CN108676347A - A kind of preparation method of the special antistatic agent of polyurethane plastics - Google Patents

A kind of preparation method of the special antistatic agent of polyurethane plastics Download PDF

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CN108676347A
CN108676347A CN201810478874.6A CN201810478874A CN108676347A CN 108676347 A CN108676347 A CN 108676347A CN 201810478874 A CN201810478874 A CN 201810478874A CN 108676347 A CN108676347 A CN 108676347A
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许水仙
万振
张烨
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/017Additives being an antistatic agent
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic

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Abstract

The invention discloses a kind of preparation methods of the special antistatic agent of polyurethane plastics, belong to technical field of polymer materials.By pre- modified alta-mud and water in mass ratio 1:10~1:15 mixing adjust pH to 10.0~10.5, and the modifying agent of 0.1~0.3 times of pre- modified alta-mud quality are added, and after being stirred, filtering pulverizes and sieves, obtains modified alta-mud;By pre- modified glass-fiber and water in mass ratio 1:5~1:10 mixing, and the silane coupling agent of 1~2 times of pre- modified glass-fiber quality is added, after being stirred, filter, it is dry, obtain modified glass-fiber;By modified alta-mud and modified glass-fiber in mass ratio 3:1~4:1 mixing is to get the special antistatic agent of polyurethane plastics.The gained special antistatic agent of polyurethane plastics of the invention has excellent antistatic effect.

Description

A kind of preparation method of the special antistatic agent of polyurethane plastics
Technical field
The invention discloses a kind of preparation methods of the special antistatic agent of polyurethane plastics, belong to high polymer material technology neck Domain.
Background technology
Along with the development of science and technology, the application of high molecular material is increasingly extensive.However, high molecular material has high surface Resistance and volume resistance, once be charged by friction, electrostatic not easily passs through conductive remove and is trapped in material surface, can not only influence Appearance characteristics, manufacture and the use of material are especially made in coal Deng Kuang factories underground more important is there are electrostatic safety hidden danger In the environment of industry, the use of high molecular material must carry out antistatic surface processing.In order to eliminate electrostatic, usually in macromolecule material Corresponding antistatic agent is added in material, to reduce sheet resistance and volume resistance, expands its use scope.Weigh macromolecule material Material antistatic property quality refers mainly to indicate:Sheet resistance, electrostatic half-life, hygroscopicity(Contact angle), saturation electrostatic potential Deng dividing the grade of high molecular material antistatic property according to charge half life and sheet resistance.
The type of antistatic agent is various, and currently used mainly surfactant can be divided into cation by chemical constitution Type, anionic, nonionic, amphoteric, polymer electrolyte, different types of antistatic agent have different structures, using model It encloses and respective advantage and disadvantage.In addition, composite antistatic agent has been to be concerned by more and more people and favors.It is compound antistatic Agent is the new varieties of antistatic agent, it is developed using the synergistic effect principle between each component.Because of single use Often there is certain defect in certain antistatic agent, ideal effect is extremely difficult in certain antistatic more demanding places, Derivative of fatty acid such as hydroxyethylation amine, polyol esters of fatty acids and alkanolamide is compound, and being applied to polyethylene, polypropylene can Obtain apparent antistatic effect.There is also the bad problems of antistatic effect for traditional antistatic agent at present, therefore also need pair It is studied.
Invention content
The present invention solves the technical problem of:For the bad problem of conventional antistatic agents antistatic effect, provide A kind of preparation method of the special antistatic agent of polyurethane plastics.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is:
(1)Sodium bentonite is crushed and is sieved, refinement sodium bentonite is obtained, by refinement sodium bentonite and water in mass ratio 1:40 ~1:50 mixing, and the green vitriol of 4~5 times of refinement sodium bentonite quality is added, under nitrogen protection, after being aerated 5~10min, Bentonite mixtures must be pre-processed, by pretreatment bentonite mixtures and no oxyethanol in mass ratio 3:1~4:1 mixing, obtains swollen Moisten earth mixtures;
(2)By potassium borohydride and sodium hydroxide solution in mass ratio 1:10~1:15 mixing, obtain sodium hydroxide mixed liquor, by swelling The sodium hydroxide mixed liquor of 0.2~0.4 times of earth mixtures quality instills in bentonite mixtures, and after being stirred, filtering must filter Filter cake anaerobic milli-Q water is used in combination deoxidation absolute ethyl alcohol to wash by cake, dry, obtains pre- modified alta-mud;
(3)By pre- modified alta-mud and water in mass ratio 1:10~1:15 mixing adjust pH to 10.0~10.5, and are added and change in advance Property 0.1~0.3 times of bentonite quality modifying agent, after being stirred, filtering pulverizes and sieves, obtains modified alta-mud;
(4)By glass fibre and inorganic agent in mass ratio 1:5~1:8 mixing are impregnated, and filtering obtains pretreated glass fiber, will be pre- Handle glass fibre and graphene oxide liquid mixture in mass ratio 1:10~1:20 mixing, impregnate, and filter, dry, obtain 1 processing Glass fibre, by 1 processing glass fibre and chitosan solution in mass ratio 1:10~1:15 mixing, impregnate, and filter, dry, Obtain pre- modified glass-fiber;
(5)By pre- modified glass-fiber and water in mass ratio 1:5~1:10 mixing, and pre- modified glass-fiber quality 1~2 is added Silane coupling agent again after being stirred, filters, dry, obtains modified glass-fiber;
(6)By modified alta-mud and modified glass-fiber in mass ratio 3:1~4:1 mixing is special anti-quiet to get polyurethane plastics Electric agent.
Step(3)The modifying agent is any one in cetyl trimethylammonium bromide or N- Alkylation of Amino Acids.
Step(4)The length of the glass fibre is 1~2mm, a diameter of 0.1~0.3mm.
Step(4)The inorganic agent be 60~70% by mass fraction sulfuric acid and hydrogen peroxide by volume 3:1 is mixed It closes, obtains inorganic agent.
Step(4)The preparation method of the graphene oxide liquid mixture is by graphene oxide and water in mass ratio 1:100 ~1:300 mixing, ultrasonic disperse are used in combination sodium hydroxide to adjust pH to 7.0~7.2, obtain graphene oxide liquid mixture.
Step(4)The preparation method of the chitosan solution is by chitosan and water in mass ratio 1:200~1:300 is mixed It closes, is used in combination second acid for adjusting pH to 4.0~4.2, obtains chitosan solution.
Step(5)The silane coupling agent is silane resin acceptor kh-550, silane coupling agent KH-560 or silane coupling agent Any one in KH-570.
The beneficial effects of the invention are as follows:
(1)Modified alta-mud is added when preparing the special antistatic agent of polyurethane plastics in the present invention, and bentonite is modified first Before first pass through pre- modification, so that bentonite surface is fixed with fe, after being added in product, due to the presence of iron, to Make the high molecular material of addition product that there is preferable electric conductivity, secondly, pre- modified alta-mud is after modification, swelling Soil is changed into lipophile by hydrophily, to which after being added in high molecular material, modified alta-mud can be dispersed in macromolecule In material, and since the fe sodium metasilicate being added in the process that can be modified that modified alta-mud surface carries is coated, from And after modified alta-mud is added in high molecular material, fe can be together scattered in bentonite in high molecular material, to Make product that can effectively improve the antistatic effect of high molecular material;
(2)Modified glass-fiber is added when preparing the special antistatic agent of polyurethane plastics in the present invention, on the one hand, glass fibre exists After modification, fiberglass surfacing is covered by graphene oxide and chitosan, to make the electric conductivity of glass fibre carry Height, and then the antistatic effect of product is made to improve, on the other hand, silane coupling agent is added to glass in glass fibre in modifying process Glass fiber is handled, can be with modification to make glass fibre that can be uniformly distributed in high molecular material after being added in product Bentonite forms good conductive path inside high molecular material, and then the antistatic effect of product is made to further increase, and And since modified alta-mud and modified glass-fiber are dispersed in high molecular material, so as to make high molecular material that there is length The antistatic property of effect.
Specific implementation mode
Sodium bentonite was crushed into 180 mesh sieve, obtains refinement sodium bentonite, refinement sodium bentonite and water are pressed into quality Than 1:40~1:50 are mixed in three-necked flask, are 30~40 DEG C in temperature, under conditions of rotating speed is 200~300r/min, stir After mixing 22~26h of mixing, the green vitriol of 4~5 times of refinement sodium bentonite quality is added into three-necked flask, and into three-necked flask It is passed through nitrogen with the rate of 15~20mL/min, after being aerated 5~10min under nitrogen atmosphere, obtains pretreatment bentonite mixtures, It will pretreatment bentonite mixtures and no oxyethanol in mass ratio 3:1~4:1 mixing, in temperature be 25~35 DEG C, rotating speed 220 Under conditions of~350r/min, after being stirred 20~40min, bentonite mixtures are obtained;By potassium borohydride and mass fraction 0.1 ~0.2% sodium hydroxide solution in mass ratio 1:8~1:15 mixing are 30~45 DEG C in temperature, and rotating speed is 200~350r/ The condition of min after being stirred 20~30min, obtains sodium hydroxide mixed liquor, by 0.2~0.5 times of bentonite mixtures quality Sodium hydroxide mixed liquor is instilled with the rate of 2~7mL/min in bentonite mixtures, and is 30~40 DEG C in temperature, and rotating speed is It is stirred under conditions of 500~800r/min to sodium hydroxide mixing drop and is use up, it is 30~40 DEG C to continue at temperature, and rotating speed is After the condition of 500~800r/min is stirred 30~40min, filtering obtains filter cake, by filter cake anaerobic milli-Q water 3~8 It is secondary, after being used in combination deoxidation absolute ethyl alcohol to wash 5~8 times, dry 15 under conditions of being 60~70 DEG C in temperature by the filter cake after washing ~40min obtains pre- modified alta-mud, by pre- modified alta-mud and water in mass ratio 1:10~1:15 are mixed in beaker, use silicon Sour sodium adjusts the pH of material in beaker to 10.0~10.5, and 0.1~0.3 times of pre- modified alta-mud quality is added into beaker Modifying agent is 40~55 DEG C in temperature, and after rotating speed is stirred 1~2h under conditions of being 300~350r/min, filtering must change Property bentonite blank, by modified alta-mud blank crushed 220 mesh sieve, obtain modified alta-mud;Glass fibre and inorganic agent are pressed Mass ratio 1:5~1:8 mixing, and after impregnating 40~50min under room temperature, filtering obtains pretreated glass fiber, will locate in advance Manage glass fibre and graphene oxide liquid mixture in mass ratio 1:10~1:20 mixing are soaked under conditions of being 40~50 DEG C in temperature Steep 15~30min after, filtering, must pre-process 1 time processing glass fibre, will pretreatment 1 time processing glass fibre in temperature be 50 Under conditions of~70 DEG C after dry 30~40min, 1 processing glass fibre is obtained, by 1 processing glass fibre and chitosan solution In mass ratio 1:10~1:15 mixing, after impregnating 15~30min under conditions of being 40~50 DEG C in temperature, filtering obtains pre- modification Glass fibre blank obtains pre- under conditions of being 60~80 DEG C in temperature by pre- modified glass-fiber blank after dry 20~30min Modified glass-fiber;By pre- modified glass-fiber and water in mass ratio 1:5~1:10 mixing, and to pre- modified glass-fiber and water Mixture in the silane coupling agent of 1~2 times of pre- modified glass-fiber quality is added, in temperature be 45~55 DEG C, rotating speed 200 After being stirred 2~3h under conditions of~300r/min, filtering obtains pretreatment modification glass fibre, by pretreatment modification glass Under conditions of fiber is 60~80 DEG C in temperature after dry 30~40min, modified glass-fiber is obtained;By modified alta-mud and modification Glass fibre in mass ratio 3:1~4:1 is mixed in blender, is 40~50 DEG C in temperature, rotating speed is 300~450r/min's Under the conditions of, it is stirred after 40~50min to get the special antistatic agent of polyurethane plastics.The modifying agent is cetyl three Any one in methyl bromide ammonium or N- Alkylation of Amino Acids.The length of the glass fibre be 1~2mm, a diameter of 0.1~ 0.3mm.The inorganic agent be 60~70% by mass fraction sulfuric acid and hydrogen peroxide by volume 3:1 mixing, must be handled Agent.The preparation method of the graphene oxide liquid mixture is by graphene oxide and water in mass ratio 1:100~1:300 mixing, Ultrasonic disperse is used in combination sodium hydroxide to adjust pH to 7.0~7.2, obtains graphene oxide liquid mixture.The preparation of the chitosan solution Method is by chitosan and water in mass ratio 1:200~1:300 mixing, are used in combination second acid for adjusting pH to 4.0~4.2, obtain chitosan Solution.The silane coupling agent is silane resin acceptor kh-550, is appointed in silane coupling agent KH-560 or Silane coupling reagent KH-570 Meaning is a kind of.
Sodium bentonite was crushed into 180 mesh sieve, obtains refinement sodium bentonite, refinement sodium bentonite and water are pressed into quality Than 1:50 are mixed in three-necked flask, in temperature be 40 DEG C, rotating speed be 300r/min under conditions of, after being stirred 26h, to three The green vitriol of 5 times of refinement sodium bentonite quality is added in mouth flask, and nitrogen is passed through with the rate of 20mL/min into three-necked flask Gas obtains pretreatment bentonite mixtures after being aerated 10min under nitrogen atmosphere, by pretreatment bentonite mixtures and anaerobic second Alcohol in mass ratio 4:1 mixing is 35 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred 40min, obtains swelling Earth mixtures;By the sodium hydroxide solution in mass ratio 1 of potassium borohydride and mass fraction 0.2%:15 mixing, in temperature be 45 DEG C, Rotating speed is the condition of 350r/min, after being stirred 30min, obtains sodium hydroxide mixed liquor, by 0.5 times of bentonite mixtures quality Sodium hydroxide mixed liquor instilled in bentonite mixtures with the rate of 7mL/min, and in temperature be 40 DEG C, rotating speed 800r/ It is stirred under conditions of min to sodium hydroxide mixing drop and is use up, it is 40 DEG C to continue at temperature, and rotating speed is the condition of 800r/min After being stirred 40min, filtering obtains filter cake, and by filter cake anaerobic milli-Q water 8 times, deoxidation absolute ethyl alcohol washing 8 times be used in combination Afterwards, by the filter cake after washing be 70 DEG C in temperature under conditions of dry 40min, pre- modified alta-mud is obtained, by pre- modified alta-mud With water in mass ratio 1:15 are mixed in beaker, with the pH of material in sodium metasilicate adjusting beaker to 10.5, and are added into beaker The modifying agent of 0.3 times of pre- modified alta-mud quality is 55 DEG C in temperature, and rotating speed is stirred 2h under conditions of being 350r/min Afterwards, it filters, obtains modified alta-mud blank, modified alta-mud blank be crushed into 220 mesh sieve, obtain modified alta-mud;By glass fibers Dimension and inorganic agent in mass ratio 1:8 mixing, and after impregnating 50min under room temperature, filtering obtains pretreated glass fiber, it will Pretreated glass fiber and graphene oxide liquid mixture in mass ratio 1:20 mixing are impregnated under conditions of being 50 DEG C in temperature After 30min, filtering must pre-process 1 processing glass fibre, the item for being 70 DEG C in temperature by 1 processing glass fibre of pretreatment Under part after dry 40min, 1 processing glass fibre is obtained, by 1 processing glass fibre and chitosan solution in mass ratio 1:15 is mixed It closes, after impregnating 30min under conditions of being 50 DEG C in temperature, filtering obtains pre- modified glass-fiber blank, by pre- modified glass-fiber Under conditions of blank is 80 DEG C in temperature after dry 30min, pre- modified glass-fiber is obtained;Pre- modified glass-fiber and water are pressed into matter Measure ratio 1:10 mix, and the silane of pre- 2 times of modified glass-fiber quality is added into the mixture of pre- modified glass-fiber and water Coupling agent is 55 DEG C in temperature, and after rotating speed is stirred 3h under conditions of being 300r/min, filtering obtains pretreatment modification glass Fiber obtains modified glass-fiber under conditions of being 80 DEG C in temperature by pretreatment modification glass fibre after dry 40min;It will change Property bentonite and modified glass-fiber in mass ratio 4:1 is mixed in blender, is 50 DEG C in temperature, rotating speed is 450r/min's Under the conditions of, it is stirred after 50min to get the special antistatic agent of polyurethane plastics.The modifying agent is cetyl trimethyl Ammonium bromide.The length of the glass fibre is 2mm, a diameter of 0.3mm.The inorganic agent be 70% by mass fraction sulfuric acid With hydrogen peroxide by volume 3:1 mixing, obtains inorganic agent.The preparation method of the graphene oxide liquid mixture is by graphite oxide Alkene and water in mass ratio 1:300 mixing, ultrasonic disperse are used in combination sodium hydroxide to adjust pH to 7.2, obtain graphene oxide liquid mixture. The preparation method of the chitosan solution is by chitosan and water in mass ratio 1:300 mixing, are used in combination second acid for adjusting pH to 4.2, Obtain chitosan solution.The silane coupling agent is silane resin acceptor kh-550.
Sodium bentonite was crushed into 180 mesh sieve, obtains refinement sodium bentonite, refinement sodium bentonite and water are pressed into quality Than 1:50 are mixed in three-necked flask, in temperature be 40 DEG C, rotating speed be 300r/min under conditions of, after being stirred 26h, to three The green vitriol of 5 times of refinement sodium bentonite quality is added in mouth flask, and nitrogen is passed through with the rate of 20mL/min into three-necked flask Gas obtains pretreatment bentonite mixtures after being aerated 10min under nitrogen atmosphere, by pretreatment bentonite mixtures and anaerobic second Alcohol in mass ratio 4:1 mixing is 35 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred 40min, obtains swelling Earth mixtures;By bentonite mixtures and water in mass ratio 1:15 are mixed in beaker, and material in beaker is adjusted with sodium metasilicate The modifying agent of 0.3 times of bentonite mixtures quality is added into beaker to 10.5 in pH, in temperature be 55 DEG C, rotating speed 350r/ After being stirred 2h under conditions of min, filtering obtains modified alta-mud blank, and modified alta-mud blank crushed 220 mesh sieve, Obtain modified alta-mud;By glass fibre and inorganic agent in mass ratio 1:8 mixing, and after impregnating 50min under room temperature, mistake Filter, obtains pretreated glass fiber, by pretreated glass fiber and graphene oxide liquid mixture in mass ratio 1:20 mixing, in temperature After impregnating 30min under conditions of being 50 DEG C, filtering must pre-process 1 processing glass fibre, by 1 processing glass fibers of pretreatment Tie up be 70 DEG C in temperature under conditions of after dry 40min, 1 processing glass fibre is obtained, by 1 processing glass fibre and chitosan Solution in mass ratio 1:15 mixing, after impregnating 30min under conditions of being 50 DEG C in temperature, filtering obtains pre- modified glass-fiber base Material obtains pre- modified glass-fiber under conditions of being 80 DEG C in temperature by pre- modified glass-fiber blank after dry 30min;It will be pre- Modified glass-fiber and water in mass ratio 1:10 mixing, and pre- modified glass is added into the mixture of pre- modified glass-fiber and water The silane coupling agent that 2 times of glass fiber quality, in temperature be 55 DEG C, rotating speed be 300r/min under conditions of be stirred 3h after, mistake Filter, obtains pretreatment modification glass fibre, under conditions of being 80 DEG C in temperature by pretreatment modification glass fibre after dry 40min, Obtain modified glass-fiber;By modified alta-mud and modified glass-fiber in mass ratio 4:1 is mixed in blender, in temperature be 50 DEG C, under conditions of rotating speed is 450r/min, it is stirred after 50min to get the special antistatic agent of polyurethane plastics.The modification Agent is cetyl trimethylammonium bromide.The length of the glass fibre is 2mm, a diameter of 0.3mm.The inorganic agent is by matter Measure sulfuric acid and hydrogen peroxide that score is 70% by volume 3:1 mixing, obtains inorganic agent.The system of the graphene oxide liquid mixture Preparation Method is by graphene oxide and water in mass ratio 1:300 mixing, ultrasonic disperse are used in combination sodium hydroxide to adjust pH to 7.2, are obtained Graphene oxide liquid mixture.The preparation method of the chitosan solution is by chitosan and water in mass ratio 1:300 mixing, are used in combination Second acid for adjusting pH obtains chitosan solution to 4.2.The silane coupling agent is silane resin acceptor kh-550.
Sodium bentonite was crushed into 180 mesh sieve, obtains refinement sodium bentonite, refinement sodium bentonite and water are pressed into quality Than 1:50 are mixed in three-necked flask, in temperature be 40 DEG C, rotating speed be 300r/min under conditions of, after being stirred 26h, to three The green vitriol of 5 times of refinement sodium bentonite quality is added in mouth flask, and nitrogen is passed through with the rate of 20mL/min into three-necked flask Gas obtains pretreatment bentonite mixtures after being aerated 10min under nitrogen atmosphere, by pretreatment bentonite mixtures and anaerobic second Alcohol in mass ratio 4:1 mixing is 35 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred 40min, obtains swelling Earth mixtures;By the sodium hydroxide solution in mass ratio 1 of potassium borohydride and mass fraction 0.2%:15 mixing, in temperature be 45 DEG C, Rotating speed is the condition of 350r/min, after being stirred 30min, obtains sodium hydroxide mixed liquor, by 0.5 times of bentonite mixtures quality Sodium hydroxide mixed liquor instilled in bentonite mixtures with the rate of 7mL/min, and in temperature be 40 DEG C, rotating speed 800r/ It is stirred under conditions of min to sodium hydroxide mixing drop and is use up, it is 40 DEG C to continue at temperature, and rotating speed is the condition of 800r/min After being stirred 40min, filtering obtains filter cake, and by filter cake anaerobic milli-Q water 8 times, deoxidation absolute ethyl alcohol washing 8 times be used in combination Afterwards, by the filter cake after washing be 70 DEG C in temperature under conditions of dry 40min, obtain pre- modified alta-mud;By glass fibre and place Manage agent in mass ratio 1:8 mixing, and after impregnating 50min under room temperature, filtering obtains pretreated glass fiber, will pre-process Glass fibre and graphene oxide liquid mixture in mass ratio 1:20 mixing, after impregnating 30min under conditions of being 50 DEG C in temperature, mistake Filter must pre-process 1 processing glass fibre, dry under conditions of being 70 DEG C in temperature by 1 processing glass fibre of pretreatment After 40min, 1 processing glass fibre is obtained, by 1 processing glass fibre and chitosan solution in mass ratio 1:15 mixing, Yu Wen After degree is impregnates 30min under conditions of 50 DEG C, filtering obtains pre- modified glass-fiber blank, by pre- modified glass-fiber blank in Temperature after dry 30min, obtains pre- modified glass-fiber under conditions of being 80 DEG C;By pre- modified glass-fiber and water in mass ratio 1: 10 mix, and the silane coupling agent of pre- 2 times of modified glass-fiber quality is added into the mixture of pre- modified glass-fiber and water, It it is 55 DEG C in temperature, after rotating speed is stirred 3h under conditions of being 300r/min, filtering obtains pretreatment modification glass fibre, will Under conditions of pretreatment modification glass fibre is 80 DEG C in temperature after dry 40min, modified glass-fiber is obtained;By pre- bentone Soil and modified glass-fiber in mass ratio 4:1 is mixed in blender, is 50 DEG C in temperature, rotating speed is the condition of 450r/min Under, it is stirred after 50min to get the special antistatic agent of polyurethane plastics.The modifying agent is cetyl trimethyl bromination Ammonium.The length of the glass fibre is 2mm, a diameter of 0.3mm.The inorganic agent be by mass fraction be 70% sulfuric acid and mistake Hydrogen oxide by volume 3:1 mixing, obtains inorganic agent.The preparation method of the graphene oxide liquid mixture be by graphene oxide with Water in mass ratio 1:300 mixing, ultrasonic disperse are used in combination sodium hydroxide to adjust pH to 7.2, obtain graphene oxide liquid mixture.It is described The preparation method of chitosan solution is by chitosan and water in mass ratio 1:300 mixing, are used in combination second acid for adjusting pH to 4.2, obtain shell Glycan solution.The silane coupling agent is silane resin acceptor kh-550.
Sodium bentonite was crushed into 180 mesh sieve, obtains refinement sodium bentonite, refinement sodium bentonite and water are pressed into quality Than 1:50 are mixed in three-necked flask, in temperature be 40 DEG C, rotating speed be 300r/min under conditions of, after being stirred 26h, to three The green vitriol of 5 times of refinement sodium bentonite quality is added in mouth flask, and nitrogen is passed through with the rate of 20mL/min into three-necked flask Gas obtains pretreatment bentonite mixtures after being aerated 10min under nitrogen atmosphere, by pretreatment bentonite mixtures and anaerobic second Alcohol in mass ratio 4:1 mixing is 35 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred 40min, obtains swelling Earth mixtures;By the sodium hydroxide solution in mass ratio 1 of potassium borohydride and mass fraction 0.2%:15 mixing, in temperature be 45 DEG C, Rotating speed is the condition of 350r/min, after being stirred 30min, obtains sodium hydroxide mixed liquor, by 0.5 times of bentonite mixtures quality Sodium hydroxide mixed liquor instilled in bentonite mixtures with the rate of 7mL/min, and in temperature be 40 DEG C, rotating speed 800r/ It is stirred under conditions of min to sodium hydroxide mixing drop and is use up, it is 40 DEG C to continue at temperature, and rotating speed is the condition of 800r/min After being stirred 40min, filtering obtains filter cake, and by filter cake anaerobic milli-Q water 8 times, deoxidation absolute ethyl alcohol washing 8 times be used in combination Afterwards, by the filter cake after washing be 70 DEG C in temperature under conditions of dry 40min, pre- modified alta-mud is obtained, by pre- modified alta-mud With water in mass ratio 1:15 are mixed in beaker, with the pH of material in sodium metasilicate adjusting beaker to 10.5, and are added into beaker The modifying agent of 0.3 times of pre- modified alta-mud quality is 55 DEG C in temperature, and rotating speed is stirred 2h under conditions of being 350r/min Afterwards, it filters, obtains modified alta-mud blank, modified alta-mud blank be crushed into 220 mesh sieve, obtain modified alta-mud;By glass fibers Dimension and water in mass ratio 1:10 mixing, and the silane of 2 times of glass fiber quality of addition is even into the mixture of glass fibre and water Join agent, is 55 DEG C in temperature, after rotating speed is stirred 3h under conditions of being 300r/min, filtering obtains pretreatment modification glass fibers Dimension obtains modified glass-fiber under conditions of being 80 DEG C in temperature by pretreatment modification glass fibre after dry 40min;It will be modified Bentonite and modified glass-fiber in mass ratio 4:1 is mixed in blender, is 50 DEG C in temperature, rotating speed is the item of 450r/min Under part, it is stirred after 50min to get the special antistatic agent of polyurethane plastics.The modifying agent is cetyl trimethyl bromine Change ammonium.The length of the glass fibre is 2mm, a diameter of 0.3mm.The inorganic agent be by mass fraction be 70% sulfuric acid with Hydrogen peroxide by volume 3:1 mixing, obtains inorganic agent.The preparation method of the graphene oxide liquid mixture is by graphene oxide With water in mass ratio 1:300 mixing, ultrasonic disperse are used in combination sodium hydroxide to adjust pH to 7.2, obtain graphene oxide liquid mixture.Institute The preparation method for stating chitosan solution is by chitosan and water in mass ratio 1:300 mixing, are used in combination second acid for adjusting pH to 4.2, obtain Chitosan solution.The silane coupling agent is silane resin acceptor kh-550.
Comparative example:The antistatic agent of Shanghai Chemical Co., Ltd. production.
1 to 4 gained antistatic agent of example and comparative example product are subjected to performance detection, specific detection method is as follows:
Above-mentioned antistatic agent is added in polyurethane plastics, detects its surface resistivity, specific testing result is as shown in table 1:
Table 1:Performance detection table
Detection content Example 1 Example 2 Example 3 Example 4 Comparative example
Surface resistivity/Ω 3.2×107 8.48×108 3.45×109 1.82×109 5.0×1010
By 1 testing result of table it is found that the present invention gained special antistatic agent of polyurethane plastics has excellent antistatic effect.

Claims (7)

1. a kind of preparation method of the special antistatic agent of polyurethane plastics, which is characterized in that specifically preparation process is:
(1)Sodium bentonite is crushed and is sieved, refinement sodium bentonite is obtained, by refinement sodium bentonite and water in mass ratio 1:40 ~1:50 mixing, and the green vitriol of 4~5 times of refinement sodium bentonite quality is added, under nitrogen protection, after being aerated 5~10min, Bentonite mixtures must be pre-processed, by pretreatment bentonite mixtures and no oxyethanol in mass ratio 3:1~4:1 mixing, obtains swollen Moisten earth mixtures;
(2)By potassium borohydride and sodium hydroxide solution in mass ratio 1:10~1:15 mixing, obtain sodium hydroxide mixed liquor, by swelling The sodium hydroxide mixed liquor of 0.2~0.4 times of earth mixtures quality instills in bentonite mixtures, and after being stirred, filtering must filter Filter cake anaerobic milli-Q water is used in combination deoxidation absolute ethyl alcohol to wash by cake, dry, obtains pre- modified alta-mud;
(3)By pre- modified alta-mud and water in mass ratio 1:10~1:15 mixing adjust pH to 10.0~10.5, and are added and change in advance Property 0.1~0.3 times of bentonite quality modifying agent, after being stirred, filtering pulverizes and sieves, obtains modified alta-mud;
(4)By glass fibre and inorganic agent in mass ratio 1:5~1:8 mixing are impregnated, and filtering obtains pretreated glass fiber, will be pre- Handle glass fibre and graphene oxide liquid mixture in mass ratio 1:10~1:20 mixing, impregnate, and filter, dry, obtain 1 processing Glass fibre, by 1 processing glass fibre and chitosan solution in mass ratio 1:10~1:15 mixing, impregnate, and filter, dry, Obtain pre- modified glass-fiber;
(5)By pre- modified glass-fiber and water in mass ratio 1:5~1:10 mixing, and pre- modified glass-fiber quality 1~2 is added Silane coupling agent again after being stirred, filters, dry, obtains modified glass-fiber;
(6)By modified alta-mud and modified glass-fiber in mass ratio 3:1~4:1 mixing is special anti-quiet to get polyurethane plastics Electric agent.
2. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (3)The modifying agent is any one in cetyl trimethylammonium bromide or N- Alkylation of Amino Acids.
3. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (4)The length of the glass fibre is 1~2mm, a diameter of 0.1~0.3mm.
4. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (4)The inorganic agent be 60~70% by mass fraction sulfuric acid and hydrogen peroxide by volume 3:1 mixing, obtains inorganic agent.
5. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (4)The preparation method of the graphene oxide liquid mixture is by graphene oxide and water in mass ratio 1:100~1:300 mixing, Ultrasonic disperse is used in combination sodium hydroxide to adjust pH to 7.0~7.2, obtains graphene oxide liquid mixture.
6. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (4)The preparation method of the chitosan solution is by chitosan and water in mass ratio 1:200~1:300 mixing, are used in combination acetic acid tune PH to 4.0~4.2 is saved, chitosan solution is obtained.
7. a kind of preparation method of the special antistatic agent of polyurethane plastics according to claim 1, it is characterised in that:Step (5)The silane coupling agent is silane resin acceptor kh-550, arbitrary in silane coupling agent KH-560 or Silane coupling reagent KH-570 It is a kind of.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112375329A (en) * 2020-11-11 2021-02-19 天津金发新材料有限公司 Antistatic high-temperature-resistant ABS composition and preparation method and application thereof
CN116376167A (en) * 2023-05-22 2023-07-04 上海廉藤实业有限公司 Modified plastic and preparation method thereof

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1686794A (en) * 2005-04-21 2005-10-26 浙江工业大学 Material of composite modified bentonite and production method
CN101260203A (en) * 2008-04-29 2008-09-10 上海工程技术大学 Electrostatic resistance rubber material and preparation method thereof
CN101486890A (en) * 2008-04-30 2009-07-22 上海工程技术大学 Anstatic agent and antistatic urethane elastomer material thereof
CN102251400A (en) * 2011-05-30 2011-11-23 四川大学 Organic Li-based bentonite-WPU (waterborne polyurethane) leather finishing agent and preparation method thereof
CN102816461A (en) * 2012-08-27 2012-12-12 暨南大学 Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application
CN103282438A (en) * 2010-11-05 2013-09-04 赢创德固赛有限公司 Polyamide 12 composition containing carbon nanotubes
CN103464091A (en) * 2013-10-08 2013-12-25 武汉科技大学 Modified bentonite load nanometer iron material and preparation method thereof
CN103772978A (en) * 2013-12-20 2014-05-07 铜陵市金利电子有限公司 Anti-static material composite for nylon gasket
CN104163928A (en) * 2014-08-25 2014-11-26 鸿纳(东莞)新材料科技有限公司 Conductive heat-conductive graphene slurry and coating
CN104449010A (en) * 2014-12-26 2015-03-25 苏州格瑞丰纳米科技有限公司 Polymer/graphene anti-static coating, preparation method and application thereof
CN104804204A (en) * 2015-04-23 2015-07-29 福州大学 Graphene/thermoplastic polyurethane composite and preparation method thereof
CN105505186A (en) * 2015-08-10 2016-04-20 国网山东省电力公司临沂供电公司 Antistatic paint
CN105507558A (en) * 2015-08-24 2016-04-20 国网山东省电力公司临沂供电公司 Anti-static PVC (polyvinyl chloride) plastic floor
CN105524542A (en) * 2015-08-10 2016-04-27 国网山东省电力公司临沂供电公司 Antistatic floor paint
CN105801913A (en) * 2014-12-31 2016-07-27 上海凯赛生物技术研发中心有限公司 Antistatic agent, antistatic polyamide composition, and preparation methods of antistatic agent and antistatic polyamide composition
CN106380585A (en) * 2016-08-31 2017-02-08 浙江理工大学 Preparation method of antistatic copolyester
WO2017037317A1 (en) * 2015-08-31 2017-03-09 Avanzare Innovacion Tecnologica S.L. Anti-static bicomponent formulation for unsaturated polyester resins and epoxy vinyl ester resins
CN106928784A (en) * 2015-12-31 2017-07-07 安炬科技股份有限公司 Transparent antistatic film
CN107573676A (en) * 2017-08-29 2018-01-12 六安永吉纳米材料科技有限公司 A kind of graphene method for preparing polyurethane elastic body

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1686794A (en) * 2005-04-21 2005-10-26 浙江工业大学 Material of composite modified bentonite and production method
CN101260203A (en) * 2008-04-29 2008-09-10 上海工程技术大学 Electrostatic resistance rubber material and preparation method thereof
CN101486890A (en) * 2008-04-30 2009-07-22 上海工程技术大学 Anstatic agent and antistatic urethane elastomer material thereof
CN103282438A (en) * 2010-11-05 2013-09-04 赢创德固赛有限公司 Polyamide 12 composition containing carbon nanotubes
CN102251400A (en) * 2011-05-30 2011-11-23 四川大学 Organic Li-based bentonite-WPU (waterborne polyurethane) leather finishing agent and preparation method thereof
CN102816461A (en) * 2012-08-27 2012-12-12 暨南大学 Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application
CN103464091A (en) * 2013-10-08 2013-12-25 武汉科技大学 Modified bentonite load nanometer iron material and preparation method thereof
CN103772978A (en) * 2013-12-20 2014-05-07 铜陵市金利电子有限公司 Anti-static material composite for nylon gasket
CN104163928A (en) * 2014-08-25 2014-11-26 鸿纳(东莞)新材料科技有限公司 Conductive heat-conductive graphene slurry and coating
CN104449010A (en) * 2014-12-26 2015-03-25 苏州格瑞丰纳米科技有限公司 Polymer/graphene anti-static coating, preparation method and application thereof
CN105801913A (en) * 2014-12-31 2016-07-27 上海凯赛生物技术研发中心有限公司 Antistatic agent, antistatic polyamide composition, and preparation methods of antistatic agent and antistatic polyamide composition
CN104804204A (en) * 2015-04-23 2015-07-29 福州大学 Graphene/thermoplastic polyurethane composite and preparation method thereof
CN105505186A (en) * 2015-08-10 2016-04-20 国网山东省电力公司临沂供电公司 Antistatic paint
CN105524542A (en) * 2015-08-10 2016-04-27 国网山东省电力公司临沂供电公司 Antistatic floor paint
CN105507558A (en) * 2015-08-24 2016-04-20 国网山东省电力公司临沂供电公司 Anti-static PVC (polyvinyl chloride) plastic floor
WO2017037317A1 (en) * 2015-08-31 2017-03-09 Avanzare Innovacion Tecnologica S.L. Anti-static bicomponent formulation for unsaturated polyester resins and epoxy vinyl ester resins
CN106928784A (en) * 2015-12-31 2017-07-07 安炬科技股份有限公司 Transparent antistatic film
CN106380585A (en) * 2016-08-31 2017-02-08 浙江理工大学 Preparation method of antistatic copolyester
CN107573676A (en) * 2017-08-29 2018-01-12 六安永吉纳米材料科技有限公司 A kind of graphene method for preparing polyurethane elastic body

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
付建伟: "石墨烯/水性聚氨酯复合涂层的制备与性能改善", 《信阳师范学院学报》 *
吴人洁: "《复合材料》", 31 December 2000, 天津大学出版社 *
张东兴: "《聚合物基复合材料科学与工程》", 31 July 2017, 哈尔滨工业大学出版社 *
张袁松: "《新型纤维材料概论》", 31 March 2012, 西南师范大学出版社 *
陈清如: "《中国洁净煤》", 30 September 2009, 中国矿业大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112375329A (en) * 2020-11-11 2021-02-19 天津金发新材料有限公司 Antistatic high-temperature-resistant ABS composition and preparation method and application thereof
CN112375329B (en) * 2020-11-11 2022-08-09 天津金发新材料有限公司 Antistatic high-temperature-resistant ABS composition and preparation method and application thereof
CN116376167A (en) * 2023-05-22 2023-07-04 上海廉藤实业有限公司 Modified plastic and preparation method thereof

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