An epoxy resin adhesive for a gas separation membrane module and a method for preparing the same

Abstract

The application provides an epoxy resin adhesive for a gas separation membrane assembly and a preparation method thereof, wherein the epoxy resin adhesive for the gas separation membrane assembly comprises component A and component B, the weight ratio of the component A and the component B is (4.50-5.02):1; the raw material of the component A comprises bisphenol A epoxy resin and alicyclic epoxy resin; the raw material of the component B comprises a composite modified amine and a low fraction section product of ethylene tar; the low fraction section product of ethylene tar is obtained by distillation of ethylene tar, the boiling range of the low fraction section product of ethylene tar is initial boiling point-290 DEG C, the closed cup flash point is greater than 50 DEG C, and the composite modified amine is obtained by reaction of amine, alkyl phenol and formaldehyde with a mass ratio of 1:1:1. The application provides an epoxy resin adhesive for a gas separation membrane assembly and a preparation method thereof, and the prepared epoxy resin adhesive has the advantages of low initial viscosity, long applicable period, high toughness, good heat resistance and high strength of the cured product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to an epoxy resin adhesive for gas separation membrane module and a preparation method thereof. BACKGROUND

[0002] Epoxy resin adhesive is an important adhesive with excellent performance, numerous varieties and wide adaptability. It has good bonding properties to various metals and most non-metallic materials, is often called "universal glue", and is widely used in the fields of bonding, sealing and the like in the industries of aircraft, missiles, automobiles, buildings, electronics and electrical appliances and wood processing.

[0003] The head of the hollow fiber membrane separation module for gas separation is sealed by pouring adhesive, and the most commonly used is epoxy resin adhesive. In order to prepare a head with mechanical strength and temperature and pressure resistance, so that the hollow fiber membrane module maintains excellent separation and permeation performance under high temperature and high pressure, it is necessary to develop an epoxy resin adhesive with excellent thermal mechanical properties.

[0004] Epoxy resin adhesive is generally composed of epoxy resin (or epoxy resin oligomer or epoxy resin base material), curing agent, toughening agent, solvent and filler, etc. The single epoxy resin has no application value and must be reacted with the curing agent at room temperature or high temperature to form a network or body structure of the cured product, so as to have excellent mechanical and bonding properties and achieve the best use purpose. At present, there are various types of commercial epoxy resins and curing agents. The crosslinking reaction of the commonly used high-temperature resistant curing agent such as alicyclic amine or aromatic amine with the epoxy resin must be carried out at high temperature, the curing conditions are harsh, and the cured product is brittle, which is not conducive to subsequent processing and application. The commonly used method is to add a toughening agent such as rubber or thermoplastic resin to the epoxy resin adhesive, but the addition of the toughening agent will cause the hardness and temperature resistance of the adhesive to decrease to some extent, and the compatibility of the toughening agent with the epoxy resin system is poor, which increases the operation difficulty.

[0005] In addition, the viscosity of the commercial high-temperature resistant epoxy resin pouring sealant is high, so the initial viscosity of the epoxy resin adhesive is large, which easily causes the adhesive to be unevenly infiltrated in the membrane filaments, and seriously affects the sealing and gas separation application of the hollow fiber membrane module. In the prior art, a certain amount of diluent is added to the adhesive system, and the commonly used one is acetone. Although the viscosity reduction effect is obvious, the acetone volatilizes seriously due to its low boiling point and the obvious heat release of the epoxy resin reaction, and bubbles are easily generated in the inside and surface of the cured product of the epoxy resin. Some researchers use a triepoxy active diluent to adjust the viscosity of the system, but the viscosity reduction effect is not good after adding, and the low viscosity requirement of the sealing adhesive cannot be met. SUMMARY

[0006] In order to overcome the deficiencies of the existing epoxy resin adhesive, the present application provides an epoxy resin adhesive for gas separation membrane assembly and a preparation method thereof, and the prepared epoxy resin adhesive has the advantages of low initial viscosity, long applicable period, high toughness, good heat resistance and high strength of the cured product.

[0007] In order to achieve the above-mentioned purpose, the technical means adopted by the present application is as follows: an epoxy resin adhesive for gas separation membrane assembly, comprising component A and component B, the weight ratio of the component A and the component B is (4.50-5.02):1;

[0008] The raw materials of the component A include bisphenol A epoxy resin 60-80 parts, alicyclic epoxy resin 10-30 parts, in parts by weight;

[0009] The raw materials of the component B include composite modified amine 3-6 parts, ethylene tar low fraction section product 9-13 parts, in parts by weight;

[0010] The ethylene tar low fraction section product is obtained by distillation of ethylene tar, the boiling range of the ethylene tar low fraction section product is initial boiling point~290℃, and the closed cup flash point of the ethylene tar low fraction section product is >50℃;

[0011] The composite modified amine is obtained by reaction of amine, alkyl phenol and formaldehyde in a mass ratio of 1:1:1.

[0012] Further, the density of the ethylene tar at 20℃ is 1.01-1.08g / cm 3 , the ash content is not more than 0.003wt%, the carbon residue content is 11wt%-16wt%, the carbon / hydrogen ratio is 11-14, the saturated fraction content is 0.1wt%-2.0wt%, the aromatic fraction content is 50wt%-66wt%, the gum content is 20wt%-33wt%, and the asphaltene content is 0.5wt%-16wt%.

[0013] Further, the bisphenol A epoxy resin can be one or several of E51 epoxy resin, E44 epoxy resin, 128 epoxy resin or 127 epoxy resin.

[0014] Further, the alicyclic epoxy resin can be any one of vinyl cyclohexene epoxy, bis(2,3-epoxidized cyclopentyl) ether, cyclohexene 1,4-biepoxy or 4,5-epoxycyclohexane-1,2-diglycidyl ester.

[0015] Further, the amine is selected from at least one of isophorone diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether or diethylmethylphenylenediamine.

[0016] The alkyl phenol is selected from any three of tert-butyl phenol, amyl phenol, heptyl phenol, octyl phenol, nonyl phenol or decyl phenol.

[0017] Further, the composite modified amine is prepared by the following method:

[0018] Any three of the alkyl phenol is respectively a first alkyl phenol, a second alkyl phenol and a third alkyl phenol, and three parts of aliphatic amine base amine and three parts of formaldehyde are taken respectively;

[0019] The first part of amine is reacted with the first alkyl phenol, the first part of formaldehyde according to the weight ratio of 1:1:1 at 80-100 DEG C to obtain the first modified amine;

[0020] The second part of amine is reacted with the second alkyl phenol, the second part of formaldehyde according to the weight ratio of 1:1:1 at 80-100 DEG C to obtain the second modified amine;

[0021] The third part of amine is reacted with the third alkyl phenol, the third part of formaldehyde according to the weight ratio of 1:1:1 at 80-100 DEG C to obtain the third modified amine;

[0022] The three kinds of modified amines are mixed to obtain the composite modified amine.

[0023] Further, the three kinds of modified amines are mixed according to the mass ratio (2-3):1:1 of the molecular weight of the modified amine from small to large.

[0024] Further, the viscosity of the B component is 19-50 cP at 25 DEG C.

[0025] In order to achieve the above purpose, the technical means adopted by the present application is as follows: a preparation method of an epoxy resin adhesive for gas separation membrane assembly, comprising the following steps:

[0026] S1: preparation of component A:

[0027] The bisphenol A epoxy resin and the alicyclic epoxy resin are mixed uniformly according to the mass ratio, then the temperature is kept at 40-60 DEG C for 1-3 h, then vacuum dehydration is carried out until no water is discharged, and then the temperature is cooled to room temperature;

[0028] S2: preparation of component B:

[0029] The composite modified amine and the low distillation fraction product of ethylene tar are heated to 40-60 DEG C respectively according to the mass ratio, then mixed and cooled to room temperature, and then stored in a sealed light-shielded container;

[0030] S3: the component A and the component B are mixed uniformly, and then vacuum defoaming is carried out, thereby obtaining the epoxy resin adhesive for gas separation membrane assembly.

[0031] The present application has the following beneficial effects:

[0032] First, the bisphenol A epoxy resin and the alicyclic epoxy resin are mixed in a certain proportion to make the high adhesion and flexibility of the bisphenol A epoxy resin and the heat resistance and rigidity of the alicyclic epoxy resin synergistically act, and the comprehensive performance of the epoxy resin adhesive is improved;

[0033] Second, the low fraction section product of ethylene tar is added to the epoxy resin curing agent, which can adjust the viscosity of the epoxy resin adhesive system as a diluent during the preparation of the epoxy resin adhesive, reduces the initial viscosity of the epoxy resin system, prolongs the pot life and slows down the curing reaction rate; on the other hand, during the curing reaction of the epoxy resin adhesive, the crosslinking reaction of the epoxy resin and the amine curing agent is an exothermic process with high temperature, which can initiate the thermal polymerization reaction of the active components in the low fraction section product of ethylene tar, and the product is an ethylene tar polymer with long side chain, condensed ring aromatic hydrocarbon structure and spatial stereostructure, which has good compatibility with the epoxy resin and can be continuously dispersed in the crosslinked structure of the epoxy resin to improve the toughness, heat resistance and rigidity of the epoxy resin curing product;

[0034] Third, the commonly used amine is modified to introduce a phenolic skeleton and an alkyl long side chain on the alicyclic or aromatic ring to form modified amines with different alkyl side chains and molecular weights, the phenolic hydroxyl group is introduced into the molecule to greatly improve the reaction activity of the epoxy resin curing reaction at room temperature, the phenolic skeleton is introduced into the molecule to improve the heat resistance and rigidity of the epoxy resin curing product, and the alkyl side chain is introduced into the molecule to enhance the toughness of the epoxy resin curing product; several modified amines are used in proportion to form a gradient effect in the epoxy resin curing product and play a reinforcing role;

[0035] In summary, the epoxy resin adhesive prepared by the present application has low initial viscosity, good impregnation of the epoxy resin in the film filament bundle, moderate curing speed, long pot life, good toughness of the curing product and excellent thermal mechanical properties, and is particularly suitable for hollow fiber membrane assemblies; the materials of the components of the present application are easy to obtain, the cost is low, the preparation conditions are mild, the operation is simple, and the present application can be used in other fields. DETAILED DESCRIPTION

[0036] To make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0037] The use amount of the raw materials involved in the present application is not limited and can be configured in g or Kg units. The present application takes g as an example.

[0038] Preparation examples of raw materials and intermediates

[0039] The sources of raw materials used in this application are shown in the following table:

[0040] Table 1 Sources of raw materials

[0041] Raw material name Origin Bisphenol A epoxy resin Nantong Xingchen Synthetic Material Co., Ltd. Vinylcyclohexene epoxy resin Guangzhou Tianda High-tech Co., Ltd. Cyclohexene 1,4-epoxide Guangzhou Tianda High-tech Co., Ltd. 4,5-Epoxy cyclohexane-1,2-dicarboxylic acid diglycidyl ester Guangzhou Tianda High-tech Co., Ltd.

[0042] The raw materials other than the complex modified amine, the low fraction section product of ethylene tar and the raw materials listed in the above table are commercially available and do not have special requirements.

[0043] Preparation example of low fraction section product of ethylene tar

[0044] Preparation example 1:

[0045] The low fraction section product of ethylene tar is prepared by distilling ethylene tar and taking the fraction section product with an initial boiling point to 290°C as the low fraction section product of ethylene tar, and the closed cup flash point of the low fraction section product of ethylene tar is > 50°C.

[0046] The properties of the ethylene tar are as follows: density (20°C) is 1.01 g / cm 3 , ash content is 0.002 wt%, carbon residue content is 13 wt%, carbon / hydrogen ratio is 12, saturates content is 1.6 wt%, aromatics content is 65 wt%, gum content is 25 wt%, and asphaltene content is 8.4 wt%.

[0047] Preparation example 2:

[0048] The low fraction section product of ethylene tar is prepared by distilling ethylene tar and taking the fraction section product with an initial boiling point to 290°C as the low fraction section product of ethylene tar, and the closed cup flash point of the low fraction section product of ethylene tar is > 50°C.

[0049] The properties of the ethylene tar are as follows: density (20°C) is 1.06 g / cm 3 , ash content is 0.003 wt%, carbon residue content is 14 wt%, carbon / hydrogen ratio is 13, saturates content is 2.0 wt%, aromatics content is 58 wt%, gum content is 30 wt%, and asphaltene content is 10 wt%.

[0050] Preparation example 3:

[0051] The low fraction section product of ethylene tar is prepared by distilling ethylene tar and taking the fraction section product with an initial boiling point to 290°C as the low fraction section product of ethylene tar, and the closed cup flash point of the low fraction section product of ethylene tar is > 50°C.

[0052] The ethylene tar has the following properties: density (20℃) 1.03 g / cm 3 , ash content 0.001 wt%, carbon residue content 15 wt%, carbon / hydrogen ratio 14, saturates content 0.8 wt%, aromatics content 60 wt%, resins content 28 wt%, asphaltenes content 11.2 wt%.

[0053] Preparation of the composite modified amine

[0054] Preparation Example 1

[0055] The preparation process of the composite modified amine is as follows:

[0056] 1 part of m-phenylenediamine and 1 part of octylphenol were added to a flask, stirred at 50℃ for 10 min, then 1 part of formaldehyde solution was added dropwise with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), the reaction temperature was controlled not to exceed 80℃, after the formaldehyde was added completely, the temperature was slowly increased at a speed of 10℃ / 10 min, and refluxed at 80℃ for 1 h. Then the obtained product was dehydrated under reduced pressure at-0.097~-0.098 MPa vacuum condition until no water was dehydrated, to obtain the first modified amine;

[0057] 1 part of m-phenylenediamine and 1 part of octylphenol were added to a flask, stirred at 50℃ for 10 min, then 1 part of formaldehyde solution was added dropwise with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), the reaction temperature was controlled not to exceed 80℃, after the formaldehyde was added completely, the temperature was slowly increased at a speed of 10℃ / 10 min, and refluxed at 80℃ for 1 h. Then the obtained product was dehydrated under reduced pressure at-0.097~-0.098 MPa vacuum condition until no water was dehydrated, to obtain the first modified amine;

[0058] 1 part of m-phenylenediamine and 1 part of octylphenol were added to a flask, stirred at 50℃ for 10 min, then 1 part of formaldehyde solution was added dropwise with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), the reaction temperature was controlled not to exceed 80℃, after the formaldehyde was added completely, the temperature was slowly increased at a speed of 10℃ / 10 min, and refluxed at 80℃ for 1 h. Then the obtained product was dehydrated under reduced pressure at-0.097~-0.098 MPa vacuum condition until no water was dehydrated, to obtain the first modified amine;

[0059] Then the three modified amines containing different alkyl side chains were mixed according to the order of molecular weight from small to large as 3:1:1 (mass ratio) to obtain the composite modified amine.

[0060] Preparation Example 2

[0061] The preparation process of the composite modified amine is as follows:

[0062] The first modified amine was obtained by adding 1 part of isophorone diamine and 1 part of tert-butyl phenol into a flask, stirring at 50°C for 10 min, then adding 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), controlling the reaction temperature not to exceed 100°C, after the formaldehyde was added completely, slowly increasing the temperature at a speed of 10°C / 10 min, and refluxing at 100°C for 1 h. Then the obtained product was dehydrated under reduced pressure under vacuum condition of-0.097 to-0.098 MPa until no water was dehydrated, to obtain the first modified amine;

[0063] The second modified amine was obtained by adding 1 part of isophorone diamine and 1 part of octyl phenol into a flask, stirring at 50°C for 10 min, then adding 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), controlling the reaction temperature not to exceed 100°C, after the formaldehyde was added completely, slowly increasing the temperature at a speed of 10°C / 10 min, and refluxing at 100°C for 1 h. Then the obtained product was dehydrated under reduced pressure under vacuum condition of-0.097 to-0.098 MPa until no water was dehydrated, to obtain the second modified amine;

[0064] The third modified amine was obtained by adding 1 part of isophorone diamine and 1 part of nonyl phenol into a flask, stirring at 50°C for 10 min, then adding 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), controlling the reaction temperature not to exceed 100°C, after the formaldehyde was added completely, slowly increasing the temperature at a speed of 10°C / 10 min, and refluxing at 100°C for 1 h. Then the obtained product was dehydrated under reduced pressure under vacuum condition of-0.097 to-0.098 MPa until no water was dehydrated, to obtain the third modified amine;

[0065] The composite modified amine was obtained by mixing the above three modified amines containing different alkyl side chains according to the mass ratio of 2:1:1 from small to large molecular weight.

[0066] Preparation Example 3:

[0067] The preparation process of the composite modified amine is as follows:

[0068] The first modified amine was obtained by adding 1 part of isophorone diamine and 1 part of tert-butyl phenol into a flask, stirring at 50°C for 10 min, then adding 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde was controlled within 1 h), controlling the reaction temperature not to exceed 95°C, after the formaldehyde was added completely, slowly increasing the temperature at a speed of 10°C / 10 min, and refluxing at 95°C for 1 h. Then the obtained product was dehydrated under reduced pressure under vacuum condition of-0.097 to-0.098 MPa until no water was dehydrated, to obtain the first modified amine;

[0069] Add 1 part of diaminodiphenylmethane and 1 part of octylphenol into a flask, stir at 50°C for 10 min, then add 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde is controlled within 1 h), control the reaction temperature not to exceed 95°C, after the formaldehyde is added completely, slowly increase the temperature at a speed of 10°C / 10 min, and keep the temperature at 95°C for 1 h. Then dehydrate the obtained product under reduced pressure at a vacuum of -0.097 to -0.098 MPa until no water is dehydrated, to obtain the third modified amine;

[0070] Add 1 part of diaminodiphenylmethane and 1 part of octylphenol into a flask, stir at 50°C for 10 min, then add 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde is controlled within 1 h), control the reaction temperature not to exceed 95°C, after the formaldehyde is added completely, slowly increase the temperature at a speed of 10°C / 10 min, and keep the temperature at 95°C for 1 h. Then dehydrate the obtained product under reduced pressure at a vacuum of -0.097 to -0.098 MPa until no water is dehydrated, to obtain the third modified amine;

[0071] Then mix the above three modified amines containing different alkyl side chains according to the order of molecular weight from small to large as 2:1:1 (mass ratio) to obtain a composite modified amine.

[0072] Preparation Example 4:

[0073] The preparation process of the composite modified amine is as follows:

[0074] Add 1 part of diethylmethylphenyldiamine and 1 part of pentylphenol into a flask, stir at 50°C for 10 min, then add 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde is controlled within 1 h), control the reaction temperature not to exceed 85°C, after the formaldehyde is added completely, slowly increase the temperature at a speed of 10°C / 10 min, and keep the temperature at 85°C for 1 h. Then dehydrate the obtained product under reduced pressure at a vacuum of -0.097 to -0.098 MPa until no water is dehydrated, to obtain the first modified amine;

[0075] Add 1 part of diethylmethylphenyldiamine and 1 part of octylphenol into a flask, stir at 50°C for 10 min, then add 1 part of formaldehyde solution drop by drop with a constant pressure dropping funnel (the dropping time of formaldehyde is controlled within 1 h), control the reaction temperature not to exceed 85°C, after the formaldehyde is added completely, slowly increase the temperature at a speed of 10°C / 10 min, and keep the temperature at 85°C for 1 h. Then dehydrate the obtained product under reduced pressure at a vacuum of -0.097 to -0.098 MPa until no water is dehydrated, to obtain the second modified amine;

[0076] Add 1 part diethylmethylphenylenediamine and 1 part nonylphenol to a flask, stir at 50°C for 10 minutes, then add 1 part formaldehyde solution dropwise using a constant pressure dropping funnel (the formaldehyde addition time is controlled within 1 hour), controlling the reaction temperature not to exceed 85°C. After the formaldehyde is added, slowly increase the temperature at a rate of 10°C / 10min and reflux at 85°C for 1 hour. The resulting product is then dehydrated under reduced pressure at -0.097 to -0.098 MPa until no water is removed, obtaining the third modified amine.

[0077] Then, three modified amines containing different alkyl side chains are mixed in a ratio of 2:1:1 (mass ratio) from small to large molecular weight to obtain a composite modified amine.

[0078] Example

[0079] Example 1:

[0080] A method for preparing an epoxy resin adhesive for a gas separation membrane assembly comprises the following steps:

[0081] S1: Preparation of component A:

[0082] 60 parts of bisphenol A epoxy resin and 15 parts of vinyl cyclohexene epoxy resin were mixed at room temperature, stirred at a stirring speed of 50 r / min for 20 minutes, then transferred to an oven, kept at 50°C for 1 hour, and then vacuum-dehydrated until no water was removed, and then aired to room temperature to obtain component A;

[0083] S2: Preparation of component B:

[0084] 4 parts of the composite modified amine and 11 parts of the low-fraction product of ethylene tar were stirred at 40° C. at a stirring speed of 50 r / min for 20 minutes, and stored in the dark at room temperature to obtain component B;

[0085] The composite modified amine was prepared by the method of Composite Modified Amine Preparation Example 1, and the viscosity of component B was 25 cP at 25°C;

[0086] The ethylene tar low-fraction fraction product is prepared by the method of Example 3 for preparing the ethylene tar low-fraction fraction product;

[0087] S3: 75 parts of component A and 15 parts of component B were stirred at a stirring speed of 80 r / min for 10 min, and vacuum degassing was performed to obtain an epoxy resin adhesive.

[0088] The prepared epoxy resin adhesive was poured into the hollow fiber membrane module to obtain a casting, which was then heated in the order of room temperature for 48 hours, 50°C for 8 hours, 80°C for 5 hours, and 140°C for 3 hours to obtain a hollow fiber membrane module head.

[0089] Example 2:

[0090] A method for preparing an epoxy resin adhesive for a gas separation membrane assembly comprises the following steps:

[0091] S1: Preparation of component A:

[0092] 60 parts of bisphenol A epoxy resin and 20 parts of vinyl cyclohexene epoxy resin were stirred at room temperature at a stirring speed of 50 r / min for 20 minutes, then transferred to an oven and kept at 40°C for 1 hour, followed by vacuum dehydration until no water was removed, and then aired to room temperature to obtain component A;

[0093] S2: Preparation of component B:

[0094] 5 parts of a composite modified amine and 12 parts of a low-fraction product of ethylene tar were stirred at 50° C. for 20 minutes at a stirring speed of 50 r / min, and stored at room temperature in a dark place to obtain component B;

[0095] The composite modified amine was prepared by the method of Composite Modified Amine Preparation Example 2, and the viscosity of component B at 25°C was 38 cP;

[0096] The ethylene tar low-fraction fraction product is prepared by the method of Example 2 for preparing the ethylene tar low-fraction fraction product;

[0097] S3: 80 parts of component A and 17 parts of component B were stirred at a stirring speed of 80 r / min for 10 minutes, and vacuum degassing was performed to obtain an epoxy resin adhesive;

[0098] The prepared epoxy resin adhesive was poured into the hollow fiber membrane module to obtain a casting, which was then heated in the order of room temperature for 48 hours, 50°C for 8 hours, 80°C for 5 hours, and 140°C for 3 hours to obtain a hollow fiber membrane module head.

[0099] Example 3:

[0100] A method for preparing an epoxy resin adhesive for a gas separation membrane assembly comprises the following steps:

[0101] S1: Preparation of component A:

[0102] 70 parts of bisphenol A epoxy resin and 18 parts of cyclohexene 1,4-diepoxy resin were stirred and dispersed at a stirring speed of 50 r / min for 20 minutes at room temperature, then transferred to an oven and kept at 60°C for 1 hour, followed by vacuum dehydration until no water was removed, and then aired to room temperature to obtain component A;

[0103] S2: Preparation of component B:

[0104] At 60℃, 6 parts of the composite modified amine and 12 parts of the low fraction section product of ethylene tar were stirred at a stirring speed of 50 r / min for 20 min, and stored in the dark at room temperature to obtain component B;

[0105] The composite modified amine was prepared by the method in the composite modified amine preparation example 3, and the viscosity of the component B was 50 cP at 25℃;

[0106] The low fraction section product of ethylene tar was prepared by the method in the low fraction section product of ethylene tar preparation example 1;

[0107] S3: 88 parts of component A and 18 parts of component B were stirred at a stirring speed of 80 r / min for 10 min, and vacuum defoaming was performed to obtain an epoxy resin adhesive.

[0108] The prepared epoxy resin adhesive was poured into a hollow fiber membrane module to obtain a pouring piece. The pouring piece was sequentially subjected to heating treatment according to the order of room temperature / 48 h, 50℃ / 8 h, 80℃ / 5 h and 140℃ / 3 h to obtain a hollow fiber membrane module head.

[0109] Example 4:

[0110] A preparation method of an epoxy resin adhesive for a gas separation membrane module, specifically comprising the following steps:

[0111] S1: Preparation of component A:

[0112] 75 parts of bisphenol A epoxy resin and 20 parts of 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester were stirred and dispersed at a stirring speed of 50 r / min for 20 min at room temperature, then transferred to an oven, and incubated at 50℃ for 1 h, followed by vacuum dehydration until no water was dehydrated, and then air-dried to room temperature to obtain component A;

[0113] S2: Preparation of component B:

[0114] 6 parts of the composite modified amine and 13 parts of the low fraction section product of ethylene tar were stirred at a stirring speed of 50 r / min for 20 min at 40℃, and stored in the dark at room temperature to obtain component B;

[0115] The composite modified amine was prepared by the method in the composite modified amine preparation example 4, and the viscosity of the component B was 36 cP at 25℃;

[0116] The low fraction section product of ethylene tar was prepared by the method in the low fraction section product of ethylene tar preparation example 3;

[0117] S3: 95 parts of component A and 19 parts of component B were stirred at a stirring speed of 80 r / min for 10 min, and vacuum defoaming was performed to obtain an epoxy resin adhesive.

[0118] The prepared epoxy resin adhesive was cast into the hollow fiber membrane module to obtain a cast part. The cast part was sequentially subjected to heat treatment according to the order of room temperature / 48 h, 50℃ / 8 h, 80℃ / 5 h, 140℃ / 3 h to obtain a hollow fiber membrane module head.

[0119] Comparative Example

[0120] Comparative Example 1: The difference from Example 1 is only that in step S2, acetone solvent (National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical pure) is used instead of the low fraction segment product of ethylene tar.

[0121] Comparative Example 2: The difference from Example 4 is only that in step S2, the low fraction segment product of ethylene tar is not added.

[0122] Comparative Example 3: The difference from Example 3 is only that in step S2, a composite modified amine is replaced by an amine, wherein the amine is diamino diphenyl methane.

[0123] Comparative Example 4: The difference from Example 2 is only that in step S1, no vinyl cyclohexene epoxy is added.

[0124] Comparative Example 5: The difference from Example 3 is only that in step S2, a single modified amine is used instead of a composite modified amine.

[0125] The single modified amine is prepared by the following method: 1 part of diamino diphenyl methane and 1 part of nonyl phenol are added to a flask, stirred at 50℃ for 10 min, then 1 part of formaldehyde solution is added dropwise with a constant pressure dropping funnel (the dropping time of formaldehyde is controlled within 1 h), the reaction temperature is controlled not to exceed 95℃, after the formaldehyde is added, the temperature is slowly increased at a rate of 10℃ / 10 min, and then refluxed at 95℃ for 1 h. Then the obtained product is dehydrated under reduced pressure at-0.097~-0.098 MPa vacuum condition until no water is dehydrated, to obtain the single modified amine.

[0126] Performance detection test

[0127] The epoxy resin adhesives prepared in Examples 1-4 and Comparative Examples 1-5 are subjected to the following performance detection, and the detection results are shown in Table 2.

[0128] Initial viscosity test method: refer to GB2794-81 method, test with a rotary viscometer, the circulating water temperature is 23℃, test after constant temperature for 30 min, the test speed is 100 r / min.

[0129] Pot life calculation method: refer to GB7123-83, the glue mixing amount in this invention is 300 g, and the environmental temperature is 23℃.

[0130] Glass transition temperature test: tested according to GB / T19466 standard by DSC method (differential scanning calorimetry).

[0131] Shore hardness is tested by using a Shore hardness tester D type. The sample is made into a flat plate. A pressure needle of a specified shape is pressed into the sample to a certain depth under the standard spring pressure, and the hardness value is read to characterize the hardness of the material.

[0132] Elastic modulus: tested according to GB / T2567-2008 standard by using a universal testing machine, and the test speed is 2 mm / min.

[0133] Tensile strength: tested according to GB / T2567-2008 standard by using a universal testing machine, and the tensile speed is 10 mm / min.

[0134] Table 2 test results

[0135]

[0136] It can be seen from Example 1, Example 4, Comparative Example 1, Comparative Example 2 and Table 2 that in Comparative Example 1, after using acetone diluent in the epoxy resin adhesive system, the initial viscosity of the system is low, the viscosity reduction effect of acetone is obvious, but the glass transition temperature is low, and the rigidity and toughness are not as good as those of Example 1. In Comparative Example 2, when the ethylene tar low-boiling fraction product is not added, the viscosity of the system is high, the density of the reactants is large, the reaction speed is relatively fast, the pot life is short, and only the amine and the epoxy resin react, so the crosslinking density of the cured product is low, and the mechanical properties of the product are poor. In Example 4, after using the ethylene tar low-boiling fraction product, the overall performance of the system is improved, which not only has a viscosity reduction effect, but also improves the thermal mechanical properties of the cured product.

[0137] It can be seen from Example 2 and Comparative Example 4 and Table 2 that in Example 2, after adding the vinyl cyclohexene epoxy in the A component, the initial viscosity of the epoxy resin adhesive is low, which is because the viscosity of the vinyl cyclohexene epoxy is low, which plays a dilution role. The Shore hardness of the hollow fiber membrane assembly head prepared from the adhesive is improved, and the elastic modulus is high, which is because in the vinyl cyclohexene epoxy molecule, the epoxy group is directly attached to the alicyclic skeleton, so that the structure of the cured product of the epoxy resin adhesive is compact, which can improve the thermal stability and rigidity of the cured product. The combination of bisphenol A epoxy resin and alicyclic epoxy resin makes the high adhesion and flexibility of bisphenol A epoxy resin and the heat resistance and rigidity of alicyclic epoxy resin synergistically act, so that the comprehensive performance of the epoxy resin adhesive is good.

[0138] In combination with Comparative Example 3 and Comparative Example 5 and Table 2, after introducing phenolic hydroxyl and alkyl side chain into the molecule of diaminodiphenylmethane, the initial viscosity of the prepared epoxy resin adhesive is slightly increased, the phenolic hydroxyl promotes the curing reaction of the epoxy resin, the suitable period is appropriately shortened, the construction period is saved; the phenolic skeleton is introduced into the molecule, the elastic modulus and hardness of the cured product of the epoxy resin adhesive are improved, and the glass transition temperature is also improved; after introducing nonyl side chain into the molecule of diaminodiphenylmethane, the tensile strength of the cured product of the prepared epoxy resin adhesive is obviously improved. Therefore, it is necessary to modify the aliphatic amine base amine.

[0139] In combination with Example 3 and Comparative Example 5 and Table 2, the composite modified amine used in Example 3 has a better comprehensive effect because the composite use of the modified amines prepared from three different alkyl phenols, the spatial steric hindrance of the amine groups in the modified amines is inconsistent when the amine groups react with the epoxy groups to form a curing crosslinking reaction, resulting in different reaction speeds, the greater the spatial steric hindrance, the more compact the structure of the cured product, and the better the rigidity and heat resistance of the product; the smaller the spatial steric hindrance, the higher the degree of stretching of the molecular chain of the finally formed cured product, which is beneficial to lengthening the molecular chain of the cured product and enhancing the toughness of the cured product. When used in combination, rigidity and toughness play a mutual reinforcing role. The hardness and elastic modulus of the epoxy resin cured product formed by the amine modified by nonyl phenol in Comparative Example 5 are not as good as those of Example 3, but the tensile strength (toughness) is better. In consideration of the overall performance, the epoxy resin adhesive prepared by the composite modified amine has superior overall performance.

[0140] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An epoxy resin adhesive for a gas separation membrane assembly, characterized in that: The invention comprises component A and component B, wherein the weight ratio of component A to component B is (4.50-5.02):1; The raw materials of component A, calculated by weight, include 60-80 parts of bisphenol A epoxy resin and 10-30 parts of alicyclic epoxy resin; The raw materials of component B include 3-6 parts of composite modified amine and 9-13 parts of ethylene tar low-fraction product in parts by weight; The low-fraction ethylene tar product is obtained by distilling ethylene tar, the boiling range of the low-fraction ethylene tar product is from the initial boiling point to 290° C., and the closed cup flash point of the low-fraction ethylene tar product is greater than 50° C. The composite modified amine is obtained by reacting amine, alkylphenol and formaldehyde in a mass ratio of 1:1:1; The amine is selected from at least one of isophorone diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether or diethylmethylphenylenediamine; The alkylphenol is selected from any three of tert-butylphenol, pentylphenol, heptylphenol, octylphenol, nonylphenol or decylphenol; The composite modified amine is prepared by the following method: any three of the alkylphenols are respectively the first alkylphenol, the second alkylphenol and the third alkylphenol, and three parts of amine and three parts of formaldehyde are taken respectively; reacting the first portion of amine with the first portion of alkylphenol and the first portion of formaldehyde in a weight ratio of 1:1:1 at 80-100° C. to obtain a first modified amine; reacting the second amine with the second alkylphenol and the second formaldehyde in a weight ratio of 1:1:1 at 80-100° C. to obtain a second modified amine; reacting a third amine with a third alkylphenol and a third formaldehyde in a weight ratio of 1:1:1 at 80-100° C. to obtain a third modified amine; The above three modified amines are mixed to obtain a composite modified amine.

2. The epoxy resin adhesive for gas separation membrane assembly according to claim 1, characterized in that: The density of the ethylene tar at 20°C is 1.01-1.08 g / cm 3 , ash content is not more than 0.003wt%, residual carbon content is 11wt%-16wt%, carbon / hydrogen ratio is 11-14, saturated content is 0.1wt%-2.0wt%, aromatic content is 50wt%-66wt%, resin content is 20wt%-33wt%, and asphaltene content is 0.5wt%-16wt%.

3. The epoxy resin adhesive for gas separation membrane assembly according to claim 1, characterized in that: The bisphenol A epoxy resin can be any one of E51 epoxy resin, E44 epoxy resin, 128 epoxy resin or 127 epoxy resin, or a mixture of several of them.

4. The epoxy resin adhesive for gas separation membrane assembly according to claim 1, characterized in that: The alicyclic epoxy resin may be any one of vinylcyclohexene epoxy, bis(2,3-epoxycyclopentyl) ether, cyclohexene 1,4-diepoxy or 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester.

5. The epoxy resin adhesive for gas separation membrane assembly according to claim 1, characterized in that: The three modified amines are mixed in a mass ratio of (2-3):1:1 from small to large molecular weight of the modified amine.

6. The epoxy resin adhesive for gas separation membrane assembly according to claim 1, characterized in that: The viscosity of the B component at 25° C. is 19-50 cP.

7. The method for preparing an epoxy resin adhesive for a gas separation membrane assembly according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Preparation of component A: Mix bisphenol A epoxy resin and alicyclic epoxy resin uniformly according to the mass ratio, then keep the mixture at 40-60°C for 1-3 hours, then vacuum dehydrate until no water is removed, and cool to room temperature; S2: Preparation of component B: Heat the composite modified amine and the low-fraction product of ethylene tar to 40-60°C respectively according to the mass ratio, mix them, cool them to room temperature, and store them in a sealed and light-proof manner; S3: Evenly mix component A and component B, and perform vacuum degassing to obtain the epoxy resin adhesive for the gas separation membrane assembly.

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