CN109337086A - A kind of the ternary polymerization composite material and preparation method and dedicated unit of functional graphene in-situ polymerization polyester - Google Patents
A kind of the ternary polymerization composite material and preparation method and dedicated unit of functional graphene in-situ polymerization polyester Download PDFInfo
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Abstract
The invention discloses a kind of ternary polymerization composite material and preparation method of functional graphene in-situ polymerization polyester and dedicated units, belong to the preparation technical field of composite material.The composite material is prepared by dihydric alcohol, binary acid and functional graphene through esterification, polycondensation reaction, the molar ratio of dihydric alcohol and binary acid is (1.2~2): 1, the quality of functional graphene accounts for the 0.01~2% of ternary polymerization composite material, and the number-average molecular weight of ternary polymerization composite material is 10000~150000.The present invention introduces active function groups on the surface of graphene, and then it is grafted to graphene in polyester segment, so that graphene and polyester form stable covalent bond between the two, reach the humidification to polyester molecule chain using the good physical mechanical property of graphite alkenes material, and then composite material exhibits is made to go out good mechanical property and comprehensive performance.
Description
Technical field
The invention belongs to the preparation technical fields of composite material, poly- in situ more specifically to a kind of functional graphene
Close the ternary polymerization composite material and preparation method and dedicated unit of polyester.
Background technique
Polyethylene terephthalate (PET) is one of currently the most important ones synthetic material, can be applied to fiber, thin
The fields such as film, plastics.PET film with its high mechanical strength, resist cold electrical insulation capability heat-resist, that shrinkage is stable and excellent
And optical property, it is widely used in the fields such as packaging, industry, electrical, electronics, magnetism, photosensitive.Terylene is with poly- terephthaldehyde
Sour glycol ester (PET) is raw material, the fiber being prepared by spinning and post-processing.Polyester fiber is most widely used in the world
General, the maximum synthetic fibers of yield occupy 70% or so of world's synthetic fibers yield.But the strand of polyester fiber closely connects
It connects, crystallinity and the degree of orientation are high, and polarity is small, thus haves the shortcomings that hygroscopicity is poor, hydrophily is poor.
Graphene is a kind of New Type of Carbon nanometer light material, has unique monoatomic layer two dimensional crystal structure, Gao Bibiao
Area, high intensity, conductivity, thermal conductivity, screening effect ideal high to the absorption efficiency of each lightlike line.Graphene is known as
The magical material of 21 century " change ", gradually mature perfect with graphene application field related process, mobile phone screen is any
Bending, electric car momentary charge, computer screen thin transparent such as blank sheet of paper these mysterious things will come true.Graphene
Material equally causes extensive concern in terms of functions of textile fabrics exploitation, adds in the polymerization or spinning process of textile fabric a small amount of
Graphene can significantly improve the mechanical property and electric property of fiber.
Publication date is that the Chinese patent 201510430677.3 on October 28th, 2015 discloses a kind of stone containing partial reduction
Macromolecule composite functional fiber of black alkene and preparation method thereof, the fiber include component A, B component, with part exposed conveying appliance, side by side
Type or core-skin type are combined, and the 20~100% of every fibrous outer surfaces product are B component.This method is by the portion 0.1~1wt%
Divide the polyester of reduced graphene and graphene containing partial reduction and TiO containing 4~20wt%2Nanocomposite filler polyester knot
Melt composite spinning is carried out after brilliant, dry, then drawing-off, relaxation heat setting at 80~160 DEG C, and fibre is made by reduction treatment
Part reduced graphene is restored to carbon oxygen atom ratio and reaches 9/1~15/1 in dimension.Fiber made from the invention can be higher
It is produced under spinning speed, high production efficiency；With lower filament number, higher-strength and low resistivity, meet antistatic need
It asks；There is antibacterial and flame retardant property simultaneously, thus have a good application prospect.
Publication date is that the Chinese patent 201510680473.5 on December 30th, 2015 discloses a kind of graphene-terylene and receives
The preparation method of rice composite fibre, includes the following steps: graphene-dacron polyester composite master batch preparation step and will be described multiple
Close the step of master batch is prepared into graphene-terylene nanometer composite fibre.Compared with existing other methods: its technique is extremely simple
Single, reinforcing material is had excellent performance and inexpensively.In addition, to assign nanometer multiple for the excellent mechanical property of graphene itself and functional characteristic
Condensating fiber high intensity and antistatic etc. functional.Surface modification and modified graphene are good in dacron polyester macromolecule matrix
Good dispersibility makes graphene and dacron polyester slice basis material efficient, uniformly compound with perfect interface compatibility.But
It is that the graphene content that the patent is added is larger, is unfavorable for the saving and industrial mass production of resource.
It is all made of in graphene enhancing modified poly ester aspect of performance although having relevant document report both at home and abroad
The problems such as mode that addition is blended realizes, that there are additive amounts is big, processing difficulties, unobvious performance boost.
Summary of the invention
For the above-mentioned problems in the prior art, it is former that one of the objects of the present invention is to provide a kind of functional graphenes
The ternary polymerization composite material of position polymeric polyester, the second object of the present invention is to provide the preparation method of the composite material, this
The third purpose of invention is to provide the dedicated unit for preparing the composite material.
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
The present invention relates to a kind of dedicated unit of ternary polymerization composite material for preparing functional graphene in-situ polymerization polyester,
Including by the sequentially connected raw material adding set of pipeline, raw material device for formulating, esterification device, prepolymer filter device,
Polycondensation reaction device and melt filter, the raw material adding set include graphene adding set and adjuvant adding device；
High-shear emulsion machine and ultrasound point are equipped in the graphene adding set, adjuvant adding device and raw material device for formulating simultaneously
Device is dissipated, high pressure homogenizer, the esterification device are equipped between the graphene adding set and the raw material device for formulating
It is connect by recyclable device with the raw material device for formulating with the waste port of polycondensation reaction device, is successively set in the recyclable device
There are waste material storage tank, rectifying column and recycling storage tank.
It is multiple that the invention further relates to a kind of ternary polymerizations of functional graphene in-situ polymerization polyester using above-mentioned dedicated unit
The preparation method of condensation material, functional graphene and auxiliary material are dispersed in dihydric alcohol, respectively obtain functional graphene dispersion liquid and
Auxiliary material dispersion liquid；Then by dihydric alcohol, binary acid, functional graphene dispersion liquid and auxiliary material dispersion liquid be added in reaction kettle into
Row dispersion, is then successively esterified, polycondensation reaction, obtains the ternary polymerization composite material.
Specifically includes the following steps:
(1) functional graphene and dihydric alcohol are used into high-shear emulsion machine and ultrasonic dispersers in graphene adding set
The mode used simultaneously is dispersed, and obtains functional graphene dispersion liquid, the mass concentration of the functional graphene dispersion liquid is
0.1~10%；
(2) auxiliary material and dihydric alcohol are used simultaneously using high-shear emulsion machine and ultrasonic dispersers in adjuvant adding device
Dispersing mode dispersed, obtain auxiliary material dispersion liquid, the mass concentration of the auxiliary material dispersion liquid is 0.1~35%；
(3) step 1 gained functional graphene dispersion liquid is passed through raw material device for formulating by high pressure homogenizer, and by step
2 gained auxiliary material dispersion liquids are passed through raw material device for formulating, while dihydric alcohol and binary acid are passed through raw material device for formulating, then use
The mode that high-shear emulsion machine and ultrasonic dispersers use simultaneously disperses material in device；
(4) step 3 resulting material is passed through esterification device, carries out esterification；
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, contracts
Poly- reaction；
(6) step 5 products therefrom is filtered by melt filter to get the ternary polymerization composite material；
(7) gaseous substance generated in step 4 and step 5 reaction process is drained into waste material storage tank, is separated by rectifying column
Dihydric alcohol out, the dihydric alcohol isolated is delivered to recycling storage tank, and reuse is into raw material device for formulating.
The dihydric alcohol be selected from one of ethylene glycol, propylene glycol, butanediol, cyclohexanediol or a variety of, described two
First acid is p-phthalic acid, and the functional graphene is carboxyl function graphene or amino functional graphene, described two
The molar ratio of the pure and mild binary acid of member is (1.2~2): 1, the quality of the functional graphene accounts for ternary polymerization composite material
0.01~2%.
Preferably, the carboxyl function graphene is prepared by one of following two method:
A, graphite oxide is divided by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
It is dispersed in good solvent, is then slowly added into amino acids and is reacted, after washing is dry；
B, pass through mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first for graphene oxide
Then dispersion removing is activated graphene oxide using monoxone or sodium chloroacetate in lye, is eventually adding carboxylic
Base reagent carries out carboxylation reaction；
The amino functional graphene is prepared by one of following two method:
C, graphite oxide is divided by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
It is dispersed in good solvent, is then slowly added into diamine compounds and is reacted, after washing is dry；
D, the method referring to described in Chinese patent 201810212266.0 is prepared.
Mixing speed >=1000r/min of the high-shear emulsion machine, the ultrasonic power of the ultrasonic dispersers are 1
~20kw, the jitter time are 1~10h, and the dispersion temperature is 10~40 DEG C.
The auxiliary material includes catalyst, and the catalyst is antimony oxide, three sour antimony, sodium germanate, germanium dioxide, adjacent benzene
Dioctyl phthalate dibutyl tin, Mono-n-butyltin, Dibutyltin oxide, Dibutyltin oxide chloride, dibutyl tin dilaurate,
The antimony such as dibutyl tin acetate, monobutyl-tin-trichloride system, titanium system, tin system or germanium system, the dosage of the catalyst are overall reaction
The 0.05~0.25% of quality of material.
The condition of the esterification are as follows: 250~265 DEG C of reaction temperature, 0.1~0.5MPa of reaction pressure, the reaction time
0.5~2.5 h, control esterification rate are not less than 96%；The condition of the polycondensation reaction are as follows: 265~280 DEG C of reaction temperature,
0.1~25kPa of vacuum degree, 0.5~5h of reaction time are reacted, control esterification rate is not less than 99.5%.
It is multiple that the invention further relates to the ternary polymerizations for the functional graphene in-situ polymerization polyester being prepared using the above method
Condensation material.
The number-average molecular weight of the composite material is 10000~150000, and inherent viscosity is 0.6~1.2dL/g.
Compared with the prior art, the invention has the benefit that
(1) the ternary polymerization composite material of functional graphene in-situ polymerization polyester of the invention, introduces on the surface of graphene
Active function groups, and then be grafted to graphene in polyester segment, achieve the purpose that in-situ modified polyester, so that graphene and poly-
Ester forms stable covalent bond between the two, is reached using the good physical mechanical property of graphite alkenes material to polyester molecule
The humidification of chain, and then composite material exhibits is made to go out good mechanical property and comprehensive performance.
(2) compared with polymer/graphene composite material in the prior art, functional graphene can be uniformly dispersed in
In polymeric matrix, so that the performance of composite material increases substantially, and required graphene content is smaller.
(3) it when functional graphene is dispersed in dihydric alcohol, does not need additionally to add surfactant or dispersing aid
It is uniformly dispersed in dihydric alcohol system, to avoid influence of the auxiliary agent of addition to in-situ polymerization；When dispersion, using high shear
Emulsification and ultrasonic disperse process integration, can be preferably to functional graphene dispersion removing and shearing, and size is small and uniform, effectively
Graphene is avoided to reunite.
(4) the preparation method technique letter of a kind of ternary polymerization composite material of functional graphene in-situ polymerization polyester of the present invention
It is single, strong operability, it is only necessary to basic transformation be carried out to existing industrial polyester production equipment, investment is small, is easy to industrialization promotion.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of ternary polymerization composite material of the invention；
Fig. 2 is the dedicated unit schematic diagram of preparation ternary polymerization composite material of the invention；
In Fig. 2: 1, graphene adding set；2, adjuvant adding device；3, high pressure homogenizer；4, raw material device for formulating；5,
Esterification device；6, prepolymer filter device；7, polycondensation reaction device；8, melt filter；9, waste material storage tank；10, smart
Evaporate tower；11, storage tank is recycled；12, recyclable device；13, granulated and dried device.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
A kind of dedicated unit of the ternary polymerization composite material for preparing functional graphene in-situ polymerization polyester of the present embodiment,
As shown in Fig. 2, including pass through the sequentially connected raw material adding set of pipeline, raw material device for formulating 4, esterification device 5, pre-
Polymers filter device 6, polycondensation reaction device 7 and melt filter 8, raw material adding set include 1 He of graphene adding set
Adjuvant adding device 2 is equipped with high-shear emulsifying in graphene adding set 1, adjuvant adding device 2 and raw material device for formulating 4
Machine and ultrasonic dispersers are equipped with high pressure homogenizer between graphene adding set 1 and raw material device for formulating 4.Esterification device 5
It is connect by recyclable device 12 with raw material device for formulating 4 with the waste port of polycondensation reaction device 7；It is successively arranged in recyclable device 12
Waste material storage tank 9, rectifying column 10 and recycling storage tank 11.
Graphene adding set 1 is the place that functional graphene carries out dispersion removing in dihydric alcohol system, is equipped with height
Emulsification pretreatment machine and ultrasonic disperse device can disperse to remove, ensure graphene in dihydric alcohol system to functional graphene
Dispersed, at the same it is internal equipped with cooling coil, and material temperature in kettle when can effectively control dispersion removing ensures effective disperse
Removing.The functional graphene dispersion liquid obtained after dispersion removing is delivered to homogenizer 3 by bottom outlet, by homogenizer
High pressure effect, further controls graphene sheet layer thickness and piece diameter size, is then delivered to raw material by pipeline and prepares
Device 4.
Adjuvant adding device 2 is the place that auxiliary material (such as titanium dioxide, catalyst) is prepared in dihydric alcohol system, is equipped with
High-shear emulsion machine and ultrasonic disperse device can ensure dispersed of the auxiliary material in dihydric alcohol system, while internal equipped with cold
But coil pipe, material temperature in kettle when can effectively control dispersion ensure effective dispersion, and the auxiliary material dispersion liquid obtained after dispersion is logical
It crosses bottom outlet and is delivered to raw material device for formulating 4.
It is anti-that raw material device for formulating 4 is that dihydric alcohol, binary acid, functional graphene dispersion liquid are mixed with auxiliary material dispersion liquid
Kettle is answered, high-shear emulsion machine, ultrasonic dispersers and mixing plant are provided with, it can the various raw materials mixing homogeneity of effective guarantee.Top
Portion is equipped with material feeding line, is connected respectively with graphene adding set 1, adjuvant adding device 2 and recyclable device 12, inside is set
There is heating coil, lower part is equipped with discharging pipeline, and bottom discharge nozzle line connects esterification device 5.
Esterification device 5 includes the reaction kettle that at least one is used to occur esterification.The gas phase that esterification generates
Substance is expelled to the waste material storage tank 9 in recyclable device 12, reaction kettle upper end feeding line and raw material from reaction kettle upper end discharge port
Device for formulating 4 is connected, and lower end discharging pipeline is connected with prepolymer filter device 6, and esterification reaction product is through prepolymer filter device 6
Polycondensation reaction device 7 is delivered to by pipeline.
Polycondensation reaction device 7 includes the reaction kettle that at least one is used to occur polycondensation reaction.Batch condensation polymerization reactor is autoclave,
The gaseous substance that reaction generates is expelled to the waste material storage tank 9 in recyclable device 12, reaction kettle upper end from reaction kettle upper end discharge port
Feeding line is connected with esterification device 5, and lower end discharging pipeline is connected with melt filter 8, and polycondensation product is through molten
It is delivered to granulated and dried device 13 through pipeline after body filter device 8, or is fed directly to spinning production line.
Recyclable device 12 is used to the waste liquid that esterification and polycondensation reaction generate being delivered to waste material storage tank 9, through rectifying work
Skill tower 10 separates and recovers separation of glycols, and the glycol monomer recycled is sent by liquid-transport pipe-line to recycling storage tank 11, storage tank
11 are connected with 4 pipeline of raw material device for formulating, so that recycling glycol monomer is recycled.
Using the preparation method of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester of above-mentioned dedicated unit
Are as follows: carboxyl function graphene and auxiliary material (including titanium dioxide, catalyst) are dispersed in ethylene glycol, function graphite is respectively obtained
Alkene dispersion liquid and auxiliary material dispersion liquid；Then by remaining ethylene glycol and p-phthalic acid, functional graphene dispersion liquid, auxiliary material point
Dispersion liquid, which is added in reaction kettle, is dispersed, and is then successively esterified, polycondensation reaction, and ternary polymerization composite material is obtained.Its
In, the quality of functional graphene accounts for the 0.5% of ternary polymerization composite material.
As shown in Figure 1, specifically includes the following steps:
(1) in graphene adding set, carboxyl function graphene and ethylene glycol are passed through into metering pump control function graphite
The mass fraction of carboxyl function graphene is 1% in alkene dispersion liquid, is used simultaneously using high-shear emulsion machine and ultrasonic dispersers
Mode carry out dispersion removing, obtain carboxyl function graphene dispersing solution, wherein pass through the cooling coil of internal setting, control
Dispersion temperature is lower than 40 DEG C, and the revolving speed of high-shear emulsion machine is 2000r/min, ultrasonic power 8kW, jitter time 60min.
(2) in adjuvant adding device, auxiliary material (including titanium dioxide and antimony oxide) and ethylene glycol are passed through into metering
The dosage of pump control titanium dioxide is the 1.2% of ternary polymerization composite material quality, and the catalytic antimony trioxide dosage is ternary
The 0.06% of copolymerized quality of materials is divided using the dispersing mode that high-shear emulsion machine and ultrasonic dispersers use simultaneously
It dissipates, by the cooling coil of inside setting, control dispersion temperature is lower than 40 DEG C, and the revolving speed of high-shear emulsion machine is 1400r/min,
Ultrasonic power is 10kW, jitter time 30min, obtains auxiliary material dispersion liquid, catalyst preparation concentration is in auxiliary material dispersion liquid
1%, titanium dioxide compound concentration 20%.
(3) step 1 gained functional graphene dispersion liquid is passed through after the effect of homogenizer high pressure by high pressure homogenizer
Raw material device for formulating, and step 2 gained auxiliary material dispersion liquid is passed through raw material device for formulating, while by remaining ethylene glycol and whole
P-phthalic acid be passed through raw material device for formulating, carried out in such a way that high-shear emulsion machine and ultrasonic dispersers use simultaneously
The uniform mixing of various raw materials controls 80 DEG C of mixing temperature by internal heating coils, and the revolving speed of high-shear emulsion machine is
1400r/min, ultrasonic power 10kW, ultrasonic time 30min obtain raw material mixed slurry.Wherein, added in step 1~3
The molar ratio for adding the adduction of ethylene glycol and whole p-phthalic acids is 1.6:1, preferentially using recycling storage tank when adding ethylene glycol
Recycling ethylene glycol in 11.
(4) step 3 resulting material is passed through esterification device, carries out esterification, reaction kettle reaction temperature control 255
DEG C, 0.1~0.5MPa of reaction pressure, reaction time 2.5h, control esterification rate reach 97.5%.
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, contracts
Poly- reaction, is reacted vacuum degree 15kPa (absolute pressure), reaction time 4.5h by 275 DEG C of reaction kettle reaction temperature, and control esterification is anti-
Should rate 99.6%, inherent viscosity reaches 1.1dL/g.
(6) step 5 products therefrom is filtered by melt filter, then passes to granulated and dried device or directly transports
To spinning production line.
(7) gaseous substance (the predominantly mixture of ethylene glycol and water) generated in step 4 and step 5 reaction process is arranged
To waste material storage tank, ethylene glycol is isolated by rectifying column, the ethylene glycol isolated is delivered to recycling storage tank, and reuse to raw material is matched
In device processed.
Above-mentioned carboxyl function graphene is prepared by following methods:
Step 1, graphite oxide and sodium hydroxide solution are put into the first Scattered Kettle, passes through high-shear emulsion machine and ultrasound
The mode that dispersal device is run simultaneously carries out dispersion removing, by adjusting sodium hydroxide solution dosage and concentration, makes system pH
To 9.0, by the cooling coil being arranged in kettle, controls dispersion temperature and be lower than 40 DEG C, the revolving speed of high-shear emulsion machine is 600r/
Min, ultrasonic power 10kW, ultrasonic time 60min obtain graphene oxide aqueous slurry.
Step 2, it is conveyed through pipeline and step 1 gained slurry is passed through activated reactor, and monoxone is added, be sufficiently stirred
Afterwards, 80 DEG C of reaction temperature are controlled, carries out activated carboxylic reaction under conditions of reaction time 4h；Wherein graphene oxide, monoxone
Mass ratio be 1:0.5.
Step 3, step 2 products therefrom is delivered in the first filtration washing tower through pipeline and is successively filtered, is washed, mistake
Filtrate is delivered in the first storage tank through discharge port pipeline, controls through pipeline and valve, and circulation is used for the first Scattered Kettle, is used for
The dispersion of graphene oxide is removed, and adds lye as needed.
Step 4, the product after step 3 washing is delivered to the second Scattered Kettle through pipeline, passes through high-shear emulsifying after adding water
The mode that machine and ultrasonic disperse device are run simultaneously carries out dispersion removing, passes through the cooling coil being arranged in kettle, control dispersion temperature
Degree is 30 DEG C, and the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min are lived
Change graphene oxide aqueous slurry, the concentration of gained slurry is 5g/mL.
Step 5, step 4 gained slurry is delivered in reaction kettle through pipeline, starting stirring is controlled using valve, by one
Determine the aminocaproic acid and N of quality, N'- Dicyclohexylcarbodiimide is added slowly in reaction kettle, and nitrogen protection flows back at 80 DEG C
React 18h；Wherein, the mass ratio of the quality of aminocaproic acid and active oxidation graphene is 1.2:1, N, N'- dicyclohexyl phosphinylidyne
The de- dosage of imines be account for activation graphene oxide quality 80%.
Step 6, step 5 products therefrom is passed through in the second filtration washing tower and is filtered, is washed, filtered fluid is through discharge port
Pipeline is delivered in the second storage tank, is controlled through pipeline and valve, and circulation is used for the second Scattered Kettle.
Step 7, the product after step 6 washing is delivered to third Scattered Kettle, passes through high-shear emulsion machine after adding water and surpassed
The mode that sound dispersal device is run simultaneously carries out dispersion removing, and by the cooling coil being arranged in kettle, controlling dispersion temperature is 30
DEG C, the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min obtain carboxyl function
Graphite alkene aqueous slurry, the concentration of gained slurry are 1g/mL.
Step 8, step 7 gained slurry is delivered in drying tower through pipeline, using upper-spraying type air-stream spraying drying mode
It is dried, is arranged 130 DEG C of drying temperature, collection obtains carboxyl-functional graphene powder.
The three of the functional graphene in-situ polymerization polyester being prepared using above-mentioned dedicated unit and method of the present embodiment
The copolymerized material of member, the number-average molecular weight of the composite material are 25000.
Embodiment 2
The same embodiment of preparation facilities of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester of the present embodiment
1, the preparation method is as follows:
Amino functional graphene and auxiliary material (including titanium dioxide, catalyst) are dispersed in ethylene glycol, function is respectively obtained
It can graphene dispersing solution and auxiliary material dispersion liquid；Then by remaining ethylene glycol and p-phthalic acid, functional graphene dispersion liquid,
Auxiliary material dispersion liquid, which is added in reaction kettle, to be dispersed, and is then successively esterified, polycondensation reaction, and ternary polymerization composite wood is obtained
Material.Wherein, the quality of functional graphene accounts for the 0.5% of ternary polymerization composite material.
As shown in Figure 1, specifically includes the following steps:
(1) in graphene adding set, amino functional graphene and ethylene glycol are passed through into metering pump control function graphite
The mass fraction of amino functional graphene is 1% in alkene dispersion liquid, is used simultaneously using high-shear emulsion machine and ultrasonic dispersers
Mode carry out dispersion removing, by inside setting cooling coil, control dispersion temperature be lower than 40 DEG C, high-shear emulsion machine
Revolving speed is 1200 r/min, and ultrasonic power 10kW, jitter time 60min obtain amino functional graphene dispersing solution.
(2) in adjuvant adding device, auxiliary material (including titanium dioxide, catalyst) and ethylene glycol are controlled by metering pump
The dosage of titanium dioxide is the 1.2% of ternary polymerization composite material quality, and catalyst Dibutyltin oxide dosage is ternary polymerization
The 0.06% of composite material quality is dispersed using the dispersing mode that high-shear emulsion machine and ultrasonic dispersers use simultaneously,
By the cooling coil of inside setting, control dispersion temperature is lower than 40 DEG C, and the revolving speed of high-shear emulsion machine is 1400r/min, surpasses
Acoustical power is 10kW, jitter time 30min, obtains auxiliary material dispersion liquid, and catalyst preparation concentration is 1% in auxiliary material dispersion liquid,
Titanium dioxide compound concentration 20%.
(3) step 1 gained functional graphene dispersion liquid is passed through after the effect of homogenizer high pressure by high pressure homogenizer
Raw material device for formulating, and step 2 gained auxiliary material dispersion liquid is passed through raw material device for formulating, while by remaining ethylene glycol and whole
P-phthalic acid be passed through raw material device for formulating, carried out in such a way that high-shear emulsion machine and ultrasonic dispersers use simultaneously
The uniform mixing of various raw materials controls 80 DEG C of mixing temperature by internal heating coils, and the revolving speed of high-shear emulsion machine is
1400r/min, ultrasonic power 10kW, ultrasonic time 30min obtain raw material mixed slurry.Wherein, added in step 1~3
The molar ratio for adding the adduction of ethylene glycol and whole p-phthalic acids is 1.6:1, preferentially using recycling storage tank when adding ethylene glycol
Recycling ethylene glycol in 11.
(4) step 3 resulting material is passed through esterification device, carries out esterification, reaction kettle reaction temperature control 255
DEG C, 0.1~0.5MPa of reaction pressure, reaction time 3h, control esterification rate reach 98.5%.
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, contracts
Poly- reaction, is reacted vacuum degree 18kPa (absolute pressure), reaction time 4.5h by 275 DEG C of reaction kettle reaction temperature, and control esterification is anti-
Should rate 99.6%, inherent viscosity reaches 1.08dL/g.
(6) step 5 products therefrom is filtered by melt filter, then passes to granulated and dried device or directly transports
To spinning production line.
(7) gaseous substance (the predominantly mixture of ethylene glycol and water) generated in step 4 and step 5 reaction process is arranged
To waste material storage tank, ethylene glycol is isolated by rectifying column, the ethylene glycol isolated is delivered to recycling storage tank, and reuse to raw material is matched
In device processed.
Above-mentioned amino functional graphene using 1 the method for embodiment preparation in Chinese patent 201810212266.0 and
At.
The three of the functional graphene in-situ polymerization polyester being prepared using above-mentioned dedicated unit and method of the present embodiment
The copolymerized material of member, the number-average molecular weight of the composite material are 24500.
Embodiment 3
The same embodiment of preparation facilities of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester of the present embodiment
1, the preparation method is as follows:
Carboxyl function graphene and auxiliary material (including catalyst) are dispersed in ethylene glycol, functional graphene point is respectively obtained
Dispersion liquid and auxiliary material dispersion liquid；Then by remaining ethylene glycol and p-phthalic acid, functional graphene dispersion liquid, auxiliary material dispersion liquid
It is added in reaction kettle and is dispersed, is then successively esterified, polycondensation reaction, obtain ternary polymerization composite material.Wherein, function
The quality of energy graphene accounts for the 2% of ternary polymerization composite material.
As shown in Figure 1, specifically includes the following steps:
(1) in graphene adding set, carboxyl function graphene and ethylene glycol are passed through into metering pump control function graphite
The mass fraction of carboxyl function graphene is 5% in alkene dispersion liquid, is used simultaneously using high-shear emulsion machine and ultrasonic dispersers
Mode carry out dispersion removing, by inside setting cooling coil, control dispersion temperature be lower than 40 DEG C, high-shear emulsion machine
Revolving speed is 2500 r/min, and ultrasonic power 8kW, jitter time 2h obtain carboxyl function graphene dispersing solution.
(2) in adjuvant adding device, auxiliary material (including catalyst) and ethylene glycol are controlled into catalyst list by metering pump
Butyl tin trichloride dosage is the 0.1% of ternary polymerization composite material quality, same using high-shear emulsion machine and ultrasonic dispersers
When the dispersing mode that uses dispersed, by the cooling coil of inside setting, control dispersion temperature is lower than 40 DEG C, high shear cream
The revolving speed of change machine is 1500r/min, ultrasonic power 5kW, jitter time 30min, obtains auxiliary material dispersion liquid, auxiliary material dispersion liquid
Middle catalyst preparation concentration is 1%.
(3) step 1 gained functional graphene dispersion liquid is passed through after the effect of homogenizer high pressure by high pressure homogenizer
Raw material device for formulating, and step 2 gained auxiliary material dispersion liquid is passed through raw material device for formulating, while by remaining ethylene glycol and whole
P-phthalic acid be passed through raw material device for formulating, carried out in such a way that high-shear emulsion machine and ultrasonic dispersers use simultaneously
The uniform mixing of various raw materials controls 80 DEG C of mixing temperature by internal heating coils, and the revolving speed of high-shear emulsion machine is
1800r/min, ultrasonic power 10kW, ultrasonic time 30min obtain raw material mixed slurry.Wherein, added in step 1~3
The molar ratio for adding the adduction of ethylene glycol and whole p-phthalic acids is 1.5:1, preferentially using recycling storage tank when adding ethylene glycol
Recycling ethylene glycol in 11.
(4) step 3 resulting material is passed through esterification device, carries out esterification, reaction kettle reaction temperature control 260
DEG C, 0.1~0.5MPa of reaction pressure, reaction time 2.5h, control esterification rate reach 98%.
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, contracts
Poly- reaction 273 DEG C of reaction kettle reaction temperature, reacts vacuum degree 25kPa (absolute pressure), reaction time 5h, controls esterification
Rate 99.6%, inherent viscosity reaches 0.8dL/g.
(6) step 5 products therefrom is filtered by melt filter, then passes to granulated and dried device or directly transports
To spinning production line.
(7) gaseous substance (the predominantly mixture of ethylene glycol and water) generated in step 4 and step 5 reaction process is arranged
To waste material storage tank, ethylene glycol is isolated by rectifying column, the ethylene glycol isolated is delivered to recycling storage tank, and reuse to raw material is matched
In device processed.
Above-mentioned carboxyl function graphene is prepared by following methods:
Graphite oxide is dispersed by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
In the n,N-Dimethylformamide of certain volume, dispersion concentration 0.5mg/mL obtains graphene oxide dispersion, so for removing
A certain amount of aminocaproic acid is added slowly in graphene oxide dispersion afterwards, the dosage of aminocaproic acid is graphite oxide powder matter
The 100% of amount, back flow reaction for 24 hours, obtains black dispersion liquid at a temperature of 130 DEG C, is sufficiently washed with dehydrated alcohol black
After color dispersion liquid, freeze-drying obtains carboxyl function graphene powder.
Embodiment 4
The same embodiment of preparation facilities of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester of the present embodiment
1, the preparation method is as follows:
Amino functional graphene and auxiliary material (including titanium dioxide, catalyst) are dispersed in propylene glycol, function is respectively obtained
It can graphene dispersing solution and auxiliary material dispersion liquid；Then by remaining propylene glycol and p-phthalic acid, functional graphene dispersion liquid,
Auxiliary material dispersion liquid, which is added in reaction kettle, to be dispersed, and is then successively esterified, polycondensation reaction, and ternary polymerization composite wood is obtained
Material.Wherein, the quality of functional graphene accounts for the 0.1% of ternary polymerization composite material.
As shown in Figure 1, specifically includes the following steps:
(1) in graphene adding set, amino functional graphene and propylene glycol are passed through into metering pump control function graphite
The mass fraction of amino functional graphene is 2% in alkene dispersion liquid, is used simultaneously using high-shear emulsion machine and ultrasonic dispersers
Mode carry out dispersion removing, by inside setting cooling coil, control dispersion temperature be lower than 40 DEG C, high-shear emulsion machine
Revolving speed is 1500 r/min, and ultrasonic power 8kW, jitter time 60min obtain amino functional graphene dispersing solution.
(2) in adjuvant adding device, auxiliary material (including titanium dioxide, catalyst) and propylene glycol are controlled by metering pump
The dosage of titanium dioxide is the 0.5% of ternary polymerization composite material quality, and catalyst Dibutyltin oxide dosage is ternary polymerization
The 0.05% of composite material quality is dispersed using the dispersing mode that high-shear emulsion machine and ultrasonic dispersers use simultaneously,
By the cooling coil of inside setting, control dispersion temperature is lower than 40 DEG C, and the revolving speed of high-shear emulsion machine is 1500r/min, surpasses
Acoustical power is 10kW, jitter time 30min, obtains auxiliary material dispersion liquid, catalyst preparation concentration is in auxiliary material dispersion liquid
0.5%, titanium dioxide compound concentration 5%.
(3) step 1 gained functional graphene dispersion liquid is passed through after the effect of homogenizer high pressure by high pressure homogenizer
Raw material device for formulating, and step 2 gained auxiliary material dispersion liquid is passed through raw material device for formulating, while by remaining propylene glycol and whole
P-phthalic acid be passed through raw material device for formulating, carried out in such a way that high-shear emulsion machine and ultrasonic dispersers use simultaneously
The uniform mixing of various raw materials controls 80 DEG C of mixing temperature by internal heating coils, and the revolving speed of high-shear emulsion machine is
1500r/min, ultrasonic power 10kW, ultrasonic time 60min obtain raw material mixed slurry.Wherein, added in step 1~3
The molar ratio for adding the adduction of propylene glycol and whole p-phthalic acids is 1.4:1, preferentially using recycling storage tank when adding propylene glycol
Recycling propylene glycol in 11.
(4) step 3 resulting material is passed through esterification device, carries out esterification, reaction kettle reaction temperature control 255
DEG C, 0.1~0.5MPa of reaction pressure, reaction time 2h, control esterification rate reach 98.5%.
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, contracts
Poly- reaction, is reacted vacuum degree 20kPa (absolute pressure), reaction time 4.5h by 275 DEG C of reaction kettle reaction temperature, and control esterification is anti-
Should rate 99.6%, inherent viscosity reaches 0.78dL/g.
(6) step 5 products therefrom is filtered by melt filter, then passes to granulated and dried device or directly transports
To spinning production line.
(7) gaseous substance (the predominantly mixture of ethylene glycol and water) generated in step 4 and step 5 reaction process is arranged
To waste material storage tank, propylene glycol is isolated by rectifying column, the propylene glycol isolated is delivered to recycling storage tank, and reuse to raw material is matched
In device processed.
Above-mentioned amino functional graphene uses the amino functional graphene that following methods are prepared:
Graphite oxide is dispersed by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
In the water of certain volume, dispersion concentration 0.8mg/mL obtains graphene oxide dispersion, and a certain amount of p-phenylenediamine is delayed
Slowly it adds in graphene oxide dispersion, the dosage of p-phenylenediamine is the 50% of graphene oxide powder quality, in 80 DEG C of temperature
Lower back flow reaction 8h, obtains black dispersion liquid, and after the black dispersion liquid sufficiently washed with dehydrated alcohol, freeze-drying is obtained
To amino functional graphene powder.
Comparative example
The preparation facilities and preparation method of the ternary polymerization composite material of the graphene in-situ polymerization polyester of this comparative example with
Embodiment 1 is essentially identical, institute the difference is that, prepared using common graphite alkene.
Correlated performance test is carried out to ternary polymerization composite material obtained by each embodiment and comparative example, test result is shown in Table 1.
1 the performance test results of table
A kind of ternary polymerization of functional graphene in-situ polymerization polyester provided by the invention is answered it can be seen from 1 data of table
The superior performance of condensation material is compared compared with without the modification of functional graphene in-situ polymerization, has antistatic property, biocidal property, remote red
Outer performance, uv resistance, excellent mechanical property.
Claims (10)
1. a kind of dedicated unit for the ternary polymerization composite material for preparing functional graphene in-situ polymerization polyester, which is characterized in that
Including by the sequentially connected raw material adding set of pipeline, raw material device for formulating, esterification device, prepolymer filter device,
Polycondensation reaction device and melt filter, the raw material adding set include graphene adding set and adjuvant adding device；
High-shear emulsion machine and ultrasound point are equipped in the graphene adding set, adjuvant adding device and raw material device for formulating simultaneously
Device is dissipated, high pressure homogenizer, the esterification device are equipped between the graphene adding set and the raw material device for formulating
It is connect by recyclable device with the raw material device for formulating with the waste port of polycondensation reaction device, is successively set in the recyclable device
There are waste material storage tank, rectifying column and recycling storage tank.
2. a kind of ternary polymerization composite material of the functional graphene in-situ polymerization polyester using dedicated unit described in claim 1
Preparation method, which is characterized in that functional graphene and auxiliary material are dispersed in dihydric alcohol, respectively obtain functional graphene dispersion
Liquid and auxiliary material dispersion liquid；Then dihydric alcohol, binary acid, functional graphene dispersion liquid and auxiliary material dispersion liquid are added to reaction kettle
In dispersed, be then successively esterified, polycondensation reaction, obtain the ternary polymerization composite material.
3. preparation method according to claim 2, which comprises the following steps:
(1) functional graphene and dihydric alcohol are used into high-shear emulsion machine and ultrasonic dispersers simultaneously in graphene adding set
The mode used is dispersed, and obtains functional graphene dispersion liquid, and the mass concentration of the functional graphene dispersion liquid is 0.1~
10%；
(2) point for using auxiliary material and dihydric alcohol simultaneously using high-shear emulsion machine and ultrasonic dispersers in adjuvant adding device
Scattered mode is dispersed, and auxiliary material dispersion liquid is obtained, and the mass concentration of the auxiliary material dispersion liquid is 0.1~35%；
(3) step 1 gained functional graphene dispersion liquid is passed through raw material device for formulating by high pressure homogenizer, and by step 2 institute
It obtains auxiliary material dispersion liquid and is passed through raw material device for formulating, while dihydric alcohol and binary acid are passed through raw material device for formulating, then using height
The mode that emulsification pretreatment machine and ultrasonic dispersers use simultaneously disperses material in device；
(4) step 3 resulting material is passed through esterification device, carries out esterification；
(5) step 4 products therefrom is filtered by prepolymer filter device, then passes to polycondensation reaction device, it is anti-to carry out polycondensation
It answers；
(6) step 5 products therefrom is filtered by melt filter to get the ternary polymerization composite material；
(7) gaseous substance generated in step 4 and step 5 reaction process is drained into waste material storage tank, isolates two by rectifying column
First alcohol, the dihydric alcohol isolated is delivered to recycling storage tank, and reuse is into raw material device for formulating.
4. preparation method according to claim 2 or 3, which is characterized in that the dihydric alcohol is selected from ethylene glycol, the third two
One of alcohol, butanediol, cyclohexanediol are a variety of, and the binary acid is p-phthalic acid, the functional graphene
For carboxyl function graphene or amino functional graphene, the molar ratio of the dihydric alcohol and binary acid is (1.2~2): 1, institute
The quality for the functional graphene stated accounts for the 0.01~2% of ternary polymerization composite material.
5. the preparation method according to claim 4, which is characterized in that the carboxyl function graphene is by following two side
The preparation of one of method:
A, graphite oxide is dispersed in by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
It in good solvent, is then slowly added into amino acids and is reacted, after washing is dry；
B, first graphite oxide is dispersed to shell by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously
From in lye, then graphene oxide is activated using monoxone or sodium chloroacetate, is eventually adding carboxylated examination
Agent carries out carboxylation reaction；
The amino functional graphene is prepared by one of following two method:
C, graphite oxide is dispersed in by the mechanical dispersion mode that high-shear emulsion machine and ultrasonic dispersers are run simultaneously first
It in good solvent, is then slowly added into diamine compounds and is reacted, after washing is dry；
D, the method referring to described in Chinese patent 201810212266.0 is prepared.
6. preparation method according to claim 3, which is characterized in that the mixing speed of the high-shear emulsion machine >=
1000r/min, the ultrasonic power of the ultrasonic dispersers are 1~20kw, and the jitter time is 1~10h, point
Dissipating temperature is 10~40 DEG C.
7. preparation method according to claim 3, which is characterized in that the auxiliary material includes catalyst, and the catalyst is
Antimony system, titanium system, tin system or germanium system, the dosage of the catalyst are the 0.05~0.25% of overall reaction quality of material.
8. preparation method according to claim 3, which is characterized in that the condition of the esterification are as follows: reaction temperature 250
~265 DEG C, 0.1~0.5MPa of reaction pressure, 0.5~2.5h of reaction time, control esterification rate is not less than 96%；The contracting
The condition of poly- reaction are as follows: 265~280 DEG C of reaction temperature, react 0.1~25kPa of vacuum degree, 0.5~5h of reaction time, control ester
Change reactivity and is not less than 99.5%.
9. the ternary for the functional graphene in-situ polymerization polyester that method described in any one of claim 2~8 is prepared is total
Poly- composite material.
10. ternary polymerization composite material according to claim 9, which is characterized in that the equal molecule of the number of the composite material
Amount is 10000~150000, and inherent viscosity is 0.6~1.2dL/g.
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