CN108951278A - A kind of preparation method of automobile filter paper styrene-acrylic emulsion - Google Patents
A kind of preparation method of automobile filter paper styrene-acrylic emulsion Download PDFInfo
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- CN108951278A CN108951278A CN201810849452.5A CN201810849452A CN108951278A CN 108951278 A CN108951278 A CN 108951278A CN 201810849452 A CN201810849452 A CN 201810849452A CN 108951278 A CN108951278 A CN 108951278A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of preparation methods of automobile filter paper styrene-acrylic emulsion, belong to paper process auxiliary agent technical field.B emulsion is mixed with water 1:10~1:15 in mass ratio, and the emulsifier of 0.1~0.2 times of B emulsion quality is added, the sodium bicarbonate of 0.1~0.3 times of B emulsion quality and the initiator of 0.1~0.2 times of B emulsion quality, are stirred to react to there is blue light, obtain seed emulsion；A emulsion is instilled in seed emulsion, time for adding is controlled in 2~3h, and 0.1~0.3 times of seed emulsion quality of initiator is added, after being stirred to react, cooling, obtains blank liquid, and the methyl of 0.1~0.2 times of tert-butyl peroxide and blank liquid quality that 0.1~0.2 times of blank liquid quality is added into blank liquid closes sodium hydrosulfide, and pH to 7~8 is adjusted, obtain automobile filter paper styrene-acrylic emulsion.The automobile filter paper of technical solution of the present invention preparation has the characteristics that excellent hydrophobic performance and absorption property with styrene-acrylic emulsion.
Description
Technical field
The invention discloses a kind of preparation methods of automobile filter paper styrene-acrylic emulsion, belong to paper process auxiliary agent technology neck
Domain.
Background technique
Automotive industrial planning is one of the raw material for producing filtering core device, also known as " three filter paper of automobile " i.e. " air filter, fuel oil
Filter, oil strainer ", be clean Modern High-Speed internal combustion engine coarse filtration material, to the economic and technical norms of engine, environmental protection index,
Safety index, the service life for improving engine have important relationship.Family-sized car, cargo vehicle and engineering machinery, because of building ring
The difference in border has different requirements to the thickness of filter material, tension stress, original intake resistance, filtering accuracy.By in fuel oil
Impurity is analyzed, and the foreign particle (wherein iron and element silicon account for 50%) of 5~20um will cause mill to accurate accessory in fuel oil
Damage.Fuel injector injects fuel directly into cylinder or air inlet pipe under pressure, it is desirable that and filter paper has certain filtering accuracy,
In order to avoid plug nozzle.In fact, filter paper other than filtering out particle, can be filtered out in fuel oil with the structure of complement filter device
Some moisture.Moisture in these fuel oils often corrodes accurate accessory, can also congeal into ice, cause in cold district and season
Internal combustion engine cannot start.To guarantee that internal combustion engine is safely and effectively run, matched filter material must have following performance: 1, wanting
Ask filter paper that there is certain physical strength, unit area has certain receiving fluid pressure energy power.2, fluid is required to pass through filter material
When, very big resistance will not be generated, filter paper has certain pore size and percent opening, and has certain dust capaciting ability.It can protect
Card fuel system has higher regurgitant volume, and filter material unit area flow meets design requirement.3, requiring filtering accuracy is 3~5um,
These diameters impurity particle near mechanical gap width can be filtered out, in order to avoid abrasion is generated to machinery.The Combustion System of internal combustion engine
System, it is desirable that guarantee the burning and discharge of engine；The air-filtering of automobile requires that engine can be improved up to 98% or more
Service life prevents premature wear.In addition, porosity filter material is a kind of effective intake muffler, resin processed micropore
Filter paper is the excellent noise elimination sound-absorbing material of porous type.In the impregnation processability treatment process to raw paper of filter paper, impregnation processability
Influence of the resin to paper properties is very big.Impregnating resin is divided into alcohol-soluble resin and water-soluble resin, with environmental protection, the energy
The aggravation of the problems such as in short supply, Used in Impregnating Automobile Filter Paper resin, which turns to water-soluble emulsion direction by alcohol-soluble, to be developed.
And there is also the problems of hydrophobic performance and absorption property deficiency for traditional automobile filter paper styrene-acrylic emulsion, therefore, such as
What improves the shortcomings that orthodox car filter paper styrene-acrylic emulsion can not be further increased there is also hydrophobic performance and absorption property, in the hope of
It is problem to be solved that exploration, which develops the automobile filter paper with good comprehensive performance with styrene-acrylic emulsion,.
Summary of the invention
The present invention solves the technical problem of: it is directed to orthodox car filter paper styrene-acrylic emulsion hydrophobic performance and adsorptivity
The shortcomings that capable of can not further increasing, provide a kind of preparation method of automobile filter paper styrene-acrylic emulsion.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of automobile filter paper styrene-acrylic emulsion, specific preparation step are as follows:
(1) cetyl trimethylammonium bromide is mixed with graphene oxide solution 1:50~1:80 in mass ratio, and is added ten
The sodium borohydride of six 0.25~0.30 times of alkyl trimethyl ammonium bromide quality, after being stirred to react, obtains graphene oxide mixed solution,
Graphene oxide mixed solution is mixed with sodium hydroxide solution 10:1~10:4 in mass ratio, it is mixed that graphene oxide must be pre-processed
Close liquid；
(2) pretreatment graphene oxide liquid mixture is mixed with ethyl orthosilicate 5:1~5:2 in mass ratio, after ultrasonic disperse, is stirred
Reaction is mixed, modified graphene oxide mixture is obtained, by hydrochloric acid mixed solution and modified graphene oxide mixture in mass ratio 1:
100~5:100 mixing, after being stirred to react, is centrifugated, and filtering obtains modified graphene oxide；
(3) pretreatment carbon nanotube is mixed with water 1:500~1:600 in mass ratio, ultrasonic disperse obtains pretreatment carbon nanotube
Dispersion liquid mixes modified graphene oxide with water 1:300~1:500 in mass ratio, and ultrasonic disperse obtains modified graphene oxide
Pretreatment carbon nano tube dispersion liquid is mixed with modified graphene oxide dispersion liquid 1:2~1:3 in mass ratio, is adjusted by dispersion liquid
After pH to 8.0~8.5, and polyethylene polyamine and the pretreatment of 0.08~0.10 times of carbon nano tube dispersion liquid quality of pretreatment is added
Aqueous solution of ester in 0.02~0.08 times of carbon nano tube dispersion liquid of glucose β after ultrasonic disperse, stands, filters, washs, dry,
Obtain modified additive；
(4) according to parts by weight, it successively weighs: 20~35 parts of butyl acrylates, 15~22 parts of styrene, 10~15 parts of methyl-props
Olefin(e) acid, 5~6 parts of silane coupling agent KH-560,12~20 parts of modified additives, 3~5 parts of emulsifiers and 40~80 parts of water, by third
Olefin(e) acid butyl ester is mixed with modified additive, and styrene is added, silane coupling agent KH-560, methacrylic acid, emulsifier and water,
After being stirred, emulsion is obtained；It is two parts that emulsion 1:3 in mass ratio, which is divided to, wherein it is A emulsion that amount is mostly, is measured few for B
Emulsion；
(5) B emulsion is mixed with water 1:10~1:15 in mass ratio, and the emulsification of 0.1~0.2 times of B emulsion quality is added
Agent, the sodium bicarbonate of 0.1~0.3 times of B emulsion quality and the initiator of 0.1~0.2 times of B emulsion quality, be stirred to react to
There is blue light, obtains seed emulsion；
(6) by A emulsion instill seed emulsion in, control time for adding in 2~3h, and be added seed emulsion quality 0.1~
0.3 times of initiator, after being stirred to react, cooling obtains blank liquid, and the mistake of 0.1~0.2 times of blank liquid quality is added into blank liquid
The methyl for aoxidizing 0.1~0.2 times of tert-butyl and blank liquid quality closes sodium hydrosulfide, and adjusts pH to 7~8, obtains automobile filter paper use
Styrene-acrylic emulsion.
Step (1) graphene oxide solution is to mix graphene oxide with water 1:300~1:400 in mass ratio,
Ultrasonic disperse obtains graphene oxide solution.
Step (2) described hydrochloric acid mixed solution be 70~80% by mass fraction ethanol solution and mass fraction be 20
4:1 is mixed~30% hydrochloric acid by volume, obtains hydrochloric acid mixed solution.
Step (3) the pretreatment carbon nanotube be by carbon nanotube and mass fraction be 60~65% nitric acid by quality
The sulfuric acid that the mass fraction for mixing than 1:5~1:6, and being added 6~8 times of carbon nanotube mass is 70~80%, after being stirred,
Filtering, washing to cleaning solution are neutrality, obtain pretreatment carbon nanotube.
Step (4) polyethylene polyamine is triethylene tetramine, any one in diethylenetriamine or ethylenediamine.
The emulsifier is lauryl sodium sulfate, any one in neopelex or emulsifier op-10.
The initiator is any one in potassium peroxydisulfate or ammonium persulfate.
The beneficial effects of the present invention are:
Modified additive is added when preparing automobile filter paper styrene-acrylic emulsion in the present invention, firstly, containing porous in modified additive
Silica, after being added in product, modification of the silica through silane coupling agent KH-560 generates hydrophobic performance, to make
After product use, the hydrophobicity of filter paper is improved, and due to the porosity characteristic of silica, to make filter paper after using product
Adsorptivity improve；Secondly, modified additive intermediary hole silica and graphene oxide can form sandwich sandwich,
After being added in product, it can be fixed on paper surface under the action of styrene-acrylic emulsion, and due to the lamellar structure of graphene oxide,
And organise after treatment, so that hydrophobic performance of the filter paper after using product is improved, furthermore, in modified additive, carbon is received
The addition of mitron can form three-dimensional net structure with graphene oxide, polyethylene polyamine, to improve filter paper after using product
The porosity on surface, and then improve the absorption property of product；Also, the carbon nanotube and graphene oxide due to addition are producing
Negative electrical charge is had in product, so that filter paper can be improved in the quantity of electric charge using product rear surface, and then is improved filter paper and is being used product
Adsorptivity afterwards.
Specific embodiment
Cetyl trimethylammonium bromide and graphene oxide solution 1:50~1:80 in mass ratio are mixed in beaker,
And 0.25~0.30 times of cetyl trimethylammonium bromide quality of sodium borohydride is added into beaker, in temperature be 60~65
DEG C, under conditions of revolving speed is 200~350r/min, after being stirred to react 30~40min, graphene oxide mixed solution is obtained, by oxygen
Graphite alkene mixed solution is mixed with sodium hydroxide solution 10:1~10:4 in mass ratio that mass fraction is 5~12%, in temperature
It is 40~50 DEG C, under conditions of revolving speed is 300~400r/min, after being stirred to react 10~12h, it is mixed that graphene oxide must be pre-processed
Close liquid；Pretreatment graphene oxide liquid mixture is mixed with ethyl orthosilicate 5:1~5:2 in mass ratio, in frequency for 45~
It under conditions of 55kHz after 20~40min of ultrasonic disperse, and is 40~60 DEG C in temperature, revolving speed is the condition of 250~300r/min
Under, after being stirred to react 5~6h, modified graphene oxide mixture is obtained, hydrochloric acid mixed solution is mixed with modified graphene oxide
Object 1:100~5:100 in mass ratio mixing is 100 DEG C in temperature, under conditions of revolving speed is 200~300r/min, is stirred to react
20~for 24 hours after, be centrifugated under conditions of 4500r/min, filter, obtain modified graphene oxide；Carbon nanotube will be pre-processed
It mixes with water 1:500~1:600 in mass ratio, under conditions of frequency is 45~55kHz after 50~60min of ultrasonic disperse, obtains
Pre-process carbon nano tube dispersion liquid, modified graphene oxide is mixed with water 1:300~1:500 in mass ratio, in frequency be 45
Under conditions of~55kHz after 40~50min of ultrasonic disperse, modified graphene oxide dispersion liquid is obtained, by pretreatment carbon nanotube point
Dispersion liquid and modified graphene oxide dispersion liquid 1:2~1:3 in mass ratio are mixed in flask, and are 5~8% with mass fraction
Sodium hydroxide solution is adjusted in flask after the pH to 8.0~8.5 of material, and pretreatment carbon nano tube dispersion liquid is added into flask
The mass fraction of 0.02~0.08 times of carbon nano tube dispersion liquid of the polyethylene polyamine and pretreatment that 0.08~0.10 times of quality is 10
Aqueous solution of ester in~18% glucose β is stood, filtering under conditions of frequency is 45~60kHz after 1~2h of ultrasonic disperse,
Modified additive blank is obtained, after modified additive blank is washed with water 5~8 times, is done under conditions of being 70~80 DEG C in temperature
After dry 1~2h, modified additive is obtained；According to parts by weight, it successively weighs: 20~35 parts of butyl acrylates, 15~22 parts of benzene second
Alkene, 10~15 parts of methacrylic acids, 5~6 parts of silane coupling agent KH-560,12~20 parts of modified additives, 3~5 parts of emulsifiers
With 40~80 parts of water, butyl acrylate and modified additive are mixed in blender, and styrene is added into blender, silicon
Alkane coupling agent KH-560, methacrylic acid, emulsifier and water are 55~65 DEG C in temperature, and revolving speed is the item of 500~800r/min
Under part, after being stirred 30~50min, emulsion is obtained；It is two parts that emulsion 1:3 in mass ratio, which is divided to, wherein it is A cream that amount is mostly
Change liquid, measures few for B emulsion；B emulsion and water 1:10~1:15 in mass ratio are mixed in three-necked flask, and to three mouthfuls
The emulsifier of 0.1~0.2 times of B emulsion quality, sodium bicarbonate and the B cream of 0.1~0.3 times of B emulsion quality are added in flask
The initiator for changing 0.1~0.2 times of liquid quality is 80~85 DEG C in temperature, under conditions of revolving speed is 300~400r/min, stirs
There is blue light to material in three-necked flask in reaction, obtains seed emulsion；Seed emulsion is added in four-hole boiling flask, and to four-hole boiling flask
Middle instillation A emulsion controls time for adding in 2~3h, then 0.1~0.3 times of seed emulsion quality is added into four-hole boiling flask
Initiator, in temperature be 80~85 DEG C, revolving speed be 300~400r/min under conditions of, after being stirred to react 2~4h, Jiang Sikou
Temperature of charge is cooled to 40~50 DEG C in flask, obtains blank liquid, and the mistake of 0.1~0.2 times of blank liquid quality is added into blank liquid
The methyl for aoxidizing 0.1~0.2 times of tert-butyl and blank liquid quality closes sodium hydrosulfide, and is adjusted with the ammonium hydroxide of mass fraction 8~12%
After the pH to 7~8 of blank liquid, automobile filter paper styrene-acrylic emulsion is obtained.The graphene oxide solution is by graphene oxide and water
The mixing of 1:300~1:400 in mass ratio, ultrasonic disperse obtain graphene oxide solution.The hydrochloric acid mixed solution is by quality point
4:1 is mixed the hydrochloric acid that the ethanol solution that number is 70~80% is 20~30% with mass fraction by volume, obtains hydrochloric acid mixed solution.
The pretreatment carbon nanotube is to mix carbon nanotube with nitric acid 1:5~1:6 in mass ratio that mass fraction is 60~65%,
And the sulfuric acid that the mass fraction for being added 6~8 times of carbon nanotube mass is 70~80%, after being stirred, filtering, washing to washing
Liquid is neutrality, obtains pretreatment carbon nanotube.The polyethylene polyamine is triethylene tetramine, any in diethylenetriamine or ethylenediamine
It is a kind of.The emulsifier is lauryl sodium sulfate, any one in neopelex or emulsifier op-10.It is described
Initiator is any one in potassium peroxydisulfate or ammonium persulfate.
Example 1
Cetyl trimethylammonium bromide and graphene oxide solution 1:80 in mass ratio are mixed in beaker, and into beaker
0.30 times of cetyl trimethylammonium bromide quality of sodium borohydride is added, is 65 DEG C in temperature, revolving speed is the item of 350r/min
Under part, after being stirred to react, graphene oxide mixed solution is obtained, the hydrogen for being 12% by graphene oxide mixed solution and mass fraction
Sodium hydroxide solution 10:4 in mass ratio mixing, in temperature be 50 DEG C, revolving speed be 400r/min under conditions of, after being stirred to react 12h,
Graphene oxide liquid mixture must be pre-processed；Pretreatment graphene oxide liquid mixture is mixed with ethyl orthosilicate 5:2 in mass ratio,
Under conditions of frequency is 55kHz after ultrasonic disperse 40min, and it is 60 DEG C in temperature, under conditions of revolving speed is 300r/min, stirs
After mixing reaction 6h, modified graphene oxide mixture is obtained, hydrochloric acid mixed solution and modified graphene oxide mixture are pressed into quality
Than 5:100 mix, in temperature be 100 DEG C, revolving speed be 300r/min under conditions of, after being stirred to react for 24 hours, in 4500r/min's
Under the conditions of be centrifugated, filter, obtain modified graphene oxide；Pretreatment carbon nanotube is mixed with water 1:600 in mass ratio, in
Frequency be 55kHz under conditions of after ultrasonic disperse 60min, obtain pretreatment carbon nano tube dispersion liquid, by modified graphene oxide with
Water 1:500 in mass ratio mixing obtains modified graphene oxide dispersion under conditions of frequency is 55kHz after ultrasonic disperse 50min
Pretreatment carbon nano tube dispersion liquid and modified graphene oxide dispersion liquid 1:3 in mass ratio are mixed in flask, and use matter by liquid
It measures the sodium hydroxide solution that score is 8% to adjust in flask after the pH to 8.5 of material, and pretreatment carbon nanometer is added into flask
The Portugal that the polyethylene polyamine of 0.10 times of pipe dispersion liquid quality and the mass fraction of 0.08 times of carbon nano tube dispersion liquid of pretreatment are 18%
Aqueous solution of ester in grape sugar β is stood under conditions of frequency is 60kHz after ultrasonic disperse 2h, and filtering obtains modified additive blank,
After modified additive blank is washed with water 8 times, under conditions of being 80 DEG C in temperature after dry 2h, modified additive is obtained；By weight
Number meter is measured, is successively weighed: 35 parts of butyl acrylates, 22 parts of styrene, 15 parts of methacrylic acids, 6 parts of silane coupling agent KH-
Butyl acrylate and modified additive are mixed in blender by 560,20 parts of modified additives, 5 parts of emulsifiers and 80 parts of water,
And styrene is added into blender, silane coupling agent KH-560, methacrylic acid, emulsifier and water are 65 DEG C in temperature, turn
Under conditions of speed is 800r/min, after being stirred 50min, emulsion is obtained；It is two parts that emulsion 1:3 in mass ratio, which is divided to,
It is A emulsion mostly middle amount, measures few for B emulsion；B emulsion and water 1:15 in mass ratio are mixed in three-necked flask,
And the emulsifier of 0.2 times of B emulsion quality is added into three-necked flask, sodium bicarbonate and the B emulsification of 0.3 times of B emulsion quality
The initiator that 0.2 times of liquid quality is 85 DEG C in temperature, under conditions of revolving speed is 400r/min, is stirred to react to three-necked flask
There is blue light in material, obtains seed emulsion；Seed emulsion is added in four-hole boiling flask, and instills A emulsion into four-hole boiling flask, control
Time for adding processed is in 3h, then 0.3 times of seed emulsion quality of initiator is added into four-hole boiling flask, is 85 DEG C in temperature, turns
Under conditions of speed is 400r/min, after being stirred to react 4h, temperature of charge in four-hole boiling flask is cooled to 50 DEG C, obtains blank liquid, to
The methyl of 0.2 times of tert-butyl peroxide and blank liquid quality that 0.2 times of blank liquid quality is added in blank liquid closes sodium hydrosulfide, and
After the pH to 8 for adjusting blank liquid with the ammonium hydroxide of mass fraction 12%, automobile filter paper styrene-acrylic emulsion is obtained.The graphene oxide is molten
Liquid is to mix graphene oxide with water 1:400 in mass ratio, and ultrasonic disperse obtains graphene oxide solution.The mixed in hydrochloric acid
Solution be 80% by mass fraction ethanol solution and mass fraction be 30% hydrochloric acid 4:1 is mixed by volume, obtain salt acid-mixed
Close solution.The pretreatment carbon nanotube be carbon nanotube is mixed with the nitric acid 1:6 in mass ratio that mass fraction is 65%, and
The sulfuric acid that the mass fraction for being added 8 times of carbon nanotube mass is 80%, after being stirred, filtering, washing to cleaning solution is neutrality,
Carbon nanotube must be pre-processed.The polyethylene polyamine is triethylene tetramine.The emulsifier is lauryl sodium sulfate.It is described to draw
Hair agent is potassium peroxydisulfate.
Example 2
Cetyl trimethylammonium bromide and graphene oxide solution 1:80 in mass ratio are mixed in beaker, and into beaker
0.30 times of cetyl trimethylammonium bromide quality of sodium borohydride is added, is 65 DEG C in temperature, revolving speed is the item of 350r/min
Under part, after being stirred to react 40min, graphene oxide mixed solution is obtained, is 12% by graphene oxide mixed solution and mass fraction
Sodium hydroxide solution 10:4 in mass ratio mixing, in temperature be 50 DEG C, revolving speed be 400r/min under conditions of, be stirred to react
After 12h, pretreatment graphene oxide liquid mixture is obtained；Pretreatment carbon nanotube is mixed with water 1:600 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 60min, pretreatment carbon nano tube dispersion liquid is obtained, graphene oxide liquid mixture will be pre-processed
It is mixed with water 1:500 in mass ratio, under conditions of frequency is 55kHz after ultrasonic disperse 50min, obtains modified graphene oxide point
Pretreatment carbon nano tube dispersion liquid and modified graphene oxide dispersion liquid 1:3 in mass ratio are mixed in flask, are used in combination by dispersion liquid
The sodium hydroxide solution that mass fraction is 8% is adjusted in flask after the pH to 8.5 of material, and pretreatment carbon is added into flask and receives
The polyethylene polyamine of 0.10 times of mitron dispersion liquid quality and the mass fraction of 0.08 times of carbon nano tube dispersion liquid of pretreatment are 18%
Aqueous solution of ester in glucose β is stood under conditions of frequency is 60kHz after ultrasonic disperse 2h, and filtering obtains modified additive base
Material after modified additive blank is washed with water 8 times, under conditions of being 80 DEG C in temperature after dry 2h, obtains modified additive；It presses
Parts by weight meter, successively weighs: 35 parts of butyl acrylates, 22 parts of styrene, 15 parts of methacrylic acids, 6 parts of silane coupling agent KH-
Butyl acrylate and modified additive are mixed in blender by 560,20 parts of modified additives, 5 parts of emulsifiers and 80 parts of water,
And styrene is added into blender, silane coupling agent KH-560, methacrylic acid, emulsifier and water are 65 DEG C in temperature, turn
Under conditions of speed is 800r/min, after being stirred 50min, emulsion is obtained；It is two parts that emulsion 1:3 in mass ratio, which is divided to,
It is A emulsion mostly middle amount, measures few for B emulsion；B emulsion and water 1:15 in mass ratio are mixed in three-necked flask,
And the emulsifier of 0.2 times of B emulsion quality is added into three-necked flask, sodium bicarbonate and the B emulsification of 0.3 times of B emulsion quality
The initiator that 0.2 times of liquid quality is 85 DEG C in temperature, under conditions of revolving speed is 400r/min, is stirred to react to three-necked flask
There is blue light in material, obtains seed emulsion；Seed emulsion is added in four-hole boiling flask, and instills A emulsion into four-hole boiling flask, control
Time for adding processed is in 3h, then 0.3 times of seed emulsion quality of initiator is added into four-hole boiling flask, is 85 DEG C in temperature, turns
Under conditions of speed is 400r/min, after being stirred to react 4h, temperature of charge in four-hole boiling flask is cooled to 50 DEG C, obtains blank liquid, to
The methyl of 0.2 times of tert-butyl peroxide and blank liquid quality that 0.2 times of blank liquid quality is added in blank liquid closes sodium hydrosulfide, and
After the pH to 8 for adjusting blank liquid with the ammonium hydroxide of mass fraction 12%, automobile filter paper styrene-acrylic emulsion is obtained.The graphene oxide is molten
Liquid is to mix graphene oxide with water 1:400 in mass ratio, and ultrasonic disperse obtains graphene oxide solution.The pretreatment carbon
Nanotube is to mix carbon nanotube with the nitric acid 1:6 in mass ratio that mass fraction is 65%, and be added 8 times of carbon nanotube mass
Mass fraction be 80% sulfuric acid, after being stirred, filtering, washing to cleaning solution be neutrality, obtain pretreatment carbon nanotube.Institute
Stating polyethylene polyamine is triethylene tetramine.The emulsifier is lauryl sodium sulfate.The initiator is potassium peroxydisulfate.
Example 3
Cetyl trimethylammonium bromide and graphene oxide solution 1:80 in mass ratio are mixed in beaker, and into beaker
0.30 times of cetyl trimethylammonium bromide quality of sodium borohydride is added, is 65 DEG C in temperature, revolving speed is the item of 350r/min
Under part, after being stirred to react 40min, graphene oxide mixed solution is obtained, is 12% by graphene oxide mixed solution and mass fraction
Sodium hydroxide solution 10:4 in mass ratio mixing, in temperature be 50 DEG C, revolving speed be 400r/min under conditions of, be stirred to react
After 12h, pretreatment graphene oxide liquid mixture is obtained；Graphene oxide liquid mixture and ethyl orthosilicate in mass ratio 5 will be pre-processed:
2 mixing under conditions of frequency is 55kHz after ultrasonic disperse 40min, and are 60 DEG C in temperature, and revolving speed is the item of 300r/min
Under part, after being stirred to react 6h, modified graphene oxide mixture is obtained, by hydrochloric acid mixed solution and modified graphene oxide mixture
5:100 in mass ratio mixing, in temperature be 100 DEG C, revolving speed be 300r/min under conditions of, after being stirred to react for 24 hours, in 4500r/
It is centrifugated under conditions of min, filters, obtain modified graphene oxide；According to parts by weight, it successively weighs: 35 parts of acrylic acid fourths
Ester, 22 parts of styrene, 15 parts of methacrylic acids, 6 parts of silane coupling agent KH-560,5 parts of emulsifiers and 80 parts of water, by acrylic acid fourth
Ester is mixed in blender, and styrene is added into blender, silane coupling agent KH-560, methacrylic acid, emulsifier and
Water is 65 DEG C in temperature, under conditions of revolving speed is 800r/min, after being stirred 50min, obtains emulsion；Emulsion is pressed into matter
It is two parts that amount is divided to than 1:3, wherein it is A emulsion that amount is mostly, is measured few for B emulsion；By B emulsion and water 1:15 in mass ratio
It is mixed in three-necked flask, and the emulsifier of 0.2 times of B emulsion quality, 0.3 times of B emulsion quality is added into three-necked flask
Sodium bicarbonate and 0.2 times of B emulsion quality initiator, in temperature be 85 DEG C, revolving speed be 400r/min under conditions of, stirring
There is blue light to material in three-necked flask in reaction, obtains seed emulsion；Seed emulsion is added in four-hole boiling flask, and to four-hole boiling flask
Middle instillation A emulsion controls time for adding in 3h, then 0.3 times of seed emulsion quality of initiator is added into four-hole boiling flask,
It is 85 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react 4h, temperature of charge in four-hole boiling flask is cooled to 50
DEG C, blank liquid is obtained, the tert-butyl peroxide of 0.2 times of blank liquid quality and the first of 0.2 times of blank liquid quality are added into blank liquid
Base closes sodium hydrosulfide, and with after the pH to 8 of the ammonium hydroxide of mass fraction 12% adjusting blank liquid, obtains automobile filter paper styrene-acrylic emulsion.Institute
Stating graphene oxide solution is to mix graphene oxide with water 1:400 in mass ratio, and it is molten to obtain graphene oxide for ultrasonic disperse
Liquid.The hydrochloric acid mixed solution be 80% by mass fraction ethanol solution and mass fraction be 30% hydrochloric acid by volume 4:
1 mixing, obtains hydrochloric acid mixed solution.The polyethylene polyamine is triethylene tetramine.The emulsifier is lauryl sodium sulfate.Institute
Stating initiator is potassium peroxydisulfate.
Comparative example: the automobile filter paper styrene-acrylic emulsion of Shanghai Chemical Manufacture Co., Ltd production.
Example 1 to 3 resulting automobile filter paper styrene-acrylic emulsion of example and comparative example product is subjected to performance detection, it is specific to examine
Survey method is as follows:
Test specimen is taken, double-sided adhesive is sticked on glass slide, test specimen is sticked on double-sided adhesive, is flattened.It is measured with contact angle analysis instrument
Water droplet specimen surface contact angle, when measurement the volume of water droplet used be 5 μ L, data are surveyed under 5 different locations
The average value of amount.
Filter efficiency: PYRX filter is used, 04 micron of dust, vacuum pump, minimum 0.7bar vacuum degree uses mass method
Measurement.Test procedure is as follows: pattern (5cm × 5cm) is sandwiched in device.Vacuum degree is debugged extremely by 100ml water in 5 seconds interior suctions
It is dry.Said sample need to be numbered, and measure its oven dry weight (m1) to each label dust parallel testing of each filter material
Product group data, are averaged；10mg dust is added in beaker, 100ml water is added, is uniformly mixed, mixed liquor is poured into funnel
In, and beaker and funnel are rinsed with 50ml water, it is ensured that there is no dust residue.After water blots, vacuum pump need to be continued starting 2 minutes,
It allows air to pass through filter material and then takes out l Water Paper sample, in 150 DEG C of baking 10mim or more, weigh (m2)。
Dust quality is added in filter efficiency=(m1-m2) ÷
Specific testing result is as shown in table 1:
Table 1 automobile filter paper styrene-acrylic emulsion performance test results
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Contact angle/° | 147 | 123 | 120 | 76 | 0 |
| Filter efficiency/% | 99.5 | 98.2 | 97.9 | 97.2 | 96.1 |
By 1 testing result of table it is found that the automobile filter paper of technical solution of the present invention preparation has excellent hydrophobicity with styrene-acrylic emulsion
It the characteristics of energy and absorption property, has broad prospects in the development of paper process auxiliary agent technology industry.
Claims (7)
1. a kind of preparation method of automobile filter paper styrene-acrylic emulsion, which is characterized in that specific preparation step are as follows:
(1) cetyl trimethylammonium bromide is mixed with graphene oxide solution 1:50~1:80 in mass ratio, and is added ten
The sodium borohydride of six 0.25~0.30 times of alkyl trimethyl ammonium bromide quality, after being stirred to react, obtains graphene oxide mixed solution,
Graphene oxide mixed solution is mixed with sodium hydroxide solution 10:1~10:4 in mass ratio, it is mixed that graphene oxide must be pre-processed
Close liquid；
(2) pretreatment graphene oxide liquid mixture is mixed with ethyl orthosilicate 5:1~5:2 in mass ratio, after ultrasonic disperse, is stirred
Reaction is mixed, modified graphene oxide mixture is obtained, by hydrochloric acid mixed solution and modified graphene oxide mixture in mass ratio 1:
100~5:100 mixing, after being stirred to react, is centrifugated, and filtering obtains modified graphene oxide；
(3) pretreatment carbon nanotube is mixed with water 1:500~1:600 in mass ratio, ultrasonic disperse obtains pretreatment carbon nanotube
Dispersion liquid mixes modified graphene oxide with water 1:300~1:500 in mass ratio, and ultrasonic disperse obtains modified graphene oxide
Pretreatment carbon nano tube dispersion liquid is mixed with modified graphene oxide dispersion liquid 1:2~1:3 in mass ratio, is adjusted by dispersion liquid
After pH to 8.0~8.5, and polyethylene polyamine and the pretreatment of 0.08~0.10 times of carbon nano tube dispersion liquid quality of pretreatment is added
Aqueous solution of ester in 0.02~0.08 times of carbon nano tube dispersion liquid of glucose β after ultrasonic disperse, stands, filters, washs, dry,
Obtain modified additive；
(4) according to parts by weight, it successively weighs: 20~35 parts of butyl acrylates, 15~22 parts of styrene, 10~15 parts of methyl-props
Olefin(e) acid, 5~6 parts of silane coupling agent KH-560,12~20 parts of modified additives, 3~5 parts of emulsifiers and 40~80 parts of water, by third
Olefin(e) acid butyl ester is mixed with modified additive, and styrene is added, silane coupling agent KH-560, methacrylic acid, emulsifier and water,
After being stirred, emulsion is obtained；It is two parts that emulsion 1:3 in mass ratio, which is divided to, wherein it is A emulsion that amount is mostly, is measured few for B
Emulsion；
(5) B emulsion is mixed with water 1:10~1:15 in mass ratio, and the emulsification of 0.1~0.2 times of B emulsion quality is added
Agent, the sodium bicarbonate of 0.1~0.3 times of B emulsion quality and the initiator of 0.1~0.2 times of B emulsion quality, be stirred to react to
There is blue light, obtains seed emulsion；
(6) by A emulsion instill seed emulsion in, control time for adding in 2~3h, and be added seed emulsion quality 0.1~
0.3 times of initiator, after being stirred to react, cooling obtains blank liquid, and the mistake of 0.1~0.2 times of blank liquid quality is added into blank liquid
The methyl for aoxidizing 0.1~0.2 times of tert-butyl and blank liquid quality closes sodium hydrosulfide, and adjusts pH to 7~8, obtains automobile filter paper use
Styrene-acrylic emulsion.
2. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: step (1)
The graphene oxide solution is to mix graphene oxide with water 1:300~1:400 in mass ratio, and ultrasonic disperse must aoxidize
Graphene solution.
3. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: step (2)
The hydrochloric acid mixed solution be 70~80% by mass fraction ethanol solution and mass fraction be 20~30% hydrochloric acid by body
Product is mixed than 4:1, obtains hydrochloric acid mixed solution.
4. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: step (3)
The pretreatment carbon nanotube is to mix carbon nanotube with nitric acid 1:5~1:6 in mass ratio that mass fraction is 60~65%,
And the sulfuric acid that the mass fraction for being added 6~8 times of carbon nanotube mass is 70~80%, after being stirred, filtering, washing to washing
Liquid is neutrality, obtains pretreatment carbon nanotube.
5. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: step (4)
The polyethylene polyamine is triethylene tetramine, any one in diethylenetriamine or ethylenediamine.
6. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: the emulsification
Agent is lauryl sodium sulfate, any one in neopelex or emulsifier op-10.
7. a kind of preparation method of automobile filter paper styrene-acrylic emulsion according to claim 1, it is characterised in that: the initiation
Agent is any one in potassium peroxydisulfate or ammonium persulfate.
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Application publication date: 20181207 |