CN107878671B - High-strength safe canoe for drifting - Google Patents
High-strength safe canoe for drifting Download PDFInfo
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- CN107878671B CN107878671B CN201711090517.4A CN201711090517A CN107878671B CN 107878671 B CN107878671 B CN 107878671B CN 201711090517 A CN201711090517 A CN 201711090517A CN 107878671 B CN107878671 B CN 107878671B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B3/00—Hulls characterised by their structure or component parts
- B63B3/14—Hull parts
- B63B3/16—Shells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention discloses a high-strength safe kayak for drifting, which comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a flexible high polymer material. The high-strength safe flow-drifting kayak has the advantages of excellent mechanical property, light weight, easy assembly, corrosion resistance, aging resistance, simple production process and long service life, and can be used at a lower temperature.
Description
Technical Field
The invention relates to the technical field of kayaks, in particular to a kayak for high-strength and safe drift.
Background
Compared with rigid materials, the flexible high polymer material has larger deformability, and is widely applied to the fields of raincoats, canoes, tents, guy cloths, soft water storage containers, soft oil storage containers and the like.
The invention patent with application number 201310330952.5 discloses a foot-operated kayak, which comprises a hull and is characterized in that: the middle part of the boat body is provided with a pedal, the pedal is connected with a pedal type transmission device, the pedal type transmission device is provided with a first gear, a first gear shaft, a second gear and a second gear shaft, the first gear is connected with the second gear, and the included angle between the first gear shaft and the second gear shaft is 90 degrees; the first gear shaft is connected with the pedal, and the second gear shaft is connected with the fins extending outwards from the bottom of the kayak.
The invention patent with application number 201310330763.8 discloses a tail-split kayak which runs more stably and safely, and comprises a hull, wherein the hull comprises a hull tail part, a hull head part and a hull middle part, and the tail-split kayak is characterized in that: the tail part of the boat body is rotationally connected with the two forked parts, and the included angle between the two forked parts is 0-160 degrees.
In the prior published patents, most of the efforts are focused on improving the structure of the kayak, so as to improve the service performance of the kayak, and less improve the adopted materials of the kayak. The flexible high polymer material has the elasticity of rubber, and also has the rigidity and the easy processing property of thermoplastic plastics.
Disclosure of Invention
The purpose of the invention is realized by the following technical scheme:
the invention aims to solve the technical problem of providing a high-strength safe kayak for drifting.
The invention provides a high-strength safe kayak for drifting, which comprises a kayak shell, a seat, a nylon rope, nuts, bolts and rubber gaskets, wherein the kayak shell is prepared from a flexible high polymer material.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
Preferably, the flexible polymer material is a polyester elastomer, a cross-linked polyester elastomer or a reinforcing, toughening and modifying cross-linked polyester elastomer.
The preparation process of the polyester elastomer comprises the following steps: diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ for 5-7 hours at the rotating speed of 190-220 r/min, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of monomer A, mixing, reacting for 6-7 hours at the temperature of 180 ℃ under the atmosphere of nitrogen, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; and drying the reactant for 10-12 hours at the temperature of 50-60 ℃ and the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer.
The preparation process of the crosslinked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ for 5-7 hours at the rotating speed of 190-220 r/min, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of monomer A, mixing, reacting for 6-7 hours at the temperature of 180 ℃ under the atmosphere of nitrogen, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; drying the reactant for 10-12 hours at 50-60 ℃ and under the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: (0.02-0.03) mixing, and banburying for 10-15 minutes by adopting a torque rheometer under the conditions that the banburying temperature is 70-80 ℃ and the screw rotating speed is 100-; and (3) carrying out reaction on the mixture obtained by banburying at 50-55 ℃ under the condition that the vacuum degree is 0.07-0.08MPa for 40-48 hours to obtain the crosslinked polyester elastomer.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ for 5-7 hours at the rotating speed of 190-220 r/min, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of monomer A, mixing, reacting for 6-7 hours at the temperature of 180 ℃ under the atmosphere of nitrogen, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; drying the reactant for 10-12 hours at 50-60 ℃ and under the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: (0.02-0.03) mixing, and banburying for 10-15 minutes by adopting a torque rheometer under the conditions that the banburying temperature is 70-80 ℃ and the screw rotating speed is 100-; the mixture obtained by banburying reacts for 40 to 48 hours at the temperature of between 50 and 55 ℃ and under the vacuum degree of between 0.07 and 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the modifier at 70-80 ℃ for 4-5 hours, and mixing the modifier with the cross-linked polyester elastomer according to a mass ratio of 1: (0.03-0.1) uniformly mixing in a high-speed mixer, and extruding and granulating by a screw extruder to obtain the high-performance composite material; wherein the temperature of each zone of the extruder is: 190 ℃ at 180 ℃, 210 ℃ at 200 ℃, and 190 ℃ at 180 ℃.
In the preparation process of the reinforced and toughened modified polyester elastomer, the modifier is one or a composition of more of a flexible graphite composite material, carboxyl butyronitrile rubber powder and amidated multi-walled carbon nanotubes. Preferably, the modifier is a composition of carboxyl butyronitrile rubber powder and amidated multi-walled carbon nanotubes, wherein the mass ratio of the carboxyl butyronitrile rubber powder to the amidated multi-walled carbon nanotubes is 1: (2-3).
The preparation process of the flexible graphite composite material comprises the following steps: mixing the expanded carbon fiber, the expandable graphite and ethanol in a ratio of 1: (50-80) (g/g/mL), ultrasonically dispersing for 20-30 minutes under the condition of ultrasonic power of 300-; and (3) expanding the bottom solid in a high-temperature expansion furnace at the temperature of 900-1000 ℃ for 10-15 seconds to obtain the flexible graphite composite material.
In the prior art, the chemical modification of the carbon nanotubes is generally to improve the dispersibility of the carbon nanotubes in a matrix, so as to improve the performance of the composite material. According to the invention, the flexible amine is grafted on the surface of the carbon nano tube by a chemical modification method, so that the effect of improving the dispersibility is achieved, and the interface state is improved and the effect of enhancing and toughening is achieved by the participation of the flexible amine in the reaction.
The preparation process of the amidated multi-walled carbon nanotube comprises the following steps: drying the multi-wall carbon nano-tube at the temperature of 100-120 ℃ for 3-4 hours; mixing the dried multi-walled carbon nano-tube with 95-98% of sulfuric acid in a solid-to-liquid ratio of 1 (70-75) (g/mL), and stirring at the temperature of 23-25 ℃ at the rotating speed of 200-; then adding nitric acid with the mass fraction of 60-65%, wherein the solid-to-liquid ratio of the carbon nano tube to the nitric acid is 1 (70-75) (g/mL), mixing, and reacting at the temperature of 130-; pouring the reaction liquid into deionized water, wherein the volume ratio of the reaction liquid to the deionized water is 1: (12-14), standing at 23-25 ℃ for 8-10 hours, discarding the supernatant, and keeping the bottom precipitate; washing the bottom precipitate with deionized water and tetrahydrofuran in sequence, wherein the ratio of the bottom precipitate to the deionized water to the tetrahydrofuran is 1: (50-80): 30(g/g/mL), drying for 12-16 hours at the temperature of 60-80 ℃ and the vacuum degree of 0.07-0.08MPa to obtain the carboxylated multi-wall carbon nano tube; mixing the carboxylated multi-wall carbon nano-tube with thionyl chloride and dimethylformamide by the ratio of 1 (100- & lt130) & gt to 10(g/g/mL), and reacting for 20-24 hours at the temperature of 60-70 ℃; after the reaction is finished, filtering the reaction solution by 80-100 meshes of filter cloth, and collecting a filter cake; after washing the filter cake with tetrahydrofuran, the ratio of the filter cake to tetrahydrofuran was 1: (40-70) (g/mL), drying for 1-3 hours at 20-25 ℃ and under the vacuum degree of 0.06-0.07MPa to obtain the multi-wall carbon nano-tube subjected to acyl chlorination; mixing acyl chlorinated multi-walled carbon nanotubes with a curing agent and dimethylformamide according to a ratio of 1:100 (10-15) (g/mL/mL), carrying out ultrasonic dispersion for 30-40 minutes under the condition of ultrasonic power of 300-400W, and then carrying out reaction for 60-72 hours at 110-120 ℃ under the condition of nitrogen; after the reaction is finished, filtering the reaction solution by using 80-100 mesh filter cloth, and collecting solids; after washing the solid with tetrahydrofuran, the ratio of the solid to tetrahydrofuran was 1: (60-80) (g/mL), drying for 12-16 hours at the temperature of 60-70 ℃ and the vacuum degree of 0.07-0.08MPa to obtain the amidated multi-wall carbon nano-tube.
The high-strength safe flow-drifting kayak has the advantages of excellent mechanical property, light weight, easy assembly, corrosion resistance, aging resistance, simple production process and long service life, and can be used at a lower temperature.
The second technical problem to be solved by the present invention is to provide a crosslinked polyester elastomer.
The preparation process of the crosslinked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ for 5-7 hours at the rotating speed of 190-220 r/min, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of monomer A, mixing, reacting for 6-7 hours at the temperature of 180 ℃ under the atmosphere of nitrogen, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; drying the reactant for 10-12 hours at 50-60 ℃ and under the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: (0.02-0.03) mixing, and banburying for 10-15 minutes by adopting a torque rheometer under the conditions that the banburying temperature is 70-80 ℃ and the screw rotating speed is 100-; and (3) carrying out reaction on the mixture obtained by banburying at 50-55 ℃ under the condition that the vacuum degree is 0.07-0.08MPa for 40-48 hours to obtain the crosslinked polyester elastomer.
The invention also provides a cross-linked polyester elastomer.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ for 5-7 hours at the rotating speed of 190-220 r/min, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of monomer A, mixing, reacting for 6-7 hours at the temperature of 180 ℃ under the atmosphere of nitrogen, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; drying the reactant for 10-12 hours at 50-60 ℃ and under the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: (0.02-0.03) mixing, and banburying for 10-15 minutes by adopting a torque rheometer under the conditions that the banburying temperature is 70-80 ℃ and the screw rotating speed is 100-; the mixture obtained by banburying reacts for 40 to 48 hours at the temperature of between 50 and 55 ℃ and under the vacuum degree of between 0.07 and 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the modifier at 70-80 ℃ for 4-5 hours, and mixing the modifier with the cross-linked polyester elastomer according to a mass ratio of 1: (0.03-0.1) uniformly mixing in a high-speed mixer, and extruding and granulating by a screw extruder to obtain the high-performance composite material; wherein the temperature of each zone of the extruder is: 190 ℃ at 180 ℃, 210 ℃ at 200 ℃, and 190 ℃ at 180 ℃.
In the preparation process of the reinforced and toughened modified polyester elastomer, the modifier is one or a composition of more of a flexible graphite composite material, carboxyl butyronitrile rubber powder and amidated multi-walled carbon nanotubes. Preferably, the modifier is a composition of carboxyl butyronitrile rubber powder and amidated multi-walled carbon nanotubes, wherein the mass ratio of the carboxyl butyronitrile rubber powder to the amidated multi-walled carbon nanotubes is 1: (2-3).
The preparation process of the flexible graphite composite material comprises the following steps: mixing the expanded carbon fiber, the expandable graphite and ethanol in a ratio of 1: (50-80) (g/g/mL), ultrasonically dispersing for 20-30 minutes under the condition of ultrasonic power of 300-; and (3) expanding the bottom solid in a high-temperature expansion furnace at the temperature of 900-1000 ℃ for 10-15 seconds to obtain the flexible graphite composite material.
The preparation process of the amidated multi-walled carbon nanotube comprises the following steps: drying the multi-wall carbon nano-tube at the temperature of 100-120 ℃ for 3-4 hours; mixing the dried multi-walled carbon nano-tube with 95-98% of sulfuric acid in a solid-to-liquid ratio of 1 (70-75) (g/mL), and stirring at the temperature of 23-25 ℃ at the rotating speed of 200-; then adding nitric acid with the mass fraction of 60-65%, wherein the solid-to-liquid ratio of the carbon nano tube to the nitric acid is 1 (70-75) (g/mL), mixing, and reacting at the temperature of 130-; pouring the reaction liquid into deionized water, wherein the volume ratio of the reaction liquid to the deionized water is 1: (12-14), standing at 23-25 ℃ for 8-10 hours, discarding the supernatant, and keeping the bottom precipitate; washing the bottom precipitate with deionized water and tetrahydrofuran in sequence, wherein the ratio of the bottom precipitate to the deionized water to the tetrahydrofuran is 1: (50-80): 30(g/g/mL), drying for 12-16 hours at the temperature of 60-80 ℃ and the vacuum degree of 0.07-0.08MPa to obtain the carboxylated multi-wall carbon nano tube; mixing the carboxylated multi-wall carbon nano-tube with thionyl chloride and dimethylformamide by the ratio of 1 (100- & lt130) & gt to 10(g/g/mL), and reacting for 20-24 hours at the temperature of 60-70 ℃; after the reaction is finished, filtering the reaction solution by 80-100 meshes of filter cloth, and collecting a filter cake; after washing the filter cake with tetrahydrofuran, the ratio of the filter cake to tetrahydrofuran was 1: (40-70) (g/mL), drying for 1-3 hours at 20-25 ℃ and under the vacuum degree of 0.06-0.07MPa to obtain the multi-wall carbon nano-tube subjected to acyl chlorination; mixing acyl chlorinated multi-walled carbon nanotubes with a curing agent and dimethylformamide according to a ratio of 1:100 (10-15) (g/mL/mL), carrying out ultrasonic dispersion for 30-40 minutes under the condition of ultrasonic power of 300-400W, and then carrying out reaction for 60-72 hours at 110-120 ℃ under the condition of nitrogen; after the reaction is finished, filtering the reaction solution by using 80-100 mesh filter cloth, and collecting solids; after washing the solid with tetrahydrofuran, the ratio of the solid to tetrahydrofuran was 1: (60-80) (g/mL), drying for 12-16 hours at the temperature of 60-70 ℃ and the vacuum degree of 0.07-0.08MPa to obtain the amidated multi-wall carbon nano-tube.
Detailed Description
Introduction of raw materials in the examples:
diethyl fumarate, CAS No.: 623-91-6 from eisen chemical ltd.
Furfuryl mercaptan, CAS number: 98-02-2, available from Shanghai Longsheng chemical Co., Ltd.
Potassium carbonate, CAS No.: 584-08-7, available from national pharmaceutical group chemical agents, Inc.
Organic microporous filter membrane with pore size of 0.45 μm, purchased from Peking Poison technologies development Ltd.
Adipic acid, CAS No.: 124-04-9, available from elegant chemical, inc.
1, 4-butanediol, CAS No.: 110-63-4, available from Shanghai Oakg Chemicals, Inc.
Tetrabutyl titanate, CAS No.: 5593-70-4, available from Nanjing Tengchuan technologies, Inc.
Hydroquinone, CAS number: 123-31-9, available from Nanjing blue whitening chemical Co.
Bismaleimide BMI, CAS number: 13676-54-5, available from Liyang Kexin chemical industry resources Ministry.
A torque rheometer, model 236865, available from fisher industries development (shanghai) ltd.
The high-speed mixer, model bc-1, was purchased from Bochang environmental protection technology Co., Ltd, Dongguan.
A twin-screw extruder, model ZSK-25WLE, from WP, Germany.
Expanded Carbon fibers, see M.Toyoda, A.Shimizu, et al.expansion of Carbon fiber composite synthesized electrochemistry [ J ]. Carbon,2001-39: 1697. preparation.
Expandable graphite which is purchased from Kyokaki graphite Co., Ltd, has the scale size of 80 meshes and the expansion rate of 280 mL/g.
Ethanol, CAS No.: 64-17-5, available from Shanghai Ringsu Biochemical technology, Inc.
The high-temperature puffing furnace is purchased from Jinnan German solid mechanical equipment Co., Ltd, and has the model of GFL-III.
The carboxyl butyronitrile rubber powder is XN-II, 25-28 mass percent of acrylonitrile and 50-150 nm of average particle size, and is purchased from Nanjing Feima polymer material development Co.
The multi-wall carbon nano tube is purchased from Shenzhen nanometer Port Limited company, the tube diameter is 20-50nm, and the tube length is 10-50 μm.
Thionyl chloride, CAS No.: 7719-09-7, available from Kyoto chemical technology, Inc.
Dimethylformamide, CAS No.: 68-12-2, available from Hefeijian chemical Co.
The curing agent is a polyether amine curing agent with the model number of T403 provided by German Bass China company.
Example 1
The utility model provides a high-strength safe kayak for drift, includes kayak shell, seat, nylon rope, nut, bolt and rubber gasket, kayak shell adopts the preparation of polyester elastomer to form.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the polyester elastomer comprises the following steps: diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; and drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer.
Example 2
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a cross-linked polyester elastomer.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the crosslinked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; and (3) carrying out reaction on the mixture obtained by banburying at 50 ℃ under the vacuum degree of 0.08MPa for 46 hours to obtain the crosslinked polyester elastomer.
Example 3
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a reinforced toughened modified cross-linked polyester elastomer.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; carrying out internal mixing on the obtained mixture, and reacting for 46 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the flexible graphite composite material at 70 ℃ for 5 hours, and then mixing the dried flexible graphite composite material with the cross-linked polyester elastomer in a mass ratio of 1: 0.07 is evenly mixed in a high-speed mixer and is extruded and granulated by a screw extruder to obtain the product; wherein the temperature of each zone of the extruder is: 180 deg.C, 200 deg.C, and 180 deg.C.
The preparation process of the flexible graphite composite material comprises the following steps: mixing the expanded carbon fiber, the expandable graphite and ethanol in a ratio of 1: 80(g/g/mL), ultrasonically dispersing for 20 minutes under the condition of ultrasonic power of 300W, centrifuging for 20 minutes at the rotating speed of 4000 revolutions per minute, and collecting bottom solids; and (3) puffing the bottom solid in a high-temperature puffing furnace at 900 ℃ for 10 seconds to obtain the flexible graphite composite material.
Example 4
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a reinforced toughened modified cross-linked polyester elastomer.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; carrying out internal mixing on the obtained mixture, and reacting for 46 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the carboxyl butyronitrile rubber powder for 5 hours at 70 ℃, and then mixing the carboxyl butyronitrile rubber powder with the cross-linked polyester elastomer according to the mass ratio of 1: 0.07 is evenly mixed in a high-speed mixer and is extruded and granulated by a screw extruder to obtain the product; wherein the temperature of each zone of the extruder is: 180 deg.C, 200 deg.C, and 180 deg.C.
Example 5
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a reinforced toughened modified cross-linked polyester elastomer.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; carrying out internal mixing on the obtained mixture, and reacting for 46 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the multi-wall carbon nano tube at 70 ℃ for 5 hours, and then mixing the multi-wall carbon nano tube with the cross-linked polyester elastomer in a mass ratio of 1: 0.07 is evenly mixed in a high-speed mixer and is extruded and granulated by a screw extruder to obtain the product; wherein the temperature of each zone of the extruder is: 180 deg.C, 200 deg.C, and 180 deg.C.
Example 6
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a reinforced toughened modified cross-linked polyester elastomer.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; carrying out internal mixing on the obtained mixture, and reacting for 46 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the amidated multi-walled carbon nanotubes at 70 ℃ for 5 hours, and then mixing the amidated multi-walled carbon nanotubes with a cross-linked polyester elastomer in a mass ratio of 1: 0.07 is evenly mixed in a high-speed mixer and is extruded and granulated by a screw extruder to obtain the product; wherein the temperature of each zone of the extruder is: 180 deg.C, 200 deg.C, and 180 deg.C.
The preparation process of the amidated multi-walled carbon nanotube comprises the following steps: drying the multi-wall carbon nano-tube at 120 ℃ for 3 hours; mixing the dried multi-walled carbon nanotubes with 98% sulfuric acid in a solid-to-liquid ratio of 1:75(g/mL), and stirring at the rotating speed of 280 revolutions per minute for 10 hours at the temperature of 23 ℃; then adding 65% nitric acid by mass, wherein the solid-to-liquid ratio of the multi-walled carbon nanotube to the nitric acid is 1:70(g/mL), mixing, and reacting at 140 ℃ for 1 hour; pouring the reaction liquid into deionized water, wherein the volume ratio of the reaction liquid to the deionized water is 1: 14, standing at 23 ℃ for 8 hours, discarding the supernatant, and keeping the bottom precipitate; washing the bottom precipitate with deionized water and tetrahydrofuran in sequence, wherein the ratio of the bottom precipitate to the deionized water to the tetrahydrofuran is 1: 80: 30(g/g/mL), drying for 12 hours at the temperature of 80 ℃ and the vacuum degree of 0.07MPa to obtain the carboxylated multi-wall carbon nano tube; mixing the carboxylated multi-walled carbon nano-tube with thionyl chloride and dimethylformamide at a ratio of 1:100:10(g/g/mL), and reacting at 70 ℃ for 24 hours; after the reaction is finished, filtering the reaction solution by 80-mesh filter cloth, and collecting a filter cake; after washing the filter cake with tetrahydrofuran, the ratio of the filter cake to tetrahydrofuran was 1: 60(g/mL), drying for 3 hours at 23 ℃ and under the vacuum degree of 0.07MPa to obtain the multi-wall carbon nano-tube subjected to acyl chlorination; mixing acyl-chlorinated multi-walled carbon nanotubes with a curing agent and dimethylformamide at a ratio of 1:100:10(g/mL/mL), ultrasonically dispersing for 40 minutes under the condition of ultrasonic power of 300W, and then reacting for 60 hours at 110 ℃ under the condition of nitrogen; after the reaction is finished, filtering the reaction solution by adopting 100-mesh filter cloth, and collecting solids; after washing the solid with tetrahydrofuran, the ratio of the solid to tetrahydrofuran was 1: 60(g/mL), and drying the mixture for 16 hours at the temperature of 70 ℃ and the vacuum degree of 0.08MPa to obtain the amidated multi-wall carbon nano-tube.
Example 7
The high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, wherein the kayak shell is prepared from a reinforced toughened modified cross-linked polyester elastomer.
The shape and the structure of the kayak shell, the seat, the nylon rope, the nut, the bolt and the rubber gasket are all made of conventional materials, which is not the innovation point of the invention.
The preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: 0.7, adding potassium carbonate accounting for 0.9 percent of the weight of diethyl fumarate, stirring and reacting at 25 ℃ for 7 hours at the rotating speed of 220 r/min, then filtering by adopting an organic microporous filter membrane with the aperture of 0.45 mu m, and collecting filtrate to obtain the monomer A; mixing adipic acid, 1, 4-butanediol and a monomer A in a mass ratio of 1: 1.3: 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25 percent of the weight of adipic acid and hydroquinone with the weight of 1 percent of the weight of the monomer A, mixing, reacting for 6 hours at 180 ℃ under the nitrogen atmosphere, and reacting for 2 hours under the condition of the vacuum degree of 100 Pa; drying the reactant for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: 0.03 mixing, and banburying for 15 minutes in a torque rheometer under the conditions that the banburying temperature is 70 ℃ and the screw rotating speed is 100 r/min; carrying out internal mixing on the obtained mixture, and reacting for 46 hours at the temperature of 50 ℃ and the vacuum degree of 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the modifier at 70 ℃ for 5 hours, and then mixing the modifier with the cross-linked polyester elastomer in a mass ratio of 1: 0.07 is evenly mixed in a high-speed mixer and is extruded and granulated by a screw extruder to obtain the product; wherein the modifier is carboxyl butyronitrile rubber powder and amidated multi-walled carbon nano-tubes in a mass ratio of 1: 2, the temperature of the extruder zones being: 180 deg.C, 200 deg.C, and 180 deg.C.
The preparation process of the amidated multi-walled carbon nanotube comprises the following steps: drying the multi-wall carbon nano-tube at 120 ℃ for 3 hours; mixing the dried multi-walled carbon nanotubes with 98% sulfuric acid in a solid-to-liquid ratio of 1:75(g/mL), and stirring at the rotating speed of 280 revolutions per minute for 10 hours at the temperature of 23 ℃; then adding 65% nitric acid by mass, wherein the solid-to-liquid ratio of the multi-walled carbon nanotube to the nitric acid is 1:70(g/mL), mixing, and reacting at 140 ℃ for 1 hour; pouring the reaction liquid into deionized water, wherein the volume ratio of the reaction liquid to the deionized water is 1: 14, standing at 23 ℃ for 8 hours, discarding the supernatant, and keeping the bottom precipitate; washing the bottom precipitate with deionized water and tetrahydrofuran in sequence, wherein the ratio of the bottom precipitate to the deionized water to the tetrahydrofuran is 1: 80: 30(g/g/mL), drying for 12 hours at the temperature of 80 ℃ and the vacuum degree of 0.07MPa to obtain the carboxylated multi-wall carbon nano tube; mixing the carboxylated multi-walled carbon nano-tube with thionyl chloride and dimethylformamide at a ratio of 1:100:10(g/g/mL), and reacting at 70 ℃ for 24 hours; after the reaction is finished, filtering the reaction solution by 80-mesh filter cloth, and collecting a filter cake; after washing the filter cake with tetrahydrofuran, the ratio of the filter cake to tetrahydrofuran was 1: 60(g/mL), drying for 3 hours at 23 ℃ and under the vacuum degree of 0.07MPa to obtain the multi-wall carbon nano-tube subjected to acyl chlorination; mixing acyl-chlorinated multi-walled carbon nanotubes with a curing agent and dimethylformamide at a ratio of 1:100:10(g/mL/mL), ultrasonically dispersing for 40 minutes under the condition of ultrasonic power of 300W, and then reacting for 60 hours at 110 ℃ under the condition of nitrogen; after the reaction is finished, filtering the reaction solution by adopting 100-mesh filter cloth, and collecting solids; after washing the solid with tetrahydrofuran, the ratio of the solid to tetrahydrofuran was 1: 60(g/mL), and drying the mixture for 16 hours at the temperature of 70 ℃ and the vacuum degree of 0.08MPa to obtain the amidated multi-wall carbon nano-tube.
Test example 1
The mechanical properties of the flexible polymer materials of examples 1 to 7 were tested: preparing the material into a dumbbell-shaped test sample with the length of 75 multiplied by 4.3 mm; placing the sample in a dryer for 48 hours before the test to eliminate internal stress; the drawing speed was 20mm/min and the force sensor was 500N.
The testing instrument adopts a universal material testing machine with model Zwick-Z020 provided by Guangzhou Kewei instruments Co.
The specific test results are shown in table 1.
Table 1: mechanical test result table
Test example 2
The low temperature resistance of the flexible polymer materials of examples 1-7 was tested according to the compression cold resistance coefficient, which is referred to GB/T6034-1985. The tester adopts a YNN-10 type compression cold-resistant coefficient tester provided by Zhongyun test machinery factories in Yangtze City.
The specific test results are shown in table 2.
Table 2: low temperature resistance test result table
| Cold resistance coefficient under compression | |
| Example 1(-50 ℃ C.) | 0.21 |
| Example 2(-50 ℃ C.) | 0.27 |
| Example 3(-50 ℃ C.) | 0.41 |
| Example 4(-50 ℃ C.) | 0.45 |
| Example 5(-50 ℃ C.) | 0.36 |
| Example 6(-50 ℃ C.) | 0.48 |
| Example 7(-50 ℃ C.) | 0.52 |
From the data, the flexible polymer material prepared by the invention still has higher compression cold-resistant coefficient at lower temperature.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (1)
1. A high-strength safe kayak for drifting comprises a kayak shell, a seat, a nylon rope, a nut, a bolt and a rubber gasket, and is characterized in that the kayak shell is made of a flexible high polymer material;
the flexible high polymer material is a reinforced toughened modified cross-linked polyester elastomer;
the preparation process of the reinforced toughened modified cross-linked polyester elastomer comprises the following steps:
(1) diethyl fumarate and furfuryl mercaptan are mixed in a mass ratio of 1: (0.6-0.7), adding potassium carbonate accounting for 0.8-0.9 percent of the weight of diethyl fumarate, stirring and reacting at 23-25 ℃ at the rotating speed of 190-220 r/min for 5-7 hours, then filtering by adopting an organic microporous filter membrane with the pore diameter of 0.4-0.5 mu m, and collecting the filtrate to obtain 2-diethyl furfurylsulfosuccinate; mixing adipic acid, 1, 4-butanediol and 2-diethyl furfurylsulfosuccinate in a mass ratio of 1: (1.2-1.3): 0.09, adding the mixture into a reaction vessel, then adding tetrabutyl titanate with the weight of 0.25-0.26 percent of adipic acid and hydroquinone with the weight of 1-2 percent of diethyl 2-furfurylthiosuccinate, mixing, reacting for 6-7 hours at the temperature of 170-180 ℃ in the nitrogen atmosphere, and reacting for 2-4 hours under the condition of the vacuum degree of 60-200 Pa; drying the reactant for 10-12 hours at 50-60 ℃ and under the vacuum degree of 0.07-0.08MPa to obtain the polyester elastomer;
(2) mixing a polyester elastomer and bismaleimide BMI in a mass ratio of 1: (0.02-0.03) mixing, and banburying for 10-15 minutes by adopting a torque rheometer under the conditions that the banburying temperature is 70-80 ℃ and the screw rotating speed is 100-; the mixture obtained by banburying reacts for 40 to 48 hours at the temperature of between 50 and 55 ℃ and under the vacuum degree of between 0.07 and 0.08MPa to obtain the crosslinked polyester elastomer;
(3) drying the modifier at 70-80 ℃ for 4-5 hours, and then mixing the modifier with the cross-linked polyester elastomer according to the mass ratio of (0.03-0.1): 1, uniformly mixing in a high-speed mixer, and extruding and granulating by a screw extruder to obtain the product; wherein the temperature of each zone of the extruder is: 190 ℃ at 180-;
the modifier is one or a combination of a plurality of flexible graphite composite materials, carboxyl butyronitrile rubber powder, multi-wall carbon nano tubes and amidated multi-wall carbon nano tubes.
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| CN105346671A (en) * | 2015-12-01 | 2016-02-24 | 王崇高 | Folding and rolling type canoeing |
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| CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of biodegradable thermoplastic polyester elastomer with side chain and preparation method thereof |
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| CN105346671A (en) * | 2015-12-01 | 2016-02-24 | 王崇高 | Folding and rolling type canoeing |
| CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of biodegradable thermoplastic polyester elastomer with side chain and preparation method thereof |
| CN106084664A (en) * | 2016-06-27 | 2016-11-09 | 义乌市运拓光电科技有限公司 | A kind of preparation method of graphene coated inorganic filler composite resin glue material |
| CN106554429A (en) * | 2016-10-10 | 2017-04-05 | 北京化工大学 | A kind of preparation method of thermal reversion cross-linked epoxy natural rubber |
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