyester polyol:

respectively taking 105-107 g of diethylene glycol, 103-105 g of isophthalic acid, 76-78 g of terephthalic acid, 182-184 g of sebacic acid and 152-154 g of polyol into a 1000mL four-neck flask, adding 0.1-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is over, sampling and measuring the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing for 3 hours under the conditions that the temperature is controlled to be 100-110 ℃ and the pressure is-0.1 MPa, so as to obtain the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g;

step two, preparation of resin:

respectively putting 200-202 g of the polyester polyol, 150-152 g of polyolefin, 35-37 g of epoxy resin and 60-62 g of phenolic resin into a 500mL four-neck flask, adding 400-402 g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78-80 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

2. The deep-drawing electrolyte resistant resin as claimed in claim 1, wherein: in the preparation of the polyester polyol, the mass of diethylene glycol was 106g, the mass of isophthalic acid was 104g, the mass of terephthalic acid was 77g, the mass of sebacic acid was 183g and the mass of polyol was 153g, the hydroxyl value was 23mg KOH/g.

3. The deep-drawing electrolyte resistant resin as claimed in claim 1, wherein: in the preparation process of the resin, the mass of the polyester polyol is 201g, the mass of the polyolefin is 151g, the mass of the epoxy resin is 36g, the mass of the phenolic resin is 61g, the mass of the methyl acetone is 401g, and the reaction temperature is 78 ℃.

Technical Field

The invention relates to a deep-drawing resistant electrolyte-resistant resin, belonging to the field of polyurethane adhesive material research.

Background

The soft package of the lithium ion battery is more and more widely applied in the field of lithium batteries, and is formed by compounding nylon, outer layer glue, aluminum foil, inner layer glue and CPP in sequence from outside to inside; wherein the inlayer is glued and is played decisive effect to the corrosion-resistant of plastic-aluminum membrane, in case the inlayer is glued and appears corroding, can cause CPP and aluminium foil layer separation, causes the problem such as lithium cell flatulence, weeping. The inner side of the traditional metal can is coated, and substances contained in the coating method have harmful effects on human bodies and the environment, particularly edible cans. The birth of the metal plate film covering technology is a revolutionary progress of the metal can production. With the wide application of the metal can, the traditional metal can production process and technology are overturned, and the production rate, the production cost, the cleanness, the sanitation, the environmental protection and other aspects are advanced. However, the common polyurethane glue can not meet the composite requirement of the coated iron (the punching depth is more than or equal to 800mm), and the requirement of the packaged content is higher and higher, for example, the package contains paint and resin of alkaline medium, most adhesives are difficult to block the corrosion of the medium to the packaging iron plate, and the requirement of the market is met in order to overcome the defects of the existing products, so that a novel deep punching resistant alkali-resistant polyurethane adhesive is developed.

Disclosure of Invention

The invention aims to provide a deep drawing resistant electrolyte resistant resin.

The technical scheme adopted by the invention is as follows:

the deep drawing resistant and electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared through the following specific steps:

first step, preparation of polyester polyol:

respectively taking 105-107 g of diethylene glycol, 103-105 g of isophthalic acid, 76-78 g of terephthalic acid, 182-184 g of sebacic acid and 152-154 g of polyol into a 1000mL four-neck flask, adding 0.1-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is over, sampling and measuring the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing for 3 hours under the conditions that the temperature is controlled to be 100-110 ℃ and the pressure is-0.1 MPa, so as to obtain the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g;

step two, preparation of resin:

respectively putting 200-202 g of the polyester polyol, 150-152 g of polyolefin, 35-37 g of epoxy resin and 60-62 g of phenolic resin into a 500mL four-neck flask, adding 400-402 g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78-80 ℃, and carrying out heat preservation reaction for 3 hours to obtain resin;

further, in the preparation of the polyester polyol, the mass of diethylene glycol was 106g, the mass of isophthalic acid was 104g, the mass of terephthalic acid was 77g, the mass of sebacic acid was 183g, the mass of polyol was 153g, and the hydroxyl value was 23mg KOH/g.

Further, the mass of the polyester polyol was 201g, the mass of the polyolefin was 151g, the mass of the epoxy resin was 36g, the mass of the phenol resin was 61g and the mass of the methyl acetone was 401g in the preparation process of the resin, and the reaction temperature was 78 ℃.

The deep drawing resistant electrolyte resistant resin has the advantages that:

the product is used for bonding the CPP and the aluminum foil, has excellent peeling strength, and the stamping resistance of a composite product reaches 800 mm; the adhesive has excellent resistance to battery electrolyte.

The preparation method has the advantages that:

the parameters of the preparation process are easy to control, and the preparation process has no emission, and belongs to an environment-friendly production scheme.

Detailed Description

The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.

Example 1:

the deep drawing resistant electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared by the following specific steps:

first step, preparation of polyester polyol: respectively putting 106g of diethylene glycol, 104g of isophthalic acid, 77g of terephthalic acid, 183g of sebacic acid and 133g of polyol into a 1000mL four-neck flask, adding 0.1 g-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is finished, sampling is carried out to measure the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing is carried out for 3 hours under the conditions that the temperature is 100-110 ℃ and the pressure is-0.1 MPa, so that the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g is obtained;

step two, preparation of resin: respectively taking 201g of the polyester polyol, 151g of polyolefin, 36g of epoxy resin and 61g of phenolic resin, putting the polyester polyol, the 151g of polyolefin, the 36g of epoxy resin and the 61g of phenolic resin into a 500mL four-neck flask, adding 401g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

Example 2:

the deep drawing resistant and electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared through the following specific steps:

first step, preparation of polyester polyol:

respectively putting 106g of diethylene glycol, 104g of isophthalic acid, 77g of terephthalic acid, 183g of sebacic acid and 143g of polyol into a 1000mL four-neck flask, adding 0.1 g-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is finished, sampling is carried out to measure the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing is carried out for 3 hours under the conditions that the temperature is 100-110 ℃ and the pressure is-0.1 MPa, so that the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g is obtained;

step two, preparation of resin:

respectively taking 201g of the polyester polyol, 151g of polyolefin, 36g of epoxy resin and 61g of phenolic resin, putting the polyester polyol, the 151g of polyolefin, the 36g of epoxy resin and the 61g of phenolic resin into a 500mL four-neck flask, adding 401g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

Example 3:

the deep drawing resistant and electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared through the following specific steps:

first step, preparation of polyester polyol:

respectively putting 106g of diethylene glycol, 104g of isophthalic acid, 77g of terephthalic acid, 183g of sebacic acid and 153g of polyol into a 1000mL four-neck flask, adding 0.1 g-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is finished, sampling is carried out to measure the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing is carried out for 3 hours under the conditions that the temperature is 100-110 ℃ and the pressure is-0.1 MPa, so that the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g is obtained;

step two, preparation of resin:

respectively taking 201g of the polyester polyol, 151g of polyolefin, 36g of epoxy resin and 61g of phenolic resin, putting the polyester polyol, the 151g of polyolefin, the 36g of epoxy resin and the 61g of phenolic resin into a 500mL four-neck flask, adding 401g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

Example 4:

the deep drawing resistant and electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared through the following specific steps:

first step, preparation of polyester polyol:

respectively putting 106g of diethylene glycol, 104g of isophthalic acid, 77g of terephthalic acid, 183g of sebacic acid and 163g of polyol into a 1000mL four-neck flask, adding 0.1 g-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is finished, sampling is carried out to measure the acid value, and if the acid value is lower than 10mg KOH/g, vacuumizing is carried out for 3 hours under the conditions that the temperature is controlled to be 100-110 ℃ and the pressure is-0.1 MPa, so that the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g is obtained;

step two, preparation of resin:

respectively taking 201g of the polyester polyol, 151g of polyolefin, 36g of epoxy resin and 61g of phenolic resin, putting the polyester polyol, the 151g of polyolefin, the 36g of epoxy resin and the 61g of phenolic resin into a 500mL four-neck flask, adding 401g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

Example 5:

the deep drawing resistant and electrolyte resistant resin consists of polyester polyol, polyolefin, epoxy resin and phenolic resin, and is prepared through the following specific steps:

first step, preparation of polyester polyol:

respectively putting 106g of diethylene glycol, 104g of isophthalic acid, 77g of terephthalic acid, 183g of sebacic acid and 173g of polyol into a 1000mL four-neck flask, adding 0.1-0.15 g of titanium catalyst as a catalyst, wherein the reaction system needs nitrogen protection, when the reaction temperature reaches 155 ℃, the reaction system starts to discharge water, the temperature rise rate needs to be controlled, when the reaction temperature reaches 235 ℃, the temperature rise is changed into a heat preservation state, the heat preservation time is 3 hours, after the heat preservation time is finished, sampling is carried out to measure the acid value, and if the acid value is lower than 10mg KOH/g, the temperature is controlled to be 100-110 ℃, and the pressure is-0.1 MPa, vacuumizing is carried out for 3 hours, so that the polyester polyol with the acid value of less than or equal to 1mg KOH/g and the hydroxyl value of 23 +/-2 mg KOH/g is obtained;

step two, preparation of resin:

respectively taking 201g of the polyester polyol, 151g of polyolefin, 36g of epoxy resin and 61g of phenolic resin, putting the polyester polyol, the 151g of polyolefin, the 36g of epoxy resin and the 61g of phenolic resin into a 500mL four-neck flask, adding 401g of methyl acetone when the temperature is raised to 65 ℃, controlling the temperature to be 78 ℃, and carrying out heat preservation reaction for 3 hours to obtain the resin.

The products obtained in the above 5 examples are applied to an aluminum plastic film, and a deep punching test is performed, and the results are as follows:

it was found that when the polyol ratio is 153g, the punching performance of the aluminum-plastic film is best, mainly because the higher functionality of the polyol improves the flexibility of the adhesive film, too low a ratio results in too low flexibility and tearing of the adhesive, and too high a ratio results in too low mechanical strength of the adhesive film (i.e. the adhesive layer is too soft).

Example 6:

the product obtained in the example 3 is used for compounding and punching an aluminum plastic film, the punched film is soaked in electrolyte for 3 days at the temperature of 60 ℃, each test is as follows,

the resin was found to be superior in peel strength, drawing strength and electrolyte resistance.

The resin prepared by the invention has excellent composite strength for the aluminum plastic film, the composite product is resistant to deep drawing and electrolyte, the parameters of the preparation process are easy to control, and the preparation process has no discharge, and belongs to an environment-friendly production scheme.