CN111117139B - Toughening modified polyacrylonitrile material - Google Patents
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- CN111117139B CN111117139B CN201911378384.XA CN201911378384A CN111117139B CN 111117139 B CN111117139 B CN 111117139B CN 201911378384 A CN201911378384 A CN 201911378384A CN 111117139 B CN111117139 B CN 111117139B
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a toughened modified polyacrylonitrile material, which is prepared by taking modified polyacrylonitrile as a base material and adding auxiliary agents such as a toughening agent, a dispersing agent and the like; wherein the modified polyacrylonitrile is prepared by modifying polyacrylonitrile as a raw material by using a modifying agent and a crosslinking agent; the modifier is prepared by taking polyethyleneimine as a base material and simultaneously adding 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol for reaction; the cross-linking agent is 4-allyl-1, 6-heptadiene-4-alcohol; the toughening agent is selected from a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate; the finally prepared toughened modified polyacrylonitrile material has good toughness, and has high tensile strength, bending strength and impact strength; meanwhile, the paint also has strong ultraviolet resistance, and the toughness is still good after long-time ultraviolet irradiation.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a toughened and modified polyacrylonitrile material.
Background
Polyacrylonitrile is a high molecular compound obtained by free radical polymerization of acrylonitrile monomer, and is a white or slightly yellowish opaque powder with a relative density of 1.12 and a glass transition temperature of about 90 ℃. Polyacrylonitrile is dissolved in polar organic solvents such as dimethylformamide, dimethyl sulfoxide, sulfolane, and ethylene nitrate. The polyacrylonitrile has better weather resistance and sun resistance, and can still keep 77 percent of the original strength after being placed outdoors for 18 months; in addition, it is resistant to chemical agents, in particular inorganic acids, bleaching powders, hydrogen peroxide and organic agents in general; therefore, polyacrylonitrile is mainly applied to the fields of synthetic fibers, medical appliances, sewage treatment and the like, and is popular with consumers. However, the toughness of polyacrylonitrile is not high, and the specific expression is that the tensile strength and the bending strength of polyacrylonitrile are poor, which greatly limits the development of polyacrylonitrile materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a toughened and modified polyacrylonitrile material which has better toughness and higher tensile strength and bending strength.
In order to realize the purpose, the invention provides the following technical scheme: the toughened modified polyacrylonitrile material comprises the following substances in parts by weight:
100 parts of modified polyacrylonitrile;
2 parts of a toughening agent;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler.
As a further improvement of the invention, the modacrylic comprises the following substances in parts by weight:
4-6 parts of polyacrylonitrile;
4-6 parts of a modifier;
1-2 parts of a crosslinking agent;
the modifier is a mixture of polyethyleneimine, 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol, and the mass portion of the modifier is 4:1: 1.
As a further improvement of the invention, the preparation method of the modifier comprises the following steps:
s1: preparing raw materials according to the set weight part, adding polyethyleneimine and 4-acyl chloride phthalic anhydride into a reaction vessel filled with acetone, and stirring and mixing to form a first mixture; then, reacting at the temperature of 60-80 ℃ for 3-5 hours;
s2: then adding (E) -4,4' - (ethylene-1, 2-diyl) diphenol into the first mixture, and stirring and mixing; after being uniformly mixed, the mixture continues to react at the temperature of 60-80 ℃ for 8-10 hours; after the reaction is finished, filtering, purifying and drying to obtain the modifier.
As a further improvement of the invention, the crosslinking agent is 4-allyl-1, 6-heptadien-4-ol.
As a further improvement of the invention, the preparation method of the modified polyacrylonitrile comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight part, adding polyacrylonitrile, a catalyst and an initiator into a reaction container filled with a solvent, stirring and mixing, and forming a second mixture after mixing uniformly;
step two: adding the modifier and the cross-linking agent into the second mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 120 ℃ for 6-10 h; after the reaction is finished, filtering, purifying and drying to obtain the modified polyacrylonitrile.
As a further improvement of the invention, the catalyst is palladium acetate; the initiator is benzoyl peroxide; the solvent is N, N-dimethylformamide.
As a further improvement of the invention, the toughening agent is a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazol-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate in a mass ratio of 1:1: 2;
the structural formula of the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine is shown in the specification
The structural formula of the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is shown in the specification
The structural formula of the benzyl methacrylate is shown in the specification
As a further improvement of the invention, the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine is prepared by adding (E) -1- (2-nitrophenyl) -3, 3-bis (trifluoromethyl) triazol-1-ene, triphenylphosphine and di-tert-butyl peroxide into a reaction vessel filled with solvent dioxane, and stirring and mixing; after being mixed evenly, the mixture is reacted at the temperature of 100-160 ℃, and the reaction time is 8-10 h; after the reaction is finished, filtering, purifying and drying to obtain N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine;
which is of the formula
As a further improvement of the present invention, the dispersant is hydroxyethyl cellulose; the lubricant is N, N' -ethylene bis stearamide; the filler is zinc borate.
As a further improvement of the invention, the preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding the modified polyacrylonitrile, the toughening agent, the dispersing agent, the lubricating agent and the filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
The invention has the beneficial effects that: the modified polyacrylonitrile fiber is prepared by taking modified polyacrylonitrile as a base material and adding auxiliary agents such as a flexibilizer, a dispersing agent and the like; the modified polyacrylonitrile is prepared by modifying polyacrylonitrile serving as a raw material by using a modifying agent and a crosslinking agent; as one of creativity of the invention, the modifier is prepared by taking polyethyleneimine as a base material and simultaneously adding 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol for reaction; the polyethyleneimine is a polymer with high reaction activity and belongs to macromolecular substances; the 4-acyl chloride phthalic anhydride contains acyl chloride groups which are very active and can fully react with other substances, so that the reaction is more complete; meanwhile, the 4-acyl chloride phthalic anhydride contains phenyl which can improve the rigidity of the product; (E) the 4,4' - (ethylene-1, 2-diyl) diphenol contains active groups such as hydroxyl and carbon-carbon double bond, and is easy to polymerize with other substances or with the diphenol; and also phenyl, thereby further improving the rigidity of the product; the modifier is prepared by the polymerization reaction of three substances of polyethyleneimine, 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol; on one hand, the modifier has larger molecular weight and better compatibility with polyacrylonitrile, and meanwhile, as the chain segment has rigid groups such as phenyl and the like, the modifier has larger tensile strength and bending strength; the cross-linking agent selects 4-allyl-1, 6-heptadiene-4-alcohol, and the 4-allyl-1, 6-heptadiene-4-alcohol contains carbon-carbon double bonds and hydroxyl groups which are active groups, so that the cross-linking agent further reacts with other substances, and the toughness of the product is improved; when preparing the modified polyacrylonitrile, benzoyl peroxide is used as a reaction, palladium acetate is used as a catalyst, N-dimethylformamide is used as a solvent, the polyacrylonitrile is modified by a modifier and a cross-linking agent, and the reaction is carried out for 6 to 10 hours at the temperature of 120 ℃, so that the modified polyacrylonitrile is prepared, and has better toughness, higher tensile strength, higher bending strength and higher impact strength.
In order to further improve the toughness of the modified polyacrylonitrile, a toughening agent is added, and a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate is selected on the toughening agent; the benzyl methacrylate contains functional groups such as carbon-carbon double bonds, phenyl and ester groups, and the phenyl is introduced into a chain segment through the polymerization reaction with the modified polyacrylonitrile, and the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane contains groups such as epoxy and silicon, so that the modified polyacrylonitrile and the toughening agent have good compatibility, and the toughness of the modified polyacrylonitrile can be further improved; the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine is prepared by directly reacting (E) -1- (2-nitrophenyl) -3, 3-bis (trifluoromethyl) triazole-1-ene serving as a reaction substrate in one step by using di-tert-butyl peroxide as an initiator and triphenylphosphine as a catalyst, and no dangerous substances such as sodium azide and the like are used, so that the reaction is safe and is beneficial to industrial production; the addition of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine can greatly improve the ultraviolet resistance of the modified polyacrylonitrile; under the synergistic effect of the substances, the toughness of the modified polyacrylonitrile can be further improved, and the tensile strength, the bending strength and the impact strength of the modified polyacrylonitrile are all higher; meanwhile, the paint also has strong ultraviolet resistance, and after long-time ultraviolet irradiation, the paint still has good toughness, can meet the market demand, and greatly expands the application range.
Detailed Description
Example 1 (preparation of modifier)
The modifier comprises the following substances in parts by weight:
4 parts of polyethyleneimine;
1 part of 4-acyl chloride phthalic anhydride;
(E) 1 part of 4,4' - (ethylene-1, 2-diyl) diphenol;
the structural formula of the 4-acyl chloride phthalic anhydride is shown in the specification
The structural formula of the (E) -4,4' - (ethylene-1, 2-diyl) diphenol is shown in the specification
The preparation method of the modifier comprises the following steps:
s1: preparing raw materials according to the set weight part, adding polyethyleneimine and 4-acyl chloride phthalic anhydride into a reaction vessel filled with acetone, and stirring and mixing to form a first mixture; then, the reaction is carried out at the temperature of 70 ℃ for 4 hours;
s2: then adding (E) -4,4' - (ethylene-1, 2-diyl) diphenol into the first mixture, and stirring and mixing; after being uniformly mixed, the mixture continues to react at the temperature of 70 ℃ for 9 hours; after the reaction is finished, filtering, purifying and drying to obtain the modifier.
Example 2 (preparation of modacrylic)
The modified polyacrylonitrile comprises the following substances in parts by weight:
5 parts of polyacrylonitrile;
5 parts of a modifier;
1 part of a crosslinking agent;
the modifier was prepared from example 1
The cross-linking agent is 4-allyl-1, 6-heptadiene-4-alcohol;
the preparation method of the modified polyacrylonitrile comprises the following steps:
the method comprises the following steps: adding 5g of polyacrylonitrile, 0.1g of catalyst palladium acetate and 0.3g of benzoyl peroxide initiator into a reaction vessel filled with 100ml of solvent N, N-dimethylformamide, stirring and mixing, and forming a second mixture after mixing uniformly;
step two: adding 5g of modifier and 1g of cross-linking agent into the second mixture, stirring and mixing, reacting at 120 ℃ after uniformly mixing, wherein the reaction time is 8 h; after the reaction is finished, filtering, purifying and drying to obtain the modified polyacrylonitrile.
Example 3 (preparation of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazol-2-amine)
The preparation method of the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine comprises the steps of adding 0.001mol of (E) -1- (2-nitrophenyl) -3, 3-bis (trifluoromethyl) triazole-1-ene, 0.003mol of triphenylphosphine and 0.001mol of di-tert-butyl peroxide into a reaction vessel filled with 10ml of solvent dioxane, and stirring and mixing; after being uniformly mixed, the mixture is reacted at the temperature of 130 ℃ for 9 hours; after the reaction is finished, filtering, purifying and drying to prepare N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine;
which is of the formula
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.92(s,2H),7.36(s,2H).
13C NMR(CDCl3,125MHz,ppm):δ141.6,133.7,125.9,116.2.
example 4 preparation of toughened modified Polyacrylonitrile Material
The toughened modified polyacrylonitrile material comprises the following substances in parts by weight:
100 parts of modified polyacrylonitrile;
2 parts of a toughening agent;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler;
the modacrylic was prepared from example 2;
the toughening agent is a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate in a mass ratio of 1:1: 2;
the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazol-2-amine was prepared from example 3 and had the structural formula
The structural formula of the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is shown in the specification
The structural formula of the benzyl methacrylate is shown in the specification
The dispersant is hydroxyethyl cellulose;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding the modified polyacrylonitrile, the toughening agent, the dispersing agent, the lubricating agent and the filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
Comparative example 1
The toughened modified polyacrylonitrile material comprises the following substances in parts by weight:
100 parts of polyacrylonitrile;
2 parts of a toughening agent;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler;
the toughening agent is a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate in a mass ratio of 1:1: 2;
wherein N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazol-2-amine was prepared from example 3;
the dispersant is hydroxyethyl cellulose;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding polyacrylonitrile, a toughening agent, a dispersing agent, a lubricating agent and a filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
Comparative example 2
The toughening modified polyacrylonitrile material comprises the following substances in parts by weight:
50 parts of polyacrylonitrile;
50 parts of polyethyleneimine;
2 parts of a toughening agent;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler;
the toughening agent is a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate in a mass ratio of 1:1: 2;
wherein N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazol-2-amine was prepared from example 3;
the dispersant is hydroxyethyl cellulose;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding polyacrylonitrile, polyethyleneimine, a toughening agent, a dispersing agent, a lubricating agent and a filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
Comparative example 3
The toughened modified polyacrylonitrile material comprises the following substances in parts by weight:
100 parts of modified polyacrylonitrile;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler;
the modacrylic was prepared from example 2;
the dispersant is hydroxyethyl cellulose;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
The preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding polyacrylonitrile, a dispersing agent, a lubricating agent and a filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
The samples obtained in example 4 and comparative examples 1 to 3 were subjected to a performance test;
tensile strength measurements were carried out on the test specimens according to standard ISO 527-2;
the test piece is subjected to bending strength measurement according to the standard ISO 178-2010;
the impact strength of the test sample is measured according to the standard ISO 178;
as can be seen from the table above, the polyacrylonitrile material prepared by the invention has better toughness, and has higher tensile strength, bending strength and impact strength, and can meet the market demand, so that the application range of the polyacrylonitrile material is further expanded.
The sample prepared in example 4 was irradiated under an ultraviolet lamp for 48 hours, and then various mechanical property tests were performed.
From the above table, after the long-term irradiation of ultraviolet rays, the polyacrylonitrile material prepared by the invention still has good toughness, and the tensile strength, the bending strength and the impact strength of the polyacrylonitrile material are still large.
The toughening modified polyacrylonitrile material is prepared by taking modified polyacrylonitrile as a base material and adding auxiliary agents such as a toughening agent, a dispersing agent and the like; the modified polyacrylonitrile is prepared by modifying polyacrylonitrile serving as a raw material by using a modifying agent and a crosslinking agent; as one of creativity of the invention, the modifier is prepared by taking polyethyleneimine as a base material and simultaneously adding 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol for reaction; the polyethyleneimine is a polymer with high reaction activity and belongs to macromolecular substances; the 4-acyl chloride phthalic anhydride contains acyl chloride groups which are very active and can fully react with other substances, so that the reaction is more complete; meanwhile, the 4-acyl chloride phthalic anhydride contains phenyl which can improve the rigidity of the product; (E) the 4,4' - (ethylene-1, 2-diyl) diphenol contains active groups such as hydroxyl and carbon-carbon double bond, and is easy to polymerize with other substances or with the diphenol; and also phenyl, thereby further improving the rigidity of the product; the modifier is prepared by the polymerization reaction of three substances of polyethyleneimine, 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol; on one hand, the modifier has larger molecular weight and better compatibility with polyacrylonitrile, and meanwhile, as the chain segment has rigid groups such as phenyl and the like, the modifier has larger tensile strength and bending strength; the cross-linking agent selects 4-allyl-1, 6-heptadiene-4-alcohol, and the 4-allyl-1, 6-heptadiene-4-alcohol contains carbon-carbon double bonds and hydroxyl groups which are active groups, so that the cross-linking agent further reacts with other substances, and the toughness of the product is improved; when preparing the modified polyacrylonitrile, benzoyl peroxide is used as a reaction, palladium acetate is used as a catalyst, N-dimethylformamide is used as a solvent, the polyacrylonitrile is modified by a modifier and a cross-linking agent, and the reaction is carried out for 6 to 10 hours at the temperature of 120 ℃, so that the modified polyacrylonitrile is prepared, and has better toughness, higher tensile strength, higher bending strength and higher impact strength.
In order to further improve the toughness of the modified polyacrylonitrile, a toughening agent is added, and a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate is selected on the toughening agent; the benzyl methacrylate contains functional groups such as carbon-carbon double bonds, phenyl and ester groups, and the phenyl is introduced into a chain segment through the polymerization reaction with the modified polyacrylonitrile, and the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane contains groups such as epoxy and silicon, so that the modified polyacrylonitrile and the toughening agent have good compatibility, and the toughness of the modified polyacrylonitrile can be further improved; the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine is prepared by directly reacting (E) -1- (2-nitrophenyl) -3, 3-bis (trifluoromethyl) triazole-1-ene serving as a reaction substrate in one step by using di-tert-butyl peroxide as an initiator and triphenylphosphine as a catalyst, and no dangerous substances such as sodium azide and the like are used, so that the reaction is safe and is beneficial to industrial production; the addition of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine can greatly improve the ultraviolet resistance of the modified polyacrylonitrile; under the synergistic effect of the substances, the toughness of the modified polyacrylonitrile can be further improved, and the tensile strength, the bending strength and the impact strength of the modified polyacrylonitrile are all higher; meanwhile, the paint also has strong ultraviolet resistance, and after long-time ultraviolet irradiation, the paint still has good toughness, can meet the market demand, and greatly expands the application range.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, and all technical solutions that belong to the idea of the present invention belong to the scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. A toughened and modified polyacrylonitrile material is characterized in that: the composition comprises the following substances in parts by weight:
100 parts of modified polyacrylonitrile;
2 parts of a toughening agent;
2 parts of a dispersing agent;
1 part of a lubricant;
4 parts of a filler;
the modified polyacrylonitrile comprises the following substances in parts by weight:
4-6 parts of polyacrylonitrile;
4-6 parts of a modifier;
1-2 parts of a crosslinking agent;
the modifier is a mixture of polyethyleneimine, 4-acyl chloride phthalic anhydride and (E) -4,4' - (ethylene-1, 2-diyl) diphenol, and the mass part of the modifier is 4: 1.
2. The toughened and modified polyacrylonitrile material as claimed in claim 1, wherein: the preparation method of the modifier comprises the following steps:
s1: preparing raw materials according to the set weight part, adding polyethyleneimine and 4-acyl chloride phthalic anhydride into a reaction vessel filled with acetone, and stirring and mixing to form a first mixture; then, reacting at the temperature of 60-80 ℃ for 3-5 hours;
s2: then adding (E) -4,4' - (ethylene-1, 2-diyl) diphenol into the first mixture, and stirring and mixing; after being uniformly mixed, the mixture continues to react at the temperature of 60-80 ℃ for 8-10 hours; after the reaction is finished, filtering, purifying and drying to obtain the modifier.
3. The toughened and modified polyacrylonitrile material as claimed in claim 2, wherein: the cross-linking agent is 4-allyl-1, 6-heptadiene-4-alcohol.
4. The toughened and modified polyacrylonitrile material as claimed in claim 3, wherein: the preparation method of the modified polyacrylonitrile comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight part, adding polyacrylonitrile, a catalyst and an initiator into a reaction container filled with a solvent, stirring and mixing, and forming a second mixture after uniformly mixing;
step two: adding the modifier and the cross-linking agent into the second mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 120 ℃ for 6-10 h; after the reaction is finished, filtering, purifying and drying to obtain the modified polyacrylonitrile.
5. The toughened and modified polyacrylonitrile material as claimed in claim 4, wherein: the catalyst is palladium acetate;
the initiator is benzoyl peroxide;
the solvent is N, N-dimethylformamide.
6. The toughened and modified polyacrylonitrile material as claimed in claim 5, wherein: the toughening agent is a mixture of N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and benzyl methacrylate in a mass ratio of 1: 2;
the structural formula of the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine is shown in the specification
The structural formula of the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is shown in the specification
The structural formula of the benzyl methacrylate is shown in the specification
7. The toughened and modified polyacrylonitrile material of claim 6, wherein: the preparation method of the N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine comprises the steps of adding (E) -1- (2-nitrophenyl) -3, 3-bis (trifluoromethyl) triazole-1-ene, triphenylphosphine and di-tert-butyl peroxide into a reaction vessel filled with solvent dioxane, and stirring and mixing; after being mixed evenly, the mixture is reacted at the temperature of 100-160 ℃, and the reaction time is 8-10 h; after the reaction is finished, filtering, purifying and drying to obtain N, N-bis (trifluoromethyl) -2H-benzo [ d ] [1,2,3] triazole-2-amine;
which is of the formula
8. The toughened and modified polyacrylonitrile material as claimed in claim 7, wherein:
the dispersant is hydroxyethyl cellulose;
the lubricant is N, N' -ethylene bis stearamide;
the filler is zinc borate.
9. The toughened and modified polyacrylonitrile material of claim 8, wherein: the preparation method of the toughened and modified polyacrylonitrile material comprises the following steps:
the method comprises the following steps: preparing raw materials according to a set weight percentage, adding the modified polyacrylonitrile, the toughening agent, the dispersing agent, the lubricating agent and the filler into a mixer, stirring and mixing to form a mixed material; wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 30-40min, and the stirring speed is 400 rad/min;
step two: putting the mixed material into a double-screw extruder for extrusion molding to prepare a toughened and modified polyacrylonitrile material; wherein the temperature of each section is 160-170 ℃ in the first section, 170-180 ℃ in the second section, 180-200 ℃ in the third section, 200-220 ℃ in the fourth section, 220-230 ℃ in the fifth section and 240 ℃ in the sixth section.
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