CN108484888A - A kind of preparation method of inorganic modified paraxylene - Google Patents
A kind of preparation method of inorganic modified paraxylene Download PDFInfo
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- CN108484888A CN108484888A CN201810065024.3A CN201810065024A CN108484888A CN 108484888 A CN108484888 A CN 108484888A CN 201810065024 A CN201810065024 A CN 201810065024A CN 108484888 A CN108484888 A CN 108484888A
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- 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
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F1/10—Other agents for modifying properties
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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Abstract
A kind of preparation method of inorganic modified paraxylene, includes the following steps：Hydro-thermal reaction will be carried out after zinc molybdate, silver orthophosphate, hydrobromic acid solution, SILICA FUME, montmorillonite, titanium oxide and fluosulfonic acid solution mixed grinding, then through filtering, calcined, washing is dry that anti-aging powder is made；It grinds, disperses after paraxylene, acetic acid, meta-xylene, acetamide cosolvent, the anti-aging powder of gained, zinc oxide, potassium hydrogen phosphate dispersion liquid are mixed, the fining inorganic modified paraxylene mother liquor of special anti-aging is made in filtering；The anti-aging inorganic modified paraxylene mother liquor of gained is added in spray form in paraxylene, inorganic modified paraxylene is made.Product, which is made, in the method for the present invention has good antiageing effect.
Description
Technical field
The present invention relates to paraxylene new varieties technical fields, and in particular to a kind of system of inorganic modified paraxylene
Preparation Method.
Background technology
Dimethylbenzene (dimethylbenzene) is colourless transparent liquid；Be on phenyl ring two hydrogen by methyl substituted product,
There are it is o-, m-, to three kinds of isomers.In these three xylene isomers, paraxylene has maximum commercial market.To two
Toluene (para-xylene), can be abbreviated as " PX ", be benzene derivate, important industrial chemicals, colourless liquid, when low temperature at
Sheet or column crystallization body, it is not soluble in water, it is dissolved in ethyl alcohol, ether, benzene, acetone, it is inflammable.Paraxylene is a kind of basic organic
Raw material, wherein preparation of 80% or so the paraxylene for terephthalic acid (TPA) and synthetic material.These synthetic materials are used extensively
In products such as engineering plastics, construction material, machine components, plastic bottle, film, film, textile fabric, adhesive, herbicides.Its
The use scope of product outdoors is also increasingly extensive, but needs constantly to be subjected to solar irradiation, air, rainwater, wind erosion, gas outdoors
The influence of the environmental factors such as variation is waited, service life substantially shortens in environment outdoors.Its endurance issues is increasingly subject to weight
Depending on.
At present for the research and development of anti-aging function, people only focus on sight in polyester synthesis monomer (PTA, second two
Alcohol) building-up process in addition with anti-aging function additive, to improve the anti-aging property of polyester.But the above method
It has the disadvantages that：Due to direct synthesizing polyester after PTA and ethylene glycol polymerization, when the interaction of age-inhibiting addition and polyester
Between it is shorter, mutually merge poor, synergistic effect is not enough, therefore cannot give full play to the ageing resistance of age-inhibiting addition
Can, and many side reactions are also will produce, influence the allomeric functions such as the mechanics of polyester and quality effect.Therefore, in order to solve this
One technical problem usually also needs to additionally increase machining process, improves cost.
In the prior art, paraxylene is generally mainly anti-by improving chain tra nsfer, disproportionation as a kind of industrial chemicals
Answer, it is prepared by isomerization, the techniques such as adsorbing separation, such as CN 101253136A, CN 101466655A, CN 102159674A
The method that paraxylene is prepared Deng disclosed in.The preparation method of existing paraxylene is typically directed to improve paraxylene
Purity reduces the generation of impurity, few to develop some pairs with specific use from the viewpoint of downstream product application
Dimethylbenzene.So the product of paraxylene is single all the time, and it is almost unalterable.In addition, at present there is no on how to
Develop the report of the paraxylene with anti-aging function.Therefore, exploitation is directly used in the paraxylene of synthesis anti-aging materials
Class product has great importance.
Invention content
In order to solve the above technical problem, the present invention provides a kind of preparation methods of inorganic modified paraxylene.
The present invention by paraxylene compound age resister develop the new varieties of paraxylene, it is modified to reach
Paraxylene is to promoting downstream product allomeric function and quality effect purpose.Zinc molybdate, silver orthophosphate, micro- silicon are combined in the present invention
The modifying agent such as powder, montmorillonite, titanium oxide can be obviously improved the allomeric function and quality effect of resin, without especially increasing
Add additional technique process to improve the dispersibility and compatibility of modifying agent.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of inorganic modified paraxylene, includes the following steps：
(1) zinc molybdate, silver orthophosphate, hydrobromic acid solution, SILICA FUME, montmorillonite, titanium oxide are mixed with fluosulfonic acid aqueous solution
Hydro-thermal reaction is carried out after grinding, then through filtering, is calcined, and washing is dry that anti-aging powder is made；
(2) by anti-aging powder, oxidation obtained by paraxylene, acetic acid, meta-xylene, acetamide cosolvent, step (1)
It grinds, disperses, filtering after zinc, the mixing of potassium hydrogen phosphate dispersion liquid, it is female that the inorganic modified paraxylene of fining special anti-aging is made
Liquid；
(3) anti-aging inorganic modified paraxylene mother liquor obtained by step (2) is added in spray form in paraxylene, is made
Obtain the inorganic modified paraxylene with anti-aging function.
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 creatively develops a kind of inorganic modified paraxylene, i.e., essence is merged in the preparation process of paraxylene
Special anti-aging agent made of refinement, special anti-aging agent used are de- by zinc molybdate, silver orthophosphate, zinc oxide, SILICA FUME, illiteracy
Soil, titanium oxide etc. are composite modified to be formed, and each component has the synergy mutually promoted.Special anti-aging agent is by diformazan
In the preparation process of the oxidation of benzene, the purifying of terephthalic acid (TPA) and synthetic material, it can fully act on, carry out with matrix
Depth integration, synergy is notable, so that the synthetic material being eventually fabricated is had good antiageing effect, fully promotes synthesis
The allomeric function and quality of material.And special anti-aging agent chemical property is stablized, and functional group is free of, it need not substantially examine
Consider its influence to the purity of terephthalic acid (TPA), therefore is increased without new purifying process；Special anti-aging agent is substantially not yet
It is dissolved in acetic acid or water etc., therefore without separation, directly generates terephthalic acid (TPA), then by its terephthalic acid (TPA) direct polymerization at tool
There is the synthetic material of anti-aging function.It does not need to especially increase additional technique process and equipment compared with traditional handicraft, and this
For kind technique because special anti-aging agent and paraxylene interaction time are long, depth integration is good.
The organic solvents such as meta-xylene with inorganic modified paraxylene after mixing by generating phase after oxidation, purifying process
The mixture for the dioctyl phthalate answered, then prepares synthetic material with combined polymerizations such as ethylene glycol, and advantage can mainly be used for adjusting
Save the aggregated structure of macromolecular in synthetic material.
Preferably, each component mass percentage is as follows when mixing in step (1)：Zinc molybdate 5-15%, silver orthophosphate 4-
15%, hydrobromic acid solution 8-30%, SILICA FUME 1-10%, montmorillonite 1-8%, titanium oxide 0.5-5%, fluosulfonic acid aqueous solution 50-
80%, above components content range so that the antiageing effect of product is apparent and does not influence to influence processing and the usability of fiber
Can, if content is not in above range, anti-ageing effect is deteriorated, or promotes anti-aging effect and decline compared with content, and shadow
Ring processing and the performance of fiber；It is preferably zinc molybdate 10-13%, silver orthophosphate 8-12%, hydrobromic acid solution 15-25%, micro-
Silica flour 3-5%, montmorillonite 2-4%, titanium oxide 1-3%, fluosulfonic acid aqueous solution 60-80%.
Preferably, a concentration of 1-5wt% of hydrobromic acid solution, preferably 2-3wt%.
Preferably, a concentration of 1-3wt% of fluosulfonic acid aqueous solution, preferably 2wt%.
Preferably, feed temperature is 45-50 DEG C when grinding, and the time of grinding is 2-3h.
Preferably, liquid phase high energy ball mill band liquid is ground to grind.
Preferably, the temperature of hydro-thermal reaction is 140-150 DEG C, pressure 0.5-1MPa, time 3-6h.Reaction can stir
Mix lower progress.Hydro-thermal reaction can carry out in the reactor that liner is polytetrafluoroethylene (PTFE).
Preferably, the temperature of calcining is 540-550 DEG C, time 2-4h.
Deionized water can be used fully to be washed.
Drying can carry out under vacuum, be preferably dried in vacuo at 80-95 DEG C.
3-5h can be ground after drying again, then preferably further sieving such as 250-350 mesh sieve is made special anti-ageing
Agent.
Preferably, acetic acid, meta-xylene, acetamide cosolvent, the anti-aging powder of step (1) gained, oxygen in step (2)
Change zinc, potassium hydrogen phosphate dispersion liquid account for paraxylene mass percent be respectively 20-30%, 2-4%, 0.6-0.8%, 3-6%,
1-2%, 3-5%.
Preferably, the mass concentration of potassium hydrogen phosphate dispersion liquid is 2-8wt%, preferably 3-5wt%.For aqueous dispersions.
Preferably, grinding carries out in agitating ball mill.
Preferably, the time of grinding is 4-6h.
Preferably, it is separated into ultrasonic disperse, is carried out at 75-85 DEG C.Until being dispersed to constant weight, then natural cooling is stood
A period of time such as 6-7d, to remove the sediment of the suspended matter and liquid bottom of liquid level.
Preferably, it is filtered into and takes intermediate suspension to filter, it is preferable to use 800-1000 mesh filters.
Preferably, inorganic modified paraxylene mother liquor injection is added in paraxylene in step (3).
Preferably, the inorganic modified paraxylene mother liquor injection of gained in step (2) is added to and is continuously stirred and ultrasonic wave
In paraxylene under effect.
Preferably, it is persistently stirred and ultrasonic combined dispersion mixing 6-8h after addition.
Preferably, the middle inorganic modified paraxylene mother liquor of gained of step (2) is the 4-10% of paraxylene quality.
Preferably, the preparation method of the present invention includes the following steps：
(1) by the zinc molybdate of weight meter 10-13%, the silver orthophosphate of 8-12%, 15-25% a concentration of 2-3wt% hydrogen
Bromic acid solution, the SILICA FUME of 3-5%, the montmorillonite of 2-4%, the titanium oxide of 1-3%, 60-80% a concentration of 2wt% fluorine sulphur
Aqueous acid mixes, and liquid phase high energy ball mill band liquid grinds 2-3h at 45-50 DEG C, then it is the anti-of polytetrafluoroethylene (PTFE) to move on to liner
It answers in device, is stirred to react 3-6h at 140-150 DEG C of temperature and 0.5-1MPa pressure, then naturally cools to continuous stirring
Room temperature, filtering, calcines 2-4h at 540-550 DEG C, and deionized water is fully washed, 80-95 DEG C of vacuum drying, in high energy ball mill
Middle grinding 3-5h, and be sieved through 250-350 mesh and anti-aging powder is made；
(2) paraxylene sequentially adds acetic acid, the 2-4% that 20-30% is calculated as with paraxylene weight with continuous stirring
Meta-xylene, 0.6-0.8% acetamide cosolvent and 3-6% anti-aging powder, the oxygen of 1-2% made from step (1)
The potassium hydrogen phosphate dispersion liquid for changing zinc, a concentration of 5wt% for adding 3-5%, is uniformly mixed, 4- is ground in agitating ball mill
6h, then it is slowly heated to 75-85 DEG C of ultrasonic wave dispersion, until constant weight, natural cooling stands 6-7d, removes the suspension of liquid level
The sediment of object and liquid bottom takes intermediate suspension, is filtered through 800-100 mesh, is made inorganic modified right with anti-aging function
Dimethylbenzene mother liquor；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added is calculated as 4- with paraxylene weight
The 10% inorganic modified paraxylene mother liquor made from (2), then lasting stirring and ultrasonic wave dispersion mixing 6-8h, are made one kind
Depth integration has the inorganic modified paraxylene of anti-aging function.
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, physics, chemistry are carried out to above-mentioned inorganic matter
After surface treatment, surface is etched and organic modification, by its with organic matrix it is compound after, over time, organic group
The molecule of body and inorganic body two-phase interface, atom are easier to interpenetrate, invade, spread, migrating, inorganic body and organic matrix two
Boundary gradually forms the cenotype all different from an inorganic body and organic matrix-interface phase (without the inorganic of above-mentioned processing
Object is then difficult or takes longer for just forming interface phase).In subsequent product, over time interface mutually constantly
The function of sprawling extension, inorganic body is extended in company with sprawling.In the process, inorganic body can be gradually thicker (like reinforcing bar long-time
In concrete, since the gradual infiltration reinforcing bar of concrete also can be thicker, i.e., reinforcing bar periphery generates interface phase), this interface phase
It is fully merged with organic matrix due to inorganic material-modified dose, thus compared to common age resister few then several months, at most
The Effective Duration of 1-2 has more lasting functional period, and functional effect also can be more preferable.But forming above-mentioned interface mutually needs
The regular hour is wanted, if only addition inorganic material is by melt blending after synthetic material is made, after product is made
Interface phase can not be formed in a short time, and the present invention just adds inorganic material in early period, obtains enough timeliness, is being made
The interface phase of anti-aging function can be comparatively fast formed after subsequent product, play effect.
The present invention passes through special anti-aging made of being modified by zinc molybdate, silver orthophosphate, SILICA FUME, montmorillonite, titanium oxide etc.
Agent is merged with paraxylene even depth, and new synergy, this coordination are will produce when subsequently preparing synthetic material
Effect be presented as in synthetic material can shift in time light, heat radiation energy, the chemical stabilization of reinforcing material macromolecular key,
The erosion of the environmental factors such as resistance to rainwater and wind, solar irradiation is improved, there is excellent anti-aging function, be also beneficial to reinforcing material
The mechanical properties such as intensity, shock resistance.The downstream product prepared with this inorganic modified paraxylene, such as engineering plastics are built
Material, machine components, plastic bottle, agricultural film, textile material, tent, film etc. are built, their outdoor service life and performance
Will significantly it improve.
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 inorganic modified paraxylene synthetic fibers produced by the present invention：Using xenon lamp aging
Case, parameter setting：65 DEG C of blackboard temperature；Babinet humidity 50%；Intensity of illumination 550W/m2；Spray the period：18min is sprayed twice
Between the anhydrous time be 102min.Synthetic fibers are placed in parallel in xenon lamp aging case sample disc, and are in relaxed state, 300h
After sample according to GB/T14337-2008 standard testing fiber strengths.
Embodiment 1
A kind of preparation method of inorganic modified paraxylene, includes the following steps：
(1) by the zinc molybdate of weight meter 12%, 10% silver orthophosphate, 20% a concentration of 2.5wt% hydrobromic acid solution,
4% SILICA FUME, 3% montmorillonite, the fluosulfonic acid aqueous solution mixing of 2% titanium oxide, 70% a concentration of 2wt%, 47
Liquid phase high energy ball mill band liquid grinds 2.5h at DEG C, then moves on in the reactor that liner is polytetrafluoroethylene (PTFE), in 145 DEG C of temperature and
It is stirred to react 5h under 0.8MPa pressure, then naturally cools to room temperature with continuous stirring, filters, calcines 3h at 545 DEG C, go
Ionized water fully washs, and 90 DEG C of vacuum drying grind 4h in high energy ball mill, and are sieved through 300 mesh and anti-aging powder is made；
(2) paraxylene sequentially adds with continuous stirring is calculated as 25% acetic acid, two between 3% with paraxylene weight
Toluene, 0.7% acetamide cosolvent and 5% anti-aging powder, 1.5% zinc oxide made from step (1) add
The potassium hydrogen phosphate dispersion liquid of 4% a concentration of 5wt% is uniformly mixed, 5h is ground in agitating ball mill, then be slowly heated to 80
The dispersion of DEG C ultrasonic wave, until constant weight until, natural cooling standing 6d removes the sediment of the suspended matter and liquid bottom of liquid level, in taking
Between suspension, through 900 mesh filter, be made with anti-aging function inorganic modified paraxylene mother liquor；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added is calculated as 4- with paraxylene weight
The 10% inorganic modified paraxylene mother liquor made from (2), then lasting stirring and ultrasonic wave dispersion mixing 6-8h, are made one kind
Depth integration has the inorganic modified paraxylene of anti-aging function.
It is manufactured fine using downstream synthetic material PET made of the inorganic modified paraxylene obtained by the present embodiment
Dimension, it is 3.05cN/dtex, extension at break 11.5% to measure ultimate strength according to above-mentioned anti-aging experimental method.As it can be seen that being made
The mechanical property of product keeps good, illustrates that anti-aging property is good.
Embodiment 2
A kind of preparation method of inorganic modified paraxylene, includes the following steps：
(1) by the zinc molybdate of weight meter 10%, 8% silver orthophosphate, the hydrobromic acid solution of 15% a concentration of 3wt%, 3%
SILICA FUME, 2% montmorillonite, 1% titanium oxide, 50% a concentration of 2wt% fluosulfonic acid aqueous solution mixing, at 45 DEG C
Liquid phase high energy ball mill band liquid grinds 3h, then moves on in the reactor that liner is polytetrafluoroethylene (PTFE), in 150 DEG C of temperature and 0.5MPa
It is stirred to react 3h under pressure, then naturally cools to room temperature with continuous stirring, filters, 2h, deionized water is calcined at 550 DEG C
Fully washing, 80 DEG C of vacuum drying grind 5h in high energy ball mill, and are sieved through 250 mesh and anti-aging powder is made；
(2) paraxylene sequentially adds with continuous stirring is calculated as 30% acetic acid, two between 2% with paraxylene weight
Toluene, 0.6% acetamide cosolvent and 6% anti-aging powder, 1% zinc oxide made from step (1) add 3%
A concentration of 5wt% potassium hydrogen phosphate dispersion liquid, be uniformly mixed, 4h is ground in agitating ball mill, then be slowly heated to 85 DEG C
Ultrasonic wave disperses, and until constant weight, natural cooling stands 6d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes centre
Suspension is filtered through 900 mesh, and the inorganic modified paraxylene mother liquor with anti-aging function is made；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added is calculated as 4% with paraxylene weight
The inorganic modified paraxylene mother liquor made from (1), then lasting stirring and ultrasonic wave dispersion mixing 8h are made a kind of depth and melt
Close the inorganic modified paraxylene with anti-aging function.
It is manufactured fine using downstream synthetic material PET made of the inorganic modified paraxylene obtained by the present embodiment
Dimension, it is 2.86cN/dtex, extension at break 8% to measure ultimate strength according to above-mentioned anti-aging experimental method.
Embodiment 3
A kind of preparation method of inorganic modified paraxylene, includes the following steps：
(1) by the zinc molybdate of weight meter 13%, 12% silver orthophosphate, 25% a concentration of 3wt% hydrobromic acid solution,
5% SILICA FUME, 4% montmorillonite, the fluosulfonic acid aqueous solution mixing of 3% titanium oxide, 80% a concentration of 2wt%, 50
Liquid phase high energy ball mill band liquid grinds 2h at DEG C, then moves on in the reactor that liner is polytetrafluoroethylene (PTFE), in 140 DEG C of temperature and
Be stirred to react 6h under 1MPa pressure, then naturally cool to room temperature with continuous stirring, filter, calcine 4h at 540 DEG C, go from
Sub- water fully washs, and 95 DEG C of vacuum drying grind 3h in high energy ball mill, and are sieved through 350 mesh and anti-aging powder is made；
(2) paraxylene sequentially adds with continuous stirring is calculated as 20% acetic acid, two between 4% with paraxylene weight
Toluene, 0.8% acetamide cosolvent and 3% anti-aging powder, 2% zinc oxide made from step (1) add 5%
A concentration of 5wt% potassium hydrogen phosphate dispersion liquid, be uniformly mixed, 6h is ground in agitating ball mill, then be slowly heated to 75 DEG C
Ultrasonic wave disperses, and until constant weight, natural cooling stands 7d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes centre
Suspension is filtered through 1000 mesh, and the inorganic modified paraxylene mother liquor with anti-aging function is made；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added and is calculated as with paraxylene weight
The 10% inorganic modified paraxylene mother liquor made from (2), then lasting stirring and ultrasonic wave dispersion mixing 6h, are made a kind of depth
Inorganic modified paraxylene of the degree fusion with anti-aging function.
It is manufactured fine using downstream synthetic material PET made of the inorganic modified paraxylene obtained by the present embodiment
Dimension, it is 3.02cN/dtex, extension at break 12% to measure ultimate strength according to above-mentioned anti-aging experimental method.
Comparative example 1
A kind of preparation method of inorganic modified paraxylene, component content include the following steps not within the scope of the application：
(1) by the zinc molybdate of weight meter 2%, 2% silver orthophosphate, 20% a concentration of 2wt% hydrobromic acid solution,
0.8% SILICA FUME, 0.6% montmorillonite, 0.4% titanium oxide, the fluosulfonic acid aqueous solution of 70% a concentration of 2wt% are mixed
It closes, liquid phase high energy ball mill band liquid grinds 3h at 45 DEG C, then moves on in the reactor that liner is polytetrafluoroethylene (PTFE), at 150 DEG C
It is stirred to react 3h under temperature and 0.5MPa pressure, then naturally cools to room temperature with continuous stirring, filters, is forged at 550 DEG C
2h is burnt, deionized water is fully washed, 80 DEG C of vacuum drying, 5h is ground in high energy ball mill, and be made anti-ageing through the sieving of 250 mesh
Change powder；
(2) paraxylene sequentially adds with continuous stirring is calculated as 30% acetic acid, two between 2% with paraxylene weight
Toluene, 0.6% acetamide cosolvent and 6% anti-aging powder, 1% zinc oxide made from step (1) add 3%
A concentration of 5wt% potassium hydrogen phosphate dispersion liquid, be uniformly mixed, 4h is ground in agitating ball mill, then be slowly heated to 85 DEG C
Ultrasonic wave disperses, and until constant weight, natural cooling stands 6d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes centre
Suspension is filtered through 900 mesh, and the inorganic modified paraxylene mother liquor with anti-aging function is made；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added is calculated as 4% with paraxylene weight
The inorganic modified paraxylene mother liquor made from (2), then lasting stirring and ultrasonic wave dispersion mixing 8h are made a kind of depth and melt
Close the inorganic modified paraxylene with anti-aging function.
It is manufactured fine using downstream synthetic material PET made of the inorganic modified paraxylene obtained by the present embodiment
Dimension, it is 2.36cN/dtex, extension at break 1% to measure ultimate strength according to above-mentioned anti-aging experimental method.
Comparative example 2
A kind of preparation method of inorganic modified paraxylene, is added without zinc molybdate and SILICA FUME compared with Example 2, including
Following steps：
(1) by the silver orthophosphate of weight meter 8%, the hydrobromic acid solution of 15% a concentration of 3wt%, 2% montmorillonite, 1%
Titanium oxide, 50% a concentration of 2wt% fluosulfonic acid aqueous solution mixing, at 45 DEG C liquid phase high energy ball mill band liquid grind
3h, then move on in the reactor that liner is polytetrafluoroethylene (PTFE), it is stirred to react 3h at 150 DEG C of temperature and 0.5MPa pressure, then
Room temperature is naturally cooled to continuous stirring, filters, 2h is calcined at 550 DEG C, and deionized water is fully washed, and 80 DEG C of vacuum are dry
It is dry, 5h is ground in high energy ball mill, and be sieved through 250 mesh and anti-aging powder is made；
(2) paraxylene sequentially adds with continuous stirring is calculated as 30% acetic acid, two between 2% with paraxylene weight
Toluene, 0.6% acetamide cosolvent and 6% anti-aging powder, 1% zinc oxide made from step (1) add 3%
A concentration of 5wt% potassium hydrogen phosphate dispersion liquid, be uniformly mixed, 4h is ground in agitating ball mill, then be slowly heated to 85 DEG C
Ultrasonic wave disperses, and until constant weight, natural cooling stands 6d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes centre
Suspension is filtered through 900 mesh, and the inorganic modified paraxylene mother liquor with anti-aging function is made；
(3) in the paraxylene under lasting stirring and ul-trasonic irradiation, mist is added is calculated as 4% with paraxylene weight
The inorganic modified paraxylene mother liquor made from (2), then lasting stirring and ultrasonic wave dispersion mixing 8h are made a kind of depth and melt
Close the inorganic modified paraxylene with anti-aging function.
It is manufactured fine using downstream synthetic material PET made of the inorganic modified paraxylene obtained by the present embodiment
Dimension, it is 2.32cN/dtex, extension at break 2% to measure ultimate strength according to above-mentioned anti-aging experimental method.
As it can be seen that the mechanical property that product is made in the present invention keeps good, illustrate that anti-aging property is good.
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 inorganic modified paraxylene, includes the following steps：
(1) by zinc molybdate, silver orthophosphate, hydrobromic acid solution, SILICA FUME, montmorillonite, titanium oxide and fluosulfonic acid aqueous solution mixed grinding
After carry out hydro-thermal reaction, then through filtering, calcine, washing is dry that anti-aging powder is made；
(2) by anti-aging powder, zinc oxide, potassium hydrogen phosphate obtained by paraxylene, acetic acid, meta-xylene, acetamide, step (1)
It grinds, disperses after dispersion liquid mixing, the fining inorganic modified paraxylene mother liquor of special anti-aging is made in filtering；
(3) anti-aging inorganic modified paraxylene mother liquor obtained by step (2) is added in spray form in paraxylene, nothing is made
Machine is modified paraxylene.
2. preparation method according to claim 1, which is characterized in that each component quality percentage contains when mixing in step (1)
Amount is as follows：Zinc molybdate 5-15%, silver orthophosphate 4-15%, hydrobromic acid solution 8-30%, SILICA FUME 1-10%, montmorillonite 1-8%, oxygen
Change titanium 0.5-5%, fluosulfonic acid aqueous solution 50-80%, preferably zinc molybdate 10-13%, silver orthophosphate 8-12%, hydrobromic acid solution
15-25%, SILICA FUME 3-5%, montmorillonite 2-4%, titanium oxide 1-3%, fluosulfonic acid aqueous solution 60-80%；
Preferably, a concentration of 1-5wt% of hydrobromic acid solution, preferably 2-3wt%；
Preferably, a concentration of 1-3wt% of fluosulfonic acid aqueous solution, preferably 2wt%.
3. preparation method according to claim 1 or 2, which is characterized in that feed temperature is 45- when grinding in step (1)
50 DEG C, the time of grinding is 2-3h；
Preferably, liquid phase high energy ball mill band liquid is ground to grind.
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 140-150 DEG C, pressure 0.5-1MPa, time 3-6h.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that the temperature of calcining is in step (1)
540-550 DEG C, time 2-4h.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that acetic acid in step (2), meta-xylene,
Anti-aging powder, zinc oxide, potassium hydrogen phosphate dispersion liquid obtained by acetamide cosolvent, step (1) account for the quality percentage of paraxylene
Than being respectively 20-30%, 2-4%, 0.6-0.8%, 3-6%, 1-2%, 3-5%；
Preferably, the mass concentration of potassium hydrogen phosphate dispersion liquid is 2-8wt%, preferably 3-5wt%.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that grinding is in stirring ball-milling in step (2)
It is carried out in machine；
Preferably, the time of grinding is 4-6h；
Preferably, it is separated into ultrasonic disperse, is carried out at 75-85 DEG C.
8. according to claim 1-7 any one of them preparation methods, which is characterized in that be filtered into step (2) and take intermediate hang
Supernatant liquid filters, it is preferable to use 800-1000 mesh filters.
9. according to claim 1-8 any one of them preparation methods, which is characterized in that inorganic modified to diformazan in step (3)
The injection of benzene mother liquor is added in paraxylene；
Preferably, the inorganic modified paraxylene mother liquor injection of gained in step (2) is added to and is continuously stirred and ul-trasonic irradiation
Under paraxylene in；
Preferably, it is persistently stirred and ultrasonic combined dispersion mixing 6-8h after addition.
10. according to claim 1-9 any one of them preparation methods, which is characterized in that inorganic modified to diformazan in step (3)
Benzene mother liquor is the 4-10% of paraxylene quality.
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| US3859344A (en) * | 1971-04-03 | 1975-01-07 | Maruzen Oil Co Ltd | Process for continuous production of highly pure terephthalic acid |
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