CN108059816A - A kind of high elongation at tear polyurethane and preparation method thereof - Google Patents
A kind of high elongation at tear polyurethane and preparation method thereof Download PDFInfo
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- CN108059816A CN108059816A CN201711458503.3A CN201711458503A CN108059816A CN 108059816 A CN108059816 A CN 108059816A CN 201711458503 A CN201711458503 A CN 201711458503A CN 108059816 A CN108059816 A CN 108059816A
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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Abstract
The invention discloses a kind of high elongation at tear polyurethane, belong to polyurethane preparing technical field, the high elongation at tear polyurethane, including following raw material：Polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber, epoxy resin, ethyl acetate, propylene-glycol ethyl ether, N methyl pyrrolidones, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, isothiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose, magnesia, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH 560, Resisting fractre modified additive, the high elongation at tear polyurethane is by preparing base-material, prepare modified materials, and by base-material, the materials such as modified materials mixing and etc. made of.The polyurethane that the present invention is prepared has excellent elongation at break.
Description
Technical field
The present invention relates to the technical field of polyurethane preparation process more particularly to a kind of high elongation at tear polyurethane and its
Preparation method.
Background technology
Polyurethane is that the polymer containing carbamate groups is known as polyurethanes, poly- ammonia in macromolecular main chain
Ester is divided into two major class of polyester polyurethane and polyether polyurethane.Polyurethane has many excellent performances, so it has extensively
General purposes.
A kind of Chinese patent application document " polyurethane material and preparation method thereof (application publication number：CN106751734A)”
A kind of polyurethane material and preparation method thereof is disclosed, the polyurethane material is mainly by organic silicon modified polyurethane performed polymer conduct
Raw material is prepared, and isocyanide acid content of dissociating is low, environmentally protective, and mechanical strength is high, and product stability is good, after construction molding
Not blistering, cohesive force is strong, can be as a kind of court plastic material of function admirable, institute in the preparation process of the base polyurethane prepolymer for use as
The poly (propylene carbonate) polyalcohol used be using carbon dioxide as raw material, it is of low cost, to environmental protection, energy saving after large-scale production
Emission reduction is respectively provided with significance, can be widely applied to the numerous areas such as the production of traditional adhesive, fluid sealant, coating, elastomer.
But its elongation at break the needs of can not but meeting in actual use.
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of high elongation at tear polyurethane and its system
Preparation Method, to solve in a kind of Chinese patent application document " polyurethane material and preparation method thereof (application publication number：
CN106751734A the problem of polyurethane elongation at break is insufficient disclosed in) ".
A kind of high elongation at tear polyurethane proposed by the present invention, including following raw material：Polyurethane, ethylene glycol ethyl ether, chlorine
Buna, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber, epoxy resin, ethyl acetate, propylene-glycol ethyl ether, N- first
Base pyrrolidones, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, isothiazolinone, gas phase hard charcoal
Black, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose, magnesia, acetic acid fourth
Ester fiber element, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive；
The butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, the weight of Resisting fractre modified additive
Than for (3-5)：(4-6)：(1-3)：(8-16).
Further, the butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre are modified
The weight ratio of auxiliary agent is 4：5：2：12.
Further, in units of parts by weight, including following raw material：60-80 parts of polyurethane, 10-20 parts of ethylene glycol ethyl ether,
4-8 parts of neoprene, 3-9 parts of EP rubbers, 2-5 parts of nbr carboxyl terminal, 1-4 parts of ethylene propylene diene rubber, epoxy resin 3-5
Part, 2-6 parts of ethyl acetate, 1-5 parts of propylene-glycol ethyl ether, 4-6 parts of N-Methyl pyrrolidone, 2-5 parts of propyl phenylate, octadecyl three
1-5 parts of ammonio methacrylate, 3-5 parts of neopelex, 2-4 parts of isothiazolinone, 3-6 parts of gas-phase silica, alumina silicate
2-6 parts, 1-4 parts of stearic acid, 3-5 parts of molybdenum disulfide, 3-6 parts of silica flour, 2-5 parts of bentonite, 1-5 parts of zinc oxide, sulphur 3-5
It is part, 1-4 parts of nitrocellulose, 2-6 parts of magnesia, 3-5 parts of butyl acetate cellulose, 4-6 parts of nano silicon dioxide, silane coupled
1-3 parts of agent KH-560,8-16 parts of Resisting fractre modified additive.
Further, the raw material of the Resisting fractre modified additive includes by weight：10-20 parts of bamboo powder, mass fraction 5-
15% 4-8 parts of sodium hydroxide solution, 3-9 parts of Silane coupling reagent KH-570,2-5 parts of neopelex, deionized water
6-9 parts, 3-6 parts of nano-calcium carbonate, 2-6 parts of butyl acrylate, 1-4 parts of potassium peroxydisulfate, mass fraction be 4-8% aluminum sulfate water
3-6 parts of solution, mass percent be 4-6% 3-5 parts of 1-4 parts of 2-5 parts of hydrochloric acid solution, carbamate, isopropyl acrylate,
4-8 parts of polyparaphenylene's benzodiazole fiber.
Further, the Resisting fractre modified additive is prepared by following technique：Bamboo powder is crossed into 90-120 mesh sieves, then
It immerses in the sodium hydroxide solution of mass fraction 5-15%, is warming up to 70-90 DEG C, keep the temperature 20-40min, be continuously heating to 100-
110 DEG C, dry 20-40min and then addition Silane coupling reagent KH-570 are uniformly mixed, and 1- is stirred in 1500-2500r/min rotating speeds
3h, then heats to 100-120 DEG C, and dry 2-5h is subsequently added into neopelex and deionized water is uniformly mixed, stirs
2-4min is mixed, then adds in nano-calcium carbonate, is stirred evenly under ultrasonic wave, 65-75 DEG C is then heated to, then adds in propylene
Acid butyl ester and potassium peroxydisulfate are uniformly mixed, and react 1-3h, and the aluminum sulfate aqueous solution that mass fraction is 4-8% is then added dropwise, is demulsified,
Filtering is dried 5-7h in 45-55 DEG C of vacuum drying oven, is cooled to room temperature, then in calcining furnace at 820-920 DEG C after washing
2-5h is calcined, cooling is put into the hydrochloric acid solution that mass percent is 4-6% and impregnates 1-3h, and filtering is taken out, and baking is cleaned with clear water
It is dry, carbamate, isopropyl acrylate and polyparaphenylene's benzodiazole fiber are added in after crushing and is uniformly mixed, is warming up to 110-
130 DEG C, 10-30min is kept the temperature, 20-30min is stirred in 650-850r/min rotating speeds, is cooled to room temperature and is modified up to Resisting fractre
Auxiliary agent.
The present invention also provides a kind of preparation methods of high elongation at tear polyurethane, include the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber,
Epoxy resin, ethyl acetate are uniformly mixed, and 30-50min is stirred in 450-650r/min rotating speeds, are warming up to 60-80 DEG C, heat preservation
Then 10-20min adds in propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, 12
Sodium alkyl benzene sulfonate, isothiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, oxidation
Zinc, sulphur, nitrocellulose, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are mixed
Uniformly, 90-100 DEG C is warming up to, 10-30min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 80-90 DEG C, keeps the temperature 20-40min, be subsequently added into modified materials and be uniformly mixed, be cooled to 60-
70 DEG C, 15-25min is kept the temperature, then stirs 15-25min in 2500-3500r/min rotating speeds, is cooled to room temperature to obtain height and be broken to stretch
Long rate polyurethane.
The invention has the advantages that：
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the disconnected of embodiment 1-3 high elongation at tear polyurethane
Elongation is split to significantly improve；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that butyl acetate cellulose, nano silicon dioxide, silane are even
Connection agent KH-560, Resisting fractre modified additive add simultaneously plays synergistic effect in high elongation at tear polyurethane is prepared, and shows
The elongation at break for improving high elongation at tear polyurethane is write, this may be：Butyl acetate cellulose, nano silicon dioxide,
Silane coupling agent KH-560, Resisting fractre modified additive are applied to as modified system in the preparation of polyurethane, make use of silane even
Join the graft modification effect of agent KH-560, realize butyl acetate cellulose, nano silicon dioxide and Resisting fractre modified additive table
The hydroxyl in face and the base-material of polyurethane, which are realized, to be grafted, and is imparted the excellent elongation at break of polyurethane, while be make use of Resisting fractre
The resistance to thermal enhancement of modified additive, wherein Resisting fractre modified additive are then immersed in mass fraction 5- by the way that bamboo powder will be sieved
In 15% sodium hydroxide solution, heating up, heat preservation continues to heat up, and dry and then addition Silane coupling reagent KH-570 is uniformly mixed,
Stirring, then heats up, dry, is subsequently added into neopelex and deionized water is uniformly mixed, and stirs, and then adds in and receives
Rice calcium carbonate, stirs evenly under ultrasonic wave, then heats, and then adds in butyl acrylate and potassium peroxydisulfate is uniformly mixed, instead
Should, aluminum sulfate aqueous solution is then added dropwise, is demulsified, filtering is dry in vacuum drying oven after washing, is cooled to room temperature, then in forging
It burns in stove and is calcined at 820-920 DEG C, cool down, be put into hydrochloric acid solution and impregnate, filtering is taken out, and drying is cleaned with clear water, is crushed
Carbamate, isopropyl acrylate and polyparaphenylene's benzodiazole fiber are added in afterwards to be uniformly mixed, heats up, keeps the temperature, and stirring is cold
But, up to Resisting fractre modified additive, applied to to room temperature in the preparation of polyurethane of the present invention, silane coupling agent KH-560's
Under effect, realize and carry out grafting with the major ingredient of polyurethane and combined, effectively increase the elongation at break of polyurethane.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
Bright rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
In embodiment, the high elongation at tear polyurethane, in units of parts by weight, including following raw material：Polyurethane
60-80 parts, 10-20 parts of ethylene glycol ethyl ether, 4-8 parts of neoprene, 3-9 parts of EP rubbers, 2-5 parts of nbr carboxyl terminal, three
First EP rubbers 1-4 parts, 3-5 parts of epoxy resin, 2-6 parts of ethyl acetate, 1-5 parts of propylene-glycol ethyl ether, N-Methyl pyrrolidone 4-6
Part, 2-5 parts of propyl phenylate, 1-5 parts of octadecyltrimethylammonium chloride, 3-5 parts of neopelex, isothiazolinone 2-
4 parts, 3-6 parts of gas-phase silica, 2-6 parts of alumina silicate, 1-4 parts of stearic acid, 3-5 parts of molybdenum disulfide, 3-6 parts of silica flour, bentonite
2-5 parts, 1-5 parts of zinc oxide, 3-5 parts of sulphur, 1-4 parts of nitrocellulose, 2-6 parts of magnesia, 3-5 parts of butyl acetate cellulose,
4-6 parts of nano silicon dioxide, 1-3 parts of silane coupling agent KH-560,8-16 parts of Resisting fractre modified additive.
The Resisting fractre modified additive is prepared by following technique：10-20 parts of bamboo powders are crossed into 90-120 mesh by weight
Sieve, is then immersed in the sodium hydroxide solution of 4-8 parts of mass fraction 5-15%, is warming up to 70-90 DEG C, keeps the temperature 20-40min, after
Continuous to be warming up to 100-110 DEG C, 3-9 parts of Silane coupling reagent KH-570s of dry 20-40min and then addition are uniformly mixed, in 1500-
2500r/min rotating speeds stir 1-3h, then heat to 100-120 DEG C, and dry 2-5h is subsequently added into 2-5 parts of detergent alkylate sulphurs
Sour sodium and deionized water are uniformly mixed 6-9 parts, stir 2-4min, then add in 3-6 parts of nano-calcium carbonates, are stirred under ultrasonic wave
Uniformly, 65-75 DEG C is then heated to, then 2-6 parts of butyl acrylates is added in and 1-4 parts of potassium peroxydisulfates is uniformly mixed, reacts 1-
3h, is then added dropwise the aluminum sulfate aqueous solution that 3-6 parts of mass fractions are 4-8%, is demulsified, and filtering is dried after washing in 45-55 DEG C of vacuum
Dry 5-7h, is cooled to room temperature, then calcines 2-5h at 820-920 DEG C in calcining furnace in case, cools down, is put into 2-5 parts of matter
Amount percentage is that 1-3h is impregnated in the hydrochloric acid solution of 4-6%, and filtering is taken out, and drying is cleaned with clear water, and 1-4 parts of ammonia are added in after crushing
Carbamate, 3-5 part isopropyl acrylate and 4-8 parts of polyparaphenylene's benzodiazole fibers are uniformly mixed, and are warming up to 110-130
DEG C, 10-30min is kept the temperature, 20-30min is stirred in 650-850r/min rotating speeds, is cooled to room temperature and is helped up to Resisting fractre modification
Agent.
The preparation method of the high elongation at tear polyurethane, comprises the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber,
Epoxy resin, ethyl acetate are uniformly mixed, and 30-50min is stirred in 450-650r/min rotating speeds, are warming up to 60-80 DEG C, heat preservation
Then 10-20min adds in propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, 12
Sodium alkyl benzene sulfonate, isothiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, oxidation
Zinc, sulphur, nitrocellulose, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are mixed
Uniformly, 90-100 DEG C is warming up to, 10-30min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 80-90 DEG C, keeps the temperature 20-40min, be subsequently added into modified materials and be uniformly mixed, be cooled to 60-
70 DEG C, 15-25min is kept the temperature, then stirs 15-25min in 2500-3500r/min rotating speeds, is cooled to room temperature to obtain height and be broken to stretch
Long rate polyurethane.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of high elongation at tear polyurethane, in units of parts by weight, including following raw material：70 parts of polyurethane, ethylene glycol
15 parts of ether, 6 parts of neoprene, 6 parts of EP rubbers, 3.5 parts of nbr carboxyl terminal, 3 parts of ethylene propylene diene rubber, epoxy resin
4 parts, 4 parts of ethyl acetate, 3 parts of propylene-glycol ethyl ether, 5 parts of N-Methyl pyrrolidone, 3.5 parts of propyl phenylate, octadecyl trimethyl
3 parts of ammonium chloride, 4 parts of neopelex, 3 parts of isothiazolinone, 4.5 parts of gas-phase silica, 4 parts of alumina silicate, stearic acid 3
Part, 4 parts of molybdenum disulfide, 4.5 parts of silica flour, 3.5 parts of bentonite, 3 parts of zinc oxide, 4 parts of sulphur, 3 parts of nitrocellulose, magnesia
4 parts, 4 parts of butyl acetate cellulose, 5 parts of nano silicon dioxide, 2 parts of silane coupling agent KH-560, Resisting fractre modified additive 12
Part.
The Resisting fractre modified additive is prepared by following technique：15 parts of bamboo powders are crossed into 105 mesh sieves by weight, then
It immerses in the sodium hydroxide solution of 6 parts of mass fractions 10%, is warming up to 80 DEG C, keep the temperature 30min, be continuously heating to 105 DEG C, drying
6 parts of Silane coupling reagent KH-570s of 30min and then addition are uniformly mixed, and are stirred 2h in 2000r/min rotating speeds, are then heated to 110
DEG C, dry 3.5h, is subsequently added into 3.5 parts of neopelexes and deionized water is uniformly mixed 7.5 parts, stirs 3min, so
4.5 parts of nano-calcium carbonates are added in afterwards, is stirred evenly under ultrasonic wave, is then heated to 70 DEG C, then add in 4 parts of butyl acrylates
It is uniformly mixed with 3 parts of potassium peroxydisulfates, reacts 2h, the aluminum sulfate aqueous solution that 4.5 parts of mass fractions are 6%, demulsification, mistake is then added dropwise
Filter dries 6h in 50 DEG C of vacuum drying ovens, is cooled to room temperature, then calcines 3.5h at 870 DEG C in calcining furnace after washing, cold
But, it is put into the hydrochloric acid solution that 3.5 parts of mass percents are 5% and impregnates 2h, filtering is taken out, and drying is cleaned with clear water, after crushing
It adds in 3 parts of carbamates, 4 parts of isopropyl acrylates and 6 parts of polyparaphenylene's benzodiazole fibers to be uniformly mixed, is warming up to 120
DEG C, 20min is kept the temperature, 25min is stirred in 750r/min rotating speeds, is cooled to room temperature up to Resisting fractre modified additive.
The preparation method of the high elongation at tear polyurethane, comprises the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber,
Epoxy resin, ethyl acetate are uniformly mixed, and are stirred 40min in 550r/min rotating speeds, are warming up to 70 DEG C, keep the temperature 15min, Ran Houjia
Enter propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, different
Thiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose
Element, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are mixed
Uniformly, 95 DEG C are warming up to, 20min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 85 DEG C, keeps the temperature 30min, be subsequently added into modified materials and be uniformly mixed, be cooled to 65 DEG C, heat preservation
20min then stirs 20min in 3000r/min rotating speeds, is cooled to room temperature to obtain high elongation at tear polyurethane.
Embodiment 2
A kind of high elongation at tear polyurethane, in units of parts by weight, including following raw material：60 parts of polyurethane, ethylene glycol
20 parts of ether, 4 parts of neoprene, 9 parts of EP rubbers, 2 parts of nbr carboxyl terminal, 4 parts of ethylene propylene diene rubber, epoxy resin 3
Part, 6 parts of ethyl acetate, 1 part of propylene-glycol ethyl ether, 6 parts of N-Methyl pyrrolidone, 2 parts of propyl phenylate, octadecyl trimethyl chlorination
5 parts of ammonium, 3 parts of neopelex, 4 parts of isothiazolinone, 3 parts of gas-phase silica, 6 parts of alumina silicate, 1 part of stearic acid, two
5 parts of molybdenum sulfide, 3 parts of silica flour, 5 parts of bentonite, 1 part of zinc oxide, 5 parts of sulphur, 1 part of nitrocellulose, 6 parts of magnesia, acetic acid
3 parts of cellulose butyrate, 6 parts of nano silicon dioxide, 1 part of silane coupling agent KH-560,16 parts of Resisting fractre modified additive.
The Resisting fractre modified additive is prepared by following technique：10 parts of bamboo powders are crossed into 120 mesh sieves by weight, then
It immerses in the sodium hydroxide solution of 4 parts of mass fractions 15%, is warming up to 70 DEG C, keep the temperature 40min, be continuously heating to 100 DEG C, drying
3 parts of Silane coupling reagent KH-570s of 40min and then addition are uniformly mixed, and are stirred 1h in 2500r/min rotating speeds, are then heated to 120
DEG C, dry 2h, is subsequently added into 5 parts of neopelexes and deionized water is uniformly mixed 6 parts, stirs 4min, then adds in 3
Part nano-calcium carbonate, stirs evenly under ultrasonic wave, is then heated to 75 DEG C, then adds in 2 parts of butyl acrylates and 4 parts of over cures
Sour potassium is uniformly mixed, and reacts 1h, and the aluminum sulfate aqueous solution that 6 parts of mass fractions are 4% is then added dropwise, is demulsified, filtering, after washing
Dry 5h, is cooled to room temperature, then calcines 2h at 920 DEG C in calcining furnace in 55 DEG C of vacuum drying ovens, cools down, is put into 5 parts of matter
Amount percentage is that 3h is impregnated in 4% hydrochloric acid solution, and filtering is taken out, and drying is cleaned with clear water, and 1 part of carbamic acid is added in after crushing
Ester, 5 parts of isopropyl acrylates and 4 parts of polyparaphenylene's benzodiazole fibers are uniformly mixed, and are warming up to 130 DEG C, keep the temperature 10min, in
850r/min rotating speeds stir 20min, are cooled to room temperature up to Resisting fractre modified additive.
The preparation method of the high elongation at tear polyurethane, comprises the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber,
Epoxy resin, ethyl acetate are uniformly mixed, and are stirred 50min in 450r/min rotating speeds, are warming up to 60 DEG C, keep the temperature 20min, Ran Houjia
Enter propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, different
Thiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose
Element, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are mixed
Uniformly, 90 DEG C are warming up to, 30min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 80 DEG C, keeps the temperature 40min, be subsequently added into modified materials and be uniformly mixed, be cooled to 60 DEG C, heat preservation
25min then stirs 25min in 2500r/min rotating speeds, is cooled to room temperature to obtain high elongation at tear polyurethane.
Embodiment 3
A kind of high elongation at tear polyurethane, in units of parts by weight, including following raw material：80 parts of polyurethane, ethylene glycol
10 parts of ether, 8 parts of neoprene, 3 parts of EP rubbers, 5 parts of nbr carboxyl terminal, 1 part of ethylene propylene diene rubber, epoxy resin 5
Part, 2 parts of ethyl acetate, 5 parts of propylene-glycol ethyl ether, 4 parts of N-Methyl pyrrolidone, 5 parts of propyl phenylate, octadecyl trimethyl chlorination
1 part of ammonium, 5 parts of neopelex, 2 parts of isothiazolinone, 6 parts of gas-phase silica, 2 parts of alumina silicate, 4 parts of stearic acid, two
3 parts of molybdenum sulfide, 6 parts of silica flour, 2 parts of bentonite, 5 parts of zinc oxide, 3 parts of sulphur, 4 parts of nitrocellulose, 2 parts of magnesia, acetic acid
5 parts of cellulose butyrate, 4 parts of nano silicon dioxide, 3 parts of silane coupling agent KH-560,8 parts of Resisting fractre modified additive.
The Resisting fractre modified additive is prepared by following technique：20 parts of bamboo powders are crossed into 90 mesh sieves by weight, then
It immerses in the sodium hydroxide solution of 8 parts of mass fractions 5%, is warming up to 90 DEG C, keep the temperature 20min, be continuously heating to 110 DEG C, drying
9 parts of Silane coupling reagent KH-570s of 20min and then addition are uniformly mixed, and are stirred 3h in 1500r/min rotating speeds, are then heated to 100 DEG C,
Dry 5h, is subsequently added into 2 parts of neopelexes and deionized water is uniformly mixed 9 parts, stirs 2min, then adds in 6 parts
Nano-calcium carbonate stirs evenly under ultrasonic wave, is then heated to 65 DEG C, then adds in 6 parts of butyl acrylates and 1 part of persulfuric acid
Potassium is uniformly mixed, and reacts 3h, and the aluminum sulfate aqueous solution that 3 parts of mass fractions are 8% is then added dropwise, is demulsified, filtering, 45 after washing
Dry 7h, is cooled to room temperature, then calcines 5h at 820 DEG C in calcining furnace in DEG C vacuum drying oven, cools down, is put into 2 parts of quality
Percentage is that 1h is impregnated in 6% hydrochloric acid solution, and filtering is taken out, and drying is cleaned with clear water, and 4 parts of carbamic acids are added in after crushing
Ester, 3 parts of isopropyl acrylates and 8 parts of polyparaphenylene's benzodiazole fibers are uniformly mixed, and are warming up to 110 DEG C, keep the temperature 30min, in
650r/min rotating speeds stir 30min, are cooled to room temperature up to Resisting fractre modified additive.
The preparation method of the high elongation at tear polyurethane, comprises the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber,
Epoxy resin, ethyl acetate are uniformly mixed, and are stirred 30min in 650r/min rotating speeds, are warming up to 80 DEG C, keep the temperature 10min, Ran Houjia
Enter propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, different
Thiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose
Element, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are mixed
Uniformly, 100 DEG C are warming up to, 10min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 90 DEG C, keeps the temperature 20min, be subsequently added into modified materials and be uniformly mixed, be cooled to 70 DEG C, heat preservation
15min then stirs 15min in 3500r/min rotating speeds, is cooled to room temperature to obtain high elongation at tear polyurethane.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the raw material of high elongation at tear polyurethane
In lack butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the raw material of high elongation at tear polyurethane
In lack butyl acetate cellulose.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the raw material of high elongation at tear polyurethane
In lack nano silicon dioxide.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the raw material of high elongation at tear polyurethane
In lack silane coupling agent KH-560.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the raw material of high elongation at tear polyurethane
In lack Resisting fractre modified additive.
Comparative example 6
Using a kind of Chinese patent application document " polyurethane material and preparation method thereof (application publication number：
CN106751734A) " technique of embodiment 1 prepares polyurethane.
The polyurethane for measuring embodiment 1-3 and comparative example 1-6 carries out indices detection, and obtained testing result is as follows
Table：
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the disconnected of embodiment 1-3 high elongation at tear polyurethane
Elongation is split to significantly improve；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that butyl acetate cellulose, nano silicon dioxide, silane are even
Connection agent KH-560, Resisting fractre modified additive add simultaneously plays synergistic effect in high elongation at tear polyurethane is prepared, and shows
The elongation at break for improving high elongation at tear polyurethane is write, this may be：Butyl acetate cellulose, nano silicon dioxide,
Silane coupling agent KH-560, Resisting fractre modified additive are applied to as modified system in the preparation of polyurethane, make use of silane even
Join the graft modification effect of agent KH-560, realize butyl acetate cellulose, nano silicon dioxide and Resisting fractre modified additive table
The hydroxyl in face and the base-material of polyurethane, which are realized, to be grafted, and is imparted the excellent elongation at break of polyurethane, while be make use of Resisting fractre
The resistance to thermal enhancement of modified additive, wherein Resisting fractre modified additive are then immersed in mass fraction 5- by the way that bamboo powder will be sieved
In 15% sodium hydroxide solution, heating up, heat preservation continues to heat up, and dry and then addition Silane coupling reagent KH-570 is uniformly mixed,
Stirring, then heats up, dry, is subsequently added into neopelex and deionized water is uniformly mixed, and stirs, and then adds in and receives
Rice calcium carbonate, stirs evenly under ultrasonic wave, then heats, and then adds in butyl acrylate and potassium peroxydisulfate is uniformly mixed, instead
Should, aluminum sulfate aqueous solution is then added dropwise, is demulsified, filtering is dry in vacuum drying oven after washing, is cooled to room temperature, then in forging
It burns in stove and is calcined at 820-920 DEG C, cool down, be put into hydrochloric acid solution and impregnate, filtering is taken out, and drying is cleaned with clear water, is crushed
Carbamate, isopropyl acrylate and polyparaphenylene's benzodiazole fiber are added in afterwards to be uniformly mixed, heats up, keeps the temperature, and stirring is cold
But, up to Resisting fractre modified additive, applied to to room temperature in the preparation of polyurethane of the present invention, silane coupling agent KH-560's
Under effect, realize and carry out grafting with the major ingredient of polyurethane and combined, effectively increase the elongation at break of polyurethane.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of high elongation at tear polyurethane, which is characterized in that including following raw material：Polyurethane, ethylene glycol ethyl ether, neoprene rubber
Glue, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber, epoxy resin, ethyl acetate, propylene-glycol ethyl ether, N- methyl pyrroles
Pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, neopelex, isothiazolinone, gas-phase silica,
Alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide, sulphur, nitrocellulose, magnesia, butyl acetate are fine
Tie up element, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive；
The butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, the weight ratio of Resisting fractre modified additive are
(3-5)：(4-6)：(1-3)：(8-16).
2. high elongation at tear polyurethane according to claim 1, which is characterized in that the butyl acetate cellulose is received
Rice silica, silane coupling agent KH-560, the weight ratio of Resisting fractre modified additive are 4：5：2：12.
3. high elongation at tear polyurethane according to claim 1 or 2, which is characterized in that in units of parts by weight, including
Following raw material：60-80 parts of polyurethane, 10-20 parts of ethylene glycol ethyl ether, 4-8 parts of neoprene, 3-9 parts of EP rubbers, end carboxyl fourth
2-5 parts of nitrile rubber, 1-4 parts of ethylene propylene diene rubber, 3-5 parts of epoxy resin, 2-6 parts of ethyl acetate, 1-5 parts of propylene-glycol ethyl ether, N-
4-6 parts of methyl pyrrolidone, 2-5 parts of propyl phenylate, 1-5 parts of octadecyltrimethylammonium chloride, neopelex 3-5
Part, 2-4 parts of isothiazolinone, 3-6 parts of gas-phase silica, 2-6 parts of alumina silicate, 1-4 parts of stearic acid, 3-5 parts of molybdenum disulfide, quartz
3-6 parts of powder, 2-5 parts of bentonite, 1-5 parts of zinc oxide, 3-5 parts of sulphur, 1-4 parts of nitrocellulose, 2-6 parts of magnesia, acetic acid fourth
3-5 parts of ester fiber element, 4-6 parts of nano silicon dioxide, 1-3 parts of silane coupling agent KH-560,8-16 parts of Resisting fractre modified additive.
4. according to claim 1-3 any one of them high elongation at tear polyurethane, which is characterized in that the Resisting fractre is modified
The raw material of auxiliary agent includes by weight：4-8 parts of the sodium hydroxide solution, silane coupled of 10-20 parts of bamboo powder, mass fraction 5-15%
3-9 parts of agent KH-570,2-5 parts of neopelex, 6-9 parts of deionized water, 3-6 parts of nano-calcium carbonate, butyl acrylate
2-6 parts, 1-4 parts of potassium peroxydisulfate, mass fraction be 4-8% 3-6 parts of aluminum sulfate aqueous solution, mass percent be 4-6% salt
2-5 parts of acid solution, 1-4 parts of carbamate, 3-5 parts of isopropyl acrylate, 4-8 parts of polyparaphenylene's benzodiazole fiber.
5. according to claim 1-4 any one of them high elongation at tear polyurethane, which is characterized in that the Resisting fractre is modified
Auxiliary agent is prepared by following technique：Bamboo powder is crossed into 90-120 mesh sieves, the sodium hydroxide for being then immersed in mass fraction 5-15% is molten
In liquid, 70-90 DEG C is warming up to, keeps the temperature 20-40min, is continuously heating to 100-110 DEG C, then dry 20-40min adds in silane
Coupling agent kh-570 is uniformly mixed, and 1-3h is stirred in 1500-2500r/min rotating speeds, then heats to 100-120 DEG C, dry 2-
5h, is subsequently added into neopelex and deionized water is uniformly mixed, and stirs 2-4min, then adds in nano-calcium carbonate,
It is stirred evenly under ultrasonic wave, is then heated to 65-75 DEG C, then added in butyl acrylate and potassium peroxydisulfate is uniformly mixed, instead
1-3h is answered, the aluminum sulfate aqueous solution that mass fraction is 4-8% is then added dropwise, is demulsified, filtering is dried after washing in 45-55 DEG C of vacuum
Dry 5-7h, is cooled to room temperature, then calcines 2-5h at 820-920 DEG C in calcining furnace in case, cools down, is put into quality percentage
Number to impregnate 1-3h in the hydrochloric acid solution of 4-6%, take out, and drying is cleaned with clear water, and carbamate, third are added in after crushing by filtering
Isopropyl gadoleate and polyparaphenylene's benzodiazole fiber are uniformly mixed, and are warming up to 110-130 DEG C, 10-30min are kept the temperature, in 650-
850r/min rotating speeds stir 20-30min, are cooled to room temperature up to Resisting fractre modified additive.
6. a kind of preparation method according to claim 1-5 any one of them high elongation at tear polyurethane, which is characterized in that
Include the following steps：
S1, by polyurethane, ethylene glycol ethyl ether, neoprene, EP rubbers, nbr carboxyl terminal, ethylene propylene diene rubber, epoxy
Resin, ethyl acetate are uniformly mixed, and are stirred 30-50min in 450-650r/min rotating speeds, are warming up to 60-80 DEG C, keep the temperature 10-
Then 20min adds in propylene-glycol ethyl ether, N-Methyl pyrrolidone, propyl phenylate, octadecyltrimethylammonium chloride, dodecane
Base benzene sulfonic acid sodium salt, isothiazolinone, gas-phase silica, alumina silicate, stearic acid, molybdenum disulfide, silica flour, bentonite, zinc oxide,
Sulphur, nitrocellulose, magnesia are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, butyl acetate cellulose, nano silicon dioxide, silane coupling agent KH-560, Resisting fractre modified additive are uniformly mixed,
90-100 DEG C is warming up to, 10-30min is kept the temperature, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 80-90 DEG C, keeps the temperature 20-40min, be subsequently added into modified materials and be uniformly mixed, be cooled to 60-70 DEG C,
15-25min is kept the temperature, then 15-25min is stirred in 2500-3500r/min rotating speeds, is cooled to room temperature to obtain high elongation at tear
Polyurethane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159585A (en) * | 2020-08-25 | 2021-01-01 | 苏州市雄林新材料科技有限公司 | High-weather-resistance shading film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602178A (en) * | 2016-03-22 | 2016-05-25 | 安徽渡江电缆集团有限公司 | Heat-resistant stretch-resistant modified polyurethane rubber cable material |
-
2017
- 2017-12-28 CN CN201711458503.3A patent/CN108059816A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602178A (en) * | 2016-03-22 | 2016-05-25 | 安徽渡江电缆集团有限公司 | Heat-resistant stretch-resistant modified polyurethane rubber cable material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159585A (en) * | 2020-08-25 | 2021-01-01 | 苏州市雄林新材料科技有限公司 | High-weather-resistance shading film and preparation method thereof |
| CN112159585B (en) * | 2020-08-25 | 2022-06-03 | 苏州市雄林新材料科技有限公司 | High-weather-resistance shading film and preparation method thereof |
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Application publication date: 20180522 |