CN107987219A - A kind of preparation method of the special unsaturated-resin of automobile Putty - Google Patents
A kind of preparation method of the special unsaturated-resin of automobile Putty Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses a kind of preparation method of the special unsaturated-resin of automobile Putty, belong to automotive coatings technical field.First pretreatment graphene oxide is made in graphene oxide, surfactant and water by the present invention, then carbon fiber and silane coupling agent ethanol solution are made modified carbon fiber；Nano-calcium carbonate dispersion is made in nano-calcium carbonate, linoleic acid and carbomer again；Then by phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed oil, pretreatment graphene oxide, modified carbon fiber and nano-calcium carbonate dispersion heating reflux reaction, add fumaric acid and maleic anhydride, continue heating reflux reaction, cooling, and vacuumize, add styrene, after being stirred, natural cooling cools down, discharging, up to the special unsaturated-resin of automobile Putty.The special unsaturated-resin of automobile Putty prepared by technical solution of the present invention has the characteristics that to significantly improve to automobile Putty mechanical property, pliability and impact resistance.
Description
Technical field
The invention discloses a kind of preparation method of the special unsaturated-resin of automobile Putty, belong to automotive coatings technical field.
Background technology
Unsaturated polyester putty is also known as poly-putty base, is using unsaturated polyester resin as base-material, coordinates crosslinking agent, accelerating agent, inhibition
Other auxiliary agents such as agent, thixotropic agent, filler etc. form main ash, grey a kind of two-component production supplemented by curing agent, pigment, activating agent
Product.Due to can thick painting, room temperature rapid curing, strong adhesive force, the excellent properties such as easily polish, do not crack, have much surmounted biography
The putty made of resin such as the alkyd of system, epoxy, Vinylidene Chloride.Poly-putty base is to study very active, development at present to be exceedingly fast, more
Preferable filleting and fill out hole material.Nowadays it is widely used in mechanical industry, electronics, wood furniture, automobile making and repaiies
Mend and metal, nonmetallic materials filleting and fill up etc..With the continuous development of automobile industry, automobile steps into house
Front yard, car repair industry expand, and make poly-putty base market demand growing, the competitiveness in the market of poly-putty base also swashing further
It is strong, the requirement of higher is proposed to pliability of the poly-putty base in the case of certain degree of hardness and impact resistance.So it is continuously improved former
Sub- ash quality, developing a kind of high-performance poly-putty base with good pliability and impact resistance has great realistic meaning.
Scratch in rejected region, fill up the out-of-flatness of workpiece surface, recover its original shape, be following repairing work work
Sequence provides smooth, bright and clean surface.The quality and construction method of poly-putty base will directly influence adhesive force and following repairing effect
Fruit, so, it selects and correctly constructs most important.Unsaturated poly-vinegar putty is in operability, decorative appearance, mechanical performance
Etc. there is very big advantage, now most of auto vendor is all using unsaturated poly-vinegar putty.The full poly-vinegar putty that closes is commonly called as original
Sub- ash, will progressively substitute traditional solvent-borne type putty.This kind of putty blade coating property is good, grinability is good, drying property is good, putty machinery
Intensity is high.But in actual use, due to various reasons caused by cracking, blistering the defects of coming off still often occur, no
The defects of being caused with reason is otherwise varied in the form of expression and time of occurrence outside
Therefore, orthodox car Putty mechanical property how is improved, the shortcomings that pliability and impact resistance are bad, to obtain higher
The automobile Putty of comprehensive performance, is that it is promoted and applies, meets industrial production demand urgent problem to be solved.
The content of the invention
The present invention solves the technical problem of：For orthodox car Putty mechanical property, pliability and impact resistance not
A kind of the shortcomings that good, there is provided preparation method of the special unsaturated-resin of automobile Putty.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）Count in parts by weight, take 10~20 parts of graphene oxides successively, 8~10 parts of surfactants, 200~300 parts of water,
Ultrasonic disperse after mixing, then through ball milling, be filtered, washed and dried, obtain pretreatment graphene oxide；
（2）It is 1 in mass ratio by carbon fiber and silane coupling agent ethanol solution：8~1：10 heating reflux reactions, then filtered,
Washing and drying, obtain modified carbon fiber；
（3）Count in parts by weight, take 10~15 parts of nano-calcium carbonates successively, 60~80 parts of linoleic acid, 20~30 parts of carbomers, in
Under argon gas guard mode, heating stirring mixing, and pH is adjusted to neutrality, then through vacuum dehydration, obtain nano-calcium carbonate dispersion；
（4）Count in parts by weight, take 8~10 parts of phthalic anhydrides successively, 10~15 parts of diethylene glycols, 8~10 parts of ethylene glycol, 4~6 part third
Glycol, 3~5 portions of cottonseed oils, 4~6 parts of fumaric acid, 10~15 parts of maleic anhydrides, 40~50 parts of styrene, 10~15
Part pretreatment graphene oxide, 8~10 parts of modified carbon fibers, 6~8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethyl two
Alcohol, ethylene glycol, propane diols, cottonseed oil, pretreatment graphene oxide, modified carbon fiber and nano-calcium carbonate dispersion are heated to reflux
4~6h is reacted, adds fumaric acid and maleic anhydride, continues 3~5h of heating reflux reaction, cooling, and is vacuumized,
Styrene is added, after being stirred, natural cooling cooling, discharging, up to the special unsaturated-resin of automobile Putty.
Step（1）The surfactant is neopelex, NaLS, sodium lignin sulfonate or ten
Any one in sodium dialkyl sulfate.
Step（2）The silane coupling agent is silane resin acceptor kh-550, silane coupling agent KH-560 or silane coupling agent
Any one in KH-570.
Step（3）The carbomer is any one in carbomer940, CARBOPOL 974P or CARBOPOL 971.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention pre-processes graphene oxide, in preprocessing process, graphene oxide sheet knot by adding
Structure is peeled off, and forms graphene oxide sheet, active function groups in graphene oxide structure is fully exposed, so as to be conducive to follow-up anti-
During answering, graphene oxide disperses in unsaturated-resin matrix, makes unsaturated-resin by graphene oxide layer structure bag
Wrap up in, avoid while secondary agglomeration occurs during storage, graphene oxide being made to combine closely with resin matrix, being used
During, can make resin form a film after, the stress being subject to is uniformly dispersed, meanwhile, the larger specific surface area of graphene oxide itself with
And pleated structure can improve its contact area with resin matrix, so that by the stress being subject to from matrix resin after being conducive to film forming
Shifted to graphene oxide, effectively improve product mechanical property；
（2）Technical solution of the present invention is handled nano-calcium carbonate by using linoleic acid and carbomer, first, linoleic acid and
Carboxyl in carbomer molecular structure can adsorb nano-calcium carbonate, during pH adjustings, linoleic acid and carbomer molecule knot
It is mutually exclusive with like charges in structure after the carboxylic ions of part, unfold linoleic acid and carbomer strand, and well
Be scattered in system so that its absorption nano-calcium carbonate can also in system fine dispersion, in addition, linoleic acid and card ripple
Contain a large amount of double bonds or carboxyl functional group in nurse molecular structure, after being added in unsaturated-resin system, resin macromolecular can be made
The increase of end of the chain double bond content, in resin curing process, terminal double bond reaction compartment steric hindrance is smaller, and has carboxyl isopolarity function
Group exists, and the performances such as automobile Putty surface drying time can be made effectively to be lifted, while the aliphatic long-chain in linoleic acid molecule
Structure can effectively improve the impact resistance and pliability of product, play good plasticization effect；
（3）Technical solution of the present invention is by the carbon fiber for being aided with threadiness and granular modified nano calcium carbonate, and first, carbon is fine
Dimension after modified, can be acted on and changed by charge adsorption between the silane coupling agent and pretreatment graphene oxide of carbon fiber surface
Reaction is learned, graphene oxide and carbon fiber is effectively combined, and combination is chemical bonds, bond strength is higher, and changes
Property nano-calcium carbonate can be in the hole of the fine dispersion filler network that is filled in carbon fiber and graphene oxide structure, and part oxygen
Graphite alkene lamellar structure can migrate to system surface during resin dry solidification, and sheet protection is formed in resin surface
Layer, so that resin system is from outward appearance to inner essence, realizes fine and close filling, on resin system surface and is internally formed filler bone from the inside to the outside
Frame, so as to effectively avoid the volume contraction in unsaturated-resin solidification process.
Embodiment
Count in parts by weight, take 10~20 parts of graphene oxides successively, 8~10 parts of surfactants, 200~300 parts of water,
Pour into No. 1 beaker, and No. 1 beaker is moved into ultrasonic disperse instrument, be 55~65 DEG C in temperature, supersonic frequency is 55~60kHz
Under the conditions of, thermostatic ultrasonic disperses 2~4h, obtains dispersion liquid, and by dispersion liquid pour into ball grinder, be by ball material mass ratio
10：1~20：1 adds zirconium oxide ball milling pearl, and after 45~60min of ball milling mixing, filtering, obtains filter residue, and filter is washed with deionized
Slag 3~5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 105~110 DEG C in temperature to constant weight, obtain pre- place
Manage graphene oxide；It is 1 in mass ratio：8~1：10 is molten for 8~10% silane coupling agent ethanol by carbon fiber and mass fraction
Liquid is poured into the three-necked flask with reflux, and under the conditions of temperature is 75~80 DEG C, 2~5h of heating reflux reaction, filtering, obtains
Filter cake, and gained filter cake 3~5 times is washed with absolute ethyl alcohol, then the filter cake after washing is transferred in baking oven, in temperature for 95~
It is dry to constant weight under the conditions of 100 DEG C, obtain modified carbon fiber；Count in parts by weight, take 10~15 parts of nano-calcium carbonates successively, 60
~80 parts of linoleic acid, 20~30 parts of carbomers, are poured into four-hole boiling flask, and are led to 8~10mL/min speed into four-hole boiling flask
Enter argon gas, be 65~75 DEG C in temperature, under the conditions of rotating speed is 400~600r/min, constant temperature stirring is mixed under argon gas guard mode
45~60min is closed, during being stirred, material in four-hole boiling flask is adjusted for 4~8% sodium hydroxide solutions with mass fraction
PH obtains nano-calcium carbonate dispersion to neutrality, then through vacuum dehydration；Count in parts by weight, take 8~10 parts of phthalic anhydrides successively, 10~
15 parts of diethylene glycols, 8~10 parts of ethylene glycol, 4~6 parts of propane diols, 3~5 portions of cottonseed oils, 4~6 parts of fumaric acid, 10~15
Part maleic anhydride, 40~50 parts of styrene, 10~15 parts of pretreatment graphene oxides, 8~10 parts of modified carbon fibers, 6~8
Part nano-calcium carbonate dispersion, first by phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed oil, pretreatment graphene oxide, change
Property carbon fiber and nano-calcium carbonate dispersion add reaction kettle in, in temperature be 180~200 DEG C under the conditions of, heating reflux reaction 4
After~6h, fumaric acid and maleic anhydride are added, it is anti-under the conditions of 150~170 DEG C, to be heated to reflux to continue at temperature
3~5h is answered, after naturally cool to 120~125 DEG C, 150~300Pa will be evacuated in reaction kettle, after 10~20min of pressurize,
Styrene is added, after being stirred 45~60min with 400~500r/min rotating speeds, natural cooling is cooled to 50~55 DEG C, goes out
Material, up to the special unsaturated-resin of automobile Putty.The surfactant is neopelex, lauryl sulfate
Any one in sodium, sodium lignin sulfonate or lauryl sodium sulfate.The silane coupling agent for silane resin acceptor kh-550,
Any one in silane coupling agent KH-560 or Silane coupling reagent KH-570.The carbomer is carbomer940, carbomer
Any one in 974P or CARBOPOL 971.
Example 1
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；It is 1 in mass ratio：Carbon fiber and mass fraction are by 10
10% silane coupling agent ethanol solution is poured into the three-necked flask with reflux, under the conditions of temperature is 80 DEG C, is heated to reflux
5h is reacted, filtering, obtains filter cake, and washs gained filter cake 5 times with absolute ethyl alcohol, then the filter cake after washing is transferred in baking oven, in
It is dry to constant weight under the conditions of temperature is 100 DEG C, obtain modified carbon fiber；Count in parts by weight, take 15 parts of nano-calcium carbonates successively,
80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and argon gas is passed through into four-hole boiling flask with 10mL/min speed,
It it is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, constant temperature is stirred 60min, is being stirred under argon gas guard mode
During, adjusting material pH in four-hole boiling flask with mass fraction for 8% sodium hydroxide solution, to neutrality, then through vacuum dehydration, must receive
Rice calcium carbonate dispersion；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols,
5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of styrene, 15 parts of pretreatment graphene oxides, 10 parts
Modified carbon fiber, 8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed oil, pretreatment
Graphene oxide, modified carbon fiber and nano-calcium carbonate dispersion are added in reaction kettle, under the conditions of temperature is 200 DEG C, heating
After back flow reaction 6h, fumaric acid and maleic anhydride are added, continues at temperature under the conditions of 170 DEG C, to be heated to reflux
5h is reacted, after naturally cool to 125 DEG C, 300Pa will be evacuated in reaction kettle, after pressurize 20min, adds styrene, with
After 500r/min rotating speeds are stirred 60min, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturation of automobile Putty
Resin.The surfactant is neopelex.The silane coupling agent is silane resin acceptor kh-550.The card
Ripple nurse is carbomer940.
Example 2
It is 1 in mass ratio：10 pour into carbon fiber and mass fraction with reflux for 10% silane coupling agent ethanol solution
In three-necked flask, under the conditions of temperature is 80 DEG C, heating reflux reaction 5h, filtering, obtains filter cake, and washs gained with absolute ethyl alcohol
Filter cake 5 times, then the filter cake after washing is transferred in baking oven, it is dry to constant weight under the conditions of temperature is 100 DEG C, obtain carbon modified fibre
Dimension；To count in parts by weight, take 15 parts of nano-calcium carbonates successively, 80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and
Argon gas is passed through into four-hole boiling flask with 10mL/min speed, under argon gas guard mode, in temperature be 75 DEG C, rotating speed 600r/
Under the conditions of min, constant temperature is stirred 60min, and during being stirred, four are adjusted for 8% sodium hydroxide solution with mass fraction
Material pH obtains nano-calcium carbonate dispersion to neutrality, then through vacuum dehydration in mouth flask；Count in parts by weight, take 10 parts successively
Phthalic anhydride, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols, 5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic acids
Acid anhydride, 50 parts of styrene, 15 parts of graphene oxides, 10 parts of modified carbon fibers, 8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethyl
Glycol, ethylene glycol, propane diols, cottonseed oil, graphene oxide, modified carbon fiber and nano-calcium carbonate dispersion add reaction kettle
In, under the conditions of temperature is 200 DEG C, after heating reflux reaction 6h, fumaric acid and maleic anhydride are added, is continued at
Under the conditions of temperature is 170 DEG C, heating reflux reaction 5h, after naturally cool to 125 DEG C, will be evacuated to 300Pa in reaction kettle, protect
After pressing 20min, styrene is added, after being stirred 60min with 500r/min rotating speeds, natural cooling is cooled to 55 DEG C, discharges,
Up to the special unsaturated-resin of automobile Putty.The silane coupling agent is silane resin acceptor kh-550.The carbomer is card
Ripple nurse 934P.
Example 3
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；Count in parts by weight, take 15 parts of nano-calcium carbonates successively,
80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and argon gas is passed through into four-hole boiling flask with 10mL/min speed,
It it is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, constant temperature is stirred 60min, is being stirred under argon gas guard mode
During, adjusting material pH in four-hole boiling flask with mass fraction for 8% sodium hydroxide solution, to neutrality, then through vacuum dehydration, must receive
Rice calcium carbonate dispersion；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols,
5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of styrene, 15 parts of pretreatment graphene oxides, 10 parts
Carbon fiber, 8 parts of nano-calcium carbonate dispersions, first aoxidize phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed oil, pretreatment
Graphene, carbon fiber and nano-calcium carbonate dispersion are added in reaction kettle, under the conditions of temperature is 200 DEG C, heating reflux reaction
After 6h, fumaric acid and maleic anhydride are added, continues at temperature as under the conditions of 170 DEG C, heating reflux reaction 5h, is treated
125 DEG C are naturally cooled to, will be evacuated to 300Pa in reaction kettle, after pressurize 20min, adds styrene, is turned with 500r/min
After speed is stirred 60min, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturated-resin of automobile Putty.The table
Face activating agent is neopelex.The carbomer is carbomer940.
Example 4
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；It is 1 in mass ratio：Carbon fiber and mass fraction are by 10
10% silane coupling agent ethanol solution is poured into the three-necked flask with reflux, under the conditions of temperature is 80 DEG C, is heated to reflux
5h is reacted, filtering, obtains filter cake, and washs gained filter cake 5 times with absolute ethyl alcohol, then the filter cake after washing is transferred in baking oven, in
It is dry to constant weight under the conditions of temperature is 100 DEG C, obtain modified carbon fiber；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 part two
Ethylene glycol, 10 parts of ethylene glycol, 6 parts of propane diols, 5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of benzene second
Alkene, 15 parts of pretreatment graphene oxides, 10 parts of modified carbon fibers, 8 parts of nano-calcium carbonates, first by phthalic anhydride, diethylene glycol, second two
Alcohol, propane diols, cottonseed oil, pretreatment graphene oxide, modified carbon fiber and nano-calcium carbonate are added in reaction kettle, are in temperature
Under the conditions of 200 DEG C, after heating reflux reaction 6h, fumaric acid and maleic anhydride are added, continues at temperature as 170 DEG C
Under the conditions of, heating reflux reaction 5h, after naturally cool to 125 DEG C, will be evacuated to 300Pa in reaction kettle, after pressurize 20min,
Styrene is added, after being stirred 60min with 500r/min rotating speeds, natural cooling is cooled to 55 DEG C, and discharging is greasy up to automobile
The sub- special unsaturated-resin of ash.The surfactant is neopelex.The silane coupling agent is silane coupled
Agent KH-550.
Example 5
It is 1 in mass ratio：10 pour into carbon fiber and mass fraction with reflux for 10% silane coupling agent ethanol solution
In three-necked flask, under the conditions of temperature is 80 DEG C, heating reflux reaction 5h, filtering, obtains filter cake, and washs gained with absolute ethyl alcohol
Filter cake 5 times, then the filter cake after washing is transferred in baking oven, it is dry to constant weight under the conditions of temperature is 100 DEG C, obtain carbon modified fibre
Dimension；To count in parts by weight, take 15 parts of nano-calcium carbonates successively, 80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and
Argon gas is passed through into four-hole boiling flask with 10mL/min speed, under argon gas guard mode, in temperature be 75 DEG C, rotating speed 600r/
Under the conditions of min, constant temperature is stirred 60min, and during being stirred, four are adjusted for 8% sodium hydroxide solution with mass fraction
Material pH obtains nano-calcium carbonate dispersion to neutrality, then through vacuum dehydration in mouth flask；Count in parts by weight, take 10 parts successively
Phthalic anhydride, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols, 5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic acids
Acid anhydride, 50 parts of styrene, 10 parts of modified carbon fibers, 8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethylene glycol, ethylene glycol, third
Glycol, cottonseed oil, modified carbon fiber and nano-calcium carbonate dispersion are added in reaction kettle, under the conditions of temperature is 200 DEG C, heating
After back flow reaction 6h, fumaric acid and maleic anhydride are added, continues at temperature under the conditions of 170 DEG C, to be heated to reflux
5h is reacted, after naturally cool to 125 DEG C, 300Pa will be evacuated in reaction kettle, after pressurize 20min, adds styrene, with
After 500r/min rotating speeds are stirred 60min, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturation of automobile Putty
Resin.The silane coupling agent is silane resin acceptor kh-550.The carbomer is carbomer940.
Example 6
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；Count in parts by weight, take 15 parts of nano-calcium carbonates successively,
80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and argon gas is passed through into four-hole boiling flask with 10mL/min speed,
It it is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, constant temperature is stirred 60min, is being stirred under argon gas guard mode
During, adjusting material pH in four-hole boiling flask with mass fraction for 8% sodium hydroxide solution, to neutrality, then through vacuum dehydration, must receive
Rice calcium carbonate dispersion；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols,
5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of styrene, 15 parts of pretreatment graphene oxides, 8 parts
Nano-calcium carbonate dispersion, first graphene oxide and receives phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed oil, pretreatment
Rice calcium carbonate dispersion is added in reaction kettle, under the conditions of temperature is 200 DEG C, after heating reflux reaction 6h, adds anti-butylene
Diacid and maleic anhydride, continue at temperature as under the conditions of 170 DEG C, heating reflux reaction 5h, after naturally cool to 125 DEG C,
It will be evacuated to 300Pa in reaction kettle, after pressurize 20min, add styrene, 60min is stirred with 500r/min rotating speeds
Afterwards, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturated-resin of automobile Putty.The surfactant is 12
Sodium alkyl benzene sulfonate.The carbomer is carbomer940.
Example 7
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；It is 1 in mass ratio：Carbon fiber and mass fraction are by 10
10% silane coupling agent ethanol solution is poured into the three-necked flask with reflux, under the conditions of temperature is 80 DEG C, is heated to reflux
5h is reacted, filtering, obtains filter cake, and washs gained filter cake 5 times with absolute ethyl alcohol, then the filter cake after washing is transferred in baking oven, in
It is dry to constant weight under the conditions of temperature is 100 DEG C, obtain modified carbon fiber；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 part two
Ethylene glycol, 10 parts of ethylene glycol, 6 parts of propane diols, 5 portions of cottonseed oils, 6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of benzene second
Alkene, 15 parts of pretreatment graphene oxides, 10 parts of modified carbon fibers, first by phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, cottonseed
Oil, pretreatment graphene oxide, modified carbon fiber are added in reaction kettle, under the conditions of temperature is 200 DEG C, heating reflux reaction 6h
Afterwards, fumaric acid and maleic anhydride are added, continues at temperature as under the conditions of 170 DEG C, heating reflux reaction 5h, treat from
125 DEG C so are cooled to, will be evacuated to 300Pa in reaction kettle, after pressurize 20min, styrene is added, with 500r/min rotating speeds
After being stirred 60min, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturated-resin of automobile Putty.The surface
Activating agent is neopelex.The silane coupling agent is silane resin acceptor kh-550.
Example 8
To count in parts by weight, take 20 parts of graphene oxides successively, 10 parts of surfactants, 300 parts of water, are poured into No. 1 beaker, and
No. 1 beaker is moved into ultrasonic disperse instrument, is 65 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, thermostatic ultrasonic disperses 4h, obtains
Dispersion liquid, and by dispersion liquid pour into ball grinder, by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 60min, filtering, obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred in baking oven, in temperature
To dry to constant weight under the conditions of 110 DEG C, pretreatment graphene oxide is obtained；It is 1 in mass ratio：Carbon fiber and mass fraction are by 10
10% silane coupling agent ethanol solution is poured into the three-necked flask with reflux, under the conditions of temperature is 80 DEG C, is heated to reflux
5h is reacted, filtering, obtains filter cake, and washs gained filter cake 5 times with absolute ethyl alcohol, then the filter cake after washing is transferred in baking oven, in
It is dry to constant weight under the conditions of temperature is 100 DEG C, obtain modified carbon fiber；Count in parts by weight, take 15 parts of nano-calcium carbonates successively,
80 parts of linoleic acid, 30 parts of carbomers, are poured into four-hole boiling flask, and argon gas is passed through into four-hole boiling flask with 10mL/min speed,
It it is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, constant temperature is stirred 60min, is being stirred under argon gas guard mode
During, adjusting material pH in four-hole boiling flask with mass fraction for 8% sodium hydroxide solution, to neutrality, then through vacuum dehydration, must receive
Rice calcium carbonate dispersion；Count in parts by weight, take 10 parts of phthalic anhydrides successively, 15 parts of diethylene glycols, 10 parts of ethylene glycol, 6 parts of propane diols,
6 parts of fumaric acid, 15 parts of maleic anhydrides, 50 parts of styrene, 15 parts of pretreatment graphene oxides, 10 parts of carbon modified fibres
Dimension, 8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethylene glycol, ethylene glycol, propane diols, pretreatment graphene oxide, modification
Carbon fiber and nano-calcium carbonate dispersion are added in reaction kettle, under the conditions of temperature is 200 DEG C, after heating reflux reaction 6h, then
Fumaric acid and maleic anhydride are added, continues at temperature as under the conditions of 170 DEG C, heating reflux reaction 5h, treats that nature is cold
But to 125 DEG C, 300Pa will be evacuated in reaction kettle, after pressurize 20min, add styrene, stirred with 500r/min rotating speeds
After mixing 60min, natural cooling is cooled to 55 DEG C, discharging, up to the special unsaturated-resin of automobile Putty.The surface-active
Agent is neopelex.The silane coupling agent is silane resin acceptor kh-550.The carbomer is carbomer940.
Comparative example：
By the special unsaturated-resin of automobile Putty and comparative example product and cyclohexanone peroxide and diformazan of the gained of example 1 to 8
The mixing pastel of acid butyl ester is carried out after being mixed and made into Putty, and obtained Putty progressive detectability can be detected, tool
Body detecting method is as follows：
1. mechanical property：Thickness is scratched on electrophoresis plate again（2.0±0.2）The Putty of mm, under the conditions of hanging 20min, then 100 DEG C
40min is toasted, by test plate (panel) 90-degree bent, viewing whether there is bottom drain foaming phenomena to characterize test specimen adhesive force；
2. pliability：Test specimen pliability is detected according to GB/T1748；
3. impact resistance：Test specimen impact resistance is detected according to GB/T1732.
Specific testing result is as shown in table 1：
Table 1：Mechanical property, pliability and the specific testing result of impact resistance
From 1 testing result of table, the special unsaturated-resin of automobile Putty prepared by technical solution of the present invention is to automobile putty
Grey mechanical property, pliability and impact resistance have the characteristics that to significantly improve, and have in the development of automotive coatings industry wide
Prospect.
Claims (4)
1. a kind of preparation method of the special unsaturated-resin of automobile Putty, it is characterised in that specifically preparation process is：
（1）Count in parts by weight, take 10~20 parts of graphene oxides successively, 8~10 parts of surfactants, 200~300 parts of water,
Ultrasonic disperse after mixing, then through ball milling, be filtered, washed and dried, obtain pretreatment graphene oxide；
（2）It is 1 in mass ratio by carbon fiber and silane coupling agent ethanol solution：8~1：10 heating reflux reactions, then filtered,
Washing and drying, obtain modified carbon fiber；
（3）Count in parts by weight, take 10~15 parts of nano-calcium carbonates successively, 60~80 parts of linoleic acid, 20~30 parts of carbomers, in
Under argon gas guard mode, heating stirring mixing, and pH is adjusted to neutrality, then through vacuum dehydration, obtain nano-calcium carbonate dispersion；
（4）Count in parts by weight, take 8~10 parts of phthalic anhydrides successively, 10~15 parts of diethylene glycols, 8~10 parts of ethylene glycol, 4~6 part third
Glycol, 3~5 portions of cottonseed oils, 4~6 parts of fumaric acid, 10~15 parts of maleic anhydrides, 40~50 parts of styrene, 10~15
Part pretreatment graphene oxide, 8~10 parts of modified carbon fibers, 6~8 parts of nano-calcium carbonate dispersions, first by phthalic anhydride, diethyl two
Alcohol, ethylene glycol, propane diols, cottonseed oil, pretreatment graphene oxide, modified carbon fiber and nano-calcium carbonate dispersion are heated to reflux
4~6h is reacted, adds fumaric acid and maleic anhydride, continues 3~5h of heating reflux reaction, cooling, and is vacuumized,
Styrene is added, after being stirred, natural cooling cooling, discharging, up to the special unsaturated-resin of automobile Putty.
A kind of 2. preparation method of special unsaturated-resin of automobile Putty according to claim 1, it is characterised in that：Step
Suddenly（1）The surfactant is neopelex, NaLS, sodium lignin sulfonate or dodecyl sulphate
Any one in sodium.
A kind of 3. preparation method of special unsaturated-resin of automobile Putty according to claim 1, it is characterised in that：Step
Suddenly（2）The silane coupling agent is in silane resin acceptor kh-550, silane coupling agent KH-560 or Silane coupling reagent KH-570
Any one.
A kind of 4. preparation method of special unsaturated-resin of automobile Putty according to claim 1, it is characterised in that：Step
Suddenly（3）The carbomer is any one in carbomer940, CARBOPOL 974P or CARBOPOL 971.
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