Epoxy resin adhesive for water treatment membrane module as well as preparation method and application of epoxy resin adhesive

Abstract

The invention relates to the technical field of epoxy resin adhesives, and discloses an epoxy resin adhesive for a water treatment membrane module and a preparation method and application thereof.The method comprises the steps that 50-60 parts by weight of second epoxy resin, 20-30 parts by weight of flexible epoxy resin, 25-40 parts by weight of second flexibilizer and 4-6 parts by weight of coupling agent are mixed to obtain a component A, 10-30 parts by weight of a polyamide curing agent, 30-50 parts by weight of a flexible curing agent, 10-30 parts by weight of a toughening curing additive and 5-20 parts by weight of a third toughening agent are mixed to obtain a component B, and the component A and the component B are mixed according to the volume ratio of 100: (40-60) to obtain the epoxy resin adhesive. The epoxy resin adhesive provided by the invention has the advantages of proper operation time, proper curing speed and proper viscosity, the construction efficiency is improved, and the process cost is reduced. And the epoxy resin adhesive also has good toughness, excellent damp-heat aging resistance, excellent water resistance and excellent solvent resistance, and is very environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin adhesive technology, specifically to a toughening and curing composition, a toughening and curing additive and its preparation method, an epoxy resin adhesive for water treatment membrane components and its preparation method and application. Background Technology

[0002] MBR (Membrane Bioreactor) water treatment technology, also known as membrane-based water treatment technology, has many advantages over traditional wastewater treatment technologies. The MBR industry can be further divided into nanofiltration membranes (NF), microfiltration membranes (MF), ultrafiltration membranes (UF), and reverse osmosis membranes.

[0003] Membrane materials can be bonded, fixed, encapsulated, and wound using resin compositions to form the smallest independent component units available for application, such as curtain, column, and roll-to-roll membranes. The performance and service life of membrane modules are closely related to the various properties of the resin compositions used. Commonly available resin compositions are epoxy and polyurethane. Polyurethane compositions are often used for potting and sealing curtain and column membrane modules and for bonding roll-to-roll membrane sheets; epoxy compositions are also commonly used for potting and sealing curtain and column membrane modules and for winding the glass fiber shell of roll-to-roll membranes.

[0004] Polyurethane compositions have good flexibility and good acid and alkali resistance, but they have disadvantages such as low bonding strength, slow curing speed and poor aging resistance, making them difficult to apply independently in the field of water treatment membranes.

[0005] Epoxy resins possess excellent mechanical properties, adhesive properties, and corrosion resistance. They also exhibit low curing shrinkage and coefficient of linear expansion, stable cured product dimensions, and good processability. Furthermore, due to the flexibility and diversity of epoxy resin adhesive formulations, epoxy materials capable of meeting almost all performance requirements can be obtained. However, existing epoxy compositions suffer from the following drawbacks: (1) Epoxy compositions with long operating times have slow curing speeds. These compositions typically require 1-2 hours of operating time and generally 5-8 hours for initial curing, hindering production efficiency and increasing process costs. (2) Epoxy compositions with fast curing speeds have short operating times, high exothermic activity, and poor toughness of the cured product.

[0006] CN111777977A discloses a room-temperature fast-curing transparent epoxy adhesive for bonding engineering plastics and its preparation method. The epoxy adhesive's A component comprises: 30-40 parts epoxy resin, 50-70 parts modified epoxy resin, 20-30 parts toughening agent, and 4-6 parts coupling agent; the B component comprises: 15-25 parts modified polyamide curing agent, 30-45 parts modified amine curing agent, and 20-30 parts rapid flexible curing agent. This prior art provides an epoxy adhesive with fast curing speed, good flexibility, high transparency, and excellent resistance to high and low temperature and humidity. However, this prior art has a short operating time, high viscosity, and high heat release, which is not conducive to on-site construction and cannot be used for potting. Furthermore, the toughness of the epoxy adhesive provided needs further improvement.

[0007] Therefore, there is an urgent need for an epoxy resin adhesive with suitable working time, appropriate viscosity, fast curing speed and good toughness, good resistance to damp heat aging, and excellent water and corrosion resistance. Summary of the Invention

[0008] The purpose of this invention is to provide an epoxy resin adhesive with suitable operating time, appropriate viscosity, good wettability, fast curing speed, good toughness, and excellent weather resistance.

[0009] To achieve the above objectives, a first aspect of the present invention provides a toughening and curing composition comprising: 100 parts by weight of a first curing agent, 15-25 parts by weight of an aminoamine curing agent, 20-30 parts by weight of a first epoxy resin, 35-45 parts by weight of a first toughening agent, 8-12 parts by weight of a blocked isocyanate toughening agent, and 65-75 parts by weight of a resin modifier.

[0010] The first curing agent is selected from at least one of 1,3-cyclohexanedimethylamine, m-phenylenediamine, isophoronediamine, and N,N'-bis(3-aminopropyl)-ethylenediamine;

[0011] The first epoxy resin is selected from at least one of epoxy resins;

[0012] The first toughening agent is a combination of an active first toughening agent and an inactive first toughening agent in a weight ratio of 1:0.8-1.2; the active group of the active first toughening agent is an epoxy group, and the epoxy value is 0.2-0.6 eq / 100g.

[0013] A second aspect of the present invention provides a method for preparing a toughening and curing additive, the method being carried out using the toughening and curing composition described in the first aspect above, comprising the following steps:

[0014] (1) The first curing agent, aminoamine curing agent, first epoxy resin, first toughening agent, and blocked isocyanate toughening agent are mixed to obtain mixture I;

[0015] (2) Mix the mixture I with the resin modifier for a second time to obtain the toughening and curing additive.

[0016] A third aspect of the present invention provides a method for preparing an epoxy resin adhesive for water treatment membrane modules, the method comprising: mixing component A and component B in a volume ratio of 100:40-60 to obtain the epoxy resin adhesive;

[0017] The preparation method of component A includes:

[0018] SA1: The components in composition a are brought into first contact to obtain component A; the composition a contains a second epoxy resin, a flexible epoxy resin, a second toughening agent, and a coupling agent;

[0019] The preparation method of component B includes:

[0020] SB1: The components in composition b are brought into a third contact to obtain component B; the composition b contains a polyamide curing agent, a flexible curing agent, a toughening curing additive, and a third toughening agent;

[0021] In step SA1, the second epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidylamine type epoxy resin, and o-cresol type phenolic epoxy resin; the second toughening agent and the third toughening agent may be the same or different, and each is independently selected from at least one toughening agent.

[0022] The toughening and curing additive is the toughening and curing additive prepared by the method described in the second aspect above.

[0023] A fourth aspect of the present invention provides an epoxy resin adhesive prepared by the method described in the third aspect above.

[0024] The fifth aspect of the present invention provides the application of the epoxy resin adhesive described in the fourth aspect above in water treatment membrane modules.

[0025] The epoxy resin adhesive provided by this invention has a suitable working time, curing speed and viscosity. While meeting the working time required for actual construction, it also has a relatively fast curing speed, which improves construction efficiency and reduces process costs.

[0026] Meanwhile, the epoxy resin adhesive provided by this invention also overcomes the defect of poor toughness in epoxy resin adhesives with fast curing speed in the prior art. The epoxy resin adhesive provided by this invention has good toughness, excellent resistance to humid heat aging, and excellent resistance to water and solvents, and is very environmentally friendly.

[0027] The epoxy resin adhesive provided by this invention has excellent wettability on substrates such as glass fiber, and can be used independently for sealing curtain and column films, as well as for winding glass fiber shells of roll films. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] The average particle size mentioned in this invention refers to the average diameter.

[0030] It should be noted that, in all aspects of the present invention, the same components or terms in each aspect are described only once in one aspect and not repeatedly, and those skilled in the art should not understand this as a limitation of the present invention.

[0031] As previously described, a first aspect of the present invention provides a toughening curing composition comprising: 100 parts by weight of a first curing agent, 15-25 parts by weight of an aminoamine curing agent, 20-30 parts by weight of a first epoxy resin, 35-45 parts by weight of a first toughening agent, 8-12 parts by weight of a blocked isocyanate toughening agent, and 65-75 parts by weight of a resin modifier.

[0032] The first curing agent is selected from at least one of 1,3-cyclohexanedimethylamine, m-phenylenediamine, isophoronediamine, and N,N'-bis(3-aminopropyl)-ethylenediamine;

[0033] The first epoxy resin is selected from at least one of epoxy resins;

[0034] The first toughening agent is a combination of an active first toughening agent and an inactive first toughening agent in a weight ratio of 1:0.8-1.2; the active group of the active first toughening agent is an epoxy group, and the epoxy value is 0.2-0.6 eq / 100g.

[0035] Preferably, the aminoamine curing agent is selected from at least one of ANCAMIDE 502, ANCAMINE2014FG, and ADP-S472.

[0036] Preferably, the first epoxy resin is selected from at least one of epoxy resin EXA-830CRP, epoxy resin YD-126, and epoxy resin AG-80.

[0037] In a preferred embodiment, the active first toughening agent is selected from at least one of XA406T, EPX-125, and EPX-225.

[0038] In a preferred embodiment, the inactive first toughening agent is selected from at least one of VL-1, VL-2, VL-3, and VP-501.

[0039] The active first toughening agent described in this invention refers to a toughening agent whose molecular chain contains active groups that can react with the matrix resin; the inactive first toughening agent described in this invention refers to a toughening agent that is well compatible with the matrix resin but does not participate in chemical reactions.

[0040] In a preferred embodiment, the resin modifier is selected from at least one of 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, and dimethyldipropyltriamine.

[0041] As previously described, a second aspect of the present invention provides a method for preparing a toughening and curing additive, the method being carried out using the toughening and curing composition described in the first aspect, comprising the following steps:

[0042] (1) The first curing agent, aminoamine curing agent, first epoxy resin, first toughening agent, and blocked isocyanate toughening agent are mixed to obtain mixture I;

[0043] (2) Mix the mixture I with the resin modifier for a second time to obtain the toughening and curing additive.

[0044] Preferably, in step (1), the temperature of the first mixing is 60-80°C and the time is 4-5 hours.

[0045] In a preferred embodiment, in step (2), the temperature of the second mixing is 20-30°C and the time is 2-3 hours.

[0046] In a preferred embodiment, the first mixing and the second mixing of the present invention are each carried out independently under stirring conditions, and the stirring rate is preferably 500-600 rpm.

[0047] The inventors of this invention discovered in their research that the toughening and curing additive prepared using the technical solution provided by this invention, when applied to the preparation of epoxy resin adhesives, can make the working time of the epoxy resin adhesives more suitable, the curing speed faster and the toughness better, and also have better wettability and weather resistance.

[0048] As mentioned above, a third aspect of the present invention provides a method for preparing an epoxy resin adhesive for water treatment membrane modules, the method comprising: mixing component A and component B in a volume ratio of 100:40-60 to obtain the epoxy resin adhesive;

[0049] The preparation method of component A includes:

[0050] SA1: The components in composition a are brought into first contact to obtain component A; the composition a contains a second epoxy resin, a flexible epoxy resin, a second toughening agent, and a coupling agent;

[0051] The preparation method of component B includes:

[0052] SB1: The components in composition b are brought into a third contact to obtain component B; the composition b contains a polyamide curing agent, a flexible curing agent, a toughening curing additive, and a third toughening agent;

[0053] In step SA1, the second epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidylamine type epoxy resin, and o-cresol type phenolic epoxy resin; the second toughening agent and the third toughening agent may be the same or different, and each is independently selected from at least one toughening agent.

[0054] The toughening and curing additive is the toughening and curing additive prepared by the method described in the second aspect above.

[0055] Preferably, the composition a contains: 50-60 parts by weight of a second epoxy resin, 20-30 parts by weight of a flexible epoxy resin, 25-40 parts by weight of a second toughening agent, and 4-6 parts by weight of a coupling agent.

[0056] Preferably, the composition b contains: 10-30 parts by weight of polyamide curing agent, 30-50 parts by weight of flexible curing agent, 10-30 parts by weight of toughening curing additive, and 5-20 parts by weight of third toughening agent.

[0057] Preferably, in composition a, the second epoxy resin is selected from at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidylamine type epoxy resin, and o-cresol type phenolic epoxy resin; and the epoxy value of the second epoxy resin is 0.4-0.9 eq / 100g, preferably 0.5-0.9 eq / 100g.

[0058] Preferably, in composition a, the bisphenol A type epoxy resin is selected from at least one of epoxy resin YD-126, epoxy resin YD-128, epoxy resin 618, and NPEF128.

[0059] Preferably, in composition a, the bisphenol F epoxy resin is selected from at least one of DER351, DER354, and NPEF170.

[0060] Preferably, in composition a, the glycidylamine epoxy resin is selected from at least one of AG80, MF-4101H, SWE-85, and S-182.

[0061] Preferably, in composition a, the o-cresol type phenolic epoxy resin is selected from at least one of EPIKOTE 678 and YECN-200.

[0062] Preferably, in the composition a, the flexible epoxy resin is selected from at least one of flexible epoxy resin ZK1918, flexible epoxy resin 102C-3, flexible epoxy resin BH-133L, flexible epoxy resin PRO-602, and flexible epoxy resin PLR-605.

[0063] More preferably, in composition a, the flexible epoxy resin is selected from at least two of flexible epoxy resin ZK1918, flexible epoxy resin 102C-3, flexible epoxy resin BH-133L, flexible epoxy resin PRO-602, and flexible epoxy resin PLR-605. The inventors have found in their research that under these preferred conditions, the epoxy resin adhesive provided by this invention has a suitable working time, fast curing speed, good toughness, and superior wetting and weather resistance.

[0064] Preferably, in composition a, the coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, and coupling agent UM956.

[0065] Preferably, in composition a, the second toughening agent is selected from at least one of VL-2, VL-3, XA-406T, and EPX-125.

[0066] In a preferred embodiment, the polyamide curing agent in composition b has an amine value of 180-600 mg KOH / g.

[0067] More preferably, in composition b, the polyamide curing agent is a general-purpose polyamide curing agent and / or a modified polyamide curing agent, and the amine value of the general-purpose polyamide curing agent is 180-450 mgKOH / g, and the amine value of the modified polyamide curing agent is 300-600 mgKOH / g.

[0068] Preferably, the general-purpose polyamide curing agent of the present invention is selected from at least one of polyamide 650 and polyamide 651; the modified polyamide curing agent of the present invention is selected from at least one of curing agent Ancamide 2634, TSG-7095A, and curing agent Ancamide 2050.

[0069] In a preferred embodiment, in composition b, the flexible curing agent is selected from at least one of curing agents R-2026, R-2019, R-3401, Ancamide 2636, Ancamide 2784, and Ancamide 2814.

[0070] More preferably, in composition b, the flexible curing agent is selected from at least three of curing agents R-2026, R-2019, R-3401, Ancamide 2636, Ancamide 2784, and Ancamide 2814. The inventors have found in their research that under these preferred conditions, the epoxy resin adhesive provided by this invention has a suitable working time, fast curing speed, good toughness, and superior wettability and weather resistance.

[0071] Preferably, in composition b, the third toughening agent is selected from at least one of VL-1, VL-2, and VP-501.

[0072] According to a preferred embodiment, the preparation method of component A further includes: firstly contacting each component in composition a to obtain intermediate product I; then contacting the intermediate product I with a first filler to obtain component A; and based on the amount of the second epoxy resin in composition a being 100 parts by weight, the amount of the first filler being 10-40 parts by weight.

[0073] According to another preferred embodiment, the preparation method of component B further includes: first, subjecting each component in composition b to a third contact to obtain intermediate product II; then, subjecting intermediate product II to a fourth contact with a second filler to obtain component B; wherein the amount of the polyamide curing agent in composition b is 100 parts by weight, and the amount of the second filler is 20-200 parts by weight.

[0074] In this invention, the first packing and the second packing may be the same or different, and each is independently selected from at least one type of packing.

[0075] Preferably, the first filler and the second filler are each independently selected from at least one of silicon micro powder, nano calcium carbonate, nano alumina, glass powder, and powdered rubber, and the average particle size of the first filler and the second filler is each independently 1-100 nm.

[0076] Preferably, the conditions for the first contact and the third contact are each independently satisfied: planetary rotation speed of 10-15 Hz, dispersion rotation speed of 500-600 rpm, pressure of -0.1 MPa to -0.095 MPa, and time of 30-40 min.

[0077] Preferably, the conditions for the second contact and the fourth contact are each independently satisfied: planetary rotation speed of 20-25 Hz, dispersion rotation speed of 700-800 rpm, pressure of -0.1 MPa to -0.095 MPa, and time of 2-3 h.

[0078] More preferably, the temperatures of the first contact, the second contact, the third contact, and the fourth contact are each independently 20-30°C.

[0079] The preparation methods of components A and B described in this invention may also include conventional post-processing methods in the art, such as vacuum degassing. These will not be elaborated upon here, and those skilled in the art should not understand them as limitations on this invention.

[0080] As previously described, a fourth aspect of the present invention provides an epoxy resin adhesive prepared by the method described in the third aspect above.

[0081] Preferably, the epoxy resin adhesive has an operating time of 50-60 min, a film drying time of 150-180 min, and an exothermic peak temperature of <60℃.

[0082] As previously stated, the fifth aspect of the present invention provides the application of the epoxy resin adhesive described in the fourth aspect in water treatment membrane modules.

[0083] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials are commercially available products, as shown in Table 1. The room temperature mentioned in the present invention refers to 25±2℃.

[0084] Table 1

[0085]

[0086]

[0087] In the following examples, each part by weight represents 1g.

[0088] Preparation Example 1

[0089] (1) The first curing agent, aminoamine curing agent, first epoxy resin, first toughening agent, and blocked isocyanate toughening agent are mixed to obtain mixture I;

[0090] (2) Mixture I with resin modifier for a second mixing to obtain toughening and curing additive.

[0091] The types, amounts, and preparation conditions of the raw materials are listed in Table 2.

[0092] Preparation Examples 2-3

[0093] The same process as in Preparation Example 1 was used, except that the types and amounts of raw materials used and the preparation conditions were different, as detailed in Table 2.

[0094] Comparative Preparation Example 1

[0095] The same process as in Preparation Example 1 was used, except that the types and amounts of raw materials used and the preparation conditions were different, as detailed in Table 2.

[0096] Table 2

[0097]

[0098] Example 1

[0099] The preparation methods for component A include:

[0100] SA1: The second epoxy resin, flexible epoxy resin, second toughening agent and coupling agent are added to the reactor for the first contact (planetary speed is 10Hz, dispersion speed is 550rpm, stirring is carried out at 25℃ for 30min, and vacuum is required during stirring to maintain a pressure of -0.095MPa). After stirring is completed, stirring is stopped and vacuum (pressure of -0.095MPa) is maintained for degassing for 30min to obtain component A.

[0101] The preparation methods for component B include:

[0102] SB1: Polyamide curing agent, flexible curing agent, toughening curing additive and third toughening agent are added to the reactor for third contact (planetary speed is 10Hz, dispersion speed is 550rpm, stirring is carried out at 25℃ for 30min, vacuum is required during stirring, and the pressure is maintained at -0.095MPa). After stirring is completed, stirring is stopped and vacuum (pressure is -0.095MPa) is maintained for degassing for 30min to obtain component B;

[0103] Component A and component B are mixed in a volume ratio of 100:50 to prepare an epoxy resin adhesive.

[0104] Example 2

[0105] The preparation methods for component A include:

[0106] SA1: The second epoxy resin, flexible epoxy resin, second toughening agent and coupling agent are added to the reactor for the first contact (planetary speed is 15Hz, dispersion speed is 500rpm, stirring is carried out at 20℃ for 35min, and vacuum is required during stirring to maintain a pressure of -0.1MPa) to obtain intermediate product I.

[0107] SA2: The first packing material is added to the reactor for the second contact (planetary speed 20Hz, dispersion speed 750rpm, stirring at 25℃ for 2h, vacuum is required during stirring to maintain a pressure of -0.095MPa, the reactor is cleaned every 30min, which means opening the reactor and scraping the material hanging on the agitator and the reactor wall into the reactor). After stirring is completed, stirring is stopped and vacuum (pressure of -0.1MPa) is maintained for degassing for 30min to obtain component B.

[0108] The preparation methods for component B include:

[0109] SB1: Polyamide curing agent, flexible curing agent, toughening curing additive and third toughening agent are added to the reactor for third contact (planetary speed is 10Hz, dispersion speed is 500rpm, stirring is carried out at 20℃ for 35min, vacuum is required during stirring to maintain pressure of -0.1MPa) to obtain intermediate product II;

[0110] SB2: Add the second packing material to the reactor for the fourth contact (planetary speed 20Hz, dispersion speed 750rpm, stirring at 25℃ for 2h, vacuum is required during stirring, maintaining a pressure of -0.095MPa, and the reactor is cleaned every 30min). After stirring is completed, stop stirring and maintain vacuum (pressure of -0.1MPa) for degassing for 30min to obtain component B.

[0111] Component A and component B are mixed in a volume ratio of 100:50 to prepare an epoxy resin adhesive.

[0112] Example 3

[0113] The preparation methods for component A include:

[0114] SA1: The second epoxy resin, flexible epoxy resin, second toughening agent and coupling agent are added to the reactor for the first contact (planetary speed is 15Hz, dispersion speed is 600rpm, stirring is carried out at 30℃ for 40min, and vacuum is required during stirring to maintain a pressure of -0.1MPa) to obtain intermediate product I.

[0115] SA2: The first packing material is added to the reactor for the second contact (planetary speed of 25Hz, dispersion speed of 800rpm, stirring at 30℃ for 2.5h, vacuum is required during stirring to maintain a pressure of -0.1MPa, and the reactor is cleaned every 30min). After stirring is completed, stirring is stopped and vacuum (pressure of -0.1MPa) is maintained for degassing for 30min to obtain component A.

[0116] The preparation methods for component B include:

[0117] SB1: Polyamide curing agent, flexible curing agent, toughening curing additive and third toughening agent are added to the reactor for third contact (planetary speed is 15Hz, dispersion speed is 600rpm, stirring is carried out at 30℃ for 40min, vacuum is required during stirring to maintain pressure of -0.1MPa) to obtain intermediate product II;

[0118] SB2: Add the second packing material to the reactor for the fourth contact (planetary speed 25Hz, dispersion speed 800rpm, stirring at 30℃ for 2.5h, vacuum is required during stirring to maintain a pressure of -0.1MPa, and the reactor is cleaned every 30min). After stirring is completed, stop stirring and maintain vacuum (pressure -0.1MPa) for degassing for 30min to obtain component B.

[0119] Component A and component B are mixed in a volume ratio of 100:50 to prepare an epoxy resin adhesive.

[0120] Example 4

[0121] The process is similar to that in Example 2, except that the types and amounts of raw materials used are different.

[0122] An epoxy resin adhesive was prepared.

[0123] The types and amounts of raw materials used in Examples 1-4 are listed in Table 3.

[0124] Example 5

[0125] The process was similar to that in Example 2, except that in the preparation of component A, 50 parts by weight of bisphenol F type epoxy resin II and 5 parts by weight of bisphenol A type epoxy resin were replaced with 55 parts by weight of glycidylamine type epoxy resin II.

[0126] The prepared epoxy resin adhesive.

[0127] Comparative Example 1

[0128] Huitian 6321G epoxy resin adhesive.

[0129] Comparative Example 2

[0130] Jinglu JLEP-708 epoxy resin adhesive.

[0131] Comparative Example 3

[0132] The process was similar to that in Example 2, except that in the preparation of component B, toughening and curing additive Z-2 was replaced with an equal part by weight of toughening and curing additive DZ-1.

[0133] An epoxy resin adhesive was prepared.

[0134] Comparative Example 4

[0135] The process was similar to that in Example 2, except that in the preparation of component B, toughening and curing additive Z-2 was replaced with an equal part by weight of commercially available toughening agent (purchased from Shandong Jinshengtai Chemical Co., Ltd., brand name DMP-30).

[0136] An epoxy resin adhesive was prepared.

[0137] Table 3

[0138]

[0139]

[0140] Test case

[0141] The epoxy resin adhesives prepared in the above embodiments and comparative examples were subjected to performance tests, and the results are shown in Table 5.

[0142] The performance testing methods are shown in Table 4:

[0143] Table 4

[0144]

[0145]

[0146] Table 5

[0147]

[0148] Note: SF represents substrate failure, and CF represents cohesive failure.

[0149] Continued from Table 5

[0150]

[0151]

[0152] Note: SF represents substrate failure, CF represents cohesive failure, and SF+CF represents mixed failure, which includes both substrate failure and cohesive failure.

[0153] The results above show that the epoxy resin adhesive prepared by the technical solution provided by the present invention has a suitable working time, while maintaining a fast curing speed and a low exothermic peak temperature; it also has low viscosity and excellent wettability and adhesion to a variety of substrates.

[0154] In summary, the embodiments of the present invention not only have a fast curing speed, good flexibility, and excellent water and solvent resistance, but are also very environmentally friendly. They have excellent wettability and adhesion to a variety of substrates and are suitable for potting and sealing of curtain films and column films, as well as glass fiber winding of the shell of spiral films.

[0155] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A toughening and curing composition, characterized in that, The toughening and curing composition contains: 100 parts by weight of a first curing agent, 15-25 parts by weight of an aminoamine curing agent, 20-30 parts by weight of a first epoxy resin, 35-45 parts by weight of a first toughening agent, 8-12 parts by weight of a blocked isocyanate toughening agent, and 65-75 parts by weight of a resin modifier. The first curing agent is selected from at least one of 1,3-cyclohexanedimethylamine, m-phenylenediamine, isophoronediamine, and N,N'-bis(3-aminopropyl)-ethylenediamine; The first epoxy resin is selected from at least one of epoxy resins; The first toughening agent is a combination of an active first toughening agent and an inactive first toughening agent in a weight ratio of 1:0.8-1.2; the active group of the active first toughening agent is an epoxy group, and the epoxy value is 0.2-0.6 eq / 100g.

2. The toughening and curing composition according to claim 1, wherein, The aminoamine curing agent is selected from at least one of ANCAMIDE502, ANCAMINE2014FG, and ADP-S472; And / or, the first epoxy resin is selected from at least one of epoxy resin EXA-830CRP, epoxy resin YD-126, and epoxy resin AG-80; And / or, the active first toughening agent is selected from at least one of XA406T, EPX-125, and EPX-225; And / or, the inactive first toughening agent is selected from at least one of VL-1, VL-2, VL-3, and VP-501.

3. A method for preparing a toughening and curing additive, wherein the method is carried out using the toughening and curing composition according to claim 1 or 2, characterized in that, Includes the following steps: (1) The first curing agent, aminoamine curing agent, first epoxy resin, first toughening agent, and blocked isocyanate toughening agent are mixed to obtain mixture I; (2) Mix the mixture I with the resin modifier for a second time to obtain the toughening and curing additive.

4. The method according to claim 3, wherein, In step (1), the temperature of the first mixture is 60-80℃, and the time is 4-5h; And / or, in step (2), the temperature of the second mixing is 20-30°C and the time is 2-3 hours.

5. A method for preparing an epoxy resin adhesive for water treatment membrane modules, characterized in that, The method includes: mixing component A and component B in a volume ratio of 100:40-60 to obtain the epoxy resin adhesive; The preparation method of component A includes: SA1: The components in composition a are brought into first contact to obtain component A; the composition a contains a second epoxy resin, a flexible epoxy resin, a second toughening agent, and a coupling agent; The preparation method of component B includes: SB1: The components in composition b are brought into a third contact to obtain component B; the composition b contains a polyamide curing agent, a flexible curing agent, a toughening curing additive, and a third toughening agent; In step SA1, the second epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidylamine type epoxy resin, and o-cresol type phenolic epoxy resin; the second toughening agent and the third toughening agent may be the same or different, and each is independently selected from at least one toughening agent. The toughening and curing additive is a toughening and curing additive prepared by the method described in claim 3 or 4.

6. The method according to claim 5, wherein, The composition a contains: 50-60 parts by weight of a second epoxy resin, 20-30 parts by weight of a flexible epoxy resin, 25-40 parts by weight of a second toughening agent, and 4-6 parts by weight of a coupling agent. The composition b contains: 10-30 parts by weight of polyamide curing agent, 30-50 parts by weight of flexible curing agent, 10-30 parts by weight of toughening curing additive, and 5-20 parts by weight of third toughening agent.

7. The method according to claim 5 or 6, wherein, In the composition a, the second epoxy resin is selected from at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidylamine type epoxy resin, and o-cresol type phenolic epoxy resin; and the epoxy value of the second epoxy resin is 0.4-0.9 eq / 100g.

8. The method according to any one of claims 5-7, wherein, In the composition a, the flexible epoxy resin is selected from at least one of flexible epoxy resin ZK1918, flexible epoxy resin 102C-3, flexible epoxy resin BH-133L, flexible epoxy resin PRO-602, and flexible epoxy resin PLR-605. And / or, in composition a, the coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, and coupling agent UM956.

9. The method according to any one of claims 5-8, wherein, In composition b, the amine value of the polyamide curing agent is 180-600 mg KOH / g; And / or, in composition b, the flexible curing agent is selected from at least one of curing agent R-2026, curing agent R-2019, curing agent R-3401, curing agent Ancamide 2636, curing agent Ancamide 2784, and curing agent Ancamide 2814.

10. The method according to any one of claims 5-9, wherein, The preparation method of component A further includes: firstly, making each component in composition a first contact to obtain intermediate product I; then making the intermediate product I a second contact with the first filler to obtain component A; based on the amount of the second epoxy resin in composition a being 100 parts by weight, the amount of the first filler is 10-40 parts by weight. The preparation method of component B further includes: first, making a third contact with each component in composition b to obtain intermediate product II; then, making a fourth contact with the intermediate product II and the second filler to obtain component B; based on the amount of the polyamide curing agent in composition b being 100 parts by weight, the amount of the second filler being 20-200 parts by weight. The first packing and the second packing may be the same or different, and each is independently selected from at least one type of packing.

11. The method according to claim 10, wherein, The conditions for the first contact and the third contact are each satisfied independently: planetary rotation speed is 10-15 Hz, dispersion speed is 500-600 rpm, pressure is -0.1 MPa to -0.095 MPa, and time is 30-40 min; And / or, the conditions for the second contact and the fourth contact are each independently satisfied: planetary rotation speed of 20-25 Hz, dispersion rotation speed of 700-800 rpm, pressure of -0.1 MPa to -0.095 MPa, and time of 2-3 h.

12. An epoxy resin adhesive prepared by the method according to any one of claims 5-11.

13. The use of the epoxy resin adhesive of claim 12 in a water treatment membrane module.

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