CN108299631A - A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation - Google Patents
A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation Download PDFInfo
- Publication number
- CN108299631A CN108299631A CN201810065281.7A CN201810065281A CN108299631A CN 108299631 A CN108299631 A CN 108299631A CN 201810065281 A CN201810065281 A CN 201810065281A CN 108299631 A CN108299631 A CN 108299631A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- modified
- pta
- polyester
- 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
- 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
- C08K3/34—Silicon-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
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives 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
- 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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to modified poly ester production technical fields, and in particular to a kind of modified PTA, and preparation method and its differential polyester and Speciality Pet Fiber for preparing further are disclosed.Modified PTA of the present invention is presented as in synthesizing polyester and polyester fiber can absorb and discharge moisture content, balance wet environment, the charge for being conducive to accumulation simultaneously shifts in time, the antistatic property of polyester and polyester fiber is improved, and has been obviously improved the allomeric function and quality effect of obtained polyester and polyester fiber.
Description
Technical field
The invention belongs to modified poly ester production technical fields, and in particular to a kind of modified PTA, and its preparation is further disclosed
Method and its differential polyester and Speciality Pet Fiber for preparing.
Background technology
Terylene, i.e. polyester fiber are the first big kinds of current synthetic fibers as one kind of textile raw material.Terylene because
Fiber macromolecular chain rigidity is larger, elasticity modulus is high and fiber is unlikely to deform, therefore its fabric intensity is good, have wash after do not wrinkle,
Can so as not to flatiron, it is strong very scrape, washable easily dry advantage, be a kind of more satisfactory to take textile raw material.Terylene can be used for making
Make special material such as flak jackets, safety belt, tire cord, fishing net, rope, filter cloth and insulating materials etc..In the prior art,
Terylene is mainly made using polyester by raw material through spinning.
Polyester is passed through for raw material with p-phthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG)
Again through polyethylene terephthalate prepared by polycondensation reaction (PET) after esterification or transesterification.The official regain of polyester
Be 0.4%, be hair, flaxen fiber 1/30, and resistivity is very high, this makes the hygroscopicity of polyester fiber very poor, and fabric resistor
Rate is up to 1015Ω cm or more.Exist so polyester fiber is typically considered insulator, when as wearing fabric it is more bored not
Ventilative, heavier, spark easy to produce static electricity and suction dust wear uncomfortable disadvantage.Existing wearing fabric relaxes in addition to fabric
Outside adaptive, more to its moisture absorption antistatic property, more stringent requirements are proposed.The performance of moisture absorption antistatic fibre is primarily referred to as anti-quiet
Electrically, i.e., it quickly eliminates the ability of electrostatic charge, under standard state (RH65%, 20 DEG C), if resistivity≤109Ω cm,
Belong to extraordinary antistatic fibre, if resistivity is 1010-1012Ω cm, the then antistatic fibre belonged in industry, are taken
There is meaning of crucial importance in field, and good hygroscopicity is more conducive to improve antistatic and fabric wearing comfort.
P-phthalic acid (Pure terephthalic acid, PTA) is important one of large Organic Ingredients, is to close
At the primary raw material of polyester, 90% or more PTA is for producing polyester in the world.And in domestic market, there is 75% polyester then
For producing polyester fiber (i.e. terylene), it is seen then that the performance of PTA has important shadow to the synthesis of polyester fiber and its performance
It rings.
Currently, the research for modified poly ester, people only focus on sight in polyester synthesis (monomer PTA, second two
Alcohol) Third monomer -- the additive with certain function is added in the process, to expect to assign polyester certain feature and function.On but
It states in modified thinking, since PTA and ethylene glycol are direct polymerizations into polyester, when this makes the interaction of additive and polyester
Between it is shorter, cause certain adverse reactions to have little time to discharge, mutually merge poor, synergistic effect is not enough, therefore cannot be abundant
The effect of playing additive, and many side reactions are also will produce, seriously affect the allomeric functions such as the mechanics of polyester and quality effect
Fruit.Therefore, it in order to solve this technical problem, usually also needs to additionally increase machining process, improves cost.
The key and core of modified poly ester and products thereof are modified PTA, and there is no inhaled on how to develop to have at present
The report of the PTA of wet antistatic property, for PTA products, the preparation of existing PTA is mainly paid attention to from purifying process, i.e.,
The content of the impurity such as p -carboxybenzaldehyde is reduced, to reduce influence of the impurity to reaction in the subsequent polycondensation reactions of PTA, almost
It does not account for being applied to some special materials by developing some new PTA kinds or modified PTA, such as preparing has specific function
Modified material etc..So PTA products are single all the time, and it is almost unalterable, never refine product and special production
The research and development of product.Therefore exploitation is for synthesizing the special PTA with moisture absorption antistatic property polyester fiber with important meaning
Justice.
Invention content
In order to solve the above technical problem, the present invention provides a kind of modified PTA, differential polyester and its difference of preparation
Change the method for polyester fiber.
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.
For this purpose, technical problem to be solved by the present invention lies in a kind of modified PTA is provided, and further disclose with described
Differential polyester and Speciality Pet Fiber prepared by modified PTA, the differential polyester and Speciality Pet Fiber have compared with
Good moisture absorption antistatic property.
In order to solve the above technical problems, the preparation method of modified PTA of the present invention a kind of, includes the following steps：
(1) it is the aqueous citric acid solution 10-20 parts by weight of 5-15%, nanoscale foresite 0.3-0.6 weights to take mass concentration
Measure part, nanoscale magadiite powder 1.0-2.5 parts by weight, the sulfosalisylic aqueous acid 4-12 weights that mass fraction is 4-6%
Part, flight graphite 0.1-0.2 parts by weight, sodium titanate crystal whisker 0.5-1.5 parts by weight are measured, hydro-thermal reaction is carried out after mixing, grinding, passes through
Filtering, dry, calcining, corona treatment is organic-silicon-modified, and modified powder is made；
(2) it takes acetic acid 12-20 parts by weight and water 2-6 parts by weight to mix, and mass fraction is added to be the calgon of 4-6%
Aqueous solution enters the modified powder 4-10 parts by weight made from 2-6 parts by weight and step (1), nanoscale hectorite 0.5-1.0
Parts by weight, white carbon 2-5 parts by weight mixings are beaten and through ultrasonic disperse, modifying agent are made；
(3) modifying agent made from step (2) is merged with crude terephthalic acid slurry, it is crystallized, it is separated by solid-liquid separation, washing,
It is dry, mashing, then be separated by solid-liquid separation back end hydrogenation and refine, modified PTA is made.
In the step (1), each raw material component includes：Mass concentration be 10% 15 parts by weight of aqueous citric acid solution, receive
0.45 parts by weight of meter level foresite, 1.8 parts by weight of nanoscale magadiite powder, the sulfosalisylic sour water that mass fraction is 5%
8 parts by weight of solution, 0.15 parts by weight of flight graphite, 1.0 parts by weight of sodium titanate crystal whisker；
In the step (2), each raw material component includes：16 parts by weight of acetic acid, 4 parts by weight of water, six that mass fraction is 5%
Sodium metaphosphate aqueous solution enters 4 parts by weight, 7 parts by weight of the modified powder, 0.8 parts by weight of nanoscale hectorite, 3.5 weight of white carbon
Measure part.
In the step (3), the mass fraction of the crude terephthalic acid slurry is 25-35%, preferably 28-30%.
In the step (1)：
The grinding steps are to grind 3-6h at 50-55 DEG C of liquid phase with high energy ball mill；
The hydrothermal synthesis step is to be handled 10-12 hours under 150-200 DEG C, 2-4MPa；
The drying steps are atomization drying；
The calcining step is to calcine 3-5h at 400-450 DEG C；
The plasma treatment step is the nitrogen buffer gas, in 40-60Pa, 30-80W in plasma reactor
RF plasma processing 0.5-1.5h is carried out under power；
The organic-silicon-modified step be 28-32% by product and the mass concentration after plasma treatment organosilicon second
Alcoholic solution mixes, and the ultrasonic disperse 1-2h at 60-70 DEG C is fully washed with absolute ethyl alcohol, and heat drying；
In the step (2), the ultrasonic disperse step is the ultrasonic disperse 2-3h at 40-50 DEG C；
In the step (3), the crystallisation step is that gradually decrease temperature and pressure crystallizes three times, i.e.,：In 185-190 DEG C, 1-
Secondary oxidation is carried out in 1.1MPa and oxygen-enriched air and is crystallized, residence time 20-30min；Then in 155-160 DEG C, 0.2-
Continue to crystallize under 0.4MPa, residence time 20-30min；It is further tied at 90-95 DEG C, (- 0.06)~(- 0.04) MPa again
Crystalline substance, residence time 25-35min.
The invention also discloses the modification PTA being prepared by the method.
The invention also discloses the purposes that the modification PTA is used to prepare differential polyester.
The invention also discloses a kind of methods preparing differential polyester, including take modified PTA, 9- described in 3-5 parts by weight
The mixture is beaten and is warming up to 60-80 DEG C of progress very by the step of 12 parts by weight ethylene glycol, 18-23 parts by weight PTA mixings
Empty dehydration carries out esterification when water content is less than 1% in 240-260 DEG C, pressure 0.1-0.2MPa, and anti-in esterification
The later stage is answered, 265-275 DEG C of reaction 40-60min is warming up to, is again heated to 280-290 DEG C, suction to 100Pa or less carries out
Copolycondensation is to get required differential copolyesters.
The invention also discloses the differential polyesters being prepared by the method.
The invention also discloses the purposes that the differential polyester is used to prepare Speciality Pet Fiber.
The invention also discloses a kind of method preparing Speciality Pet Fiber, include with the differential polyester be original
Material, through melt spinning, the step of required differentiation polyester fiber is made by profiled filament spinning technique.
Preferably, the fusing spinning step is using trilobal, hollow shape, linear type, cross, H-shaped, Y shape, W-shaped, T
The high polymorphic structure spinneret orifice of at least one of shape carries out；
The Speciality Pet Fiber includes POY, FDY, DTY, BCF, BSY, short fibre, non-woven fabrics fiber, non-profiled fiber
Or composite fibre.
The invention also discloses the Speciality Pet Fibers being prepared by the method.
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 a cenotype all different from inorganic body and organic matrix --- and interface phase is (without the nothing of above-mentioned processing
Machine object is then difficult or takes longer for just forming interface phase).In subsequent product, interface is mutually continuous over time
Ground sprawling extension, the function of inorganic body are extended in company with sprawling.In the process, inorganic body can be gradually thicker (when long like reinforcing bar
Between in concrete, since the gradual infiltration reinforcing bar of concrete also can be thicker, i.e., reinforcing bar periphery generate interface phase), this interface
It is mutually fully merged with organic matrix due to inorganic material-modified dose, thus lacks the then several months compared to common antistatic agent, it is more
The then Effective Duration of 1-2 has more lasting functional period, and functional effect also can be more preferable.But form above-mentioned interface phase
The regular hour is needed, if only product is made by melt blending in addition inorganic material after synthetic material is made
After can not form interface phase in a short time, and the present invention just adds inorganic material in early period, obtains enough timeliness, is making
The interface phase of anti-static function can be comparatively fast formed after subsequent product.
Modified PTA of the present invention is boiled by being added in the reaction for preparing PTA by aqueous citric acid solution, nanoscale brightness
Stone, nanoscale magadiite, sulfosalisylic acid solution, flight graphite, sodium titanate crystal whisker, acetic acid, hectorite, white carbon etc. are
Property-modifying additive carries out fining and merges, Monofunctional reagents are not contained in these modifying agent, are also insoluble in water or acetic acid
Equal solvent, but it is crystallized with PTA and be separated by solid-liquid separation and the techniques such as drying, hydrofinishing after PTA of the generation containing modifying agent.Respectively
There is component the synergy mutually promoted, these modifying agent to be combined with PTA, subsequently prepare polyester and polyester fiber
When will produce new synergy, it is not soluble in water as PTA to be also insoluble in acetic acid and because modifying agent is free of active group,
Therefore it can be merged always with PTA in the preparation process of PTA, nor use the new purifying or separating technology of increase,
Modifying agent and matrix interaction time are long, mutually merge, and synergistic effect is abundant, to reach modified PTA to promoting downstream
The purpose of product allomeric function and quality effect.This synergy is presented as in synthesizing polyester and polyester fiber to be absorbed
With release moisture content, wet environment is balanced, while the charge for being conducive to accumulation shifts in time, improves the antistatic of polyester and polyester fiber
Performance, and it has been obviously improved the allomeric function and quality effect of obtained polyester and polyester fiber.
The differential polyester being prepared by modified PTA of the present invention, due to the high score of the whisker containing nanoscale of selection
Sub- polymer, whisker used have larger draw ratio, help stream effect, and synergy is presented as the water conservancy diversion work in whisker
Under, synthesizing polyester material thermorheologic property improves, and is conducive to melt spinning molding and the hot orientation stretching of fiber, can reinforcing fiber
Mechanical properties and the fiber surface finish such as intensity, toughness.
It is prepared by the differential polyester by Speciality Pet Fiber of the present invention, it is the hygroscopicity of fiber, antistatic
Performance greatly improves, and good hygroscopicity is more conducive to improve antistatic and fabric wearing comfort so that polyester fiber
Comprehensive performance can all be greatly improved, and use field to widen it, improve use value.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the structural schematic diagram that the present invention prepares the modified PTA systems；
Reference numeral is expressed as in figure：0- reaction raw materials, 1- aoxidize bubble tower, 2,3- metering pumps, 4-, and 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 connecting tube, the first round platforms of 11- crystallization kettle, 12- connecting tubes, 13- the second round platform crystallization kettles, 14- evaporation of the solvent recovery tubes,
Two layers of paddle of 15-, 16 first mashing kettles, 17- second are beaten kettle, the first centrifuges of 18-, the second centrifuges of 19-, 20- thirds
Centrifuge, 21- recovery systems, 22- acetic acid, 23,26- acetic acid recycle reactor, 24,27- recovery systems, 25- screw conveyors,
28- drying machines.
Specific implementation mode
Structure as shown in Figure 1, the as present invention prepare the system construction drawing of the modified PTA, the reaction system packet
The oxidation bubble tower 1 being sequentially connected in series, metering pump 2, stirring dynamic mixer 6, disc secondary oxidation crystallization kettle 9, first is included to justify
Platform crystallization kettle 11, the second round platform crystallization kettle 13, the first centrifuge 18, first mashing kettle 16, the second centrifuge 19, second are beaten kettle
17, third centrifuge 20, auger conveyor 25 and steam dryer 28；The secondary oxidation is simultaneously crystallized in disc secondary oxidation
It is carried out in crystallization kettle, continues crystallization and further crystallize to carry out in round platform crystallization kettle.
The diameter of the disc secondary oxidation crystallization kettle and round platform crystallization kettle is more than 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 modifying agent and matrix is long, mutually merge.
Preferably, the diameter of disc secondary oxidation crystallization kettle and height ratio are 2：1-1.5 crystallization effect is more preferable.Disk
Shape secondary oxidation crystallization kettle bottom is equipped with injection oxygen-enriched air injection pipe 7 and fumarole pipe 8, and bottom minimum point is equipped with modified CTA
Slurry exports connecting tube 10, and top is equipped with evaporation of the solvent recovery tube 5, and secondary oxidation crystallization kettle center 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, bottom minimum point is equipped with modified CTA slurries output slurry connecting tube 10, and top is equipped with evaporation of the solvent recovery tube 14, round platform
Crystallization kettle center is equipped with two layers of paddle 15.
System process process as shown in Figure 1, detailed process are：In oxidation bubble tower 1 and disc secondary oxidation
9 connecting line of crystallization kettle is equipped with metering pump 2, stirring dynamic mixer 6, is set before stirring dynamic mixer 6 described in an importing
The branch pipe and metering pump 3 of modifying agent, the reaction raw materials 0 (CTA slurries) for carrying out autoxidation bubble tower 1 are measured through metering pump 2 in proportion
Modified CTA slurries are mixed by stirring dynamic mixer 6 with the modifying agent imported through the metering of metering pump 3, are injected into
Disc secondary oxidation crystallization kettle 9 carries out secondary oxidation and crystallizes；The spray that oxygen-enriched air is equipped with through oxygen-enriched air injection pipe 7
Stoma tube 8 injects disc secondary oxidation crystallization kettle 9, and the solvent in crystallization process is recycled through evaporation of the solvent recovery tube 4, can also
Pass through 5 recovered system of evaporation of the solvent recovery tube, 21 recycling design；Then, modified CTA slurries is defeated by slurry connecting tube 10
Enter into the first round platform crystallization kettle 11 and continue to crystallize, two layers of paddle 15 drives slurry agitation, and the solvent in crystallization process is logical
Cross 14 recovered system of evaporation of the solvent recovery tube, 21 recycling design；Then, then by modified CTA slurries it is input to by connecting tube 12
It is further crystallized in second round platform crystallization kettle 13；Then the modification CTA slurries of crystallization will be completed successively through the first centrifuge 18
Simultaneously the washing of acetic acid 22 is added in centrifugal dewatering, and the first mashing mashing stirring of kettle 16, the second centrifuge 19 continues centrifugal dewatering and is added
Acetic acid 22 washs, the second mashing mashing stirring of kettle 17, then through 20 centrifugal dewatering of third centrifuge, the acetic acid of removing is recycled through acetic acid
Reactor 23 recycles, and obtains modified CTA filtrates and is mixed through screw conveyor 25, the screw conveyor 25 is connected with recovery system
24, the modified CTA slurries are delivered to steam dryer 28 and are dried, then hydrogenated process for refining, and compound PTA is made.Institute
It states the first mashing kettle 16 and second mashing kettle 17 and is connected separately with acetic acid recycling reactor 26 and recovery system 27, carry out acetic acid
Recycling.
Preferably, the modifying agent of the metering of the metering pump 3 injection is the metering injection CTA oxidation slurry mass parts of metering pump 2
Several 4-10%.
Embodiment 1
The preparation method of modified PTA, includes the following steps described in the present embodiment：
(1) the aqueous citric acid solution 10kg, nanoscale foresite 0.6kg, nanoscale wheat hydroxyl silicon for being 15% by mass fraction
The sulfosalisylic aqueous acid 12kg, flight graphite 0.1kg, sodium titanate crystal whisker 1.5kg that sodium mountain flour 1.0kg, mass fraction are 4%
Mixing is ground 3h at 50 DEG C of liquid phase with high energy ball mill, is then moved on in the hydrothermal reaction kettle that liner is titanium, at 150 DEG C,
It is handled 12 hours under 4MPa, then atomization drying, 5h is calcined at 400 DEG C, with ball mill grinding 4h, move on to stirring-type plasma
In reactor, nitrogen buffer gas carries out RF plasma processing 0.5h under 40Pa, 80W power, is then added to 12kg
Mass fraction is 32% in Ethoxysilane-ethanol solution, ultrasonic disperse 2h, then abundant with absolute ethyl alcohol at 60 DEG C
Washing after reheating drying, and is sieved through 250-350 mesh, modified powder is made；
(2) with continuous stirring, acetic acid 12kg and deionized water 6kg is mixed, add that mass fraction is 6% six are partially
Modified powder 10kg, nanoscale hectorite 0.5kg, white carbon 5kg made from sodium phosphate aqueous dispersant 2kg and step (1)
Mixing, and it is beaten processing, then the ultrasonic disperse 3h at 40 DEG C, is made modifying agent；
(3) with reference to process system as shown in Figure 1, in oxidation bubble tower 1 and 9 connecting tube of disc secondary oxidation crystallization kettle
Road is equipped with CTA metering pumps 2, stirring dynamic mixer 6, and modifying agent branch obtained by an injection is set before stirring dynamic mixer 6
Pipe and modifying agent metering pump 3, the CTA slurry in proportion for carrying out 1 mass fraction 28% of autoxidation bubble tower are measured and are passed through through metering pump 2
(modifying agent of the metering injection of the metering pump 3 is the metering injection CTA oxidation slurries of metering pump 2 to the modifying agent of the metering injection of metering pump 3
Expect the 4% of mass fraction) disc secondary oxidation knot is injected by the mixed modified CTA slurries of stirring dynamic mixer 6
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 20- at 185-190 DEG C, in 1-1.1MPa and oxygen-enriched air
30min；Modified CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, under 155-160 DEG C, 0.2-0.4MPa
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 90-95 DEG C, further crystallizes under the MPa of (- 0.06)~(- 0.04), residence time 25-35min；Then changing for crystallization will be completed
Property CTA slurries through 1 centrifugal dewatering of centrifuge and wash successively, mashing kettle 1 mashing stirring, centrifuge 2 continue centrifugal dewatering washing,
It is beaten the mashing stirring of kettle 2, then through 3 centrifugal dewatering of centrifuge, obtains the modification CTA filtrates that water capacity is 10% through screw conveyor
Mixing, is delivered to steam dryer and is dried, then through conventional hydrofining technology, modified PTA is made.
Embodiment 2
The preparation method of modified PTA, includes the following steps described in the present embodiment：
(1) the aqueous citric acid solution 20kg, nanoscale foresite 0.3kg, nanoscale wheat hydroxyl silicon sodium for being 5% by mass fraction
The sulfosalisylic aqueous acid 4kg, flight graphite 0.2kg, sodium titanate crystal whisker 0.5kg that mountain flour 2.5kg, mass fraction are 6% are mixed
It closes, grinds 6h at 55 DEG C of liquid phase with high energy ball mill, then move on in the hydrothermal reaction kettle that liner is titanium, at 200 DEG C, 2MPa
Lower processing 10 hours, then atomization drying, calcine 3h at 450 DEG C, with ball mill grinding 2h, move on to stirring-type plasma reaction
In device, nitrogen buffer gas carries out RF plasma processing 1.5h under 60Pa, 30W power, is then added to 18kg mass
Score is 28% in Ethoxysilane-ethanol solution, the ultrasonic disperse 1h at 70 DEG C is then fully washed with absolute ethyl alcohol
It washs, after reheating drying, and is sieved through 250-350 mesh, modified powder is made；
(2) with continuous stirring, acetic acid 20kg and deionized water 2kg is mixed, add that mass fraction is 4% six are partially
Modified powder 4kg, nanoscale hectorite 1.0kg, white carbon 2kg made from sodium phosphate aqueous dispersant 6kg and step (1) are mixed
It is even, and it is beaten processing, then the ultrasonic disperse 2h at 50 DEG C, is made modifying agent；
(3) with reference to process system as shown in Figure 1, in oxidation bubble tower 1 and 9 connecting tube of disc secondary oxidation crystallization kettle
Road is equipped with CTA metering pumps 2, stirring dynamic mixer 6, and modifying agent branch obtained by an injection is set before stirring dynamic mixer 6
Pipe and modifying agent metering pump 3, the CTA slurry in proportion for carrying out 1 mass fraction 30% of autoxidation bubble tower are measured and are passed through through metering pump 2
(modifying agent of the metering injection of the metering pump 3 is the metering injection CTA oxidation slurries of metering pump 2 to the modifying agent of the metering injection of metering pump 3
Expect the 10% of mass fraction) disc secondary oxidation knot is injected by the mixed modified CTA slurries of stirring dynamic mixer 6
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 20- at 185-190 DEG C, in 1-1.1MPa and oxygen-enriched air
30min；Modified CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, under 155-160 DEG C, 0.2-0.4MPa
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 90-95 DEG C, further crystallizes under the MPa of (- 0.06)~(- 0.04), residence time 25-35min；Then changing for crystallization will be completed
Property CTA slurries through 1 centrifugal dewatering of centrifuge and wash successively, mashing kettle 1 mashing stirring, centrifuge 2 continue centrifugal dewatering washing,
It is beaten the mashing stirring of kettle 2, then through 3 centrifugal dewatering of centrifuge, obtains the modification CTA filtrates that water capacity is 10% through screw conveyor
Mixing, is delivered to steam dryer and is dried, then through conventional hydrofining technology, modified PTA is made.
Embodiment 3
The preparation method of modified PTA, includes the following steps described in the present embodiment：
(1) the aqueous citric acid solution 15kg, nanoscale foresite 0.45kg, nanoscale wheat hydroxyl silicon for being 10% by mass fraction
The sulfosalisylic aqueous acid 8kg, flight graphite 0.15kg, sodium titanate crystal whisker 1.0kg that sodium mountain flour 1.8kg, mass fraction are 5%
Mixing is ground 5h at 52 DEG C of liquid phase with high energy ball mill, is then moved on in the hydrothermal reaction kettle that liner is titanium, at 175 DEG C,
It is handled 11 hours under 3MPa, then atomization drying, 4h is calcined at 425 DEG C, with ball mill grinding 3h, move on to stirring-type plasma
In reactor, nitrogen buffer gas carries out RF plasma processing 1h under 50Pa, 55W power, is then added to 15kg matter
Score is measured as 30% in Ethoxysilane-ethanol solution, ultrasonic disperse 1.5h, then abundant with absolute ethyl alcohol at 65 DEG C
Washing after reheating drying, and is sieved through 250-350 mesh, modified powder is made；
(2) with continuous stirring, acetic acid 16kg and deionized water 4kg is mixed, add that mass fraction is 5% six are partially
Modified powder 7kg, nanoscale hectorite 0.75kg, white carbon made from sodium phosphate aqueous dispersant 4kg and step (1)
3.5kg mixings, and it is beaten processing, then the ultrasonic disperse 2.5h at 45 DEG C, is made modifying agent；
(3) with reference to process system as shown in Figure 1, in oxidation bubble tower 1 and 9 connecting tube of disc secondary oxidation crystallization kettle
Road is equipped with CTA metering pumps 2, stirring dynamic mixer 6, and modifying agent branch obtained by an injection is set before stirring dynamic mixer 6
Pipe and modifying agent metering pump 3, the CTA slurry in proportion for carrying out 1 mass fraction 29% of autoxidation bubble tower are measured and are passed through through metering pump 2
(modifying agent of the metering injection of the metering pump 3 is the metering injection CTA oxidation slurries of metering pump 2 to the modifying agent of the metering injection of metering pump 3
Expect the 7% of mass fraction) disc secondary oxidation knot is injected by the mixed modified CTA slurries of stirring dynamic mixer 6
Brilliant kettle 9 agitated progress secondary oxidation and crystallizes, residence time 20- at 185-190 DEG C, in 1-1.1MPa and oxygen-enriched air
30min；Modified CTA slurries are input to by connecting tube 10 in round platform crystallization kettle 11, under 155-160 DEG C, 0.2-0.4MPa
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 90-95 DEG C, further crystallizes under the MPa of (- 0.06)~(- 0.04), residence time 25-35min；Then changing for crystallization will be completed
Property CTA slurries through 1 centrifugal dewatering of centrifuge and wash successively, mashing kettle 1 mashing stirring, centrifuge 2 continue centrifugal dewatering washing,
It is beaten the mashing stirring of kettle 2, then through 3 centrifugal dewatering of centrifuge, obtains the modification CTA filtrates that water capacity is 10% through screw conveyor
Mixing, is delivered to steam dryer and is dried, then through conventional hydrofining technology, modified PTA is made.
Embodiment 4
The preparation of differential polyester described in the present embodiment, includes the following steps：Take the modification prepared in 3kg embodiments 1
PTA, 12kg ethylene glycol and 18kg routines PTA are blended, and are beaten, and then raise temperature to 60 DEG C of progress vacuum dehydrations, work as water content
It is added to polyplant when less than 1% and is warming up to 240 DEG C, pressure 0.1MPa progress esterifications, esterification later stage, heating
To 265 DEG C of reaction 60min, 280 DEG C are again heated to, suction to 100Pa or less carries out copolycondensation, until difference is made
Change copolyesters.
Embodiment 5
The preparation of differential polyester described in the present embodiment, includes the following steps：Take the modification prepared in 5kg embodiments 2
PTA, 9kg ethylene glycol and 23kg routines PTA are blended, and are beaten, and 80 DEG C of progress vacuum dehydrations are then raised temperature to, when water content is small
It is added to polyplant when 1% and is warming up to 260 DEG C, pressure 0.2MPa progress esterifications, in the esterification later stage, is heated to
275 DEG C of reaction 40min, are again heated to 290 DEG C, and suction to 100Pa or less carries out copolycondensation, until being made differential
Copolyesters.
Embodiment 6
The preparation of differential polyester described in the present embodiment, includes the following steps：Take the modification prepared in 4kg embodiments 3
PTA, 10.5kg ethylene glycol and 20.5kg routines PTA are blended, and are beaten, and then raise temperature to 70 DEG C of progress vacuum dehydrations, when containing
Water is added to polyplant when being less than 1% and is warming up to 250 DEG C, pressure 0.15MPa progress esterifications, after esterification
Phase is heated to 270 DEG C of reaction 50min, is again heated to 285 DEG C, and suction to 100Pa or less carries out copolycondensation, until
Differential copolyesters is made.
Comparative example 1
The preparation of polyester described in this comparative example, it is same as Example 6, differ only in, with 24.5kg routines PTA and
10.5kg ethylene glycol is that raw material is reacted, other reaction conditions are same as Example 6.
Embodiment 7
The preparation method of Speciality Pet Fiber described in the present embodiment, includes the following steps：With the high polymorphic structure of cross
The differential copolyesters made from step embodiment 4 is that raw material carries out melt spinning, by profiled filament spinning work by spinneret orifice
Skill is made with lightweight, antistatic, moisture absorption, leads wet, ventilative differential profiled filament.
Speciality Pet Fiber manufactured in the present embodiment uses same process system relative to polyester to be made in comparative example 1
Standby polyester fiber, fibre strength promote 9.5%, and the promotion 6.0% of toughness, thermal stability improves 4.0 DEG C.
It being measured according to GB/T14344-20008, GB/T6503-2008 standard, the regain of polyester fiber is 0.90%, than
Resistance is 3.0 × 109(conventional polyester fiber official regain is 0.4% to Ω cm, resistivity 1015Ω cm or more), show
The hygroscopicity of gained polyester fiber, antistatic property greatly improve, and good hygroscopicity is more conducive to improve antistatic and fabric
Wearing comfort, have meaning of crucial importance to the field of taking.
Embodiment 8
The preparation method of Speciality Pet Fiber described in the present embodiment, includes the following steps：With the high polymorphic structure of hollow shape
The differential copolyesters made from step embodiment 5 is that raw material carries out melt spinning, by profiled filament spinning work by spinneret orifice
Skill is made with lightweight, antistatic, moisture absorption, leads wet, ventilative differential profiled filament.
Speciality Pet Fiber manufactured in the present embodiment uses same process system relative to polyester to be made in comparative example 1
Standby polyester fiber, fibre strength promote 9.6%, and the promotion 6.1% of toughness, thermal stability improves 4.1 DEG C.
It being measured according to GB/T14344-20008, GB/T6503-2008 standard, the regain of polyester fiber is 0.92%, than
Resistance is 3.1 × 109(conventional polyester fiber official regain is 0.4% to Ω cm, resistivity 1015Ω cm or more), show
The hygroscopicity of gained polyester fiber, antistatic property greatly improve, and good hygroscopicity is more conducive to improve antistatic and fabric
Wearing comfort, have meaning of crucial importance to the field of taking.
Embodiment 9
The preparation method of Speciality Pet Fiber described in the present embodiment, includes the following steps：With the high polymorphic structure of trilobal
The differential copolyesters made from step embodiment 6 is that raw material carries out melt spinning, by profiled filament spinning work by spinneret orifice
Skill is made with lightweight, antistatic, moisture absorption, leads wet, ventilative differential profiled filament.
Speciality Pet Fiber manufactured in the present embodiment uses same process system relative to polyester to be made in comparative example 1
Standby polyester fiber, fibre strength promote 9.9%, and the promotion 6.5% of toughness, thermal stability improves 4.5 DEG C.
It being measured according to GB/T14344-20008, GB/T6503-2008 standard, the regain of polyester fiber is 0.96%, than
Resistance is 3.5 × 109(conventional polyester fiber official regain is 0.4% to Ω cm, resistivity 1015Ω cm or more), show
The hygroscopicity of gained polyester fiber, antistatic property greatly improve, and good hygroscopicity is more conducive to improve antistatic and fabric
Wearing comfort, have meaning of crucial importance to the field of taking.
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 modified PTA, which is characterized in that include the following steps：
(1) take mass concentration be the aqueous citric acid solution 10-20 parts by weight of 5-15%, nanoscale foresite 0.3-0.6 parts by weight,
Nanoscale magadiite powder 1.0-2.5 parts by weight, mass fraction be 4-6% sulfosalisylic aqueous acid 4-12 parts by weight,
Flight graphite 0.1-0.2 parts by weight, sodium titanate crystal whisker 0.5-1.5 parts by weight carry out hydro-thermal reaction after mixing, grinding, through filtering,
Dry, calcining, corona treatment is organic-silicon-modified, and modified powder is made；
(2) it takes acetic acid 12-20 parts by weight and water 2-6 parts by weight to mix, and adds the calgon that mass fraction is 4-6% water-soluble
The modified powder 4-10 parts by weight made from liquid 2-6 parts by weight and step (1), nanoscale hectorite 0.5-1.0 weight
Part, white carbon 2-5 parts by weight mixings are beaten and through ultrasonic disperse, modifying agent are made；
(3) modifying agent made from step (2) is merged with crude terephthalic acid slurry, it is crystallized, it is separated by solid-liquid separation, washs, it is dry,
Mashing, then be separated by solid-liquid separation back end hydrogenation and refine, modified PTA is made.
2. the preparation method of modified PTA according to claim 1, it is characterised in that：
In the step (1), each raw material component includes：Mass concentration be 10% 15 parts by weight of aqueous citric acid solution, nanoscale
0.45 parts by weight of foresite, 1.8 parts by weight of nanoscale magadiite powder, the sulfosalisylic aqueous acid 8 that mass fraction is 5%
Parts by weight, 0.15 parts by weight of flight graphite, 1.0 parts by weight of sodium titanate crystal whisker；
In the step (2), each raw material component includes：16 parts by weight of acetic acid, 4 parts by weight of water, the six inclined phosphorus that mass fraction is 5%
4 parts by weight of acid sodium aqueous solution, 7 parts by weight of the modified powder, 0.8 parts by weight of nanoscale hectorite, 3.5 parts by weight of white carbon.
3. the preparation method of modified PTA according to claim 1 or 2, it is characterised in that：
In the step (1)：
The grinding steps are to grind 3-6h at 50-55 DEG C of liquid phase with high energy ball mill；
The hydrothermal synthesis step is to be handled 10-12 hours under 150-200 DEG C, 2-4MPa；
The drying steps are atomization drying；
The calcining step is to calcine 3-5h at 400-450 DEG C；
The plasma treatment step is the nitrogen buffer gas, in 40-60Pa, 30-80W power in plasma reactor
Lower progress RF plasma processing 0.5-1.5h；
The organic-silicon-modified step be 28-32% by product and the mass concentration after plasma treatment organosilicon ethyl alcohol it is molten
Liquid mixes, and the ultrasonic disperse 1-2h at 60-70 DEG C is fully washed with absolute ethyl alcohol, and heat drying；
In the step (2), the ultrasonic disperse step is the ultrasonic disperse 2-3h at 40-50 DEG C；
In the step (3), the crystallisation step is：Secondary oxidation is carried out in 185-190 DEG C, 1-1.1MPa and oxygen-enriched air
And it crystallizes, residence time 20-30min；Then continue to crystallize at 155-160 DEG C, 0.2-0.4MPa, residence time 20-
30min；It is further crystallized at 90-95 DEG C, (- 0.06)~(- 0.04) MPa again, residence time 25-35min.
4. the modification PTA being prepared by any one of claim 1-3 methods.
5. the modification PTA described in claim 4 is used to prepare the purposes of differential polyester.
6. a kind of method preparing differential polyester, which is characterized in that modified described in 3-5 parts by weight claims 4 including taking
The step of PTA, 9-12 parts by weight ethylene glycol, 18-23 parts by weight PTA mixings, the mixture is beaten and is warming up to 60-80 DEG C
Vacuum dehydration processing is carried out, when water content is less than 1% in 240-260 DEG C, pressure 0.1-0.2MPa progress esterifications, and in
The esterification later stage is warming up to 265-275 DEG C of reaction 40-60min, is again heated to 280-290 DEG C, suction to 100Pa with
Lower progress copolycondensation is to get required differential copolyesters.
7. the differential polyester being prepared by method of claim 6.
8. the differential polyester described in claim 7 is used to prepare the purposes of Speciality Pet Fiber.
9. a kind of method preparing Speciality Pet Fiber, which is characterized in that include with the differential polyester described in claim 7
For raw material, through melt spinning, the step of required differentiation polyester fiber is made by profiled filament spinning technique.
10. the Speciality Pet Fiber being prepared by the method described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065281.7A CN108299631A (en) | 2018-01-23 | 2018-01-23 | A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065281.7A CN108299631A (en) | 2018-01-23 | 2018-01-23 | A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108299631A true CN108299631A (en) | 2018-07-20 |
Family
ID=62866056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810065281.7A Pending CN108299631A (en) | 2018-01-23 | 2018-01-23 | A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299631A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790910A (en) * | 2019-10-15 | 2020-02-14 | 南通大学 | Crystallized self-refined polyester and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1763275A (en) * | 2004-10-21 | 2006-04-26 | 天津石油化工公司化纤厂 | Method for manufacturing fire retardant-antistatic polyester fiber |
| EP2210910B1 (en) * | 2009-01-21 | 2013-01-02 | Nan Ya Plastics Corporation | Antimony-free PET resin and PET polyester fiber made therefrom |
| CN102978744A (en) * | 2012-11-26 | 2013-03-20 | 浙江理工大学 | Method for manufacturing conductive polyester fibers |
| CN103361765A (en) * | 2012-03-30 | 2013-10-23 | 浙江恒逸高新材料有限公司 | Anti-static modified polyester staple fiber and preparation method thereof |
-
2018
- 2018-01-23 CN CN201810065281.7A patent/CN108299631A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1763275A (en) * | 2004-10-21 | 2006-04-26 | 天津石油化工公司化纤厂 | Method for manufacturing fire retardant-antistatic polyester fiber |
| EP2210910B1 (en) * | 2009-01-21 | 2013-01-02 | Nan Ya Plastics Corporation | Antimony-free PET resin and PET polyester fiber made therefrom |
| CN103361765A (en) * | 2012-03-30 | 2013-10-23 | 浙江恒逸高新材料有限公司 | Anti-static modified polyester staple fiber and preparation method thereof |
| CN102978744A (en) * | 2012-11-26 | 2013-03-20 | 浙江理工大学 | Method for manufacturing conductive polyester fibers |
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》", 28 February 2005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790910A (en) * | 2019-10-15 | 2020-02-14 | 南通大学 | Crystallized self-refined polyester and preparation method thereof |
| CN110790910B (en) * | 2019-10-15 | 2021-12-28 | 南通大学 | Crystallized self-refined polyester and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105585701B (en) | A kind of polyether-modified copolyesters continuous preparation method | |
| CN109322007B (en) | Preparation method of polyester-nylon composite elastic fiber | |
| CN103789865B (en) | A kind of preparation method of high hydrophilic easy-to-dye polyester fiber | |
| CN101469060B (en) | Preparation of cationic dyeable poly(trimethylene terephthalate) | |
| CN104404647B (en) | Hydrophilic polyesters fiber that a kind of Cellulose nanocrystal is modified and preparation method thereof | |
| CN103774267B (en) | A kind of preparation method of polyhydroxy flexible polyester fiber | |
| CN110358061B (en) | Polyester chip for producing low-melting-point sheath-core composite filament and preparation method thereof | |
| CN112844280B (en) | Horizontal reaction kettle, functional polyester production system applying same and production method | |
| CN104499082B (en) | A kind of high dye-uptake polyester fiber DTY silk and preparation method thereof | |
| CN105442082B (en) | A kind of low aberration polyester HOY silks and preparation method thereof | |
| CN106811829A (en) | A kind of crystallinity low melting point polyester fiber and preparation method thereof | |
| CN105463619B (en) | A kind of low aberration polyester POY silks and preparation method thereof | |
| CN105671675B (en) | A kind of low aberration polyester imitates cotton abnormal contraction composite filament and preparation method thereof | |
| CN108299631A (en) | A kind of modified PTA, differential polyester and its Speciality Pet Fiber of preparation | |
| CN106400197A (en) | Making method of comfortable polyester filament | |
| CN108484887A (en) | A kind of preparation method of compound PTA | |
| CN101376705B (en) | Preparation of modified PTT polyester chip | |
| CN104031251B (en) | A kind of cation dye chromophil, the continuous polymerization preparation method of anlistatig PTT copolymer | |
| 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 | |
| CN105648594B (en) | A kind of low aberration polyester imitates linen look abnormal contraction composite filament and preparation method thereof | |
| CN106397751A (en) | Method for synthesis of comfortable copolyester | |
| CN108383985A (en) | A kind of modified PTA, modified poly ester and its antibiotic health care polyester fiber of preparation | |
| CN102850534B (en) | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst | |
| CN108341938A (en) | A kind of preparation method of function presetting p-phthalic acid |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180720 |