CN109853072A - A kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament - Google Patents
A kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of modification by copolymerization anti-pollution terylene bulk filament, the preparation method of preparation and modification by copolymerization anti-pollution terylene bulk filament including copolyester；As raw material and inhibitor be added be prepared copolyester slice using fluorine-containing terephthalic acid (TPA) and ethylene glycol in the preparation process of copolyester, slice through screw rod melting extrusion, cooling, oil, stretch and deform obtained modification by copolymerization anti-pollution terylene bulk filament.Novel copolymerized modified anti-pollution terylene bulk filament produced by the present invention, 2~4cN/dtex of its breaking strength, elongation at break is 35~55%, hot rolling song is 20~40%, due to the introducing of fluorine atom, super-hydrophobicity, hydrophobic and oil repellent, the antifouling aspect performance for improving terylene bulk filament have vast potential for future development in waterproof, the carpet to bear dirty manufacture.
Description
Technical field
The present invention relates to a kind of preparation methods of modification by copolymerization anti-pollution terylene bulk filament, more particularly on a kind of phenyl ring
Hydrogen by the preparation method of fluorine-substituted modification by copolymerization anti-pollution terylene bulk filament.
Background technique
Polyester (PET) is the first big kind of current synthetic fibers, because fiber macromolecular chain rigidity is larger, elasticity modulus
Height, fiber are unlikely to deform, and have good heat-resisting, cold-resistant, sun-proof and wearability, are a kind of more satisfactory textile raw materials, especially
It is terylene BCF with its stable three-dimensional crimp, good feel and high fluffy, elasticity and spreadability, is widely used in
Carpet weaving has biggish market.
With the development of the society, the raising of living standards of the people, increasingly to the differential of polyester fiber, functionalization demand
It is high.Therefore the modification of polyester also becomes particularly important, and polyester modification purpose is other than optimizing conventional polyester performance, mainly
It is to assign new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, it is antifouling,
Deodorization etc..Currently, the main new varieties of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity are poly-
Ester and anti-pollution polyester etc..
Currently, by introducing fluorine atom in the polymer, so as to improve the surface property of material, such as hydro-oleophobicity and anti-
Dirt etc., and assign the various functions of polyester material.Since fluoropolymer usually has low-surface-energy, low-friction coefficient and glues
Attached property, dust dirt such as is difficult to adhere at the characteristics, therefore fluoropolymer-containing anti-pollution wearability is good.And current fluoropolymer is with fluorine
For based on olefin polymer (such as: polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethylene~tetrafluoro second
Alkene copolymer etc.)；The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. then relatively lags behind.
Many scholars study fluorochemical modified poly ester, and achieve certain achievement.At present containing fluorination
The mode of polymer modified polyester, which mainly passes through fluorine-containing end-capping reagent to be added, or Fluorinated dihydric alcohol, fluorine-containing binary acid is added etc., to be contained
Fluorine compounds carry out modified poly ester as Third monomer.Wang Xue etc. is " polyethylene terephthalate is copolymerized/is blended hydrophobic research "
Opinion the article pointed out: by by poly terephthalic acid hydroxyl ethyl ester (BHET) and fluorinated silicone modified dose of (FGX) copolycondensation, acquisition fluorinated volume
The hydrophobic modified polyester (MPET) low, hydrophobic performance is excellent, by adding the FGX of different viscosities, (additive amount of FGX is BHET
6%-20%), obtain different molecular weight hydrophobic modified polyester (MPET) --- (2014 both sides of the Straits of the Chinese Technology Association are super imitative
Cotton processing technology application study scientist seminar).Wang Zhonggang, Li Wenjuan etc. " fluorine-containing linear and hyperbranched poly Lipase absobed and
Performance study " opinion the article pointed out: synthesized the polybutylene terephthalate (PBT) (FPBT) of different fluorinated volumes, passed through one-step method
Synthesis N ethoxy perfluoro-octanoyl amine is fluorochemical monomer, and by ester-interchange method, using DMT and BDO as raw material, butyl titanate is to urge
Agent, by changing the dosage of fluorochemical monomer, the FPBT of synthesis fluoroalkyl sealing end, as a result, it has been found that the fusing point of polymer is with fluorine-containing list
The increase of body and decline, the increase of fluorochemical monomer content, water contact angle increases to the hydro-oleophobicity of 110 degree of polymer by 75 degree
Can be improved --- Dalian University of Technology's Master's thesis.CN103467721B and CN103467723B are individually disclosed with tetrafluoro
Terephthalic acid (TPA), 1-3 propylene glycol, 1-4 butanediols are raw material, through esterification and polycondensation reaction, respectively obtain PTT and PBT copolymerization
Ester improves the hydrophobic anti-pollution of polyester.
However, the polyester that these are contained fluorine element is applied to have certain limitation in textile material, main problem exists
It is low in the molecular weight of polyesters in the prior art containing fluorine element, there is higher requirement to spinning；And the prior art is presently mainly
Its water proof anti-soil function is assigned by the fluorine-containing final finishing mode of textile fabric, and the disadvantage of such methods maximum is to be difficult to
The problems such as solving timeliness, durability and wearability, and it is time-consuming and laborious.
Therefore, modification of the fluorine-containing polyester fiber for the super-hydrophobic of textile material, hydrophobic and oil repellent, anti-pollution is developed, it must
It will be with important theory significance and application value.
Summary of the invention
The technical problem to be solved by the present invention is overcome the deficiencies in the existing technology, a kind of modification by copolymerization anti-pollution is provided and is washed
The preparation method of synthetic fibre bulk filament, the hydrogen being especially to provide on a kind of phenyl ring are long by fluorine-substituted modification by copolymerization anti-pollution terylene varicosity
The preparation method of silk, the copolyester in this method is to introduce fluorine atom on the main chain of polymer, passes through original fluorine-containing on phenyl ring
The terephthalic acid (TPA) and ethylene glycol of son, the novel fluorine polyester obtained through over-churning and polycondensation carry out polyester by copolymerization method
Hydrophobic antifouling modification, the problems such as can fundamentally solving timeliness, durability and the wearability of hydrophobic antifouling polyester, can also be with
The time-consuming and laborious problem of very good solution.
The technical solution adopted by the present invention to solve the technical problems is: a kind of modification by copolymerization anti-pollution terylene bulk filament
Preparation method, the modification by copolymerization anti-pollution terylene bulk filament be by copolyester slice through screw rod melting extrusion, cooling, on
Oil is stretched and is deformed obtained；The copolyester refer to the hydrogen on phenyl ring by fluorine-substituted polyethylene terephthalate,
General structure are as follows:
Wherein, n=80~200；
The preparation method of the copolyester is divided into two step of esterification and polycondensation reaction, specific steps are as follows:
1. esterification: using fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material, inhibitor is added, is made into uniform sizing material
After carry out esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled in normal pressure~0.4MPa,
Temperature at 220~255 DEG C, esterification water quantity reach theoretical value 90% the above are esterification terminals；
2. polycondensation reaction: including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig,
A. polycondensation reaction low vacuum stage: catalyst and stabilizer are added in the esterification products, in the condition of negative pressure
Lower beginning polycondensation reaction, which by normal pressure is steadily evacuated to absolute pressure 1KPa hereinafter, temperature control is at 250~270 DEG C,
Reaction time is 40~60 minutes；
B. polycondensation reaction high vacuum stage of Fig: after above-mentioned polycondensation reaction low vacuum stage, continue to vacuumize, make reaction pressure
Absolute pressure is down to less than lOOPa, the reaction temperature system of fastening is at 270~285 DEG C, the reaction time 1~2 hour.
In esterification stage of the invention, reaction end reaches theoretical value by the water quantity of distillate actually generated in esterification
90% or more grasps.Theoretical value is the quantity of distillate of gained water when reacting completely by chemical equation.Due to esterification
, as reversible reaction, and with the progress of reaction, the viscosity of system increases for this, will lead to the shipwreck of esterification generation with from
Middle discharge.
In polycondensation reaction high vacuum stage of Fig of the invention, reaction end is by reactor agitator motor power and online viscosity
Calculated value reaches the numerical value of setting to grasp, its reactor agitator motor power of different devices and in-line viscometer calculation value
Setting numerical value is not necessarily identical, and the determination for setting numerical value can be obtained by the analysis to polyester slice.
Fluorine-containing terephthalic acid (TPA) in the step (1) is tetrafluoro terephthalic acid (TPA) or 2,5- difluoro terephthalic acid (TPA).
Inhibitor in the step (1) is one of magnesia, silica, calcium oxide, zinc oxide and manganese oxide.By
In there are fluorine atoms on the phenyl ring of dicarboxylic acids used, the electronegativity of fluorine atom is big, in being total to for esterification stage fluorine atom
Often effect makes the acid enhancing of dicarboxylic acids, and the activity for also resulting in carboxyl in dicarboxylic acids increases, so that reaction speed adds
Fastly, and reaction speed increase is easy to generate side reaction, these side reaction products have large effect to subsequent polycondensation reaction,
The end-cap product for especially generating alkene and aldehyde, constrains the increase of molecular weight of product；Judging from the experimental results, if be added without
The molecular weight of polyesters of inhibitor, synthesis is relatively low, is not able to satisfy the demand of spinning；The addition of inhibitor is for controlling esterification rank
The speed of section, reduces side reaction, improves the molecular weight of product, so that copolyester meets spinning requirement.
In general, being hydrogen ion the urging as esterification ionized out by dicarboxylic acids used during polyester esterification
Agent carries out self-catalyzed reaction, and the temperature, pressure and ejecting for small molecule by adjusting esterification control its esterification
Rate, however the premise for carrying out esterification is that esterification can be just carried out under certain reaction temperature and pressure.Temperature
Spend that low esterification in the case that perhaps pressure is inadequate can not carry out or speed is extremely slow, to influence subsequent technique.
If the small molecule in esterification, which fails to be discharged in time, easily causes unnecessary side reaction.In the synthesis process of copolyester,
Due to the total often effect of fluorine, makes the acid enhancing of dicarboxylic acids in esterification stage fluorine atom, also result in dicarboxylic acids
The activity of middle carboxyl increases, so that reaction speed is accelerated, side reaction increases, it is difficult to control, and then influence the increasing of molecular weight of product
It is long, therefore inhibitor is added, i.e., it is adjusted by selecting metal oxide used.Metal oxide can be by the following two kinds mode solution
From:
Here M is metal ion, if the electronegativity of M is quite big, to the electronics of oxonium ion to there is stronger attraction, that
O-H key can be made to weaken, be conducive to reaction dissociation；On the contrary, will just generate alkali center if the electronegativity of M is small.M—
0-H is similar with amphoteric compound, and in the presence of having alkaline matter, reaction will carry out in the way of acid dissociation；And work as acid
In the presence of matter, then carried out in the way of the ionization of alkali formula.The M-0 and M of back reaction from acid dissociation mode and alkali formula ionization mode+
As it can be seen that M+As acid centre, intensity only has a direct relationship with the electronegativity of metal ion, and the O ion conduct in M-0
The intensity at alkali center is then related with the negative charge density on oxygen, and negative charge density is bigger, and intensity is also bigger.It can be seen that on oxonium ion
Negative charge density and metal ion electronegativity have close relationship, and metal ion electronegativity is smaller, and negative charge density is bigger.
So, the acidity of metal oxide and alkalinity are just all connected with the electronegativity of metal ion, metal ion
The big oxide of electronegativity be mainly acidity, and electronegativity it is small be then alkalinity.
As a preferred technical scheme:
The additional amount of the inhibitor is the 0.01%~0.05% of fluorine-containing terephthalic acid (TPA) weight.
The molar ratio of ethylene glycol and fluorine-containing terephthalic acid (TPA) in the step (1) is 1.2~2.0:1.
Catalyst in the step (2a) is one of antimony oxide, antimony glycol and antimony acetate, and catalyst is used
Amount is the 0.01%~0.05% of fluorine-containing terephthalic acid (TPA) weight.
Stabilizer in the step (2a) is one of triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite,
Stabilizing agent dosage is the 0.01%~0.05% of fluorine-containing terephthalic acid (TPA) weight.
Wherein, by copolyester be sliced through screw rod melting extrusion, cooling, oil, stretch and deforming step be made copolymerization change
Property anti-pollution terylene bulk filament, wherein extrusion temperature be 270~295 DEG C, cooling wind temperature be 18~5 DEG C, the finish that oils be Germany
BCF finish, oil tanker 18~30r/min of revolving speed, oil applying rate are 0.6~1.2%；Stretcher strain the first hot-rolling speed be 600~
800m/min, temperature are 70~100 DEG C, and the second hot-rolling speed is 620~820m/min, and temperature is 100~120 DEG C, draw roll
Speed is 2400~3500m/min, and temperature is 180~200 DEG C, and deformation temperature is 150~195 DEG C, and cooling disk rotating speed is 20
~30r/min, first adjusts roller speed as 1900~2800m/min, and second adjusts roller speed as 1950~2850m/min, rolls up
It is 2000~2850m/min around speed.
In the above scheme, the cooling wind is side-blown air cooling, and temperature is 18~25 DEG C, and humidity is 70 ± 5%, wind speed
For 0.4~0.8m/s.
In the above scheme, 2~4cN/dtex of breaking strength of the modification by copolymerization anti-pollution terylene bulk filament, fracture are stretched
Long rate is 35~55%, and hot rolling song is 20~40%.Due to the introducing of fluorine atom, super-hydrophobic, the hydrophobic of polyester material are improved
Hate oil, antifouling aspect performance, has vast potential for future development in waterproof, the carpet weaving to bear dirty.
The beneficial effects of the present invention are:
1, modification by copolymerization anti-pollution terylene bulk filament produced by the present invention contains fluorine atom, high due to the strong electronegativity of fluorine
C-F bond energy and the shielding protection of carbochain is acted on so that final modification by copolymerization anti-pollution terylene bulk filament obtained have it is fine
Capacitor heat-resisting, ageing-resistant, resistant to chemical etching and low, low combustible, the performances such as low-refraction, while also have it is certain special
The advantages that electric property, such as low-k, high-insulativity, extend application range；
2, novel copolymerized modified anti-pollution terylene bulk filament hot rolling song produced by the present invention is compared with conventional polyester BCF high, feel
Smooth softness, suitable for weaving more high-end carpet；
3, novel copolymerized modified anti-pollution terylene bulk filament produced by the present invention is by using fluorine atom is introduced, to have
Hydrophobic antifouling characteristic；
4, novel copolymerized modified anti-pollution terylene bulk filament produced by the present invention is fundamentally solved by using modification by copolymerization
Determined hydrophobic antifouling polyester timeliness, durability and wearability the problems such as.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read the content that the present invention is told about, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
A kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament is to be melted to squeeze through screw rod by copolyester slice
Out, it cools down, oil, stretch and deforms and be made, copolyester refers to the hydrogen on phenyl ring by fluorine-substituted poly terephthalic acid second two
Alcohol ester, general structure are as follows:
Wherein, n=80~200；2~4cN/dtex of breaking strength of modification by copolymerization anti-pollution terylene bulk filament, fracture are stretched
Long rate is 35~55%, and hot rolling song is 20~40%.
Embodiment 1
Prepare copolyester: using molar ratio is the ethylene glycol of 1.2:1 and tetrafluoro terephthalic acid (TPA) as raw material, is added simultaneously
0.01% zinc oxide for entering tetrafluoro terephthalic acid (TPA) weight carries out esterification after being made into uniform sizing material；Esterification is in nitrogen
During atmosphere is enclosed, pressure control is in 0.4MPa, and at 255 DEG C, esterification water quantity reaches the 90% of theoretical value for esterification for temperature control
Reaction end；0.01% the catalytic antimony trioxide and tetrafluoro pair of tetrafluoro terephthalic acid (TPA) weight are added in esterification products
The stabilizer triphenyl phosphate of the 0.01% of phthalic acid weight, starts polycondensation reaction under conditions of negative pressure, the staged pressure
Absolute pressure is steadily evacuated to by normal pressure less than lKPa, at 255 DEG C, the reaction time is 60 minutes for temperature control；It is low through polycondensation reaction
After vacuum stages, continue to vacuumize, so that reaction pressure is down to absolute pressure less than l00Pa, reaction temperature is controlled at 270 DEG C, instead
Answer time 2 h, reaction kettle stirring motor power is subject in polycondensation reaction or in-line viscometer reading judges reaction end；
Prepare modification by copolymerization anti-pollution terylene bulk filament: by above-mentioned copolyester slice through screw rod melting extrusion, cooling, on
Oil stretches and deforms obtained modification by copolymerization anti-pollution terylene bulk filament；The temperature of extrusion is 275 DEG C, is cooled to side-blown air cooling,
Temperature is 20 DEG C, humidity 65%, wind speed 0.4m/s；The finish to oil is Germany's BCF finish, and oil tanker revolving speed is 18r/min,
Oil applying rate is 0.6%；The hot rod speed of stretcher strain first is 600m/min, and temperature is 80 DEG C, and the second hot-rolling speed is 620m/
Min, temperature are 100 DEG C, and drawing-off roller speed is 2400m/min, and temperature is 180 DEG C, and deformation temperature is 150 DEG C, and cooler pan turns
Speed is 20r/min, and first adjusts roller speed 1900m/min, and second adjusts roller speed 1950m/min, winding speed 2000m/
min；
Finally obtained modification by copolymerization anti-pollution terylene bulk filament, breaking strength 2.8cN/dtex, elongation at break are
52%, hot rolling song is 36%.
Embodiment 2
The preparation method of copolyester uses molar ratio for the ethylene glycol of 1.4:1 and 2,5- difluoro terephthalic acid (TPA) conduct
Raw material, while 0.04% silica of 2,5- difluoro terephthalic acid (TPA) weight is added, be esterified instead after being made into uniform sizing material
It answers；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is controlled in 0.3MPa, temperature at 245 DEG C, and esterification water quantity reaches
The 90% of theoretical value is esterification terminal；Urging for the 0.02% of 2,5- difluoro terephthalic acid (TPA) weight is added in esterification products
Agent antimony glycol and 2,0.02% stabilizer trimethyl phosphate of 5- difluoro terephthalic acid (TPA) weight, under conditions of negative pressure
Start polycondensation reaction, which is steadily evacuated to absolute pressure by normal pressure less than 800Pa, and temperature is controlled at 250 DEG C, reaction
Between be 50 minutes；After polycondensation reaction low vacuum stage, continue to vacuumize, so that reaction pressure is down to absolute pressure and be less than 80Pa,
At 275 DEG C, the reaction time 2 hours, polycondensation reaction is read with reaction kettle stirring motor power or in-line viscometer for reaction temperature control
Reaction end is judged subject to number.
Preparation modification by copolymerization anti-pollution terylene bulk filament: by copolyester slice through screw rod melting extrusion, cooling, oil,
It stretches and deforms and modification by copolymerization anti-pollution terylene bulk filament is made；The temperature of extrusion is 280 DEG C, is cooled to side-blown air cooling, temperature
Degree is 22 DEG C, humidity 70%, wind speed 0.45m/s；The finish to oil is Germany's BCF finish, and oil tanker revolving speed is 20r/min,
Oil applying rate is 0.7%；Stretcher strain the first hot-rolling speed is 650m/min, and temperature is 85 DEG C, and the second hot-rolling speed is 670m/
Min, temperature are 105 DEG C, and drawing-off roller speed is 2600m/min, and temperature is 185 DEG C, and deformation temperature is 160 DEG C, and cooler pan turns
Speed is 22r/min, and first adjusts roller speed as 2100m/min, and the second adjusting roller speed is 2150m/min, and winding speed is
2200m/min；
Finally obtained modification by copolymerization anti-pollution terylene bulk filament, breaking strength 2.86cN/dtex, elongation at break are
45%, hot rolling song is 34%.
Embodiment 3
Prepare copolyester: using molar ratio is the ethylene glycol of 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, is added simultaneously
0.02% calcium oxide for entering tetrafluoro terephthalic acid (TPA) weight carries out esterification after being made into uniform sizing material；Esterification is in nitrogen
Atmosphere encloses middle pressurization, and pressure control is in 0.2MPa, and at 240 DEG C, what esterification water quantity reached theoretical value 90% is for temperature control
Esterification terminal；The 0.03% catalyst acetic acid antimony and tetrafluoro pair of tetrafluoro terephthalic acid (TPA) weight are added in esterification products
The stabilizer Trimethyl phosphite of the 0.03% of phthalic acid weight, starts polycondensation reaction under conditions of negative pressure, stage pressure
Power is steadily evacuated to absolute pressure by normal pressure less than 600Pa, and at 260 DEG C, the reaction time is 50 minutes for temperature control；Polycondensation reaction is low
After vacuum stages, continue to vacuumize, so that reaction pressure is down to absolute pressure less than 60Pa, reaction temperature controls the reaction at 280 DEG C
Time be 1.5 hours, polycondensation reaction be subject to reaction kettle stirring motor power or in-line viscometer reading judge reaction end.
Prepare modification by copolymerization anti-pollution terylene bulk filament: by the copolyester slice through screw rod melting extrusion, cooling, on
Oil stretches and deforms obtained modification by copolymerization anti-pollution terylene bulk filament, and the temperature of extrusion is 285 DEG C, is cooled to side-blown air cooling,
Temperature is 23 DEG C, humidity 70%, wind speed 0.6m/s；The finish to oil be Germany's BCF finish, oil tanker revolving speed 22r/min, on
Oil cut rate is 0.8%；Stretcher strain the first hot-rolling speed is 700m/min, and temperature is 90 DEG C, and the second hot rod speed is 720m/min,
Temperature is 110 DEG C, and drawing-off roller speed is 2850m/min, and temperature is 190 DEG C, and deformation temperature is 175 DEG C, and cooling disk rotating speed is
25r/min, first adjusts roller speed 2250m/min, and second adjusts roller speed 2300m/min, winding speed 2350m/min；
Finally obtained modification by copolymerization anti-pollution terylene bulk filament, breaking strength 3.0cN/dtex, elongation at break are
42%, hot rolling song is 32%.
Embodiment 4
Copolyester is prepared, using molar ratio is the ethylene glycol of 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, is added simultaneously
0.03% manganese oxide for entering tetrafluoro terephthalic acid (TPA) weight carries out esterification after being made into uniform sizing material；Esterification is in nitrogen
Atmosphere encloses middle pressurization, and pressure control is in 0.2MPa, and at 235 DEG C, what esterification water quantity reached theoretical value 90% is for temperature control
Esterification terminal；0.04% the catalytic antimony trioxide and four of tetrafluoro terephthalic acid (TPA) weight is added in esterification products
0.04% stabilizer trimethyl phosphate of fluorine terephthalic acid (TPA) weight, starts polycondensation reaction under conditions of negative pressure, the stage
Pressure is steadily evacuated to absolute pressure by normal pressure less than 500Pa, and at 265 DEG C, the reaction time is 50 minutes, anti-through polycondensation for temperature control
After answering low vacuum stage, continuing to vacuumize, reaction pressure is made to be down to absolute pressure less than 50Pa, reaction temperature is controlled at 280 DEG C,
Reaction time 1 hour, polycondensation reaction be subject to reaction kettle stirring motor power or in-line viscometer reading judge reaction end；
Prepare modification by copolymerization anti-pollution terylene bulk filament: by the copolyester slice through screw rod melting extrusion, cooling, on
Oil stretches and deforms obtained modification by copolymerization anti-pollution terylene bulk filament, and the temperature of extrusion is 290 DEG C, is cooled to side-blown air cooling,
Temperature is 24 DEG C, humidity 70%, wind speed 0.65m/s；The finish to oil is Germany's BCF finish, and oil tanker revolving speed is 25r/
Min, oil applying rate 0.9%；Stretcher strain the first hot-rolling speed is 750m/min, and temperature is 95 DEG C, and the second hot-rolling speed is
770m/min, temperature are 115 DEG C, and drawing-off roller speed is 3000m/min, and temperature is 195 DEG C, and deformation temperature is 18 DEG C, cooling
Disk rotating speed 26r/min, first adjusts roller speed 2400m/min, and second adjusts roller speed 2450m/min, and winding speed is
2500m/min；
Finally obtained modification by copolymerization anti-pollution terylene bulk filament, breaking strength 3.2cN/dtex, elongation at break are
40%, hot rolling song is 30%.
Embodiment 5
It prepares copolyester: using molar ratio for the ethylene glycol of 2.0:1 and 2,5- difluoro terephthalic acid (TPA) is as raw material, together
When 0.01% magnesia of 2,5- difluoro terephthalic acid (TPA) weight is added, carry out esterification after being made into uniform sizing material；Esterification
Reaction is pressurizeed in nitrogen atmosphere, and pressure control is controlled in normal pressure, temperature at 230 DEG C, and esterification water quantity reaches theoretical value
90% is esterification terminal；0.05% three oxygen of catalyst of 2,5- difluoro terephthalic acid (TPA) weight is added in esterification products
Change two antimony and 2,0.05% stabilizer triphenyl phosphate of 5- difluoro terephthalic acid (TPA) weight starts to contract under conditions of negative pressure
Poly- reaction, the staged pressure are steadily evacuated to absolute pressure by normal pressure less than 400Pa, and temperature control is at 270 DEG C, the reaction time 40
Minute, after polycondensation reaction low vacuum stage, continue to vacuumize, reaction pressure is made to be down to absolute pressure less than 50Pa, reaction temperature
At 285 DEG C, the reaction time 1 hour, reaction kettle stirring motor power or in-line viscometer reading are subject in polycondensation reaction for degree control
Judge reaction end；
Preparation modification by copolymerization anti-pollution terylene bulk filament: by copolyester slice through screw rod melting extrusion, cooling, oil,
It stretches and deforms and modification by copolymerization anti-pollution terylene bulk filament is made, the temperature of extrusion is 295 DEG C, is cooled to side-blown air cooling, temperature
Degree is 25 DEG C, humidity 70%, wind speed 0.7m/s；The finish to oil is Germany's BCF finish, and oil tanker revolving speed 26r/min oils
Rate is 1.2%；Stretcher strain the first hot-rolling speed is 800m/min, and temperature is 100 DEG C, and the second hot-rolling speed is 820m/min,
Temperature is 120 DEG C, drawing-off roller speed 3300m/min, and temperature is 200 DEG C, and deformation temperature is 200 DEG C, and cooling disk rotating speed is
27r/min, first adjusts roller speed as 2650m/min, and second adjusts roller speed as 2700m/min, winding speed 2750m/
min；
Finally obtained modification by copolymerization anti-pollution terylene bulk filament, breaking strength 3.8cN/dtex, elongation at break are
38%, hot rolling song is 25%.
Each embodiment and comparative example test result are as follows:
| Breaking strength (Cn/dtex) | Elongation at break (%) | Hot rolling song (%) | |
| Embodiment 1 | 2.80 | 52 | 36 |
| Embodiment 2 | 2.86 | 45 | 34 |
| Embodiment 3 | 3.00 | 42 | 32 |
| Embodiment 4 | 3.20 | 40 | 30 |
| Embodiment 5 | 3.80 | 38 | 25 |
| Comparative example | 2.65 | 55 | 22 |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand the contents of the present invention and be implemented, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament, it is characterized in that: the modification by copolymerization anti-pollution terylene is swollen
Body long filament be by copolyester slice through screw rod melting extrusion, cooling, oil, stretch and deform it is obtained；The copolyester is
Refer to the hydrogen on phenyl ring by fluorine-substituted polyethylene terephthalate, general structure are as follows:
Wherein, n=80~200；
The preparation method of the copolyester is divided into two step of esterification and polycondensation reaction, specific steps are as follows:
1. esterification: using fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material, inhibitor is added, it is laggard to be made into uniform sizing material
Row esterification, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled in normal pressure~0.4MPa, temperature
At 220~255 DEG C, esterification water quantity reach theoretical value 90% the above are esterification terminals；
2. polycondensation reaction: including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig,
A. polycondensation reaction low vacuum stage: catalyst and stabilizer are added in the esterification products, is opened under conditions of negative pressure
Beginning polycondensation reaction, the staged pressure are steadily evacuated to absolute pressure 1KPa hereinafter, temperature control is reacted at 250~270 DEG C by normal pressure
Time is 40~60 minutes；
B. polycondensation reaction high vacuum stage of Fig: after above-mentioned polycondensation reaction low vacuum stage, continue to vacuumize, be down to reaction pressure
Absolute pressure is less than lOOPa, and the reaction temperature system of fastening is at 270~285 DEG C, the reaction time 1~2 hour.
2. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 1, it is characterised in that: institute
Stating the fluorine-containing terephthalic acid (TPA) in step (1) is tetrafluoro terephthalic acid (TPA) or 2,5- difluoro terephthalic acid (TPA).
3. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 2, it is characterised in that: institute
Stating the inhibitor in step (1) is one of magnesia, silica, calcium oxide, zinc oxide and manganese oxide.
4. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 3, it is characterised in that: institute
The additional amount for stating inhibitor is the 0.01%~0.05% of fluorine-containing terephthalic acid (TPA) weight.
5. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 2, it is characterised in that: institute
The molar ratio for stating ethylene glycol and fluorine-containing terephthalic acid (TPA) in step (1) is 1.2~2.0:1.
6. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 2, it is characterised in that: institute
Stating the catalyst in step (2a) is one of antimony oxide, antimony glycol and antimony acetate, and catalyst amount is fluorine-containing right
The 0.01%~0.05% of phthalic acid weight.
7. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 2, it is characterised in that: institute
Stating the stabilizer in step (2a) is one of triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, stabilizing agent dosage
It is the 0.01%~0.05% of fluorine-containing terephthalic acid (TPA) weight.
8. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 1, it is characterised in that: by
Copolyester slice through screw rod melting extrusion, cooling, oil, stretch and deforming step be made modification by copolymerization anti-pollution terylene varicosity it is long
Silk, wherein extrusion temperature is 270~295 DEG C, and cooling wind temperature is 18~5 DEG C, and the finish that oils is Germany's BCF finish, oil tanker revolving speed
18~30r/min, oil applying rate are 0.6~1.2%；Stretcher strain the first hot-rolling speed be 600~800m/min, temperature be 70~
100 DEG C, the second hot-rolling speed is 620~820m/min, and temperature is 100~120 DEG C, and drawing-off roller speed is 2400~3500m/
Min, temperature are 180~200 DEG C, and deformation temperature is 150~195 DEG C, and cooling disk rotating speed is 20~30r/min, and first is adjusted
Roller speed be 1900~2800m/min, second adjust roller speed be 1950~2850m/min, winding speed be 2000~
2850m/min。
9. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 8, it is characterised in that: institute
Stating cooling wind is side-blown air cooling, and temperature is 18~25 DEG C, and humidity is 70 ± 5%, and wind speed is 0.4~0.8m/s.
10. a kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament according to claim 8, it is characterised in that:
2~4cN/dtex of breaking strength of the modification by copolymerization anti-pollution terylene bulk filament, elongation at break are 35~55%, and hot rolling is bent
It is 20~40%.
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| CN111235689A (en) * | 2020-03-24 | 2020-06-05 | 张家港市科达化纤有限公司 | Anti-fouling type bulk textured yarn and preparation method thereof |
| CN113005531A (en) * | 2021-03-03 | 2021-06-22 | 太仓逸枫化纤有限公司 | Lustrous crystal polyester filament, preparation method and preparation device |
| CN113005539A (en) * | 2021-03-01 | 2021-06-22 | 太仓逸枫化纤有限公司 | Preparation method and equipment of copolymerization modified anti-fouling polyester bulked filament yarn |
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