A kind of fluorine-containing PET-PTT copolyesters and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing PET-PTT copolyesters and preparation method thereof, particularly relate to copolyesters that a kind of main chain is made up of fluorine-containing PET and PTT structure and preparation method thereof.
Background technology
Polyester is one of the most widely used synthetic high polymer of the current mankind; ethylene glycol terephthalate (PET) has just been synthesized the forties as far back as twentieth century; and find that it has excellent performance, and be widely used in the fields such as weaving, packaging, health care, automobile, electronic apparatus, safety precaution, environment protection.
Poly(Trimethylene Terephthalate) (PTT) is a kind of new polyester macromolecular material having development prospect of new research and development after polyethylene terephthalate (PET) and mutual-phenenyl two acid bromide two alcohol ester (PBT), within 1998, is chosen as one of six large petrochemical industry product innovations by the U.S..Compared with PET, PBT, PTT has better elasticity, dimensional stability and dyeability etc.There is the multiple good characteristics such as uvioresistant, anti-internal stress, low water absorbable, low electrostatic and good biological degradability, reusable edible simultaneously, be therefore widely used in the fields such as carpet industry, dress materials, engineering plastics.
But in application process, being the deficiency that PET or PTT shows some aspect of performance: when applying as engineering plastics, there is the shortcomings such as crystallization rate is slow, the shrinking percentage of moulded products is large in PET; PTT due to one of its raw material be 1, ammediol (PDO) price comparison is expensive, make production cost higher, and the poor heat stability of PTT, intensity is not high and the high temperature dimensional stability of fiber is bad, particularly many predicted performances of PTT still can not fully demonstrate in post-treatment.Therefore, Many researchers is conceived to the mode finding a kind of economical rationality, and these two kinds of polyester material performances are farthest played.Carrying out copolymerization to PET and PTT is effective means.
Along with the progress of society, the raising of living standards of the people, needs more and more higher to differential, the functionalization of trevira.What therefore the modification of polyester also became particularly is important, and polyester modification object, except being optimized conventional polyester performance, mainly gives new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new variety of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.
At present, by introducing fluorine atom in the polymer, thus improving the surface property of material, as hydro-oleophobicity and didirtresistance etc., and giving polyester material various function.Because fluoropolymer has low surface energy, low-friction coefficient and non-adhesivity usually, dust dirt is difficult to the characteristics such as attachment, and therefore the anti-soil wear resistance of fluoropolymer is good.And current fluoropolymer is based on fluoroolefins base polymer (such as: tetrafluoroethylene, polyvinylidene difluoride (PVDF), fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. then relatively lags behind.
Many scholars are studied fluorochemicals modified poly ester, and achieve certain achievement.The mode of current fluorochemicals modified poly ester mainly by adding fluorine-containing end-capping reagent, or adds the fluorochemicals such as Fluorinated dihydric alcohol, fluorine-containing diprotic acid and carrys out modified poly ester as Third monomer.Adopt adding of fluorine-containing end-capping reagent in Chinese patent CN101139434A, dimethyl isophthalate and butyleneglycol adopt ester-interchange method, add fluorine-containing end-capping reagent N-hydroxyethyl perfluoro-octanoyl amine, have prepared the low and polyester material that contaminated resistance is good of fluorine content.Hu Juan (Hu Juan. the molecular designing of fluorine-containing polyester and photoresist material waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) principle of molecular designing is utilized, by adding the mode of Fluorinated dihydric alcohol copolymerization, p-phthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol terpolymer are synthesized the polyester of novel high fluorine content.This polyester has excellent performance and is applied to optical waveguide material.
But the polyester these being contained fluorine element is applied in weaving and wrapping material certain limitation, subject matter is that the molecular weight of polyesters containing fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art mainly gives its water proof anti-soil function by the fluorine-containing Final finishing mode of fabric at present, and the maximum shortcoming of these class methods is to be difficult to solve the problems such as ageing, weather resistance and wear resistance, and wastes time and energy.
Therefore, developing fluorine-containing polyester for weaving and the modification of super-hydrophobic, hydrophobic and oil repellent, antifouling property of wrapping material, important theory significance and using value will be had.
Summary of the invention
The object of this invention is to provide a kind of fluorine-containing PET-PTT copolyesters and preparation method thereof, particularly relate to copolyesters that a kind of main chain is made up of fluorine-containing PET and PTT structure and preparation method thereof.Fluorine-containing PET-PTT copolyesters of the present invention introduces fluorine atom on the main chain of polymkeric substance, and the fluorine-containing PET-PTT copolyesters sheet prepared can be directly used in spinning, film forming etc.Fluorine-containing PET-PTT copolyesters described in the present invention is the copolyesters obtained through copolymerization by fluorine-containing ethylene glycol terephthalate and propylene glycol ester terephthalate, and this fluorine-containing PET-PTT copolyester section can direct fabrics, film forming.And by copolymerization method, hydrophobic antifouling modification is carried out to polyester, fundamentally can solve ageing, the problem such as weather resistance and wear resistance of hydrophobic antifouling polyester, also can well solve this kind of problem that wastes time and energy.
The invention provides a kind of preparation method of fluorine-containing PET-PTT copolyesters, be divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction; Concrete steps are:
Step 1): adopt fluorine-containing terephthalic acid and ethylene glycol as raw material, add inhibitor, the add-on of inhibitor is 0.01% ~ 0.05% of described fluorine-containing terephthalic acid weight, carries out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure ~ 0.4MPa, and temperature is at 230 ~ 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer, continue to vacuumize, be steadily evacuated to below absolute pressure 1KPa by normal pressure, temperature controls at 250 ~ 270 DEG C, carrying out prepolymerization reaction, 1 ~ 2 hour reaction times, is prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.3dL/g ~ 0.4dL/g;
Step 2): adopt terephthalic acid and 1,3-PD as raw material, after being made into uniform sizing material, carry out esterification again; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure ~ 0.3MPa, and temperature is at 250 ~ 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer, continue to vacuumize, be steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, carrying out prepolymerization reaction, 1 ~ 2 hour reaction times, is prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.4dL/g ~ 0.5dL/g;
Step 3): by step 1) in obtained precondensation product, step 2) in obtained precondensation product, catalyzer and stablizer add in reaction unit, stir, then under 270 ~ 280 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 100Pa, react 1 ~ 5 hour, being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.
Method of the present invention obtains a kind of fluorine-containing PET-PTT copolyesters, and refer to the copolyesters of fluorine-containing ethylene glycol terephthalate and propylene glycol ester terephthalate, its general structure is
Or
Wherein m=60 ~ 100, n=40 ~ 80.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described fluorine-containing terephthalic acid and the mol ratio of ethylene glycol are 1:1.3 ~ 2.0; Described terephthalic acid and 1,3-PD mol ratio are 1:1.3 ~ 2.0; Described step 3) in the step 1 that adds) obtained precondensation product and step 2) obtained precondensation product, its weight ratio is 0.1 ~ 0.9:0.9 ~ 0.1.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described fluorine-containing terephthalic acid is tetrafluoro terephthalic acid or 2,5-difluoro terephthalic acid.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described step 1) in catalyzer be selected from one in antimonous oxide, antimony glycol and antimony acetate, catalyst levels is 0.01% ~ 0.03% of described fluorine-containing terephthalic acid weight.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described step 2) in catalyzer be selected from one in tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, catalyst levels is 0.01% ~ 0.03% of described terephthalic acid weight.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described step 3) in catalyzer be selected from one in tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, catalyst levels is step 3) in added precondensation total product weight 0.01% ~ 0.05%.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described step 3) in stablizer be selected from one in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, stabilizing agent dosage is step 3) in added precondensation total product weight 0.01% ~ 0.05%.
The preparation method of a kind of fluorine-containing PET-PTT copolyesters as above, described inhibitor is the one in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom in the phenyl ring due to di-carboxylic acid used, the electronegativity of fluorine atom is large, in the conjugative effect of esterification stage fluorine atom, the acidity of di-carboxylic acid is strengthened, cause the activity of carboxyl in di-carboxylic acid to increase simultaneously, speed of response is accelerated, and speed of response increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation, particularly generate the end-cap product of alkene and aldehyde, constrain the increase of molecular weight of product; From experimental result, if do not add inhibitor, the molecular weight of polyesters of synthesis is on the low side, can not meet the demand of spinning and film forming; The speed added for controlling the esterification stage of inhibitor, decreases side reaction, improves the molecular weight of product, make to meet spinning requirement.
Usually, it is the hydrogen ion that ionized out by the di-carboxylic acid used catalyzer as esterification in polyester esterification process, carry out self-catalyzed reaction, by regulating the temperature of esterification, pressure and the micromolecular speed ejecting its esterification of control, but the prerequisite of carrying out esterification under certain temperature of reaction and pressure, just will can carry out esterification.When temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thus affect follow-up technique.If the small molecules in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, due to the conjugative effect of fluorine, at esterification stage fluorine atom, the acidity of di-carboxylic acid is strengthened, cause the activity of carboxyl in di-carboxylic acid to increase, speed of response is accelerated, and side reaction increases simultaneously, be difficult to control, and then affect the growth of molecular weight of product, therefore add inhibitor, namely by selecting metal oxide used to regulate.Described metal oxide can dissociate by the following two kinds mode:
Here M is metal ion, if the electronegativity of M is quite large, has stronger magnetism, O-H key so just can be made to weaken to the electron pair of oxonium ion, is conducive to reacting dissociation; On the contrary, if the electronegativity of M is little, so just alkali center will be generated.M-O-H is similar with amphoteric substance, when there being alkaline matter to exist, reacting and the mode by acid dissociation being carried out; And when acidic substance exist, then undertaken by the mode of alkali formula ionization.The M-O of reversed reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid sites, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in O ion then relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, and intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and metal ion electronegativity is less, and negative charge density is larger.So, acidity and the alkalescence of metal oxide have just all connected with the electronegativity of metal ion, and the oxide compound that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is then alkalescence.
In the esterification stage of the present invention, reaction end reaches theoretical value more than 90% by the water quantity of distillate produced actual in esterification to be grasped.Theoretical value is the quantity of distillate by gained water during chemical equation complete reaction.Because esterification is originally as reversible reaction, moreover raw material has residual in transport pipe, and along with the carrying out reacted, the viscosity of system increases, and the shipwreck that esterification can be caused to produce is therefrom to discharge.
Final minification of the present invention gathers in step of reaction, and final minification gathers the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value to be grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and the determination of setting numerical value can by obtaining the analysis of polyester slice.
The fluorine-containing PET-PTT copolyesters of gained of the present invention, due to the introducing of fluorine atom, improves super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, has huge prospect in the working suit manufacture of the working suit born dirty and some special industry.
Beneficial effect:
1, obtained copolyesters contain fluorine atoms; due to the strong electronegativity of fluorine; high C-F bond energy and make the copolyesters synthesized also have well heat-resisting, ageing-resistant except promoting the performance of conventional polyester further to the shielding protection effect of carbochain, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction, also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, extend range of application.
2, the speed of esterification can be controlled in polyester esterification process by inhibiting, reduce the generation of side reaction.
3, the fluorine-containing PET-PTT copolyester section of gained can direct fabrics, film forming.
4, gained fluorine-containing PET-PTT copolyesters has good thermostability and workability.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The fluorine-containing PET-PTT copolyesters of one of the present invention, refer to the copolyesters of fluorine-containing ethylene glycol terephthalate and propylene glycol ester terephthalate, its general structure is
Or
Wherein m=60 ~ 100, n=40 ~ 80.
Embodiment 1
A preparation method for fluorine-containing PET-PTT copolyesters, is divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction.Concrete steps are:
Step 1): adopt mol ratio be the tetrafluoro terephthalic acid of 1:1.3 and ethylene glycol as raw material, add the magnesium oxide of 0.01% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.4MPa, and temperature is at 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add the catalytic antimony trioxide, continue to vacuumize, system pressure controls at below absolute pressure 1KPa, and temperature controls, at 260 DEG C, to carry out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein the consumption of the catalytic antimony trioxide is 0.01% of tetrafluoro terephthalic acid weight used.
Step 2): adopt mol ratio be the terephthalic acid of 1:1.3 and 1,3-PD as raw material, carrying out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.3MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer tetrabutyl titanate, continue to vacuumize, system pressure controls at below absolute pressure 500Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein catalyzer tetrabutyl titanate consumption is 0.01% of terephthalic acid weight used.
Step 3): by step 1) in obtained precondensation product and step 2) in obtained precondensation product by weight for 0.1:0.9 joins in reaction unit, add the stablizer triphenylphosphate of the catalyzer tetrabutyl titanate of 0.01% of precondensation total product weight and 0.01% of precondensation total product weight simultaneously, stir, then under 270 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 100Pa, and being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PET-PTT copolyester section.
Embodiment 2
A preparation method for fluorine-containing PET-PTT copolyesters, is divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction.Concrete steps are:
Step 1): adopt mol ratio be 2, the 5-difluoro terephthalic acids of 1:1.5 and ethylene glycol as raw material, add the silicon oxide of 0.03% of 2,5-difluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.3MPa, and temperature is at 245 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyst glycol antimony, continue to vacuumize, system pressure controls at below absolute pressure 800Pa, and temperature controls, at 260 DEG C, to carry out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein the consumption of catalyst glycol antimony is 0.01% of 2,5-difluoro terephthalic acid weight used.
Step 2): adopt mol ratio be the terephthalic acid of 1:1.5 and 1,3-PD as raw material, carrying out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.3MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer metatitanic acid four isopropyl ester, continue to vacuumize, system pressure controls at below absolute pressure 400Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein catalyzer metatitanic acid four isopropyl ester consumption is 0.01% of terephthalic acid weight used.
Step 3): by step 1) in obtained precondensation product and step 2) in obtained precondensation product by weight for 0.2:0.8 joins in reaction unit, add the stablizer trimethyl phosphite 99 of catalyzer metatitanic acid four isopropyl ester of 0.02% of precondensation total product weight and 0.02% of precondensation total product weight simultaneously, stir, then under 275 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 80Pa, and being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PET-PTT copolyester section.
Embodiment 3
A preparation method for fluorine-containing PET-PTT copolyesters, is divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction.Concrete steps are:
Step 1): adopt mol ratio be the tetrafluoro terephthalic acid of 1:1.8 and ethylene glycol as raw material, add the calcium oxide of 0.05% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 240 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyst acetic acid antimony, continue to vacuumize, system pressure controls at below absolute pressure 600Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein the consumption of catalyst acetic acid antimony is 0.02% of tetrafluoro terephthalic acid weight used.
Step 2): adopt mol ratio be the terephthalic acid of 1:1.8 and 1,3-PD as raw material, carrying out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer tetraethyl titanate, continue to vacuumize, system pressure controls at below absolute pressure 400Pa, and temperature controls, at 260 DEG C, to carry out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein catalyzer tetraethyl titanate consumption is 0.02% of terephthalic acid weight used.
Step 3): by step 1) in obtained precondensation product and step 2) in obtained precondensation product by weight for 0.4:0.6 joins in reaction unit, add the stablizer trimethyl phosphite of the catalyzer tetraethyl titanate of 0.03% of precondensation total product weight and 0.03% of precondensation total product weight simultaneously, stir, then under 280 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 60Pa, and being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PET-PTT copolyester section.
Embodiment 4
A preparation method for fluorine-containing PET-PTT copolyesters, is divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction.Concrete steps are:
Step 1): adopt mol ratio be 2, the 5-difluoro terephthalic acids of 1:2.0 and ethylene glycol as raw material, add the manganese oxide of 0.04% of 2,5-difluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure, and temperature is at 230 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add the catalytic antimony trioxide, continue to vacuumize, system pressure controls at below absolute pressure 500Pa, and temperature controls, at 270 DEG C, to carry out prepolymerization reaction, reacts 1 hour, obtains precondensation product; Wherein the consumption of the catalytic antimony trioxide is 0.02% of 2,5-difluoro terephthalic acid weight used.
Step 2): adopt mol ratio be the terephthalic acid of 1:2.0 and 1,3-PD as raw material, carrying out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure, and temperature is at 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer tetraethyl titanate, continue to vacuumize, system pressure controls at below absolute pressure 300Pa, and temperature controls, at 270 DEG C, to carry out prepolymerization reaction, reacts 1 hour, obtains precondensation product; Wherein catalyzer tetraethyl titanate consumption is 0.02% of terephthalic acid weight used.
Step 3): by step 1) in obtained precondensation product and step 2) in obtained precondensation product by weight for 0.7:0.3 joins in reaction unit, add the stablizer triphenylphosphate of the catalyzer tetraethyl titanate of 0.05% of precondensation total product weight and 0.05% of precondensation total product weight simultaneously, stir, then under 275 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 50Pa, and being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PET-PTT copolyester section.
Embodiment 5
A preparation method for fluorine-containing PET-PTT copolyesters, is divided into esterification stage, prepolymerization reaction stage and final minification to gather step of reaction.Concrete steps are:
Step 1): adopt mol ratio be the tetrafluoro terephthalic acid of 1:1.6 and ethylene glycol as raw material, add the zinc oxide of 0.03% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 240 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyst glycol antimony, continue to vacuumize, system pressure controls at below absolute pressure 800Pa, and temperature controls, at 250 DEG C, to carry out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein the consumption of catalyst glycol antimony is 0.02% of tetrafluoro terephthalic acid weight used.
Step 2): adopt mol ratio be the terephthalic acid of 1:1.6 and 1,3-PD as raw material, carrying out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer tetrabutyl titanate, continue to vacuumize, system pressure controls at below absolute pressure 300Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein catalyzer tetrabutyl titanate consumption is 0.02% of terephthalic acid weight used.
Step 3): by step 1) in obtained precondensation product and step 2) in obtained precondensation product by weight for 0.9:0.1 joins in reaction unit, add the stablizer trimethyl phosphite 99 of the catalyzer tetraethyl titanate of 0.02% of precondensation total product weight and 0.02% of precondensation total product weight simultaneously, stir, then under 270 DEG C of temperature condition, system pressure controls to carry out whole polycondensation at below 100Pa, and being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PET-PTT copolyester section.