CN108383986A - A kind of preparation method of differential PTA - Google Patents
A kind of preparation method of differential PTA Download PDFInfo
- Publication number
- CN108383986A CN108383986A CN201810065815.6A CN201810065815A CN108383986A CN 108383986 A CN108383986 A CN 108383986A CN 201810065815 A CN201810065815 A CN 201810065815A CN 108383986 A CN108383986 A CN 108383986A
- Authority
- CN
- China
- Prior art keywords
- parts
- pta
- modified
- crystallization kettle
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of differential PTA, includes the following steps：(1) by bismuth molybdate, graphene oxide, hypochloric acid water solution, zinc oxide, white carbon, potassium titanate crystal whisker and hydrofluoric acid aqueous solution mixed grinding, hydro-thermal reaction is then carried out, through filtering, calcining, corona treatment, it is organic-silicon-modified, special anti-aging agent is made；(2) sodium hexametaphosphate solution, nickel fluoborate, artificial schellite and step (1) gained special anti-aging agent are added after mixing acetic acid and water, dedicated modified liquid is made in mashing dispersion, it is merged with crude terephthalic acid slurry, crystallization, then it is washed after being separated by solid-liquid separation, dry, mashing, it is refined that it is separated by solid-liquid separation back end hydrogenation again, differential PTA is made.Product prepared by the method for the present invention has apparent antiageing effect.
Description
Technical field
The invention belongs to PTA variety development technical fields, and in particular to a kind of preparation method of differential PTA.
Background technology
PTA, that is, p-phthalic acid is a kind of large chemical industry raw material, and concentration is compared in application, in the world 90%
For above PTA for producing polyethylene terephthalate, other parts are for producing polypropylene terephthalate
With the synthetic materials such as polybutylene terephthalate.These synthetic materials have excellent performance, as initial modulus is high, intensity
It is good, elasticity is big, shape-retaining ability and heat-resist etc., is widely used in people’s lives and industrial production, such as can tailoring, beverage
Bottle, packing film, proximate matter etc. can also be applied to open air, such as advertisement lamp house cloth, shelter cloth.These synthetic materials are outdoors
During use, the erosion for being subjected to the environmental factors such as sunlight, heat, air, rainwater, service life is needed to greatly shorten, compeled
The anti-aging characteristic for improving this kind of synthetic material is cut, extends their service lifes outdoors, therefore study the new varieties of PTA,
The synthesis material with anti-aging function is used to prepare to be of great significance.
Usually using paraxylene as raw material, liquid phase oxidation generates crude terephthalic acid, then hydrogenated refined for the preparation of PTA,
Crystallization detaches, dry, obtains p-phthalic acid.Such as patent US5723656, US006307099 and US4241220 are retouched
Typical p-phthalic acid's production technology is stated.Raw material paraxylene is dissolved in the acetic acid containing cobalt manganese bromine catalyst first
In solvent, be passed through air or it is oxygen-enriched aoxidized, generate crude terephthalic acid (CTA).Typical reaction pressure is 0.6~
1.6MPa, temperature are 160~200 DEG C, and reaction time is 50~130min；Reaction heat is removed by evaporation of the solvent, is contained
The slurry of CTA by crystallization, filtering and it is dry carry out solid-liquor separation, while recovering energy and catalyst；Oxidation operation is obtained
Solid be sent into refined unit by catalytic hydrogenation remove impurity purified crystals, obtain PTA products.
For the production technology aspect of PTA, the general activity mainly reacted from raising p xylene oxidation and conversion ratio,
The generation of the impurity such as intermediate product, such as p -carboxybenzaldehyde are reduced, the purity of PTA is improved, due to being single to carboxyl benzoic acid
Functional compounds, and not soluble in water, the acetic acid equal solvent as PTA, therefore be difficult to be detached with PTA, at present mainly by adding
It is separated off with PTA after being dissolved in water after hydrogen reduction, generally requires p -carboxybenzaldehyde in content in 25ppm or less.
The key and core of modified poly ester and products thereof are modified PTA, and in existing document, preparing for PTA is main
Accounted for from purifying process, that is, reduce the content of the impurity such as p -carboxybenzaldehyde, reduce PTA in subsequent polycondensation reaction this
Influence of the kind impurity to reaction, almost without considering by developing some new PTA varities practices in some special materials, such as system
The standby modified material etc. with specific function.So PTA products are single all the time, and it is almost unalterable.
Invention content
In order to solve the above technical problem, the present invention provides a kind of preparation methods of differential PTA.
The present invention develops the new varieties of PTA by combining ageing resistance agent in the oxidation reaction of paraxylene, to
Reach modified PTA to promoting downstream product allomeric function and quality effect purpose.Bismuth molybdate, graphite oxide are combined in the present invention
The modifying agent such as alkene, zinc oxide, white carbon, potassium titanate crystal whisker, nickel fluoborate, artificial schellite can be obviously improved the whole work(of resin
With quality effect the dispersibility and compatibility of modifying agent can be improved without especially increasing additional technique process.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of differential PTA, includes the following steps：
(1) by bismuth molybdate, graphene oxide, hypochloric acid water solution, zinc oxide, white carbon, potassium titanate crystal whisker and hydrofluoric acid
Then aqueous solution mixed grinding carries out hydro-thermal reaction, through filtering, calcining, corona treatment is organic-silicon-modified, is made special
Age resister；
(2) sodium hexametaphosphate solution, nickel fluoborate, artificial schellite and step (1) institute are added after mixing acetic acid and water
Special anti-aging agent is obtained, mashing dispersion is made dedicated modified liquid, is merged with crude terephthalic acid slurry, crystallized, and then solid-liquid divides
It is dry from rear washing, mashing, then be separated by solid-liquid separation back end hydrogenation and refine, differential PTA is made.
Inorganic material has fire-retardant, barrier, anti-aging, antibacterial, antistatic, health care, the functions such as enhancing；Ancestor uses already
Must be familiar, such as brick and tile, ceramics, stone, jade, glass, cement, mud.Brick and tile, mud wall expose to the sun and rain wind light at one's discretion
According to, can centuries it is immortal；The barrier property of ceramics, which is modern barrier material, to be compared, and the canned yellow rice wine many decades still alcohol of ceramics is aromatic
It is strongly fragrant；Jade can antibiotic health care have long enjoyed a good reputation, long with not waning.But how people apply inorganic material, modified organic material, especially
It is high molecular material, assigning high molecular material, there are certain functions, typically inorganic functional material simply to add blending and modifying,
Single application of function, functional effect is insufficient, and especially organic matrix functional effect is insufficient, and the quality of matrix is difficult to protect
Card.For overcome the deficiencies in the prior art, the present invention is through analysis comprehensively, complex optimum prescription, applicating modern times technology means depth
Physics and chemistry pre-treatment, then inorganic material is evenly dispersed is fused to organic material, the original function of inorganic material in subsequent product
Depth integration is into high-molecular organic material, and over time, inorganic body gradually forms interface with organic matrix two-phase interface
Phase, interface mutually constantly sprawling extension, the function of inorganic body are extended in company with sprawling into organism over time.Assign it
The functional effect of 1+1 ＞ 2, and promote the comprehensive physical performance of high-molecular organic material.
The present invention in the oxidation reaction product CTA slurries of PX creatively by adding the nothings such as PTA special anti-aging agent
Machine component does not contain active function groups in these inorganic material, is also insoluble in water or acetic acid equal solvent, but crystallized with CTA
Be separated by solid-liquid separation and the techniques such as drying, polishing purification after differential PTA of the generation containing inorganic component, compared with traditional handicraft simultaneously
Additional technique process need not especially be increased, for this technique because of the long action time of modified component and matrix, syncretizing effect is excellent
It is good.The diameter of disc secondary oxidation crystallization kettle and two round platform crystallization kettles is more than the structure of height, and CTA slurries is made to be stirred in bilayer
It mixes down, is more easy to obtain the suspension seethed upwards and fully oxidized and crystallization, promotion oxidation crystal growth, realization rapid crystallization,
Sufficient crystallising and homogeneously crystallized effect；It does not need to especially increase additional technique process, this technique compared with traditional handicraft
Because the interaction time of inorganic component and matrix is long, mutually merge.
The present invention develops the new varieties of PTA by adding inorganic component in the oxidation reaction product of PX, to reach
Purposes of the modified PTA to promotion downstream product allomeric function and quality effect.PTA special anti-aging agent etc. is added in the present invention
Inorganic component is substantially insoluble in acetic acid or water, without active function groups, after being mixed with CTA slurries through crystallizing, detaching, dry,
Just differential PTA is made after hydrofinishing.This PTA can be used for prepare with anti-aging function synthetic material, as film,
Fiber, binder, proximate matter etc., the synthetic material made from this PTA are mutually merged because inorganic component and matrix time are long,
Synergistic effect is abundant, is obviously improved the allomeric function and quality effect of synthetic material.
Preferably, to count content in parts by weight as follows for each component when mixing in step (1)：0.7-1 parts of bismuth molybdate, oxidation
0.7-1 parts of graphene, 10-15 parts of hypochloric acid water solution, 0.3-0.5 parts of zinc oxide, 0.3-0.5 parts of white carbon, potassium titanate crystal whisker
0.2-0.3 parts, 8-10 parts of hydrofluoric acid aqueous solution.Above components content range so that the antiageing effect of product is apparent and does not influence
Processing and the performance of fiber are influenced, if content is not in above range, anti-ageing effect is deteriorated, or promotes anti-aging effect
Fruit declines compared with content, and influences processing and the performance of fiber.
Preferably, the mass fraction of hypochloric acid water solution be 1-3%, preferably 2%.
Preferably, the mass fraction of hydrofluoric acid aqueous solution be 3-8%, preferably 5%.
Preferably, potassium titanate crystal whisker is conductive potassium titanate crystal whisker.
Preferably, grinding is carried out by high energy ball mill.
Preferably, feed temperature is 45-55 DEG C when grinding, and the time of grinding is 3-4h.
Preferably, the temperature of hydro-thermal reaction is 150-180 DEG C, pressure 2-4MPa, time 8-12h.
Preferably, the temperature of calcining is 530-550 DEG C, time 4-5h.
Preferably, the material after calcining carries out corona treatment after being cooled to room temperature grinding 2-3h.
Preferably, corona treatment carries out in plasma reactor.
Preferably, corona treatment nitrogen buffer gas carries out radio frequency plasma under 45-55Pa, 40-60W power
Body handles 6-8min.
Preferably, organic-silicon-modified to be specially：Product after corona treatment is mixed with the ethanol solution of organosilicon
The ultrasonic disperse 2-3h at 50-70 DEG C.
Preferably, the product after corona treatment occupies the 15-20% of the siliceous amount of machine.
The mass fraction of organosilicon is 20-40% in the ethanol solution of organosilicon, begins with the dispersion conducive to age resister,
Preferably 30%.
Preferably, a point meter each component addition in parts by weight is respectively 10-15 parts of acetic acid, water 3-5 in step (2)
Part, 1-3 parts of calgon aqueous dispersant, 0.8-1 parts of nickel fluoborate, 0.8-1 parts of artificial schellite, special anti-aging agent 2-3
Part.
Preferably, the mass fraction of calgon aqueous dispersant be 3-8%, preferably 5%.
Preferably, dedicated modified liquid is the 3-12% of crude terephthalic acid slurry quality.
Preferably, the mass fraction of crude terephthalic acid slurry is 25-35%, preferably 28-30%.
Preferably, it is separated into ultrasonic disperse, the ultrasonic disperse 3-4h preferably at 40-45 DEG C.
Preferably, crystallization detailed process is：Secondary oxidation is carried out in 185-190 DEG C, 1-1.1MPa and oxygen-enriched air simultaneously
Crystallization, residence time 20-30min；Then continue to crystallize under 155-160 DEG C, 0.2-0.4MPa, residence time 20-30min；
It is further crystallized under 90-95 DEG C, (- 0.06)-(- 0.04) MPa again, residence time 25-35min.Above-mentioned method for crystallising can obtain
Rapid crystallization, sufficient crystallising and homogeneously crystallized effect are obtained, the generation of monofunctional impurities is reduced.The pairs of benzene of p xylene oxidation
Dioctyl phthalate slurry is referred to as once oxidation, is carried out in first left kettle 1 in Fig. 1, and this time oxidation is insufficient, and here two
Secondary oxidation refers to being carried out in first crystallization kettle.
Secondary oxidation and crystallize preferably carry out under stiring.
Preferably, secondary oxidation and crystallize carried out in disc secondary oxidation crystallization kettle, continue crystallization and further knot
Crystalline substance carries out in round platform crystallization kettle.
Preferably, the diameter of disc secondary oxidation crystallization kettle and round platform crystallization kettle is more than height, makes CTA slurries in bilayer
It under stirring, is more easy to obtain the suspension seethed upwards and fully oxidized and crystallization, promotes oxidation crystal growth, realize quickly knot
Brilliant, sufficient crystallising and homogeneously crystallized effect；It does not need to especially increase additional technique process, this work compared with traditional handicraft
Skill is mutually merged because the interaction time of modifying agent and matrix is long.
Preferably, the diameter of disc secondary oxidation crystallization kettle and height ratio are 2:1-1.5 crystallization effect is more preferable.
Preferably, disc secondary oxidation crystallization kettle bottom is equipped with injection oxygen-enriched air injection pipe 7 and fumarole pipe 8, bottom
Portion's minimum point is equipped with modified CTA slurries and exports connecting tube 10, and top is equipped with evaporation of the solvent recovery tube 5, in secondary oxidation crystallization kettle
The heart is equipped with two layers of paddle.
Preferably, the diameter of appearing on the stage of round platform crystallization kettle：Platform is high：Base frame a diameter of 2.5：1.8-2.2：1-1.2, crystallization effect
More preferably.
Preferably, round platform crystallization kettle bottom minimum point is equipped with modified CTA slurries and exports connecting tube, and top is equipped with evaporation of the solvent
Recovery tube 14, round platform crystallization kettle center are equipped with two layers of paddle 15.
It is washed after separation of solid and liquid, dry, mashing can carry out 1 time or more, such as 2 times, 3 inferior.
It is final be separated by solid-liquid separation after the water capacities of CTA filtrates be 5-15%, preferably 10% or so.
The water used in step (2) can be deionized water.
Preferably, the preparation method of the CTA slurries is as follows：
A) cobalt-manganese-bromide catalizer and acetic acid are mixed, be heated to 50-60 DEG C stir evenly after, after vacuum drying is added
Graphene, heat preservation are stood, and are then added acetic acid and are carried out ultrasonic disperse, the graphene dispersing solution for being adsorbed with catalyst is made；
B) using acetic acid as solvent, PX is passed through with the graphene dispersing solution for being adsorbed with catalyst in reaction kettle respectively, then
It is passed through oxygen into reaction kettle, catalytic oxidation is carried out at 190-200 DEG C, 1.2-1.6MPa, CTA slurries are made.
Preferably, the mass ratio of graphene and cobalt-manganese-bromide catalizer is 1-2 in step a):1.
Preferably, PX in step b), oxygen, graphene dispersing solution mass ratio be 65-67:33-35:1-3.
It is well known that graphene can effectively enhance such as intensity of organic polymer, wearability physical property, usually exist
It is added during synthesis high molecular material.Similarly with modifying agent described previously, graphene is added in the synthesis process,
It is shorter with the interaction time of matrix, mutually merges poor, and the not high, synergistic effect of dispersibility is not enough, therefore can not
Its functionality can be given full play to.Further, since being easy mutually to draw close between graphene sheet layer structure, lead to lamella hypotelorism,
Extent of exfoliation reduces, and hardness increases so that synthetic material made from final, such as plastics, film surface smoothness reduce, and use hand
Jagged sense is stroked, sense organ is influenced.If graphene is added very little, without enhancing effect, too many, then easy to reunite, influence is added
The finish etc. of subsequent product.It is therefore preferable that the mass ratio of graphene and cobalt-manganese-bromide catalizer is 1-2:1.PX, oxygen, stone
The mass ratio of black alkene dispersion liquid is preferably 65-67:33-35:1-3.
Preferably, the preparation method of the present invention includes the following steps：
(1) mass fraction is pressed, is by 0.7-1 parts of bismuth molybdate, 0.7-1 parts of graphene oxide, 10-15 parts of mass fractions
2% hypochloric acid water solution, 0.3-0.5 parts of zinc oxide, 0.3-0.5 parts of white carbon, 0.2-0.3 parts of conductive potassium titanate are brilliant
It must be added sequentially to mix in the hydrofluoric acid aqueous solution that 8-10 parts of mass fractions are 5%, be ground at 45-55 DEG C with high energy ball mill
Mill processing 3-4h, then moves on in the hydrothermal reaction kettle that liner is titanium, then handle 8-12h under 150-180 DEG C, 2-4MPa, cold
But it filters, 4-5h is calcined at 530-550 DEG C, after being cooled to room temperature, then in ball mill grinding 2-3h, move on to stirring-type plasma
In reactor, nitrogen buffer gas carries out RF plasma processing 6-8min under 45-55Pa, 40-60W power, then adds
In the ethanol solution for entering the organosilicon for being 30% to 8-12 parts of mass fractions, the ultrasonic disperse 2-3h at 50-70 DEG C is filtered, and is used
Absolute ethyl alcohol fully washs, and reheats drying, and be sieved through 250-300 mesh, PTA special anti-aging agent is made；
(2) mass fraction is pressed, 10-15 parts of acetic acid and 3-5 parts of deionized water are mixed with continuous stirring, added
1-3 parts of mass fractions are 5% calgon aqueous dispersant, 0.8-1 parts of nickel fluoborate, 0.8-1 parts of artificial schellite
With the 2-3 parts of PTA special anti-agings agent made from (1), mashing is uniform, then the ultrasonic disperse 3-4h at 40-55 DEG C, is made special
Use modification liquid；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets an importing by B before stirring dynamic mixer 6) made from dedicated modified liquid branch pipe and metering pump 3, come from oxygen
Change the CTA slurry in proportion of bubble tower 1 mass fraction 28-30% through metering pump 2 measure with through the metering of metering pump 3 import by
(2) dedicated modified liquid made from is mixed into modified CTA slurries by stirring dynamic mixer 6, is injected into the secondary oxygen of disc
Change crystallization kettle 9, agitated progress secondary oxidation and is crystallized, the residence time at 185-190 DEG C, in 1-1.1MPa and oxygen-enriched air
20-30min；Modified CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, at 155-160 DEG C, 0.2-0.4MPa
Under continue to crystallize, residence time 20-30min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again,
It is further crystallized under 90-95 DEG C, (- 0.06)-(- 0.04) MPa, residence time 25-35min；Then crystallization will be completed
Modified CTA slurries through 18 centrifugal dewatering of centrifuge and wash successively, and the mashing mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering
Washing, the mashing mashing stirring of kettle 17, then through 20 centrifugal dewatering of centrifuge, the modification CTA filtrates that water capacity is 10% are obtained through spiral shell
Conveyer mixing is revolved, steam dryer is delivered to and is dried, then hydrogenated process for refining, a kind of differential PTA is made.
The present invention has the advantages that：
The inorganic material of the present invention is after the combined type depth materializing strategy of step (1) and step (2), on the one hand,
Its dispersibility and compatibility in organic matrix can be greatly improved.On the other hand, to above-mentioned inorganic matter (especially whisker)
Carry out physics, after chemical surface treatment, surface is etched and organic modification, by its with organic matrix it is compound after, with the time
Passage, molecule, the atom of organic matrix and inorganic body two-phase interface are easier to interpenetrate, invade, spread, migrating, inorganic
Body gradually forms a cenotype all different with inorganic body and organic matrix from organic matrix two-phase interface --- interface phase (without
It crosses the inorganic matter of above-mentioned processing then and is difficult or takes longer for just forming interface phase).In subsequent product, with the time
Interface mutually constantly sprawling extension is elapsed, the function of inorganic body is extended in company with sprawling.In the process, whisker can be gradually thicker
(like reinforcing bar for a long time in concrete, since the gradual infiltration reinforcing bar of concrete also can be thicker, i.e., reinforcing bar periphery generation interface
Phase), this interface is mutually fully merged due to inorganic material-modified dose with organic matrix, thus compared to common age resister
At least several months, the at most Effective Duration of 1-2 have more lasting functional period, and functional effect also can be more preferable.But it is formed
Above-mentioned interface mutually needs the regular hour, if only after synthetic material is made addition inorganic material by melt blending, that
Interface phase can not be formed in a short time after product is made, and the present invention just adds inorganic material in early period, obtains enough
Timeliness can comparatively fast form the interface phase of anti-aging function after subsequent product is made, and play effect.
The present invention is will the PTA made of bismuth molybdate, graphene oxide, zinc oxide, white carbon, conductive potassium titanate crystal whisker
Special anti-aging agent and nickel fluoborate, artificial schellite inorganic component and PTA are combined, and can be produced when subsequently preparing synthetic material
Raw new synergy, this trade-off effect be presented as in synthetic material can shift in time light, heat radiation energy, enhancing
The chemical stabilization of macromolecular key in material, improves the erosion of the environmental factors such as resistance to rainwater and wind, has excellent anti-aging function,
It is also beneficial to the mechanical properties such as intensity, the shock resistance of reinforcing material.With the subsequent material of this differential PTA, such as film, fibre
Dimension, binder, proximate matter, their outdoor performance all can significantly improve.
Description of the drawings
Fig. 1 is the PTA production technological process of one embodiment of the invention；
In figure：0- oxidation reaction raw materials, 1- aoxidize bubble tower, and 2,3- metering pumps, two layers of paddle of 4-, 5- evaporation of the solvent is returned
Closed tube, 6- stirring dynamic mixers, 7- oxygen-enriched air injection pipes, 8- fumarole pipes, 9- disc secondary oxidation crystallization kettles, 10-
Slurry exports connecting tube, and 11,13- round platform crystallization kettles, 12- connecting tubes, 14- evaporation of the solvent recovery tubes, two layers of paddle of 15-, 16,
17- be beaten kettle, 18,19,20- centrifuges, 21- recovery systems, 22- acetic acid, 23,26- acetic acid recycle reactor, 24,27- recycling
System, 25- screw conveyors, 28- drying machines.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
By the anti-aging experimental method of differential PTA synthetic fibers produced by the present invention：Using xenon lamp aging case, parameter is set
It is fixed：65 DEG C of blackboard temperature；Babinet humidity 50%；Intensity of illumination 550W/m2；Spray the period：18min, it is anhydrous between spraying twice
Time is 102min.Synthetic fibers are placed in parallel in xenon lamp aging case sample disc, and are in relaxed state, are sampled and are pressed after 300h
According to GB/T14337-2008 standard testing fiber strengths.
Fig. 1 is a process flow chart of the specific embodiment of the invention.Detailed process is：In oxidation bubble tower 1 and circle
9 connecting line of dish type secondary oxidation crystallization kettle is equipped with metering pump 2, stirring dynamic mixer 6, before stirring dynamic mixer 6
If one imports the branch pipe of dedicated modified liquid made from (2) and metering pump 3, carry out the CTA slurry in proportion warp of autoxidation bubble tower 1
Metering pump 2 measure with through metering pump 3 metering importing by B) made from dedicated modified liquid be mixed by stirring dynamic mixer 6
For modified CTA slurries, it is injected into disc secondary oxidation crystallization kettle 9, carry out secondary oxidation and is crystallized；Modified CTA slurries are led to
It crosses connecting tube 10 and is input in round platform crystallization kettle 11 and continue to crystallize；Modified CTA slurries are input to round platform by connecting tube 12 again
It is further crystallized in crystallization kettle 13；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively
Wash, mashing kettle 16 mashing stirring, centrifuge 19 continue centrifugal dewatering washing, mashing kettle 17 mashing stirring, then through centrifuge 20 from
The heart takes off liquid, obtains modified CTA filtrates and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried, then hydrogenated essence
Differential PTA is made in technique processed.
Embodiment 1
A kind of preparation method of differential PTA, includes the following steps：
(1) mass fraction is pressed, time for being 2% by 0.8 part of bismuth molybdate, 0.9 part of graphene oxide, 12 parts of mass fractions
Chloric acid aqueous solution, 0.4 part of zinc oxide, 0.4 part of white carbon, 0.25 part of conductive potassium titanate crystal whisker are added sequentially to 9 parts of matter
Amount score be 5% hydrofluoric acid aqueous solution in mix, with high energy ball mill at 50 DEG C milled processed 3.5h, then move on to liner
For in the hydrothermal reaction kettle of titanium, then 10h is handled under 165 DEG C, 3MPa, cold filtration calcines 4.5h at 540 DEG C, is cooled to often
Wen Hou, then in ball mill grinding 2.5h, move on in stirring-type plasma reactor, nitrogen buffer gas, in 50Pa, 50W work(
RF plasma processing 7min is carried out under rate, is then added to the ethanol solution for the organosilicon that 10 parts of mass fractions are 30%
In, the ultrasonic disperse 2.5h at 60 DEG C, filtering is fully washed with absolute ethyl alcohol, is reheated drying, and be sieved through 270 mesh, is made
PTA special anti-aging agent；
(2) mass fraction is pressed, 12 parts of acetic acid and 4 parts of deionized water are mixed with continuous stirring, add 2 parts of matter
Amount score is 5% calgon aqueous dispersant, 0.9 part of nickel fluoborate, 0.9 part of artificial schellite and 2.5 parts by (1)
PTA special anti-agings agent obtained, mashing is uniform, then the ultrasonic disperse 3.5h at 50 DEG C, and dedicated modified liquid is made；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets importing branch pipe of compound age resister made from (2) and metering pump 3 before stirring dynamic mixer 6, comes
The CTA slurry in proportion of 1 mass fraction 29% of autoxidation bubble tower through metering pump 2 measure with through metering pump 3 metering import by
(2) compound age resister made from is mixed into modified CTA slurries by stirring dynamic mixer 6, and it is secondary to be injected into disc
Oxidizing and crystallizing kettle 9 agitated progress secondary oxidation and crystallizes, residence time 25min at 187 DEG C, in 1MPa and oxygen-enriched air；It will
Modified CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, continue to crystallize under 158 DEG C, 0.3MPa, the residence time
25min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again, at 93 DEG C, under -0.05MPa further
Crystallization, residence time 30min；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively,
It is beaten the mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering and washs, the mashing mashing stirring of kettle 17, then centrifuges and take off through centrifuge 20
Liquid obtains the modification CTA filtrates that water capacity is 10% and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried,
Differential PTA is made in hydrogenated process for refining again.
The diameter of disc secondary oxidation crystallization kettle is with height than being 2:1；The diameter of appearing on the stage of round platform crystallization kettle：Platform is high：Bottom
Platform a diameter of 2.5：2.2：1.
Synthetic material is made using the differential PTA originally applied obtained by example and ethylene glycol combined polymerization, modified synthesis is then made
Fiber, it is 3.18cN/dtex, extension at break that gained modified synthetic fibers measure ultimate strength according to following anti-aging experimental method
It is 13%.
Embodiment 2
A kind of preparation method of differential PTA, includes the following steps：
(1) mass fraction is pressed, the secondary chlorine for being 2% by 0.7 part of bismuth molybdate, 1 part of graphene oxide, 15 parts of mass fractions
Aqueous acid, 0.3 part of zinc oxide, 0.5 part of white carbon, 0.3 part of conductive potassium titanate crystal whisker are added sequentially to 8 parts of quality point
Number to be mixed in 5% hydrofluoric acid aqueous solutions, with high energy ball mill at 45 DEG C milled processed 4h, it is titanium then to move on to liner
In hydrothermal reaction kettle, then 12h being handled under 150 DEG C, 4MPa, cold filtration calcines 4h at 550 DEG C, after being cooled to room temperature, then
Ball mill grinding 3h is moved on in stirring-type plasma reactor, nitrogen buffer gas, and radio frequency is carried out under 55Pa, 40W power
Corona treatment 6min is then added in the ethanol solution for the organosilicon that 12 parts of mass fractions are 30%, is surpassed at 70 DEG C
Sound disperses 2h, and filtering is fully washed with absolute ethyl alcohol, reheats drying, and be sieved through 300 mesh, PTA special anti-agings are made
Agent；
(2) mass fraction is pressed, 15 parts of acetic acid and 3 parts of deionized water are mixed with continuous stirring, add 3 parts of matter
Amount score is that 5% calgon aqueous dispersant, 1 part of nickel fluoborate, 0.8 part of artificial schellite and 2 parts are obtained by (1)
PTA special anti-aging agent, mashing is uniform, then the ultrasonic disperse 3h at 55 DEG C, and dedicated modified liquid is made；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets importing branch pipe of dedicated modified liquid made from (2) and metering pump 3 before stirring dynamic mixer 6, comes from
The CTA slurry in proportion for aoxidizing 1 mass fraction 28% of bubble tower is measured through metering pump 2 and through the metering importing of metering pump 3 by (2)
Dedicated modified liquid obtained is mixed into modified CTA slurries by stirring dynamic mixer 6, is injected into disc secondary oxidation knot
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 20min at 190 DEG C, in 1MPa and oxygen-enriched air；It will be modified
CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, continue to crystallize under 160 DEG C, 0.4MPa, the residence time
20min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again, at 90 DEG C, under -0.04MPa further
Crystallization, residence time 25min；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively,
It is beaten the mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering and washs, the mashing mashing stirring of kettle 17, then centrifuges and take off through centrifuge 20
Liquid obtains the modification CTA filtrates that water capacity is 10% and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried,
Differential PTA is made in hydrogenated process for refining again.
The diameter of disc secondary oxidation crystallization kettle is with height than being 2:1.5；The diameter of appearing on the stage of round platform crystallization kettle：Platform is high：
Base frame a diameter of 2.5：1.8：1.2.
Synthetic material is made using the differential PTA originally applied obtained by example and ethylene glycol combined polymerization, modified synthesis is then made
Fiber, it is 3.06cN/dtex, extension at break that gained modified synthetic fibers measure ultimate strength according to following anti-aging experimental method
It is 11%.
Embodiment 3
A kind of preparation method of differential PTA, includes the following steps：
(1) mass fraction is pressed, the secondary chlorine for being 2% by 1 part of bismuth molybdate, 0.7 part of graphene oxide, 10 parts of mass fractions
Aqueous acid, 0.5 part of zinc oxide, 0.3 part of white carbon, 0.2 part of conductive potassium titanate crystal whisker are added sequentially to 10 parts of quality
Score be 5% hydrofluoric acid aqueous solution in mix, with high energy ball mill at 55 DEG C milled processed 3h, then move on to liner be titanium
Hydrothermal reaction kettle in, then 8h is handled under 180 DEG C, 2MPa, cold filtration calcines 5h at 530 DEG C, after being cooled to room temperature, then
It in ball mill grinding 2h, moves on in stirring-type plasma reactor, nitrogen buffer gas, is penetrated under 45Pa, 60W power
Frequency corona treatment 8min is then added in the ethanol solution for the organosilicon that 8 parts of mass fractions are 30%, is surpassed at 50 DEG C
Sound disperses 3h, and filtering is fully washed with absolute ethyl alcohol, reheats drying, and be sieved through 250 mesh, PTA special anti-agings are made
Agent；
(2) mass fraction is pressed, 10 parts of acetic acid and 5 parts of deionized water are mixed with continuous stirring, add 1 part of matter
Amount score is that 5% calgon aqueous dispersant, 0.8 part of nickel fluoborate, 1 part of artificial schellite and 3 parts are obtained by (1)
PTA special anti-aging agent, mashing is uniform, then the ultrasonic disperse 4h at 40 DEG C, and dedicated modified liquid is made；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets importing branch pipe of dedicated modified liquid made from (2) and metering pump 3 before stirring dynamic mixer 6, comes from
The CTA slurry in proportion for aoxidizing 1 mass fraction 29% of bubble tower is measured through metering pump 2 and through the metering importing of metering pump 3 by (2)
Dedicated modified liquid obtained is mixed into modified CTA slurries by stirring dynamic mixer 6, is injected into disc secondary oxidation knot
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 25min at 185 DEG C, in 1MPa and oxygen-enriched air；It will be modified
CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, continue to crystallize under 160 DEG C, 0.4MPa, the residence time
20min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again, at 95 DEG C, under -0.05MPa further
Crystallization, residence time 30min；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively,
It is beaten the mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering and washs, the mashing mashing stirring of kettle 17, then centrifuges and take off through centrifuge 20
Liquid obtains the modification CTA filtrates that water capacity is 10% and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried,
Differential PTA is made in hydrogenated process for refining again.
The diameter of disc secondary oxidation crystallization kettle is with height than being 2:1.2；The diameter of appearing on the stage of round platform crystallization kettle：Platform is high：
Base frame a diameter of 2.5：2：1.1.
Synthetic material is made using the differential PTA originally applied obtained by example and ethylene glycol combined polymerization, modified synthesis is then made
Fiber, it is 3.08cN/dtex, extension at break that gained modified synthetic fibers measure ultimate strength according to following anti-aging experimental method
It is 10%.
Comparative example 1
A kind of preparation method of differential PTA, component content include the following steps not within the scope of the application：
(1) mass fraction is pressed, the secondary chlorine for being 2% by 1 part of bismuth molybdate, 0.5 part of graphene oxide, 10 parts of mass fractions
Aqueous acid, 0.1 part of zinc oxide, 0.2 part of white carbon, 0.1 part of conductive potassium titanate crystal whisker are added sequentially to 8 parts of quality point
Number to be mixed in 5% hydrofluoric acid aqueous solutions, with high energy ball mill at 55 DEG C milled processed 3h, it is titanium then to move on to liner
In hydrothermal reaction kettle, then 8h being handled under 180 DEG C, 2MPa, cold filtration calcines 5h at 530 DEG C, after being cooled to room temperature, then
Ball mill grinding 2h is moved on in stirring-type plasma reactor, nitrogen buffer gas, and radio frequency is carried out under 45Pa, 60W power
Corona treatment 8min is then added in the ethanol solution for the organosilicon that 8 parts of mass fractions are 30%, ultrasonic at 50 DEG C
Disperse 3h, filtering is fully washed with absolute ethyl alcohol, reheats drying, and be sieved through 250 mesh, PTA special anti-aging agent is made；
(2) mass fraction is pressed, 10 parts of acetic acid and 5 parts of deionized water are mixed with continuous stirring, add 1 part of matter
Amount score is that 5% calgon aqueous dispersant, 0.8 part of nickel fluoborate, 1 part of artificial schellite and 3 parts are obtained by (1)
PTA special anti-aging agent, mashing is uniform, then the ultrasonic disperse 4h at 40 DEG C, and dedicated modified liquid is made；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets importing branch pipe of dedicated modified liquid made from (2) and metering pump 3 before stirring dynamic mixer 6, comes from
The CTA slurry in proportion for aoxidizing 1 mass fraction 29% of bubble tower is measured through metering pump 2 and through the metering importing of metering pump 3 by (2)
Dedicated modified liquid obtained is mixed into modified CTA slurries by stirring dynamic mixer 6, is injected into disc secondary oxidation knot
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 25min at 185 DEG C, in 1MPa and oxygen-enriched air；It will be modified
CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, continue to crystallize under 160 DEG C, 0.4MPa, the residence time
20min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again, at 95 DEG C, under -0.05MPa further
Crystallization, residence time 30min；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively,
It is beaten the mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering and washs, the mashing mashing stirring of kettle 17, then centrifuges and take off through centrifuge 20
Liquid obtains the modification CTA filtrates that water capacity is 10% and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried,
Differential PTA is made in hydrogenated process for refining again.
The diameter of disc secondary oxidation crystallization kettle is with height than being 2:1.2；The diameter of appearing on the stage of round platform crystallization kettle：Platform is high：
Base frame a diameter of 2.5：2：1.1.
Synthetic material is made using the differential PTA originally applied obtained by example and ethylene glycol combined polymerization, modified synthesis is then made
Fiber, it is 2.55cN/dtex, extension at break that gained modified synthetic fibers measure ultimate strength according to following anti-aging experimental method
It is 3%.
Comparative example 2
A kind of preparation method of differential PTA, is added without graphene oxide and zinc oxide, including such as compared with Example 3
Lower step：
(1) mass fraction is pressed, by 1 part of bismuth molybdate, the hypochloric acid water solution that 10 parts of mass fractions are 2%, 0.3 part white
Carbon black, 0.2 part of conductive potassium titanate crystal whisker are added sequentially to mix in the hydrofluoric acid aqueous solution that 10 parts of mass fractions are 5%, use
Then high energy ball mill milled processed 3h at 55 DEG C is moved on in the hydrothermal reaction kettle that liner is titanium, then at 180 DEG C, under 2MPa
8h is handled, cold filtration calcines 5h at 530 DEG C, after being cooled to room temperature, then in ball mill grinding 2h, moves on to stirring-type plasma
In reactor according, nitrogen buffer gas carries out RF plasma processing 8min under 45Pa, 60W power, is then added to 8
In the ethanol solution for the organosilicon that part mass fraction is 30%, the ultrasonic disperse 3h at 50 DEG C, filtering is fully washed with absolute ethyl alcohol
It washs, reheats drying, and be sieved through 250 mesh, PTA special anti-aging agent is made；
(2) mass fraction is pressed, 10 parts of acetic acid and 5 parts of deionized water are mixed with continuous stirring, add 1 part of matter
Amount score is that 5% calgon aqueous dispersant, 0.8 part of nickel fluoborate, 1 part of artificial schellite and 3 parts are obtained by (1)
PTA special anti-aging agent, mashing is uniform, then the ultrasonic disperse 4h at 40 DEG C, and dedicated modified liquid is made；
(3) metering pump 2, stirring dynamic are equipped on oxidation bubble tower 1 and 9 connecting line of disc secondary oxidation crystallization kettle
Mixer 6 sets importing branch pipe of dedicated modified liquid made from (2) and metering pump 3 before stirring dynamic mixer 6, comes from
The CTA slurry in proportion for aoxidizing 1 mass fraction 29% of bubble tower is measured through metering pump 2 and through the metering importing of metering pump 3 by (2)
Dedicated modified liquid obtained is mixed into modified CTA slurries by stirring dynamic mixer 6, is injected into disc secondary oxidation knot
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 25min at 185 DEG C, in 1MPa and oxygen-enriched air；It will be modified
CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, continue to crystallize under 160 DEG C, 0.4MPa, the residence time
20min；Modified CTA slurries are input to by connecting tube 12 in round platform crystallization kettle 13 again, at 95 DEG C, under -0.05MPa further
Crystallization, residence time 30min；Then the modification CTA slurries that crystallization is completed through 18 centrifugal dewatering of centrifuge and are washed successively,
It is beaten the mashing stirring of kettle 16, centrifuge 19 continues centrifugal dewatering and washs, the mashing mashing stirring of kettle 17, then centrifuges and take off through centrifuge 20
Liquid obtains the modification CTA filtrates that water capacity is 10% and is mixed through screw conveyor, is delivered to steam dryer 28 and is dried,
Differential PTA is made in hydrogenated process for refining again.
The diameter of disc secondary oxidation crystallization kettle is with height than being 2:1.2；The diameter of appearing on the stage of round platform crystallization kettle：Platform is high：
Base frame a diameter of 2.5：2：1.1.
Synthetic material is made using the differential PTA originally applied obtained by example and ethylene glycol combined polymerization, modified synthesis is then made
Fiber, it is 2.63cN/dtex, extension at break that gained modified synthetic fibers measure ultimate strength according to following anti-aging experimental method
It is 3%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of differential PTA, includes the following steps：
(1) bismuth molybdate, graphene oxide, hypochloric acid water solution, zinc oxide, white carbon, potassium titanate crystal whisker and hydrofluoric acid is water-soluble
Then liquid mixed grinding carries out hydro-thermal reaction, through filtering, calcining, corona treatment is organic-silicon-modified, is made special anti-ageing
Agent；
(2) it is added after mixing acetic acid and water obtained by sodium hexametaphosphate solution, nickel fluoborate, artificial schellite and step (1) specially
With age resister, mashing dispersion is made dedicated modified liquid, is merged with crude terephthalic acid slurry, crystallized, after being then separated by solid-liquid separation
Washing, dry, mashing, then be separated by solid-liquid separation back end hydrogenation and refine, differential PTA is made.
2. preparation method according to claim 1, which is characterized in that each component is in parts by weight when mixing in step (1)
It is as follows to count content：0.7-1 parts of bismuth molybdate, 0.7-1 parts of graphene oxide, 10-15 parts of hypochloric acid water solution, zinc oxide 0.3-0.5
Part, 0.3-0.5 parts of white carbon, 0.2-0.3 parts of potassium titanate crystal whisker, 8-10 parts of hydrofluoric acid aqueous solution；
Preferably, the mass fraction of hypochloric acid water solution be 1-3%, preferably 2%；
Preferably, the mass fraction of hydrofluoric acid aqueous solution be 3-8%, preferably 5%；
Preferably, potassium titanate crystal whisker is conductive potassium titanate crystal whisker.
3. preparation method according to claim 1 or 2, which is characterized in that in step (1) grinding by high energy ball mill into
Row；
Preferably, feed temperature is 45-55 DEG C when grinding, and the time of grinding is 3-4h.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that the temperature of hydro-thermal reaction in step (1)
It is 150-180 DEG C, pressure 2-4MPa, time 8-12h；
Preferably, the temperature of calcining is 530-550 DEG C, time 4-5h；
Preferably, the material after calcining carries out corona treatment after being cooled to room temperature grinding 2-3h.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that the processing of step (1) plasma exists
It is carried out in plasma reactor；
Preferably, corona treatment nitrogen buffer gas carries out under 45-55Pa, 40-60W power at radio frequency plasma
Manage 6-8min；
Preferably, organic-silicon-modified to be specially：The ethanol solution of product and organosilicon after corona treatment is blended in 50-
Ultrasonic disperse 2-3h at 70 DEG C；
Preferably, the product after corona treatment occupies the 15-20% of the siliceous amount of machine.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that divide in step (2) and count in parts by weight
Each component addition is respectively 10-15 parts of acetic acid, 3-5 parts of water, 1-3 parts of calgon aqueous dispersant, nickel fluoborate
0.8-1 parts, 0.8-1 parts of artificial schellite, 2-3 parts of special anti-aging agent；
Preferably, the mass fraction of calgon aqueous dispersant be 3-8%, preferably 5%.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that special modification liquid is thick in step (2)
The 3-12% of terephthalic acid slurry quality；
Preferably, the mass fraction of crude terephthalic acid slurry is 25-35%, preferably 28-30%；
Preferably, it is separated into ultrasonic disperse, the ultrasonic disperse 3-4h preferably at 40-45 DEG C.
8. according to claim 1-7 any one of them preparation methods, which is characterized in that crystallization detailed process is in step (2)：
At 185-190 DEG C, carries out secondary oxidation in 1-1.1MPa and oxygen-enriched air and crystallize, residence time 20-30min；Then exist
155-160 DEG C, continue to crystallize under 0.2-0.4MPa, residence time 20-30min；Again at 90-95 DEG C, (- 0.06)-(- 0.04)
It is further crystallized under MPa, residence time 25-35min；
Preferably, secondary oxidation and crystallize carried out in disc secondary oxidation crystallization kettle, continue crystallization and further crystallization exist
It is carried out in round platform crystallization kettle.
9. preparation method according to claim 8, which is characterized in that disc secondary oxidation crystallization kettle or round platform crystallization kettle
Diameter be more than height；
Preferably, the diameter of disc secondary oxidation crystallization kettle and height ratio are 2:1-1.5；
Preferably, disc secondary oxidation crystallization kettle bottom is equipped with injection oxygen-enriched air injection pipe and fumarole pipe, bottom are minimum
Point is equipped with modified CTA slurries and exports connecting tube, and top is equipped with evaporation of the solvent recovery tube, and secondary oxidation crystallization kettle center is equipped with two layers
Paddle.
10. preparation method according to claim 8 or claim 9, which is characterized in that the diameter of appearing on the stage of round platform crystallization kettle：Platform is high：Bottom
Platform a diameter of 2.5：1.8-2.2：1-1.2；
Preferably, round platform crystallization kettle bottom minimum point is equipped with modified CTA slurries and exports connecting tube, and top is recycled equipped with evaporation of the solvent
Pipe, round platform crystallization kettle center are equipped with two layers of paddle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065815.6A CN108383986A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of differential PTA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065815.6A CN108383986A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of differential PTA |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108383986A true CN108383986A (en) | 2018-08-10 |
Family
ID=63077222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810065815.6A Pending CN108383986A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of differential PTA |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108383986A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914013A (en) * | 2010-07-30 | 2010-12-15 | 浙江大学 | Water-saving terephthalic acid production method |
| EP2210910B1 (en) * | 2009-01-21 | 2013-01-02 | Nan Ya Plastics Corporation | Antimony-free PET resin and PET polyester fiber made therefrom |
| CN106380583A (en) * | 2016-08-31 | 2017-02-08 | 浙江盛元化纤有限公司 | Synthetic method of reactive ageing-resistant copolyester |
| CN106400198A (en) * | 2016-08-31 | 2017-02-15 | 荣盛石化股份有限公司 | Manufacturing method of polyester fiber with anti-aging function |
-
2018
- 2018-01-23 CN CN201810065815.6A patent/CN108383986A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2210910B1 (en) * | 2009-01-21 | 2013-01-02 | Nan Ya Plastics Corporation | Antimony-free PET resin and PET polyester fiber made therefrom |
| CN101914013A (en) * | 2010-07-30 | 2010-12-15 | 浙江大学 | Water-saving terephthalic acid production method |
| CN106380583A (en) * | 2016-08-31 | 2017-02-08 | 浙江盛元化纤有限公司 | Synthetic method of reactive ageing-resistant copolyester |
| CN106400198A (en) * | 2016-08-31 | 2017-02-15 | 荣盛石化股份有限公司 | Manufacturing method of polyester fiber with anti-aging function |
Non-Patent Citations (1)
| Title |
|---|
| 环境保护部环境工程评估中心: "《环境影响评价案例分析》", 31 March 2015, 中国环境出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965721B (en) | Method for preparing calcium sulfate crystal whisker in low cost | |
| CN108484887A (en) | A kind of preparation method of compound PTA | |
| CN104947179A (en) | Method for preparing calcium sulfate whiskers | |
| CN106925239A (en) | A kind of novel drier and preparation method thereof | |
| CN113353964A (en) | Method for preparing anhydrous calcium sulfate from industrial solid waste gypsum | |
| CN105111423B (en) | A kind of polymer waterborne polyester and preparation method thereof | |
| CN109850941B (en) | Method for preparing high-purity titanium dioxide by hydrolyzing industrial titanium sulfate solution | |
| CN104512896A (en) | Method for preparing white carbon black by using high aluminum fly ash, and white carbon black | |
| CN109502637A (en) | A kind of method that Hydrolyze method prepares high-purity nm grade titanium dioxide | |
| CN104556116B (en) | A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve | |
| CN108383986A (en) | A kind of preparation method of differential PTA | |
| CN108439451A (en) | The method for preparing precipitated calcium carbonate using ardealite | |
| CN101050278B (en) | Half dullspon slices of caprone and production method | |
| CN103087203B (en) | Low-viscosity sodium carboxymethyl cellulose is adopted to prepare the method for ultralow-viscosity sodium carboxymethyl cellulose | |
| CN104790041B (en) | Method for preparing semi-hydrated gypsum whisker from mirabilite and calcium solution | |
| CN109180917A (en) | A kind of preparation method of EG | |
| CN110040740A (en) | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite | |
| CN104891504B (en) | A kind of method for extracting white carbon from cinder | |
| CN106964399A (en) | A kind of isobutene polymerisation catalyst and preparation method thereof | |
| CN111099595A (en) | Preparation method of high-performance silicon dioxide | |
| CN108341938A (en) | A kind of preparation method of function presetting p-phthalic acid | |
| CN100431967C (en) | Process for producing superfine barium carbonate and strontium carbonate | |
| CN108299631A (en) | A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation | |
| CN108299630A (en) | A kind of modified PTA, modified poly ester and its flame-proof anti-aging polyester fiber of preparation | |
| CN108301064A (en) | The manufacturing method and its device of a kind of doping vario-property copolyesters, profiled filament |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180810 |
|
| RJ01 | Rejection of invention patent application after publication |