CN109679289B - Preparation method of high-toughness wear-resistant epoxy resin composite material and composite material - Google Patents
Preparation method of high-toughness wear-resistant epoxy resin composite material and composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-toughness wear-resistant epoxy resin composite material, which comprises the steps of preparing liquid rubber and montmorillonite to obtain a liquid rubber intercalation modified montmorillonite nanocomposite material, and preparing the epoxy resin composite material from the liquid rubber intercalation modified montmorillonite nanocomposite material and epoxy resin through a curing agent. The impact strength of the epoxy resin composite material is 19-36KJ/m 2; the abrasion resistance is improved by more than 30 percent. The invention improves the epoxy resin by virtue of the advantages of the organic/inorganic nano composite material, in particular to an organic/inorganic multidimensional nano structure composite material prepared by liquid rubber quaternary ammonium salt intercalation modified montmorillonite, which improves the epoxy resin and endows the epoxy resin with good toughness and wear resistance.
Description
Technical Field
The invention belongs to the technical field of epoxy resin modification, and particularly relates to a high-toughness wear-resistant epoxy resin composite material.
Background
Because of its good electrical insulation property, epoxy resin has excellent bonding strength to the surface of metal and non-metal materials, small curing shrinkage, good dimensional stability, high hardness, solvent resistance, and is widely used in the fields of adhesives, coatings, semiconductor packaging materials, composite materials, building traffic, and the like. In general, epoxy resin has high crosslinking density and large internal stress after being cured, and the obtained product has insufficient toughness and poor wear resistance, thereby limiting the application of the epoxy resin in many aspects. Therefore, how to improve the toughness and the wear resistance of the cured epoxy resin has important research significance and application value.
It is reported that the wear resistance of the epoxy resin is improved mainly by modifying the nano material at present. For example, the epoxy resin is modified with a material such as nano-silica, nano-silicon carbide, nano-aluminum trioxide, or carbon nanotube. However, the nano material has large specific surface and high surface energy, and is easy to agglomerate, thereby influencing the improvement of the mechanical properties of the epoxy resin, such as toughness and wear resistance.
Compared with single modification, the organic-inorganic composite modification has wider selection, is beneficial to the advantage complementation among all components, and even can play a synergistic effect. Liquid rubbers are relatively effective modifiers in epoxy resin modification processes that have been found to significantly improve the toughness of epoxy resins. However, as the amount of the liquid rubber used increases, its dispersibility in the epoxy resin and particle size are difficult to control, and thus, the epoxy resin is disadvantageously deteriorated in modulus and heat resistance.
Disclosure of Invention
Therefore, aiming at the defects of the prior art, the invention aims to provide an organic-inorganic composite modification method for improving the wear resistance and toughness of epoxy resin by using nano materials. The invention also provides a high-toughness wear-resistant epoxy resin composite material obtained by the method.
The technical scheme of the invention is that the preparation method of the high-toughness wear-resistant epoxy resin composite material comprises the preparation of a nano material, wherein the nano material is a liquid rubber intercalation modified montmorillonite nano composite material, and the preparation of the liquid rubber intercalation modified montmorillonite nano composite material comprises the following steps of one step to three steps:
the method comprises the following steps: dissolving liquid rubber in proper amount of dimethylbenzene, adding the solution into a reaction vessel with a condensing device, stirring, introducing inert gas by taking hexamethylenetetramine as a catalyst and p-hydroxyanisole as a polymerization inhibitor; heating to 40-80 ℃, dropwise and slowly adding epoxy chloropropane from a dropping funnel, reacting for a certain time, and stopping; removing most of the solvent and unreacted epichlorohydrin by decompression; repeatedly extracting and cleaning the product liquid chloropropanol intermediate by using a large amount of methanol for many times; vacuum drying, and placing in a dryer for later use;
step two: taking the liquid chloropropanol intermediate prepared in the step (1), dissolving a proper amount of Tetrahydrofuran (THF), and adding into a reaction vessel; slowly dripping a slightly excessive trimethylamine aqueous solution into the mixture by using a constant-pressure dropping funnel under stirring, and completely reacting at normal temperature; removing most of THF under reduced pressure to obtain brown viscous liquid; adding a large amount of methanol for purification and washing, and then washing at least twice by using a mixed solution of methanol and deionized water; vacuum drying to constant weight to obtain a product, namely liquid rubber quaternary ammonium salt;
step three: adding montmorillonite subjected to sodium treatment into deionized water according to the mass ratio of 1:20-40, stirring for 18-36 hours at 70-90 ℃, then dropwise adding THF (tetrahydrofuran) accounting for 1-3 times of the volume of the deionized water, and continuously stirring to obtain a suspension; dissolving liquid rubber quaternary ammonium salt in Tetrahydrofuran (THF), dropwise adding the solution into the suspension, and stirring at the same temperature for a certain time to obtain a crude product; adding the obtained crude product into a centrifuge tube, carrying out high-speed centrifugation for 5-30min, and removing the upper layer liquid; washing the mixture for more than 1 time by using a mixed solvent of THF and deionized water, washing the mixture by using deionized water, and drying the mixture in vacuum at 50-60 ℃ to constant weight; grinding and sieving to obtain the liquid rubber intercalation modified montmorillonite nanocomposite.
Step four, mixing the epoxy resin and the obtained liquid rubber intercalation modified montmorillonite nano composite material according to the mass ratio of 100: 3-30, putting the mixture into a reaction container, stirring the mixture at the temperature of 50-70 ℃ to fully mix the mixture, adding a curing agent, epoxy resin: the mass ratio of the curing agent is 100: 10-40, uniformly stirring, vacuumizing at 30-100 ℃, removing bubbles, and curing to obtain the epoxy resin composite material. The curing is carried out under conventional curing conditions.
Hexamethylenetetramine is a catalyst for organic reactions, and is beneficial to the reaction under alkaline conditions, but not beneficial to side reactions. P-hydroxyanisole is a polymerization inhibitor, which has the effect of preventing the liquid rubber from polymerizing, and the polymerization reaction is a side reaction.
And performing nucleophilic substitution reaction on the epichlorohydrin and the terminal group of the liquid rubber. The end group is then replaced and introduced to react with a base to form a quaternary ammonium salt group. The above only toluene is the solvent, and the others are the reagents required for the reaction.
The stirring in the reaction is for the reaction to be uniform, and is also beneficial to the full contact between the end group of the liquid rubber and the epichlorohydrin.
The stirring in the first step and the second step is magnetic stirring.
In the first step, the reactant needs to be slowly dropped, so that a common dropping funnel, also called a constant pressure dropping funnel, needs to be used. Step three is preferably to pass through a 100-300 mesh sieve after grinding.
Preferably, in the fourth step, the mass ratio of the epoxy resin to the liquid rubber intercalated modified montmorillonite nanocomposite material is 100: 3 to 6.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, the liquid rubber is preferably selected from the following group: carboxyl-terminated nitrile rubber (CTBN), hydroxyl-terminated nitrile rubber (HTBN), amino-terminated nitrile rubber (ATBN), epoxy-terminated nitrile rubber (ETBN), vinyl-terminated nitrile rubber (VTBN), hydroxyl-terminated polybutadiene rubber (HTPB), amino-terminated polybutadiene rubber (ATPB), Polyurethane (PU) liquid rubber and acrylate liquid (ACM) rubber.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, the volume ratio of the liquid rubber to the xylene in the step one is preferably 1: 50-100; the vacuum drying in the step one is vacuum drying for 12 to 36 hours at the temperature of between 40 and 60 ℃; step one, the inert gas is selected from nitrogen and argon. The ratio of the liquid rubber to the xylene is not particularly required, and the liquid rubber can be dissolved.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, preferably, the mass ratio of the liquid rubber chloropropanol intermediate to tetrahydrofuran in the second step is 1:2 to 1: 6. the liquid rubber chloropropanol intermediate can be dissolved without special requirements.
Preferably, the normal-temperature reaction time in the second step is 12-36 h;
preferably, the concentration of the trimethylamine aqueous solution in the second step is 20 to 50 wt%.
Preferably, the volume of the methanol in the second step is 2 to 5 times of the volume of the mixed product.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, the washing times of the dimethyl carbinol in the step are preferably 4-7 times; more preferably, the number of methanol washes is 5 to 6.
Preferably, in the mixed solution of methanol and deionized water in the second step, the volume ratio of methanol to deionized water is 3-5: 1;
preferably, the temperature of the vacuum drying in the second step is 50-70 ℃.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, the stirring time in the step three is preferably 1-5 hours;
preferably, the mass ratio of the liquid rubber quaternary ammonium salt to the tetrahydrofuran in the step three is 1: 5-20;
preferably, the volume ratio of THF to deionized water in the mixed solvent of THF and deionized water in the step three is 7: 1-4; the THF and deionized water mixed solvent washing is used for removing the liquid rubber molecules which are not adsorbed on the montmorillonite.
Preferably, the centrifugal rotation speed in the third step is 6000-;
preferably, the step three-way THF and deionized water mixed solvent is washed for 3 times or more;
preferably, the deionized water washing in the third step is twice or more.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, the aqueous solution of trimethylamine further contains CH3Cl, said CH3The molar ratio of Cl to TMA was 1:1 to 1.5. CH (CH)3Cl is a promoting reactionThe solvent (4) is mixed with an aqueous trimethylamine solution, and the mixture is added dropwise to the reaction mixture to carry out the reaction. CH (CH)2Cl can play a role in uniformly dispersing reactants and reducing local heat, and is beneficial to the implementation of quaternary ammonification reaction of chlorine atoms and trimethylamine carried on the end group of the intermediate liquid rubber.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, preferably, the curing agent in the step four is one or two selected from modified amine curing agents, low-molecular polyamide curing agents, imidazole curing agents, phenolic aldehyde amine curing agents and anhydride curing agents.
According to the preparation method of the high-toughness wear-resistant epoxy resin composite material, preferably, after the mixture is stirred at 50-70 ℃ and fully mixed, an accelerator accounting for 1-5% of the resin can be added.
Preferably, the stirring time for stirring and thoroughly mixing in the fourth step is 1 to 4 hours.
The promoter is selected from one or more of phenol, DMP-30, pyridine, fatty amine, etc. The accelerator can accelerate the curing of the epoxy resin, reduce the curing temperature and shorten the curing time.
In the preparation method, the mass part ratio of the liquid rubber, the montmorillonite and the epoxy resin matrix is 2-35: 2-20: 100.
the invention also provides the high-toughness wear-resistant epoxy resin composite material prepared by the preparation method of the high-toughness wear-resistant epoxy resin composite material, and the epoxy resin and the obtained liquid rubber intercalation modified montmorillonite nanocomposite material are mixed according to the mass ratio of 100: 3-30, putting the mixture into a reaction container, stirring the mixture at the temperature of 50-70 ℃ to fully mix the mixture, adding a curing agent, epoxy resin: the mass ratio of the curing agent is 100: 10-40, uniformly stirring, vacuumizing at 30-100 ℃, removing bubbles, and curing to obtain the epoxy resin composite material; the impact strength of the epoxy resin composite material is 19-36KJ/m 2; the abrasion resistance is improved by more than 30 percent.
Preferably, when the addition amount of the nano composite structure modifier is 3-6%, the impact strength of the epoxy resin composite material is 29-36KJ/m 2; the abrasion resistance is improved by more than 40 percent.
The invention has the beneficial effects that:
the layered silicate has a lamellar structure, and is endowed with a plurality of unique properties, especially the polymer-layered nano composite material, so that the mechanical property, the flame retardant property and the thermal stability of the polymer are improved. Montmorillonite can be used as template agent of nano structure in polymer system to prepare nano composite material. The liquid rubber is modified to obtain the liquid rubber quaternary ammonium salt, and then the quaternary ammonium salt is taken as the intercalation agent of the phyllosilicate, and the intercalation is stripped from the montmorillonite to obtain the modifier with the organic-inorganic multi-dimensional nano structure, so that the epoxy resin is modified, and the epoxy resin has good flexibility and wear resistance.
The high-toughness wear-resistant epoxy resin composite material is obtained by using organic-inorganic composite modified epoxy resin. The specific method is based on commercially available liquid rubber serving as an excellent toughness modifier of epoxy resin, the liquid rubber quaternary ammonium salt with long chain is prepared by modification, then the surface of montmorillonite is directly modified, intercalated and in-situ prepared into an organic-inorganic multi-dimensional nano structure, and the high-toughness wear-resistant epoxy resin composite material is obtained by utilizing the unique nano scale effect and the structure morphology of the nano structure and the mechanism of mutual synergy of organic and inorganic composites. The invention has the advantages of overcoming the adverse effect of the montmorillonite modifier being alkyl with low molecular chain in the existing montmorillonite modified epoxy resin composite material, effectively utilizing the liquid rubber, reasonably controlling the appearance and the size of the liquid rubber, and leading the obtained organic-inorganic composite modified epoxy resin to have good toughness and wear resistance.
Drawings
FIG. 1 is a diagram showing the abrasion resistance of a liquid rubber quaternary ammonium salt montmorillonite epoxy resin composite material.
FIGS. 2a and 2b are scanning electron micrographs of the surface of a sample after the liquid rubber quaternary ammonium salt montmorillonite epoxy resin composite material is abraded.
Detailed Description
Example 1 liquid nitrile rubber quaternary ammonium salt intercalated montmorillonite modified epoxy resin composite material
Dissolving carboxyl-terminated butadiene-acrylonitrile rubber (CTBN) in a proper amount of dimethylbenzene, adding the mixture into a three-neck flask with a condensing device, and magnetically stirring, wherein hexamethylenetetramine is used as a catalyst, and p-hydroxyanisole is used as a polymerization inhibitor. N2 was passed in. After the temperature is raised to a certain temperature, Epichlorohydrin (ECH) is added dropwise and slowly from a constant pressure dropping funnel, and the reaction is stopped after a certain time. Most of the solvent and unreacted Epichlorohydrin (ECH) were removed under reduced pressure. Repeatedly extracting and cleaning the product acrylonitrile butadiene rubber chloropropanol intermediate (CTBN-CDPP) by using a large amount of methanol for many times. Vacuum drying at 50 deg.C for 24h, and placing in a desiccator.
And (3) dissolving a proper amount of tetrahydrofuran in the CTBN-CDPP prepared in the step, and adding the dissolved solution into a three-neck flask. Slowly dropping a slight excess of 33% trimethylamine aqueous solution (-CH) by using a constant pressure dropping funnel under magnetic stirring3Cl: TAM 1:1.3(mol/mol)), and reacted at room temperature for 24 hours. After removal of most of the tetrahydrofuran under reduced pressure, a brown viscous liquid was obtained. Adding a large amount of methanol (about 3 times the volume of the mixed product), purifying, washing for 5-6 times, and washing for at least two times by using methanol/deionized water (v/v: 4: 1). Vacuum drying at 60 deg.c to constant weight to obtain the product, namely nitrile butadiene rubber quaternary ammonium salt (CTBN-QAS).
The sodium modification process of montmorillonite is as follows: 50g of montmorillonite is added into 1000ml of deionized water to prepare a suspension, 50g of analytical pure grade NaCl is added, and the mixture is stirred for 10 hours at 80 ℃ and then filtered. Washing with 500ml of deionized water for 6 times, then washing with 50ml of absolute ethyl alcohol for 3-4 times, vacuum drying at room temperature for 24 hours, and storing in a dryer for later use.
1g of sodium-treated montmorillonite is added into 30ml of deionized water, stirred for 24 hours at 80 ℃, then 60ml of tetrahydrofuran is dripped into the mixture, and the mixture is continuously stirred for 2 hours to obtain suspension. And dissolving a certain amount of liquid nitrile butadiene rubber quaternary ammonium salt in 20ml of tetrahydrofuran, dropwise adding the mixture into the suspension, and stirring the mixture for a certain time at the same temperature to obtain a crude product. The resulting mixture was added to a 15ml centrifuge tube, treated by high speed centrifugation (8000rap/min) for 15min, and the supernatant liquid was removed. In the same method, the montmorillonite is washed 3 times by a THF/deionized water mixed solvent (VTHF: Vwater: 7:3) to remove liquid rubber molecules which are not adsorbed on the montmorillonite, then washed twice by deionized water, and dried in vacuum at 50-60 ℃ to constant weight. Grinding and sieving with a 200-mesh sieve to obtain the CTBN-QAS-MMT nano composite material.
Mixing an organic-inorganic composite material modifier with epoxy resin and a curing agent (triethylene tetramine), and curing under proper process conditions (room temperature vacuumizing for 15min, 20 ℃/4d) to obtain the high-toughness wear-resistant epoxy resin composite material.
FIG. 1 is a graph of the abrasion resistance of a liquid rubber quaternary ammonium salt montmorillonite epoxy resin composite material. The left ordinate is the wear rate, the horizontal axis is the dosage of the nano-structure composite modifier, and the wear rate of the composite material is reduced by 80% when the dosage is 3-6 phr, so that the composite modifier can obviously improve the wear resistance of the epoxy resin.
Example 2
Hydroxyl-terminated polybutadiene liquid rubber (HTPB) and boron trifluoride diethyl etherate (BF 3. Et2O) are dissolved in a proper amount of xylene, then the mixture is added into a three-neck flask, and Epichlorohydrin (ECH) is added dropwise when the temperature is raised to a set temperature. Controlling the dropping speed, and keeping the temperature to react for 1 h. The solvent and Epichlorohydrin (ECH) were removed by distillation under reduced pressure, and the residue was added slowly to a large amount of methanol with stirring to give a milky viscous substance which settled to the bottom. Removing the upper layer liquid, and continuously washing for 5-6 times by using methanol. Vacuum drying at 60 ℃ for 24h to obtain the polybutadiene chloropropanol intermediate (HTPB-CDPP).
HTPB-CDPP and 0.3% p-hydroxyanisole (based on the mass of HTPBE) are dissolved in a proper amount of xylene, a system is adjusted to be neutral by concentrated hydrochloric acid, after the temperature is raised to 60 ℃, 33% trimethylamine water solution (epoxy group: 33% trimethylamine water solution is 1:1.2, mol ratio) is added dropwise, and the reaction is carried out for 4 hours at 60 ℃. And treating the crude product to obtain polybutadiene macromolecular quaternary ammonium salt HTPB-QAS.
The sodium modification process of montmorillonite is as follows: 50g of montmorillonite is added into 1000ml of deionized water to prepare a suspension, 50g of analytical pure grade NaCl is added, and the mixture is stirred for 10 hours at 80 ℃ and then filtered. Washing with 500ml of deionized water for 6 times, then washing with 50ml of absolute ethyl alcohol for 3-4 times, vacuum drying at room temperature for 24 hours, and storing in a dryer for later use.
Adding 10g of sodium montmorillonite (Na-MMT) and 300ml of deionized water into a 1000ml three-neck flask, and stirring and reacting at 80 ℃ for 24 hours to prepare suspension; adding 600ml tetrahydrofuran drop by drop and continuing stirring for 2 h; dissolving CTBN quaternary ammonium salt with corresponding ratio of Na-MMT Cation Exchange Capacity (CEC) in 200ml of tetrahydrofuran, dropwise adding the solution into the suspension, and stirring and reacting for a certain time at the same temperature; pouring the prepared mixed solution into 15ml centrifuge tubes respectively, centrifuging for 10min at 9000rmp/min, and taking white precipitate at the bottom; the unreacted quaternary ammonium salt of HTPB was removed by two washes (8000rmp/min) with 70/30 of a THF/deionized water mixed solution (v/v) and then washed with deionized water at least three times in the same manner until no Cl-was detected with AgNO3 solution. And (3) drying the mixture in vacuum at the temperature of 80-90 ℃ to constant weight, grinding, and sieving by a 200-mesh sieve to obtain the HTPB-QAS-MMT nano composite material.
Mixing an organic-inorganic composite material modifier with epoxy resin and a curing agent (2-ethyl-4 methylimidazole), and curing under a proper process condition (80 ℃/4h, and vacuumizing at 120 ℃ for 15min) to obtain the high-toughness wear-resistant epoxy resin composite material.
Example 3
Hydroxyl-terminated polyurethane liquid rubber (HTPU) is dissolved in proper amount of dimethylbenzene, added into a three-neck flask with a condensing device and stirred by magnetic force, and hexamethylenetetramine is used as a catalyst. N2 was passed in. After the temperature is raised to a certain temperature, Epichlorohydrin (ECH) is added dropwise and slowly from a constant pressure dropping funnel, and the reaction is stopped after a certain time. Most of the solvent and unreacted Epichlorohydrin (ECH) were removed under reduced pressure. Repeatedly extracting and cleaning the product polyurethane liquid rubber chloropropanol intermediate (HTPU-CDPP) by using a large amount of methanol for many times. Vacuum drying at 50 deg.C for 24h, and placing in a desiccator.
And (3) dissolving an appropriate amount of tetrahydrofuran in the HTPU-CDPP prepared in the step, and adding the dissolved tetrahydrofuran into a three-neck flask. Slowly dropping a slight excess of 33% trimethylamine aqueous solution (-CH) by using a constant pressure dropping funnel under magnetic stirring3Cl: TAM 1:1.3(mol/mol)), and reacted at room temperature for 24 hours. After removal of most of the tetrahydrofuran under reduced pressure, a brown viscous liquid was obtained. Adding a large amount of methanol (about 3 times the volume of the mixed product), purifying, washing for 5-6 times, and washing for at least two times by using methanol/deionized water (v/v: 4: 1). Vacuum drying at 60 deg.c to constant weight to obtain the product, namely nitrile butadiene rubber quaternary ammonium salt (CTBN-QAS).
The sodium modification process of montmorillonite is as follows: 50g of montmorillonite is added into 1000ml of deionized water to prepare a suspension, 50g of analytical pure grade NaCl is added, and the mixture is stirred for 10 hours at 80 ℃ and then filtered. Washing with 500ml of deionized water for 6 times, then washing with 50ml of absolute ethyl alcohol for 3-4 times, vacuum drying at room temperature for 24 hours, and storing in a dryer for later use.
1g of sodium-treated montmorillonite is added into 30ml of deionized water, stirred for 24 hours at 80 ℃, then 60ml of tetrahydrofuran is dripped into the mixture, and the mixture is continuously stirred for 2 hours to obtain suspension. And dissolving a certain amount of liquid polyurethane rubber quaternary ammonium salt in 20ml of tetrahydrofuran, dropwise adding the mixture into the suspension, and stirring the mixture for a certain time at the same temperature to obtain a crude product. The resulting mixture was added to a 15ml centrifuge tube, treated by high speed centrifugation (8000rap/min) for 15min, and the supernatant liquid was removed. In the same method, the montmorillonite is washed 3 times by a THF/deionized water mixed solvent (VTHF: Vwater: 7:3) to remove liquid rubber molecules which are not adsorbed on the montmorillonite, then washed twice by deionized water, and dried in vacuum at 50-60 ℃ to constant weight. Grinding and sieving with a 200-mesh sieve to obtain the HTPU-QAS-MMT nano composite material.
Mixing an organic-inorganic composite material modifier with epoxy resin and a curing agent (tetrahydrophthalic anhydride), and curing under proper process conditions (vacuum pumping at 120 ℃ for 15min, 140 ℃/20h) to obtain the high-toughness wear-resistant epoxy resin composite material.
Example 4
Hydroxyl-terminated polybutadiene liquid rubber (HTPB), hydroxyl-terminated isocyanate polyurethane liquid rubber (HTPU) and boron trifluoride diethyl etherate (BF 3. Et2O) are dissolved in a proper amount of xylene and then added into a three-neck flask, and Epichlorohydrin (ECH) is added dropwise when the temperature is raised to a set temperature. Controlling the dropping speed, and keeping the temperature to react for 1 h. The solvent and Epichlorohydrin (ECH) were removed by distillation under reduced pressure, and the residue was added slowly to a large amount of methanol with stirring to give a milky viscous substance which settled to the bottom. Removing the upper layer liquid, and continuously washing for 5-6 times by using methanol. Vacuum drying at 60 deg.C for 24h to obtain polybutadiene chloropropanol intermediate (HTPB-CDPP) and polyurethane chloropropanol intermediate (HTPU-CDPP).
HTPB-CDPP, HTPU-CDPP and 0.3% p-hydroxyanisole (based on the mass of HTPBE) are dissolved in a proper amount of xylene, the system is adjusted to be neutral by concentrated hydrochloric acid, after the temperature is raised to 60 ℃, 33% trimethylamine water solution (epoxy group: 33% trimethylamine water solution is 1:3.2, mol ratio) is added dropwise, and the reaction is carried out for 8 hours at 50 ℃. And treating the crude product to obtain polybutadiene macromolecular quaternary ammonium salt HTPB-QAS and liquid polyurethane quaternary ammonium salt (HTPU-QAS).
The sodium modification process of montmorillonite is as follows: 50g of montmorillonite is added into 1000ml of deionized water to prepare a suspension, 50g of analytical pure grade NaCl is added, and the mixture is stirred for 10 hours at 80 ℃ and then filtered. Washing with 500ml of deionized water for 6 times, then washing with 50ml of absolute ethyl alcohol for 3-4 times, vacuum drying at room temperature for 24 hours, and storing in a dryer for later use.
Adding 10g of sodium montmorillonite (Na-MMT) and 300ml of deionized water into a 1000ml three-neck flask, and stirring and reacting at 80 ℃ for 24 hours to prepare suspension; adding 600ml tetrahydrofuran drop by drop and continuing stirring for 2 h; dissolving CTBN quaternary ammonium salt with corresponding ratio of Na-MMT Cation Exchange Capacity (CEC) in 200ml of tetrahydrofuran, dropwise adding the solution into the suspension, and stirring and reacting for a certain time at the same temperature; pouring the prepared mixed solution into 15ml centrifuge tubes respectively, centrifuging for 10min at 9000rmp/min, and taking white precipitate at the bottom; the unreacted quaternary ammonium salt of HTPB was removed by two washes (8000rmp/min) with 70/30 of a THF/deionized water mixed solution (v/v) and then washed with deionized water at least three times in the same manner until no Cl-was detected with AgNO3 solution. And (3) drying at 80-90 ℃ in vacuum to constant weight, grinding, and sieving with a 200-mesh sieve to obtain the mixed quaternary ammonium salt modified MMT nano composite material.
Mixing an organic-inorganic composite material modifier with epoxy resin and a curing agent (4,4' -diaminodiphenylmethane), and curing under a proper process condition (vacuumizing at 120 ℃ for 15min, 100 ℃/2h +120 ℃/1.5h) to obtain the high-toughness wear-resistant epoxy resin composite material.
The impact strength data of the epoxy resin composite material obtained by curing the epoxy resin and the liquid rubber intercalation modified montmorillonite nanocomposite material with different proportions are shown in Table 1.
TABLE 1 impact Strength of high toughness, abrasion resistant epoxy resin composites
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-toughness wear-resistant epoxy resin composite material comprises the preparation of a nano material, and is characterized in that: the nano material is a liquid rubber intercalation modified montmorillonite nano composite material, and the preparation of the liquid rubber intercalation modified montmorillonite nano composite material comprises the following steps:
the method comprises the following steps: dissolving liquid rubber in proper amount of dimethylbenzene, adding the solution into a reaction vessel with a condensing device, stirring, introducing inert gas by taking hexamethylenetetramine as a catalyst and p-hydroxyanisole as a polymerization inhibitor; heating to 40-80 ℃, dropwise and slowly adding epoxy chloropropane from a dropping funnel, reacting for a certain time, and stopping; removing most of the solvent and unreacted epichlorohydrin by decompression; repeatedly extracting and cleaning the product liquid chloropropanol intermediate by using a large amount of methanol for many times; vacuum drying, and placing in a dryer for later use; the volume ratio of the liquid rubber to the dimethylbenzene is 1: 50-100;
step two: taking the liquid rubber chloropropanol intermediate prepared in the step one, dissolving a proper amount of Tetrahydrofuran (THF), and adding into a reaction vessel; slowly dripping a slightly excessive trimethylamine aqueous solution into the mixture by using a constant-pressure dropping funnel under stirring, and completely reacting at normal temperature; removing most of THF under reduced pressure to obtain brown viscous liquid; adding a large amount of methanol for purification and washing, and then washing at least twice by using a mixed solution of methanol and deionized water; vacuum drying to constant weight to obtain a product, namely liquid rubber quaternary ammonium salt; the mass ratio of the liquid rubber chloropropanol intermediate to the tetrahydrofuran is 1:2 to 1: 6;
step three: adding the montmorillonite subjected to sodium treatment into deionized water according to the mass ratio of 1:20-40, stirring for 18-36 hours at 70-90 ℃, then dropwise adding THF (tetrahydrofuran) accounting for 1-3 times of the volume of the deionized water, and continuously stirring to obtain a suspension; dissolving liquid rubber quaternary ammonium salt in Tetrahydrofuran (THF), dropwise adding the solution into the suspension, and stirring at the same temperature for a certain time to obtain a crude product; adding the obtained crude product into a centrifuge tube, carrying out high-speed centrifugation for 5-30min, and removing the upper layer liquid; washing the mixture for more than 1 time by using a mixed solvent of THF and deionized water, washing the mixture by using deionized water, and drying the mixture in vacuum at 50-60 ℃ to constant weight; grinding and sieving to obtain liquid rubber intercalation modified montmorillonite nanocomposite;
step four, mixing the epoxy resin and the obtained liquid rubber intercalation modified montmorillonite nano composite material according to the mass ratio of 100: 3-30, putting the mixture into a reaction container, stirring the mixture at the temperature of 50-70 ℃ to fully mix the mixture, adding a curing agent, epoxy resin: the mass ratio of the curing agent is 100: 10-40, uniformly stirring, vacuumizing at 30-100 ℃, removing bubbles, and curing to obtain the epoxy resin composite material.
2. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the liquid rubber is selected from: carboxyl-terminated nitrile rubber (CTBN), hydroxyl-terminated nitrile rubber (HTBN), amino-terminated nitrile rubber (ATBN), epoxy-terminated nitrile rubber (ETBN), vinyl-terminated nitrile rubber (VTBN), hydroxyl-terminated polybutadiene rubber (HTPB), amino-terminated polybutadiene rubber (ATPB), Polyurethane (PU) liquid rubber and acrylate liquid (ACM) rubber.
3. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the vacuum drying in the step one is vacuum drying for 12 to 36 hours at the temperature of between 40 and 60 ℃; step one, the inert gas is selected from nitrogen and argon.
4. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the reaction time at normal temperature in the second step is 12-36 h;
the concentration of the trimethylamine aqueous solution in the second step is 20 to 50 weight percent;
and step two, the volume of the methanol is 2-5 times of that of the brown viscous liquid.
5. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the washing times of the dimethanol in the step are 4-7 times;
in the mixed solution of the methanol and the deionized water in the step two, the volume ratio of the methanol to the deionized water is 3-5: 1;
the temperature of the vacuum drying in the second step is 50-70 ℃.
6. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: step three, the stirring time is 1-5 hours; the mass ratio of the liquid rubber quaternary ammonium salt to the tetrahydrofuran in the step three is 1: 5-20;
in the step three, the volume ratio of THF to deionized water in the mixed solvent of THF and deionized water is 7: 1-4;
step three, the centrifugal rotating speed is 6000-;
washing the three-way THF and deionized water mixed solvent for more than three times; step three, the deionized water washing is washing more than twice.
7. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the trimethylamine aqueous solution in the second step also contains CH3Cl, said CH3The molar ratio of Cl to trimethylamine is =1: 1-1.5.
8. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: and step four, selecting one or two of a modified amine curing agent, a low-molecular polyamide curing agent, an imidazole curing agent, a phenolic aldehyde amine curing agent and an anhydride curing agent as the curing agent.
9. The preparation method of the high-toughness wear-resistant epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: and step four, stirring at 50-70 ℃ to fully mix, and then adding an accelerator accounting for 1-5% of the resin.
10. The high-toughness wear-resistant epoxy resin composite material prepared by the preparation method of the high-toughness wear-resistant epoxy resin composite material disclosed by claim 1 is characterized in that: epoxy resin and the obtained liquid rubber intercalation modified montmorillonite nano composite material are mixed according to the mass ratio of 100: 3-30, putting the mixture into a reaction container, stirring the mixture at the temperature of 50-70 ℃ to fully mix the mixture, adding a curing agent, epoxy resin: the mass ratio of the curing agent is 100: 10-40, uniformly stirring, vacuumizing at 30-100 ℃, removing bubbles, and curing to obtain the epoxy resin composite material; the impact strength of the epoxy resin composite material is 19-36KJ/m2(ii) a The abrasion resistance is improved by more than 30 percent.
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