CN108456297A - A kind of preparation method of differential EG - Google Patents
A kind of preparation method of differential EG Download PDFInfo
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- CN108456297A CN108456297A CN201810065023.9A CN201810065023A CN108456297A CN 108456297 A CN108456297 A CN 108456297A CN 201810065023 A CN201810065023 A CN 201810065023A CN 108456297 A CN108456297 A CN 108456297A
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- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- 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
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- 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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- 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
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- 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
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- 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
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K3/32—Phosphorus-containing compounds
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- 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
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- 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
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- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
Abstract
A kind of preparation method of differential EG, includes the following steps：Oxalic acid solution, hypochlorite solution, pucherite, graphene oxide, zinc oxide, Titanium Dioxide Rutile Top grade, hydrotalcite are mixed and ground after carrying out hydro-thermal reaction, filters, calcines, wash, it is dry, EG special anti-aging agent is made；It grinds, disperses after ethylene glycol, propylene glycol, glycerine, lactic acid, the agent of gained EG special anti-agings, silica, mica powder, potassium hydrogen phosphate dispersion liquid are mixed, the differential EG mother liquors with anti-aging function are made in filtering；Differential EG mother liquors obtained by spray form are added in EG, depth integration, which is made, has the differential EG of anti-aging function.Product, which is made, in the method for the present invention has excellent anti-aging function.
Description
Technical field
The invention belongs to EG variety development technical fields, and in particular to a kind of preparation method of differential EG.
Background technology
EG Chinese name ethylene glycol, English entitled ethylene glycol, abbreviation EG.Its chemical formula is (CH2OH)2, it is most
Simple dihydric alcohol.For EG as a kind of chemical fundamentals raw material, property is active, can rise esterification, etherificate, alcoholization, oxidation, acetal,
The reactions such as dehydration.There are two hydroxy functional groups for EG molecules, therefore mainly for the preparation of synthetic materials such as high polymers, can such as do engineering
The products such as plastics, construction material, machine components, beverage bottle, packing film, film, dress ornament, film, and had increasingly
More products applications are constantly subjected to the factors such as wind and weather, the irradiation of UV sunlight, the cold and hot variation of temperature in outdoor environment
Erosion, generally shorter than the service life in environment indoors more of service life outdoors.It needs to improve this thus
The outdoor performance of a little synthetic materials extends its service life, therefore develops the modification EG tools for anti-aging synthetic material
There is important meaning.
As a kind of chemical raw material, the method prepared mainly has including following several method EG：(1) epoxyethane water
It is legal, it is divided into direct hydration method and catalytic hydration, hydro-combination process carries out also carrying out under elevated pressure under normal pressure.Normal pressure is hydrated
Method generally uses a small amount of inorganic acid for catalyst, is reacted at 50~70 DEG C.Ethylene oxide direct hydration method is industry at present
Large-scale production ethylene glycol is compared with mature production method, the method as disclosed in CN 1463960A, CN 1990441A etc.；(2) second
Alkene direct hydration method, ethylene is in catalyst (such as antimony oxide TeO2, palladium catalyst) in the presence of in acetic acid solution oxidation generate it is single
Acetic acid esters or diacetate esters, further hydrolysis obtains ethylene glycol, as disclosed in CN 105001058A, CN 105418376A etc.
Method；(3) chlorethanol method is to hydrolyze to obtain in alkaline medium as raw material using chlorethanol, and the reaction is generally under 100 DEG C or so
Progress, etc. other methods.
No matter which kind of preparation method is used, typically from the quality (such as purity) for reducing the cost prepared and raising EG
On consider the preparation process of EG, it is few that some EG new varieties are developed from the viewpoint of application, there is no consideration
Modification to EG improves the added value of EG.So EG single varieties all the time, and it is almost unalterable.
Invention content
The present invention provides a kind of preparation method of differential EG according to the purposes of existing downstream product, prepared by this method
Differential EG prepares the synthetic material with anti-aging function, has more lasting antiageing effect.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of differential EG, includes the following steps：
(1) by oxalic acid solution, hypochlorite solution, pucherite, graphene oxide, zinc oxide, Titanium Dioxide Rutile Top grade, neatly
Stone mixing is ground after carrying out hydro-thermal reaction, is filtered, and is calcined, and is washed, dry, and EG special anti-aging agent is made；
(2) by the agent of gained EG special anti-agings, silica, cloud in ethylene glycol, propylene glycol, glycerine, lactic acid, step (1)
It grinds, disperses after female powder, the mixing of potassium hydrogen phosphate dispersion liquid, the differential EG mother liquors with anti-aging function are made in filtering；
(3) the differential EG mother liquors of gained in step (2) are added in spray form in EG, depth integration is made with anti-ageing
Change the differential EG of function.
The preparation method of differential EG disclosed by the invention a kind of, addition is with anti-aging function in the preparation process of EG
Modifying agent, excellent anti-aging function can be obtained with the modification of synthetic materials of anti-aging function dedicated for preparing, added
The modifying agent added mainly has pucherite, graphene oxide, zinc oxide, Titanium Dioxide Rutile Top grade, hydrotalcite and propylene glycol, glycerine
Deng.
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
The function companion sprawling of phase, interface mutually constantly sprawling extension over time, inorganic body is extended into organism, assigns it
The functional effect of 1+1 ＞ 2, and promote the comprehensive physical performance of high-molecular organic material.
Preferably, each component content by weight is as follows when mixing in step (1)：60-85 parts of oxalic acid solution, secondary chlorine
7-30 parts of acid solution, 3-10 parts of pucherite, 3-10 parts of graphene oxide, 0.5-4 parts of zinc oxide, Titanium Dioxide Rutile Top grade 0.5-4
Part, 0.5-2 parts of hydrotalcite, above components content range so that the antiageing effect of product is apparent and does not influence to influence adding for fiber
Work and performance, if content is not in above range, anti-ageing effect is deteriorated, or promotes anti-aging effect compared with content
Decline, and influences processing and the performance of fiber；Preferably oxalic acid solution 70-80 parts, 12-24 parts of hypochlorite solution, vanadic acid
6-8 parts of bismuth, 6-8 parts of graphene oxide, 1-2 parts of zinc oxide, 1-2 parts of Titanium Dioxide Rutile Top grade, 0.8-1 parts of hydrotalcite.
Preferably, a concentration of 5-15wt% of oxalic acid solution, preferably 10wt%.
Preferably, a concentration of 2-5wt% of hypochlorite solution, preferably 3wt%.
Oxalic acid solution, hypochlorite solution can be aqueous solution.
Preferably, the temperature of hydro-thermal reaction is 120-150 DEG C, pressure 0.1-0.2MPa, time 3-5h.Reaction can be
Continuously stir lower progress.
Preferably, grinding is ground with high energy ball mill band liquid.
Preferably, feed temperature is 40-55 DEG C when grinding, and the time of grinding is 2-3h.
Preferably, the temperature of calcining is 500-520 DEG C, time 3-4h.
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.
Reusable ball mill grinding 2-3h after drying, and be sieved through 200-300 mesh and EG special anti-aging agent is made.
Preferably, the middle gained EG special anti-agings agent of propylene glycol, glycerine, lactic acid, step (1), titanium dioxide in step (2)
The mass percent that silicon, mica powder, potassium hydrogen phosphate dispersion liquid account for ethylene glycol is respectively 8-12%, 2-3%, 0.5-0.8%, 4-
10%, 1.0-2.5%, 1.5-2%, 6-8%.
Preferably, the mass concentration of potassium hydrogen phosphate dispersion liquid is 5-8wt%, can be aqueous solution.
Preferably, grinding carries out in liquid phase stirring and milling machine.
Preferably, the time of grinding is 4-5h.
Preferably, it is separated into ultrasonic disperse, is carried out at 85-90 DEG C.Until being dispersed to constant weight, then natural cooling is quiet
A period of time such as 3-4d is set, 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, differential EG mother liquors injection is added in EG in step (3).
Preferably, the differential EG mother liquors injection of gained in step (2) is added to continuously stir under ul-trasonic irradiation
In EG.
Preferably, the middle differential EG mother liquors of gained of step (2) are the 3-12% of EG mass.
Preferably, it is persistently stirred and ultrasonic combined dispersion mixing 3-6h after addition.
The present invention prepares the differential EG mother liquors with anti-aging function using liquid phase stirring and milling machine, ensure that EG mother liquors
Then the fineness and the uniformity of middle modifying agent are continuously stirring and are preparing the difference with anti-aging function under ultrasonic wave compound action
Do not change EG, further ensure the depth integration and stability of differential EG, being prepared with this differential EG has anti-aging work(
The synthetic material of energy has more lasting antiageing effect.
Preferably, the preparation method of the present invention includes the following steps：
(1) by time of the oxalic acid solution of a concentration of 10wt% of 70-80 parts of parts by weight meter, 12-24 parts of a concentration of 3wt%
Solution chlorate aoxidizes with 6-8 parts of pucherite, 6-8 parts of graphene oxide, 1-2 parts of zinc oxide, 1-2 parts of rutile-type
Titanium, 0.8-1 parts of hydrotalcite mixing, moves on in hydrothermal reactor, continuous at 120-150 DEG C of temperature and 0.1-0.2MPa pressure
It is stirred to react 3-5h, then natural cooling is filtered with high energy ball mill band liquid grinding 2-3h at 40-55 DEG C under stiring, then
3-4h is calcined at 500-520 DEG C, deionized water is fully washed, 80-95 DEG C of vacuum drying, then with ball mill grinding 2-3h, and
It is sieved through 200-300 mesh, EG special anti-aging agent is made；
(2) continuously stir down sequentially added in EG with EG weight be calculated as the propylene glycol of 8-12%, the glycerine of 2-3%,
The EG special anti-agings agent made from (1) of the lactic acid and 4-10% of 0.5-0.8%, 1.0-2.5% silica, 1.5-2% clouds
Female powder adds the potassium hydrogen phosphate dispersion liquid of a concentration of 5-8wt% of the 6-8% in terms of EG weight, is uniformly mixed, and is stirred in liquid phase
4-5h is ground in ball mill, is slowly heated to 85-90 DEG C of ultrasonic wave dispersion, and until constant weight, natural cooling stands 3-4d, goes
Except the sediment of the suspended matter and liquid bottom of liquid level, intermediate suspension is taken, is filtered through 800-1000 mesh, being made has anti-aging function
Differential EG mother liquors；
(3) continuously stir in the EG under ul-trasonic irradiation spray form be added with EG weight be calculated as 3-12% by (2) make
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 3-6h, be made a kind of depth integration have it is anti-
The differential EG of 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, chemical surface are carried out to inorganic matter
After processing, surface is etched and organic modification, by its with organic matrix it is compound after, over time, organic matrix and
Molecule, the atom of inorganic body two-phase interface are easier to interpenetrate, invade, spread, migrating, inorganic body and two phase boundary of organic matrix
Face gradually form the cenotype all different from an inorganic body and organic matrix-interface phase (without above-mentioned processing inorganic matter then
It is difficult to or take longer for just forming interface phase).In subsequent product, interface is mutually constantly spread over time
The function of extension, inorganic body is extended in company with sprawling.In the process, whisker can be gradually thicker (like reinforcing bar is for a long time in coagulation
In soil, since the gradual infiltration reinforcing bar of concrete also can be thicker, i.e., reinforcing bar periphery generates interface phase), this interface is mutually due to nothing
Machine material modification agent is fully merged with organic matrix, thus lacks the then several months compared to common age resister, at most 1-2's
Effective Duration has more lasting functional period, and functional effect also can be more preferable.But formed above-mentioned interface mutually need it is certain
Time, if only for addition inorganic material by melt blending, being made after product can not be short after synthetic material is made
Interface phase is formed in time, and the present invention just adds inorganic material in early period, obtains enough timeliness, in obtained subsequent product
The interface phase of anti-aging function can be comparatively fast formed afterwards, play effect.
The present invention merges pucherite, graphene oxide, zinc oxide, Titanium Dioxide Rutile Top grade, hydrotalcite and EG etc. one
It rises, new synergy is will produce when subsequently preparing synthetic material, this trade-off effect is presented as in synthetic material can
In time transfer light, heat radiation energy, the chemical stabilization of macromolecular key, improves the environmental factors such as resistance to rainwater and wind in reinforcing material
Erosion, have excellent anti-aging function, be also beneficial to the mechanical properties such as intensity, the shock resistance of reinforcing material.With this difference
Not Hua EG prepare downstream product, as engineering plastics, construction material, machine components, beverage bottle, packing film, film, dress ornament,
The products such as film, their outdoor performance all can significantly 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.
The resistant fiber senile experiment method synthesized by the differential EG of the present invention is as follows：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, anhydrous time between spraying twice
For 102min.Synthetic fibers are placed in parallel in xenon lamp aging case sample disc, and are in relaxed state, after 300h sampling according to
GB/T14337-2008 standard testing fiber strengths.
Embodiment 1
A kind of preparation method of differential EG, includes the following steps：
(1) oxalic acid solution, the hypochlorous acid of 18 parts of a concentration of 3wt% of a concentration of 10wt% of 75 parts of parts by weight meter is molten
Liquid and 7 parts of pucherite, 7 parts of graphene oxide, 1.5 parts of zinc oxide, 1.5 parts of Titanium Dioxide Rutile Top grade, 0.9 part of water
Talcum mixes, and moves on in hydrothermal reactor, and reaction 4h is continuously stirred at 135 DEG C of temperature and 0.15MPa pressure, is then being stirred
Lower natural cooling grinds 2.5h, filtering with high energy ball mill band liquid at 47 DEG C, then calcines 3.5h, deionized water at 510 DEG C
Fully washing, 90 DEG C of vacuum drying, then ball mill grinding 2.5h is used, and be sieved through 250 mesh, obtained EG special anti-aging agent；
(2) continuously stir down sequentially added in EG with EG weight be calculated as 10% propylene glycol, 2.5% glycerine,
0.65% lactic acid and the 7% EG special anti-agings agent made from (1), 1.75% silica, 1.75% mica powder add
The potassium hydrogen phosphate dispersion liquid of 7% a concentration of 6.5wt% is uniformly mixed, 4.5h is ground in liquid phase stirring and milling machine, slowly adds
Heat to 87 DEG C of ultrasonic waves disperse, and until constant weight, and natural cooling stands 3.5d, removes the precipitation of the suspended matter and liquid bottom of liquid level
Object takes intermediate suspension, is filtered through 900 mesh, and the differential EG mother liquors with anti-aging function are made；
(3) EG weight is added with spray form in the EG under ul-trasonic irradiation to be calculated as 7.5% obtained by (2) continuously stirring
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 4.5h, be made a kind of depth integration have it is anti-aging
The differential EG of function.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by the present embodiment,
Manufactured polyester fiber, it is 3.26cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
12%.Ultimate strength improves compared with the ordinary polyester fiber of same specification is according to above-mentioned anti-aging experimental method check plot
32.5%, extension at break improves 23.6%.
Embodiment 2
A kind of preparation method of differential EG, includes the following steps：
(1) by the oxalic acid solution of a concentration of 15wt% of 73.2 parts of parts by weight meter, the hypochlorous acid of 12 parts of a concentration of 5wt%
Solution and 6 parts of pucherite, 6 parts of graphene oxide, 1 part of zinc oxide, 1 part of Titanium Dioxide Rutile Top grade, 0.8 part of neatly
Stone mixes, and moves on in hydrothermal reactor, reaction 5h is continuously stirred at 150 DEG C of temperature and 0.1MPa pressure, then under stiring
Natural cooling grinds 2h, filtering with high energy ball mill band liquid at 55 DEG C, then calcines 3h at 520 DEG C, and deionized water is fully washed
It washs, 95 DEG C of vacuum drying, then uses ball mill grinding 2h, and be sieved through 300 mesh, obtained EG special anti-aging agent；
(2) it continuously stirs down to sequentially add in EG and 8% propylene glycol, 2% glycerine, 0.8% is calculated as with EG weight
Lactic acid and the 10% EG special anti-agings agent made from (1), 2.5% silica, 1.5% mica powder add 6% concentration
For the potassium hydrogen phosphate dispersion liquid of 5wt%, it is uniformly mixed, grinds 5h in liquid phase stirring and milling machine, be slowly heated to 90 DEG C of ultrasounds
Wavelength-division dissipates, and until constant weight, and natural cooling stands 4d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes intermediate suspension
Liquid is filtered through 1000 mesh, and the differential EG mother liquors with anti-aging function are made；
(3) continuously stir in the EG under ul-trasonic irradiation spray form be added with EG weight be calculated as 12% by (2) be made
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 6h, be made a kind of depth integration have it is anti-aging
The differential EG of function.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by the present embodiment,
Manufactured polyester fiber, it is 3.01cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
10%.Ultimate strength improves compared with the ordinary polyester fiber of same specification is according to above-mentioned anti-aging experimental method check plot
32.5%, extension at break improves 23.6%.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by the present embodiment,
Manufactured polyester fiber, it is 3.01cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
10%.Ultimate strength improves 30% compared with the ordinary polyester fiber of same specification is according to above-mentioned anti-aging experimental method, fracture
Elongation improves 19.7%.
Embodiment 3
A kind of preparation method of differential EG, includes the following steps：
(1) oxalic acid solution, the hypochlorous acid of 20 parts of a concentration of 2wt% of a concentration of 5wt% of 60 parts of parts by weight meter is molten
Liquid and 5 parts of pucherite, 8 parts of graphene oxide, 3 parts of zinc oxide, 3 parts of Titanium Dioxide Rutile Top grade, 1 part of hydrotalcite are mixed
It closes, moves on in hydrothermal reactor, reaction 3h is continuously stirred at 120 DEG C of temperature and 0.2MPa pressure, it is then natural under stiring
It is cooling, 3h, filtering are ground with high energy ball mill band liquid at 40 DEG C, then 4h is calcined at 500 DEG C, deionized water is fully washed,
80 DEG C of vacuum drying, then ball mill grinding 3h is used, and be sieved through 200 mesh, obtained EG special anti-aging agent；
(2) it continuously stirs down to sequentially add in EG and 12% propylene glycol, 3% glycerine, 0.5% is calculated as with EG weight
Lactic acid and the 4% EG special anti-agings agent made from (1), 1.0% silica, 2% mica powder, add 8% it is a concentration of
The potassium hydrogen phosphate dispersion liquid of 8wt% is uniformly mixed, grinds 4h in liquid phase stirring and milling machine, be slowly heated to 85 DEG C of ultrasonic waves
Dispersion, and until constant weight, natural cooling stands 3d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes intermediate suspension,
It is filtered through 800 mesh, the differential EG mother liquors with anti-aging function is made；
(3) it is added that be calculated as 3% with EG weight obtained by (2) with spray form in the EG under ul-trasonic irradiation continuously stirring
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 3h, a kind of depth integration, which is made, has anti-aging work(
The differential EG of energy.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by the present embodiment,
Manufactured polyester fiber, it is 2.93cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
9%.Ultimate strength improves 29.2% compared with the ordinary polyester fiber of same specification is according to above-mentioned anti-aging experimental method, fracture
Elongation improves 17.7%.
Embodiment 4
A kind of preparation method of differential EG, includes the following steps：
(1) oxalic acid solution, the hypochlorous acid of 7 parts of a concentration of 3wt% of a concentration of 10wt% of 80 parts of parts by weight meter is molten
Liquid and 3 parts of pucherite, 3 parts of graphene oxide, 4 parts of zinc oxide, 1 part of Titanium Dioxide Rutile Top grade, 2 parts of hydrotalcite are mixed
It closes, moves on in hydrothermal reactor, reaction 3-5h is continuously stirred at 120-150 DEG C of temperature and 0.1-0.2MPa pressure, is then existed
The lower natural cooling of stirring, grinds 2-3h, filtering, then calcine 3- at 500-520 DEG C at 40-55 DEG C with high energy ball mill band liquid
4h, deionized water are fully washed, 80-95 DEG C of vacuum drying, then use ball mill grinding 2-3h, and are sieved through 200-300 mesh, obtained
EG special anti-aging agent；
(2) it continuously stirs down to sequentially add in EG and 10% propylene glycol, 2% glycerine, 0.6% is calculated as with EG weight
Lactic acid and the 6% EG special anti-agings agent made from (1), 2% silica, 1.7% mica powder, add 7% it is a concentration of
The potassium hydrogen phosphate dispersion liquid of 7wt% is uniformly mixed, grinds 4h in liquid phase stirring and milling machine, be slowly heated to 90 DEG C of ultrasonic waves
Dispersion, and until constant weight, natural cooling stands 4d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes intermediate suspension,
It is filtered through 900 mesh, the differential EG mother liquors with anti-aging function is made；
(3) it is added that be calculated as 6% with EG weight obtained by (2) with spray form in the EG under ul-trasonic irradiation continuously stirring
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 5h, a kind of depth integration, which is made, has anti-aging work(
The differential EG of energy.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by the present embodiment,
Manufactured polyester fiber, it is 2.87cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
7%.Ultimate strength improves 28.6% compared with the ordinary polyester fiber of same specification is according to above-mentioned anti-aging experimental method, fracture
Elongation improves 13.8%.
Comparative example 1
A kind of content of the preparation method of differential EG, pucherite and graphene oxide not within the scope of the application, including
Following steps：
(1) oxalic acid solution, the hypochlorous acid of 7 parts of a concentration of 3wt% of a concentration of 30wt% of 85 parts of parts by weight meter is molten
Liquid and 12 parts of pucherite, 12 parts of graphene oxide, 4 parts of zinc oxide, 4 parts of Titanium Dioxide Rutile Top grade, 2 parts of hydrotalcite
Mixing, moves on in hydrothermal reactor, reaction 3-5h is continuously stirred at 120-150 DEG C of temperature and 0.1-0.2MPa pressure, then
Natural cooling under stiring is ground 2-3h, filtering with high energy ball mill band liquid at 40-55 DEG C, then is calcined at 500-520 DEG C
3-4h, deionized water are fully washed, 80-95 DEG C vacuum drying, then use ball mill grinding 2-3h, and through 200-300 mesh be sieved, make
Obtain EG special anti-aging agent；
(2) it continuously stirs down to sequentially add in EG and 12% propylene glycol, 3% glycerine, 0.8% is calculated as with EG weight
Lactic acid and the 8% EG special anti-agings agent made from (1), 1.0% silica, 2% mica powder, add 7% it is a concentration of
The potassium hydrogen phosphate dispersion liquid of 7wt% is uniformly mixed, grinds 4h in liquid phase stirring and milling machine, be slowly heated to 90 DEG C of ultrasonic waves
Dispersion, and until constant weight, natural cooling stands 4d, removes the sediment of the suspended matter and liquid bottom of liquid level, takes intermediate suspension,
It is filtered through 900 mesh, the differential EG mother liquors with anti-aging function is made；
(3) continuously stir in the EG under ul-trasonic irradiation spray form be added EG weight be calculated as 6% made from (2) it is poor
Not Hua EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 5h, a kind of depth integration, which is made, has anti-aging function
Differential EG.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by this comparative example,
Manufactured polyester fiber, it is 2.52cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
1%.Ultimate strength is remarkably decreased with extension at break compared with product is made using differential EG obtained by the present invention.
Comparative example 2
A kind of preparation method of differential EG includes the following steps compared with Example 1 that graphene oxide is not added：
(1) oxalic acid solution, the hypochlorous acid of 18 parts of a concentration of 3wt% of a concentration of 10wt% of 75 parts of parts by weight meter is molten
Liquid is mixed with 5 parts of pucherite, 1.5 parts of zinc oxide, 1.5 parts of Titanium Dioxide Rutile Top grade, 0.9 part of hydrotalcite, moves on to water
In thermal reactor, reaction 4h is continuously stirred at 135 DEG C of temperature and 0.15MPa pressure, then natural cooling under stiring, 47
2.5h, filtering are ground with high energy ball mill band liquid at DEG C, then calcines 3.5h at 510 DEG C, deionized water is fully washed, and 90 DEG C true
Sky is dry, then uses ball mill grinding 2.5h, and is sieved through 250 mesh, obtained EG special anti-aging agent；
(2) continuously stir down sequentially added in EG with EG weight be calculated as 10% propylene glycol, 2.5% glycerine,
0.65% lactic acid and the 7% EG special anti-agings agent made from (1), 1.75% silica, 1.75% mica powder add
The potassium hydrogen phosphate dispersion liquid of 7 parts of a concentration of 6.5wt% is uniformly mixed, 4.5h is ground in liquid phase stirring and milling machine, slowly adds
Heat to 87 DEG C of ultrasonic waves disperse, and until constant weight, and natural cooling stands 3.5d, removes the precipitation of the suspended matter and liquid bottom of liquid level
Object takes intermediate suspension, is filtered through 900 mesh, and the differential EG mother liquors with anti-aging function are made；
(3) EG weight is added with spray form in the EG under ul-trasonic irradiation to be calculated as 7.5% obtained by (2) continuously stirring
Differential EG mother liquors, then lasting stirring and ultrasonic combined dispersion mixing 4.5h, be made a kind of depth integration have it is anti-aging
The differential EG of function.
The polyester synthesized with 1.5 parts of terephthalic acid (TPA) using 1 part of differential EG of mass fraction obtained by this comparative example,
Manufactured polyester fiber, it is 2.46cN/dtex to measure ultimate strength according to above-mentioned anti-aging experimental method, and extension at break is
2%.
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 EG, includes the following steps：
(1) oxalic acid solution, hypochlorite solution, pucherite, graphene oxide, zinc oxide, Titanium Dioxide Rutile Top grade, hydrotalcite are mixed
It closes and is ground after carrying out hydro-thermal reaction, filtered, calcined, washed, it is dry, EG special anti-aging agent is made；
(2) by ethylene glycol, propylene glycol, glycerine, lactic acid, gained EG special anti-agings agent in step (1), silica, mica powder,
It grinds, disperses after the mixing of potassium hydrogen phosphate dispersion liquid, differential EG mother liquors are made in filtering；
(3) the differential EG mother liquors of gained in step (2) are added in spray form in EG, differential EG is made.
2. preparation method according to claim 1, which is characterized in that each component is by weight when mixing in step (1)
Content is as follows：60-85 parts of oxalic acid solution, 7-30 parts of hypochlorite solution, 3-10 parts of pucherite, 3-10 parts of graphene oxide, oxidation
0.5-4 parts of zinc, 0.5-4 parts of Titanium Dioxide Rutile Top grade, 0.5-2 parts of hydrotalcite, preferably oxalic acid solution 70-80 parts, hypochlorous acid is molten
12-24 parts of liquid, 6-8 parts of pucherite, 6-8 parts of graphene oxide, 1-2 parts of zinc oxide, 1-2 parts of Titanium Dioxide Rutile Top grade, hydrotalcite
0.8-1 parts；
Preferably, a concentration of 5-15wt% of oxalic acid solution, preferably 10wt%；
Preferably, a concentration of 2-5wt% of hypochlorite solution, preferably 3wt%.
3. preparation method according to claim 1 or 2, which is characterized in that the temperature of hydro-thermal reaction is 120- in step (1)
150 DEG C, pressure 0.1-0.2MPa, time 3-5h.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that grinding high-energy ball milling in step (1)
Machine band liquid is ground；
Preferably, feed temperature is 40-55 DEG C when grinding, and the time of grinding is 2-3h.
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)
500-520 DEG C, time 3-4h.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that propylene glycol, glycerine, breast in step (2)
The agent of EG special anti-agings, silica, mica powder, potassium hydrogen phosphate dispersion liquid obtained by acid, step (1) account for the quality hundred of ethylene glycol
Divide than being respectively 8-12%, 2-3%, 0.5-0.8%, 4-10%, 1.0-2.5%, 1.5-2%, 6-8%；
Preferably, the mass concentration of potassium hydrogen phosphate dispersion liquid is 5-8wt%.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that grinding is stirred in liquid phase in step (2)
It is carried out in ball mill；
Preferably, the time of grinding is 4-5h；
Preferably, it is separated into ultrasonic disperse, is carried out at 85-90 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 gained is poor in step (2) in step (3)
Not Hua EG mother liquors be EG mass 3-12%；
Preferably, differential EG mother liquors injection is added in EG；
Preferably, the differential EG mother liquors injection of gained in step (2) is added to continuously stir in the EG under ul-trasonic irradiation.
10. according to claim 1-9 any one of them preparation methods, which is characterized in that persistently stirred after being added in step (3)
With ultrasonic combined dispersion mixing 3-6h.
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| CN106349469A (en) * | 2016-08-31 | 2017-01-25 | 浙江省现代纺织工业研究院 | Synthesis method of reaction-type multifunctional copolyesters |
| 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 |
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- 2018-01-23 CN CN201810065023.9A patent/CN108456297A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013012705A1 (en) * | 2011-07-15 | 2013-01-24 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
| CN106243332A (en) * | 2016-08-31 | 2016-12-21 | 浙江省现代纺织工业研究院 | A kind of manufacture method of enhancement mode flame-proof anti-aging polyester film |
| CN106349469A (en) * | 2016-08-31 | 2017-01-25 | 浙江省现代纺织工业研究院 | Synthesis method of reaction-type multifunctional copolyesters |
| 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 |
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