CN117736499A - Epoxy resin toughening agent and preparation method thereof - Google Patents
Epoxy resin toughening agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxy resin toughening agent and a preparation method thereof, wherein the reaction raw materials of the epoxy resin toughening agent comprise a first component and a second component; the first component at least comprises diamine and a first epoxy group compound, and the second component at least comprises isocyanate-terminated liquid rubber. The toughening effect of the epoxy resin toughening agent can be obviously improved by limiting specific components of the epoxy resin toughening agent, and the epoxy resin toughening agent can be applied to a system needing toughening, so that the impact resistance and the shearing resistance of the system can be further improved while the glass transition temperature of the system is ensured.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to an epoxy resin toughening agent and a preparation method thereof.
Background
Thermosetting resins, typified by epoxy resins, are widely used as adhesives, electric materials, insulating materials, and the like because of their excellent heat resistance, mechanical strength, electrical insulating properties, and adhesion. However, epoxy resins have insufficient toughness after curing, poor impact resistance and shearing resistance, and are prone to brittle fracture and debonding. Therefore, how to improve the impact resistance and the shear resistance of epoxy resins is an important research in the art.
The main toughening modification method at present is to add reactive liquid rubber and non-reactive liquid rubber into an epoxy resin system so as to improve the impact resistance and shearing resistance of the epoxy resin. After the reactive liquid rubber is added into the epoxy resin system, the phase separation process is needed in the curing process, the phase separation effect has different effects according to different types of epoxy resin, curing conditions, curing speed, types of curing agents and the like, part of the reactive rubber is dissolved and does not participate in the curing of the epoxy resin, and the reactive liquid rubber remains in the cured epoxy resin, so that the toughening effect is difficult to be exerted to the greatest extent, even the glass transition temperature of the system is reduced, and the quality of the epoxy resin product is reduced. The non-reactive rubber does not participate in the curing reaction of the epoxy resin after being added into the epoxy resin system, but only forms a micro-liquid disperse phase of the liquid rubber in the curing process of the epoxy resin, and the toughness of the system is improved, but the glass transition temperature, strength and other performances of the system are obviously reduced. Therefore, the liquid rubber is adopted to toughen the epoxy, and no matter whether the epoxy reacts or not, the glass transition temperature, the strength and the like of the system can be greatly influenced.
In order to toughen and reduce the influence on the glass transition temperature of the system, core-shell polymers are mostly utilized to improve the impact resistance and shearing resistance of the epoxy resin system at the present stage. The existing core-shell polymer is mainly prepared by emulsion polymerization, then dry powder is formed by demulsification, dehydration, drying and other processes, then a proper amount of solvent is added to wet the powder, the powder is added into epoxy resin, and the aggregated powder is uniformly distributed in the whole epoxy resin system by means of banburying, heating, stirring, grinding, negative pressure desolventizing and the like. The toughening modification method has the advantages of long production process flow, high processing cost, large amount of solvents, environmental pollution, easy precipitation or floating separation of the core-shell polymer, and unstable toughening effect. Therefore, how to provide an epoxy resin toughening agent which is simple and convenient in production process, low in production cost, environment-friendly and excellent in toughening effect is a technical problem to be solved in the field.
Disclosure of Invention
The invention provides the epoxy resin toughening agent, which can obviously improve the toughening effect of the epoxy resin toughening agent by limiting specific components of the epoxy resin toughening agent, has simple preparation process, is environment-friendly and low in production cost, is favorable for realizing mass production, and can further improve the impact resistance and shearing resistance of a system when being applied to the system needing toughening and ensuring the glass transition temperature of the system.
The invention also provides a preparation method of the epoxy resin toughening agent, which can prepare the epoxy resin toughening agent with excellent performance, has simple preparation process, is environment-friendly, has low production cost and is beneficial to realizing mass production.
In a first aspect of the invention, an epoxy resin toughening agent is provided, wherein the reaction raw materials of the epoxy resin toughening agent comprise a first component and a second component;
the first component at least comprises diamine and a first epoxy group compound, and the second component at least comprises isocyanate-terminated liquid rubber.
The epoxy resin toughening agent comprises a first component, a second component, a third component, a fourth component and a third component, wherein the first component comprises a first epoxy group compound, low-molecular-weight raw rubber, functional powder, a cross-linking agent and a crosslinking assistant.
The epoxy resin toughening agent as described above, wherein the isocyanate group content of the isocyanate group-terminated liquid rubber is 0.5 to 15%, preferably 2 to 10%; and/or the number of the groups of groups,
the comprehensive epoxy value of the first epoxy compound is 0.1-1.0 mol/100g; and/or the number of the groups of groups,
the number average molecular weight of the low molecular weight raw rubber is 1500-10000, and the softening point is 10-100 ℃.
The epoxy resin toughening agent comprises the following components in percentage by mass: (1-15); and/or the number of the groups of groups,
the mass ratio of the isocyanate-terminated liquid rubber to the second epoxy compound to the low molecular weight raw rubber to the functional powder to the crosslinking agent to the auxiliary crosslinking agent is (30-75): (0-12): (0-35): (0-20): (0-3): (0-10).
An epoxy resin toughening agent as described above, wherein, the diamine comprises diethyl toluenediamine, 4 '-dimethylene-bis (3-chloro-2, 6-diethyl aniline), dimethyl thiotoluenediamine, 1, 3-propanediol bis (4-aminobenzoate), 4' -dimethylene bis (2-ethyl) aniline, 3-chloro-3 '-ethyl-4, 4' -diamino diphenyl methane, 3 '-dichloro-4, 4' -diamino diphenyl methane at least one of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane, 4 '-methylenebis (2, 6-diethylaniline), 4' -methylene-bis- (2.6-diisopropylaniline), 4 '-methylene-bis (2-methyl-6-ethylaniline), 4' -bis-sec-butylamino-diphenylmethane, 1, 4-bis-iso-sec-amino-benzene, isophorone diamine, and modifications thereof; and/or the number of the groups of groups,
the isocyanate-terminated liquid rubber comprises at least one of isocyanate-terminated polybutadiene rubber, isocyanate-terminated nitrile rubber and isocyanate-terminated polyisoprene rubber.
The epoxy resin toughening agent as described above, wherein the second epoxy-based compound comprises at least one of glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl alkyl (meth) acrylate, epoxy-terminated polybutadiene rubber, epoxy-terminated nitrile rubber, epoxy-terminated polyisoprene rubber.
The epoxy resin toughening agent is prepared by a method comprising the following steps: the first component and the second component are subjected to high shear mixing, micro rubber phase powder is formed preliminarily and dispersed in a first epoxy group compound, and then curing and reinforcing treatment is carried out, so that an epoxy resin toughening agent is obtained;
wherein the rotating speed of the high shear mixing is 10-8000 r/min, the temperature of the curing enhancement treatment is 20-170 ℃ and the time is 0.1-5 h.
In a second aspect of the present invention, there is provided a method for preparing the epoxy resin toughening agent according to the first aspect, comprising the steps of:
mixing raw materials at least comprising diamine and a first epoxy compound to obtain a first component;
mixing raw materials at least comprising isocyanate-terminated liquid rubber to obtain a second component;
and (3) mixing the first component and the second component in a high shear manner, primarily forming micro rubber phase powder, dispersing the micro rubber phase powder in the first epoxy compound, and then performing curing and reinforcing treatment to obtain the epoxy resin toughening agent.
The preparation method comprises the following specific processes of carrying out the curing reinforcement treatment after the first component and the second component are subjected to high shear mixing:
high-shear mixing is carried out on the second component to obtain a second mixture;
adding the second mixture into the first component in a stirring state, continuously stirring to initially form micro rubber phase powder, uniformly dispersing the micro rubber phase powder into the first epoxy group compound, and then carrying out curing reinforcement treatment;
the rotation speed of the high shear mixing is 10-8000 r/min, the temperature of the curing and reinforcing treatment is 20-170 ℃ and the time is 0.1-5 h.
The preparation method comprises the steps of simultaneously adding a second epoxy compound, low-molecular-weight raw rubber, functional powder, a cross-linking agent and a secondary cross-linking agent into isocyanate-terminated liquid rubber, uniformly mixing, and carrying out banburying treatment under the protection of nitrogen and in the dark to obtain a second mixture;
wherein the banburying treatment temperature is 20-100 ℃.
The implementation of the invention has at least the following beneficial effects:
when the epoxy resin toughening agent is applied, the first component and the second component are mixed in a high shear mode to form micro rubber phase powder which is uniformly distributed in a first epoxy group compound, then solidification and reinforcement treatment are carried out, the epoxy resin toughening agent with excellent toughening effect is beneficial to obtaining, the preparation process of the epoxy resin toughening agent is simple, environment-friendly and low in production cost, mass production is beneficial to realizing, and the epoxy resin toughening agent can be applied to a blending system needing toughening, and can further improve the impact resistance and the shearing resistance of the system while maintaining the glass transition temperature of the system.
The preparation method of the epoxy resin toughening agent provided by the invention can prepare the epoxy resin toughening agent with excellent performance, has the advantages of simple preparation process, environmental friendliness and low production cost, and is beneficial to realizing mass production.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In a first aspect of the present invention, there is provided an epoxy resin toughening agent, the reaction raw materials of the epoxy resin toughening agent comprising a first component and a second component; the first component comprises at least diamine, a first epoxy compound or a mixture, and the second component comprises at least isocyanate-terminated liquid rubber.
The diamine can be specifically sterically hindered amine with lower reactivity, and can react with isocyanate-terminated liquid rubber to form polyurea substances with high elasticity and toughness, thereby being beneficial to improving the toughening effect. The invention selects diamine with low reactivity, which is beneficial to regulating and controlling the reaction degree and speed, thereby controlling the structure of the final product.
The first epoxy group compound refers to a compound having an epoxy group in the molecule, for example, an epoxy resin E51, an epoxy resin E44, an epoxy resin 128, or the like, or a diluent having an epoxy group, or the like.
It can be appreciated that when the toughening agent is required to be applied, the first component and the second component including the raw materials can be subjected to high shear mixing, and then micro rubber phase powder formed by the reaction is uniformly dispersed in the first epoxy compound, and then the curing is enhanced; the mixing process is accompanied by high shear stirring, which is helpful for obtaining the epoxy resin toughening agent with specific dispersing effect.
In addition, after the first component and the second component are mixed, the second component with higher viscosity is rapidly dispersed, ultra-fine high-viscosity liquid microbeads are gradually formed and dispersed in the first component, meanwhile, the surface of the newly formed liquid microbeads is subjected to in-situ reaction between isocyanate groups and diamine in the first component, the molecular chain is gradually increased, and finally the polymer tends to be solidified, so as to form micro rubber phase powder; in the process, the first epoxy compound is used as a continuous phase, and the dispersed liquid rubber particles can be isolated, prevented from sticking, adjusted in viscosity and controlled in fluidity until the liquid rubber particles are gradually converted into solid rubber micropowder, namely micro rubber phase powder, so that the micro rubber phase powder is uniformly dispersed in the first epoxy compound.
In some embodiments, the second component further comprises a second epoxy compound, a low molecular weight raw rubber, a functional powder, a crosslinking agent, and a co-crosslinking agent; the second epoxy compound contains at least an unsaturated double bond. That is, the second epoxy group compound includes at least an unsaturated double bond and an epoxy group.
In the process of forming and curing reinforcing the micro rubber phase powder, the unsaturated double bond in the second epoxy group compound is crosslinked with the rubber phase in the curing reaction process, and epoxy groups contained in the molecular structure are reserved; when the epoxy resin toughening agent is applied to the epoxy resin system, the retained epoxy groups are involved in the simultaneous curing of the external continuous phase epoxy resin system; thus, the interfacial force between the epoxy resin of the continuous phase and the rubber particles of the disperse phase is greatly enhanced; further, the final toughening effect is further improved. Meanwhile, the compatibility between the rubber phase interface and the continuous epoxy resin system is effectively improved through the tie function of the second epoxy compound connection, so that the stability of the system is improved, and the method is greatly helpful for dispersing the toughening agent in the initial state of the manufacturing process, forming fine particles as much as possible and preventing the particles from coarsening.
The epoxy resin toughening agent is subjected to high-shear mixing and curing reinforcement of all components, and the obtained cured product has excellent toughening performance. The cured product at least comprises micro rubber phase powder in a disperse phase and a first epoxy group compound in a continuous phase, wherein the micro rubber phase powder is uniformly distributed in the interior and/or the surface of the first epoxy group compound in a granular form.
In the present invention, the isocyanate group content of the isocyanate-terminated liquid rubber is in the range of 0.5 to 15%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 10%, 12%, 15% or any two thereof, preferably 2 to 10%, and the content of free isocyanate groups in the isocyanate-terminated liquid rubber is ensured to be less than 0.1%. This helps to increase the reaction rate and reduce side reactions.
In some embodiments, the low molecular weight raw rubber has a number average molecular weight of 1500 to 10000 and a softening point of 10 to 100 ℃; and/or the first epoxy compound has a combined epoxy value of 0.1 to 1mol/100g.
In some embodiments, the mass ratio of the first epoxy compound to the sterically hindered diamine is 100: (3-15), for example 100: 3. 100: 6. 100: 8. 100: 11. 100:15 or any two thereof; and/or the mass ratio of the isocyanate-terminated liquid rubber to the second epoxy compound to the low molecular weight raw rubber to the functional powder to the crosslinking agent to the auxiliary crosslinking agent is (30-75): (0-12): (0-35): (0-20): (0-3): (0-10).
The invention is not limited to a particular choice of materials, for example, in some embodiments, the diamine comprises diethyl toluenediamine, 4 '-dimethylene-bis (3-chloro-2, 6-diethyl aniline), dimethyl thiotoluenediamine, 1, 3-propanediol bis (4-aminobenzoate), 4' -dimethylene bis (2-ethyl) aniline, 3-chloro-3 '-ethyl-4, 4' -diamino diphenyl methane, 3 '-dichloro-4, 4' -diamino diphenyl methane at least one of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane, 4 '-methylenebis (2, 6-diethylaniline), 4' -methylene-bis- (2.6-diisopropylaniline), 4 '-methylene-bis (2-methyl-6-ethylaniline), 4' -bis-sec-butylamino-diphenylmethane, 1, 4-bis-iso-sec-amino-benzene, isophorone diamine, and modifications thereof; and/or the first epoxy compound comprises at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic type epoxy resin, alicyclic type epoxy resin, alkylene glycidyl ether, butyl glycidyl ether, 1,4 butanediol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, aliphatic chain monoglycidyl ether, benzyl monoglycidyl ether, 1,6 hexanediol diglycidyl ether, propylene oxide o-tolyl ether, neopentyl glycol diglycidyl ether; and/or the isocyanate-terminated liquid rubber comprises at least one of isocyanate-terminated polybutadiene rubber, isocyanate-terminated nitrile rubber and isocyanate-terminated polyisoprene rubber; and/or the second epoxy compound comprises at least one of glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl alkyl (meth) acrylate, epoxy-terminated polybutadiene rubber, epoxy-terminated nitrile rubber, epoxy-terminated polyisoprene rubber; and/or the low molecular weight raw rubber comprises at least one of polybutadiene, polyisoprene, butyronitrile, butylbenzene, polybutene, butylenes styrene copolymer, butylenes propylene copolymer and butylenes ethylene copolymer.
In the invention, the crosslinking agent and the auxiliary crosslinking agent are insoluble substances for forming a three-dimensional structure by further forming a bridge bond between polybutadiene structural chains; the functional powder can enhance cohesive force and reduce cost.
Wherein the cross-linking agent comprises at least one of sulfur, sulfur-containing vulcanizing agent, peroxide and photoinitiator; the auxiliary crosslinking agent comprises at least one of (methyl) acrylic ester modified polyol, triallyl polyisocyanurate and other compounds containing polyunsaturated double bonds; the functional powder comprises powder and pigment; the powder comprises at least one of calcium carbonate, sodium sulfate, talcum powder, silicon dioxide, sodium carbonate and calcium sulfate; the pigment comprises at least one of titanium dioxide, barium sulfate, carbon black, iron oxide, and ferroferric oxide.
The invention is not limited to the preparation process of the epoxy resin toughening agent, and only needs to comprise the raw materials. For example, in some embodiments, the epoxy resin toughener is prepared by a process comprising: and (3) carrying out high-shear mixing on the first component and the second component, initially forming micro rubber phase powder under the high-shear mixing, dispersing the micro rubber phase powder in the first epoxy group compound, and then carrying out curing and reinforcing treatment to obtain the epoxy resin toughening agent. Wherein the rotation speed of high shear mixing is 10-8000 r/min, the curing and reinforcing treatment temperature is 20-170 ℃ and the time is 0.1-5 h.
In a second aspect of the present invention, there is provided a method of preparing an epoxy resin toughening agent comprising the steps of:
mixing raw materials at least comprising steric diamine and a first epoxy compound to obtain a first component;
mixing raw materials at least comprising isocyanate-terminated liquid rubber to obtain a second component;
and (3) mixing the first component and the second component in a high shear manner to initially form micro rubber phase powder, and dispersing the micro rubber phase powder in the first epoxy compound to obtain the epoxy resin toughening agent.
In some embodiments, the specific process of mixing the first component and the second component followed by the cure reinforcement treatment includes: high-shear mixing is carried out on the second component to obtain a second mixture; adding the second mixture into the first component in a stirring state, continuously stirring to initially form micro rubber phase powder, uniformly dispersing the micro rubber phase powder into the first epoxy group compound, and then carrying out curing reinforcement treatment; the rotation speed of high shear mixing is 10-8000 r/min, the curing and reinforcing treatment temperature is 20-170 ℃ and the time is 0.1-5 h.
In the invention, the high shear mixing is to uniformly mix the materials of the second component, the second mixture is added into the first component in a stirring state, the stirring is continued, the curing reaction is carried out, and finally the crosslinking curing reinforcing treatment is carried out, so that the obtained final cured product is the epoxy resin toughening agent.
In some embodiments, after mixing the raw materials including at least the isocyanate-terminated liquid rubber, the second epoxy compound, the low molecular weight raw rubber, the raw materials are dehydrated and banburying under nitrogen protection and light shielding conditions; wherein the banburying treatment temperature is 20-100 ℃.
The present invention will be further illustrated by the following specific examples and comparative examples. The reagents, materials and instruments used in the following are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents and materials involved can be synthesized by conventional synthesis methods, unless otherwise specified.
The specifications of some of the materials used in the following examples are as follows:
isocyanate-terminated polybutadiene rubber (1): isocyanate content is 0.5%, and normal temperature (20 ℃) viscosity is 20000-40000 cPs;
terminal isocyanate group poly nitrile rubber (2): the isocyanate content is 2.56%, and the viscosity at normal temperature (20 ℃) is 12000-14000 cPs;
terminal isocyanato nitrile rubber (3): the isocyanate content is 5.56%, and the viscosity at normal temperature (20 ℃) is 7000-8000 cPs;
isocyanate-terminated polybutadiene rubber (4): the isocyanate content is 8.3 percent, and the viscosity at normal temperature (20 ℃) is 6000 to 7000cPs;
isocyanate-terminated polybutadiene rubber (5): the isocyanate content is 15 percent, and the viscosity at normal temperature (20 ℃) is 5000 to 6000cPs;
polyamide curing agent R651: an amine value of 400+ -20 mgKOH/g;
epoxy resin E51, epoxy group content of 0.50+/-0.02 mol/100g;
epoxy resin E55, epoxy group content of 0.54+/-0.02 mol/100g;
photoinitiator 184: alpha-hydroxyalkyl benzophenone photoinitiators;
BIBP: di-tert-butyl diisopropylbenzene peroxide;
TAIC: triallyl polyisocyanurate;
silica filler: average particle diameter 0.2 μm;
polybutadiene raw rubber: average molecular weight 4000-5000 and softening point 50 ℃;
a second epoxy compound: glycidyl methacrylate;
MX154: purchased from brillouin chemical core-shell rubber epoxy resin toughener MX-154;
carboxyl-terminated liquid nitrile rubber CTBN1300 x 13: purchased from hounsmei corporation, usa.
Example 1
Uniformly mixing 100 parts by mass of epoxy resin E51, 0.5 part by mass of 4,4' -dimethylene-bis (3-chloro-2, 6-diethylaniline) and 0.5 part by mass of dimethyl thiotoluenediamine to obtain a mixture 1;
75 parts by mass of an isocyanate-terminated polybutadiene rubber (1) alone as a second component;
adding the second component into the stirred mixture 1 at the temperature of 20-25 ℃ at the stirring speed of 1000r/min for 30min at normal temperature to finally obtain a milky substance with the viscosity of 30000 cps;
and curing the milky white substance at 70 ℃ for 1 hour to finally prepare the epoxy resin toughening agent A.
Epoxy resin E51, a toughening agent A and a polyamide curing agent R651 are mixed according to the mass ratio of 100:
20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition a.
Example 2
Uniformly mixing 100 parts by mass of epoxy resin E51 and 8.5 parts by mass of dimethyl thiotoluene diamine to obtain a mixture 1;
59.5 parts by mass of an isocyanate-terminated nitrile rubber (3) alone as a second component;
adding the second component into the stirred mixture 1 at the temperature of 20-25 ℃ at the stirring speed of 1000r/min for 30min at normal temperature, and finally obtaining a milky substance with the viscosity of 40000cps;
solidifying the milky white substance at 70 ℃ for 1 hour to finally prepare the epoxy resin toughening agent B;
epoxy resin E51, a toughening agent B and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition b.
Example 3
Uniformly mixing 100 parts by mass of epoxy resin E55, 5 parts by mass of dimethyl thiotoluene diamine, and 10 parts by mass of 4,4' -dimethyl-bis (3-chloro-2, 6-diethylaniline) (15 parts of diamine total) to obtain a mixture 1;
mixing 40 parts by mass of isocyanate-terminated polybutadiene rubber (5), 10 parts by mass of polybutadiene rubber and 5 parts by mass of silica filler, and banburying under the protection of nitrogen; forming a mixture 2;
adding the mixture 2 into the stirred mixture 1 at the temperature of 20-25 ℃ and stirring at the stirring speed of 1000r/min for 30min at normal temperature, and finally obtaining a milky substance with the viscosity of 52000 cps;
solidifying the milky white substance at 70 ℃ for 1 hour to finally prepare the epoxy resin toughening agent C;
epoxy resin E51, a toughening agent C and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 deg.c for 6 hr, at 100 deg.c for 2 hr, and cooling to room temperature to obtain the epoxy resin composition c.
Example 4
Uniformly mixing 100 parts by mass of epoxy resin E55, 2 parts by mass of dimethyl thiotoluene diamine, 8 parts by mass of 4,4' -dimethyl-bis (3-chloro-2, 6-diethylaniline) (total 10 parts of diamine) to obtain a mixture 1;
mixing 30 parts by mass of isocyanate-terminated polybutadiene rubber (4), 35 parts by mass of raw polybutadiene rubber and 3 parts by mass of sulfur powder, and banburying under the protection of nitrogen; forming a mixture 2;
adding the mixture 2 into the stirred mixture 1 at the temperature of 20-25 ℃ and stirring at the stirring speed of 600r/min for 30min at normal temperature, and finally obtaining a pale yellow substance with the viscosity of 115000 cps;
solidifying the milky white substance at 170 ℃ for half an hour to finally prepare the epoxy resin toughening agent D;
epoxy resin E51, a toughening agent D and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition d.
Example 5
Uniformly mixing 100 parts by mass of epoxy resin E55 and 5 parts by mass of 4,4' -di-sec-butylamino diphenyl methane to obtain a mixture 1;
50 parts by mass of isocyanate-terminated poly (nitrile rubber) (2), 5 parts by mass of polybutadiene rubber and 20 parts by mass of silica filler are mixed and banburying is carried out under the protection of nitrogen; forming a mixture 2;
adding the mixture 2 into the stirred mixture 1 at the temperature of 20-25 ℃ and stirring at the stirring speed of 600r/min for 30min at normal temperature, and finally obtaining a milky substance with the viscosity of 83000 cps;
solidifying the milky white substance at 70 ℃ for 2 hours to finally prepare the epoxy resin toughening agent E;
epoxy resin E51, a toughening agent E and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition e.
Example 6
Uniformly mixing 100 parts by mass of epoxy resin E55 and 5 parts by mass of 4,4' -di-sec-butylamino diphenyl methane to obtain a mixture 1;
50 parts by mass of isocyanate-terminated poly (nitrile rubber) (2), 12 parts by mass of glycidyl methacrylate, 3 parts by mass of photoinitiator 184 and 10 parts by mass of TAIC are banburying under the protection of nitrogen and in a light-shielding state to form a mixture 2;
adding the mixture 2 into the stirred mixture 1 at the temperature of 20-25 ℃ and stirring at the stirring speed of 600r/min for 30min at normal temperature, and finally obtaining a milky substance with the viscosity of 53000 cps;
forming a film with the thickness of 1mm by the milky white substance scraping plate, irradiating for 10min by ultraviolet rays to fully react and solidify unsaturated double bonds inside, collecting the unsaturated double bonds from the scraping plate, and finally preparing the epoxy resin toughening agent F;
epoxy resin E51, a toughening agent F and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition f.
Example 7
Uniformly mixing 100 parts by mass of epoxy resin E55 and 5 parts by mass of 4,4' -di-sec-butylamino diphenyl methane to obtain a mixture 1;
mixing 50 parts by mass of isocyanate-terminated poly (nitrile) rubber (2), 12 parts by mass of glycidyl methacrylate, 5 parts by mass of polybutadiene rubber, 5 parts by mass of TAIC and 0.5 part by mass of BIBP under the protection of nitrogen; forming a mixture 2;
adding the mixture 2 into the stirred mixture 1 at the temperature of 20-25 ℃ and stirring at the stirring speed of 600r/min for 30min at normal temperature, and finally obtaining a milky substance with the viscosity of 53000 cps;
heating the milky white substance at 150 ℃ for 45min to crosslink the interior of the rubber micropowder, and finally preparing the epoxy resin toughening agent G;
epoxy resin E51, a toughening agent G and a polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55, and curing at 20-25 ℃ for 6h, and then at 100 ℃ for 2h, and cooling to room temperature to obtain the epoxy resin composition g.
Comparative example 1
The epoxy resin E51 and the polyamide curing agent R651 are mixed according to the mass ratio of 100:50 is evenly mixed at normal temperature, is solidified for 6 hours at 20-25 ℃, is solidified for 2 hours at 100 ℃, and is cooled to room temperature, thus obtaining the epoxy resin composition R.
Comparative example 2
Epoxy resin E51, MX-154 and polyamide curing agent R651 are mixed according to the mass ratio of 100:20:55 are uniformly mixed at normal temperature, are solidified for 6 hours at 20-25 ℃, are solidified for 2 hours at 100 ℃, and are cooled to room temperature to obtain the epoxy resin composition M.
Comparative example 3
Epoxy resin E51 and carboxyl-terminated liquid nitrile rubber CTBN1300, 13 and R651 are mixed according to the mass ratio of 100:20:55 are uniformly mixed at normal temperature, are solidified for 6 hours at 20-25 ℃, are solidified for 2 hours at 100 ℃, and are cooled to room temperature, so that the epoxy resin composition T is obtained.
The following tests were performed on the above epoxy resin composition:
glass transition temperature: reference is made to GB/T29611-2013 Differential Scanning Calorimetry (DSC) of determination of the glass transition temperature (Tg) of raw rubber;
impact resistance: reference is made to GB/T2571-1995 resin casting impact test method;
shear resistance: referring to a method for measuring the tensile shear strength of GB/T7124-2008 adhesive;
low temperature resistance: the epoxy resin composition sample was fixed on a peeling table of a peeling tester, and the initial value of the peeling force was measured at room temperature (20 ℃) and the temperature was continuously lowered to measure the change of the peeling force, and when the peeling force was lowered to 50% of the initial value of the peeling force, the temperature at this time was recorded as the temperature tolerance point.
The test results are shown in Table 1.
TABLE 1
Comparative examples 1 to 7 and comparative example 1 show that the epoxy resin toughening agent of the present invention can significantly improve the impact resistance and the shear resistance of the epoxy resin composition without affecting the glass transition temperature; meanwhile, the low temperature resistance of the system can be greatly enhanced.
As can be seen from comparative examples 1-7 and comparative example 2, the epoxy resin toughening agent of the invention can flexibly adjust the process according to the requirement, and can meet the improvement of specific properties such as low temperature resistance, high shear property, high impact resistance and the like; meanwhile, by comparison, the toughening agent prepared by the method has higher epoxy toughening effect than that of a bid product, and the anti-shearing strength of the toughening agent is obviously superior to that of the bid product.
Comparative examples 1-7 and comparative example 3 show that CTBN of comparative example 3 has a greater effect on the glass transition temperature of the epoxy resin, reducing Tg to 67 ℃, while the epoxy resin toughening agent of examples has a lesser effect on the glass transition temperature of the epoxy resin; and the shearing resistance of the epoxy resin composition of the comparative example 3 is obviously lower than that of the examples, which shows that the invention has the outstanding advantage of toughening the epoxy resin that the influence on the glass transition temperature of the system is far less than that of CTBN toughening epoxy.
Preferred embodiments of the present invention and experimental verification are described in detail above. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical schemes which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the technical personnel in the field according to the conception of the invention are within the protection scope of the invention.
Claims (10)
1. The epoxy resin toughening agent is characterized in that the reaction raw materials of the epoxy resin toughening agent comprise a first component and a second component;
the first component at least comprises diamine and a first epoxy group compound, and the second component at least comprises isocyanate-terminated liquid rubber.
2. The epoxy resin toughener of claim 1, wherein the second component further comprises a second epoxy compound, a low molecular weight green rubber, a functional powder, a cross-linking agent, a co-cross-linking agent.
3. The epoxy resin toughening agent according to claim 2, wherein the isocyanate group-terminated liquid rubber has an isocyanate group content of 0.5 to 15%, preferably 2 to 10%; and/or the number of the groups of groups,
the comprehensive epoxy value of the first epoxy compound is 0.1-1.0 mol/100g; and/or the number of the groups of groups,
the number average molecular weight of the low molecular weight raw rubber is 1500-10000, and the softening point is 10-100 ℃.
4. The epoxy resin toughening agent according to claim 2, wherein the mass ratio of the first epoxy compound to the diamine is 100: (1-15); and/or the number of the groups of groups,
the mass ratio of the isocyanate-terminated liquid rubber to the second epoxy compound to the low molecular weight raw rubber to the functional powder to the crosslinking agent to the auxiliary crosslinking agent is (30-75): (0-12): (0-35): (0-20): (0-3): (0-10).
5. The epoxy resin toughener of any one of claim 1-4, wherein, the diamine comprises diethyl toluenediamine, 4 '-dimethylene-bis (3-chloro-2, 6-diethyl aniline), dimethyl thiotoluenediamine, 1, 3-propanediol bis (4-aminobenzoate), 4' -dimethylene bis (2-ethyl) aniline, 3-chloro-3 '-ethyl-4, 4' -diamino diphenyl methane, 3 '-dichloro-4, 4' -diamino diphenyl methane at least one of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane, 4 '-methylenebis (2, 6-diethylaniline), 4' -methylene-bis- (2.6-diisopropylaniline), 4 '-methylene-bis (2-methyl-6-ethylaniline), 4' -bis-sec-butylamino-diphenylmethane, 1, 4-bis-iso-sec-amino-benzene, isophorone diamine, and modifications thereof; and/or the number of the groups of groups,
the isocyanate-terminated liquid rubber comprises at least one of isocyanate-terminated polybutadiene rubber, isocyanate-terminated nitrile rubber and isocyanate-terminated polyisoprene rubber.
6. The epoxy resin toughener of any one of claims 2-4, wherein the second epoxy-based compound comprises at least one of glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl alkyl (meth) acrylate, epoxy-terminated polybutadiene rubber, epoxy-terminated nitrile rubber, epoxy-terminated polyisoprene rubber.
7. The epoxy resin toughener of any one of claims 1-6, wherein the epoxy resin toughener is prepared by a process comprising: the first component and the second component are subjected to high shear mixing, micro rubber phase powder is formed preliminarily and dispersed in a first epoxy group compound, and then curing and reinforcing treatment is carried out, so that an epoxy resin toughening agent is obtained;
wherein the rotating speed of the high shear mixing is 10-8000 r/min, the temperature of the curing enhancement treatment is 20-170 ℃ and the time is 0.1-5 h.
8. A method of preparing the epoxy resin toughening agent according to any one of claims 1 to 7, comprising the steps of:
mixing raw materials at least comprising diamine and a first epoxy compound to obtain a first component;
mixing raw materials at least comprising isocyanate-terminated liquid rubber to obtain a second component;
and (3) mixing the first component and the second component in a high shear manner, primarily forming micro rubber phase powder, dispersing the micro rubber phase powder in the first epoxy compound, and then performing curing and reinforcing treatment to obtain the epoxy resin toughening agent.
9. The method of claim 8, wherein the step of high shear mixing the first component and the second component followed by the curing reinforcement comprises:
high-shear mixing is carried out on the second component to obtain a second mixture;
adding the second mixture into the first component in a stirring state, continuously stirring to initially form micro rubber phase powder, uniformly dispersing the micro rubber phase powder into the first epoxy group compound, and then carrying out curing reinforcement treatment;
the rotation speed of the high shear mixing is 10-8000 r/min, the temperature of the curing and reinforcing treatment is 20-170 ℃ and the time is 0.1-5 h.
10. The preparation method according to claim 8 or 9, wherein a second epoxy group compound, a low molecular weight raw rubber, a functional powder, a cross-linking agent and a secondary cross-linking agent are added into the isocyanate group-terminated liquid rubber at the same time, and after being uniformly mixed, the mixture is subjected to banburying treatment under the condition of nitrogen protection and light shielding, so as to obtain a second mixture;
wherein the banburying treatment temperature is 20-100 ℃.
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| CN120082175A (en) * | 2025-03-28 | 2025-06-03 | 北玻院(滕州)复合材料有限公司 | A flame retardant high modulus, high toughness winding epoxy resin composition and preparation method thereof |
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| CN120082175A (en) * | 2025-03-28 | 2025-06-03 | 北玻院(滕州)复合材料有限公司 | A flame retardant high modulus, high toughness winding epoxy resin composition and preparation method thereof |
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