CN103467720B - Fluorine-containing poly(ethylene terephthalate) (PET)-poly(butylene terephthalate) (PBT) copolyester and preparation method thereof - Google Patents
Fluorine-containing poly(ethylene terephthalate) (PET)-poly(butylene terephthalate) (PBT) copolyester and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorine-containing poly(ethylene terephthalate) (PET)-poly(butylene terephthalate) (PBT) copolyester and a preparation method thereof, and especially relates to a copolyester of which a main chain comprises fluorine-containing PET and PBT structures, and a preparation method of the copolyester. Fluorine-containing terephthalic acid, terephthalic acid, glycol and 1,4-butylene glycol are used as main raw materials; in a nitrogen atmosphere, fluorine-containing terephthalic acid, glycol and an inhibitor undergo an esterification reaction and the esterification product undergoes a pre-polycondensation reaction to produce a pre-polycondensation product, and terephthalic acid and 1,4-butylene glycol undergo an esterification reaction and the esterification product undergoes a pre-polycondensation reaction to produce a pre-polycondensation product; and the above pre-polycondensation products undergo a final polycondensation reaction to produce the fluorine-containing PET-PBT copolyester. The fluorine-containing PET-PBT copolyester has good heat stability and machinability, and can be directly used for spinning and film formation. Through use of fluorine atoms, super-hydrophobic, hydrophobic, oleophobic and antifouling performances of a polyester material are improved. The fluorine-containing PET-PBT copolyester has a wide application prospect in manufacture of waterproof and antifouling working clothes and special industry working clothes.
Description
Technical field
The present invention relates to a kind of fluorine-containing PET-PBT copolyesters and preparation method thereof, particularly relate to copolyesters that a kind of main chain is made up of fluorine-containing PET and PBT 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.
Polybutylene terephthalate (PBT) is a kind of crystallinity line style saturated polyester, have high temperature resistant, moisture-proof, electrical insulation capability are good, oil resistant, resistance to chemical attack, the shaping feature such as soon.Its some application examples in the industry demonstrate its superiority that can not be substituted in some aspects, now it has become the fifth-largest general engineering plastic after polymeric amide (PA), polycarbonate (PC), polyoxymethylene (POM) and Noryl (MPPO), is widely used in automotive industry, electronic apparatus industry, food medicine equipment, wrapping material, environmental engineering, communication equipment, Sport & Casual apparatus etc.Deepen constantly along with to the research of PBT stuctures and properties, not only develop different stage, dissimilar engineering plastics, as HI high impact, heat-resisting, fire-retardant etc., and its application in synthon is more and more paid attention to.PBT fibrous elasticity is superior, soft, and dyeing is convenient, has the advantage of terylene, polyamide fibre, spandex three concurrently.
PET polyester becomes the main raw material of textile industry due to the mechanical property of its excellence, but the shortcoming such as its dyeability and rebound resilience difference limits its further application.The dyeability of PBT polyester and rebound resilience are extremely excellent, but forming difficulty in fibre spinning process, woven into fabric body bone is not endured.In order to comprehensive PET and PBT fiber advantage separately, PET-PBT copolyesters and conjugated fibre etc. arise at the historic moment.PET-PBT copolyesters takes into account both advantage, is with a wide range of applications in the industry such as clothes and carpet.
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 CN 101139434A, 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-PBT copolyesters and preparation method thereof, particularly relate to fluorine-containing PET and PBT copolyesters and preparation method thereof on a kind of main chain.Fluorine-containing PET-PBT copolyesters of the present invention introduces fluorine atom on the main chain of polymkeric substance, and the fluorine-containing PET-PBT copolyesters sheet prepared can be directly used in spinning, film forming etc.Fluorine-containing PET-PBT copolyesters described in the present invention is the copolyesters obtained through copolymerization by fluorine-containing ethylene glycol terephthalate and mutual-phenenyl two acid bromide two alcohol ester, and this fluorine-containing PET-PBT 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-PBT 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, after being made into uniform sizing material, carry out esterification; 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 BDO as raw material, after being made into uniform sizing material, carry out esterification; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 1KPa, and temperature is at 180 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer, continue to vacuumize, pressure-controlling is at below absolute pressure 500Pa, and temperature controls, at 260 ~ 270 DEG C, to carry out prepolymerization reaction, and 2 ~ 3 hours reaction times was prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.5dL/g ~ 0.6dL/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 ~ 6 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-PBT copolyesters, and refer to the copolyesters of fluorine-containing ethylene glycol terephthalate and mutual-phenenyl two acid bromide two alcohol ester, its general structure is
Wherein m=50 ~ 90, n=40 ~ 80.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described fluorine-containing terephthalic acid and the mol ratio of ethylene glycol are 1:1.4 ~ 2.0; Described terephthalic acid and BDO mol ratio are 1:1.4 ~ 2.0; Described step 3) in step 1) 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-PBT 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-PBT 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-PBT copolyesters as above, described step 2) in catalyzer be selected from one in tetrabutyl titanate, metatitanic acid four isopropyl ester and tetraethyl titanate, catalyst levels is 0.01% ~ 0.03% of described terephthalic acid weight.
The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described step 3) in catalyzer be selected from one in tetrabutyl titanate, metatitanic acid four isopropyl ester and 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-PBT 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-PBT 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.
The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, the add-on of described inhibitor is 0.01% ~ 0.05% of described fluorine-containing terephthalic acid weight.
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-PBT 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-PBT copolyester section of gained can direct fabrics, film forming.
4, gained fluorine-containing PET-PBT 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-PBT copolyesters of one of the present invention, refer to the copolyesters of fluorine-containing ethylene glycol terephthalate and mutual-phenenyl two acid bromide two alcohol ester, its general structure is
Wherein m=50 ~ 90, n=40 ~ 80.
Embodiment 1
A preparation method for fluorine-containing PET-PBT 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 1:1.4 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 1:1.4 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 1KPa, and temperature is at 220 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, pressure-controlling is at below absolute pressure 500Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, in 3 hours reaction times, 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-PBT copolyester section.
Embodiment 2
A preparation method for fluorine-containing PET-PBT 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 BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 900Pa, and temperature is at 210 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, pressure-controlling is at below absolute pressure 500Pa, and temperature controls, at 260 DEG C, to carry out prepolymerization reaction, in 3 hours reaction times, 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-PBT copolyester section.
Embodiment 3
A preparation method for fluorine-containing PET-PBT 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 BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 800Pa, and temperature is at 200 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, pressure-controlling is at below absolute pressure 400Pa, and temperature controls, at 270 DEG C, to carry out prepolymerization reaction, in 2.5 hours reaction times, 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-PBT copolyester section.
Embodiment 4
A preparation method for fluorine-containing PET-PBT 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 BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 600Pa, and temperature is at 180 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, pressure-controlling is at below absolute pressure 300Pa, and temperature controls, at 270 DEG C, to carry out prepolymerization reaction, in 2 hours reaction times, 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-PBT copolyester section.
Embodiment 5
A preparation method for fluorine-containing PET-PBT 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 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 1:1.8 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 600Pa, and temperature is at 200 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, pressure-controlling is at below absolute pressure 300Pa, and temperature controls, at 265 DEG C, to carry out prepolymerization reaction, in 2.5 hours reaction times, 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-PBT copolyester section.
Claims (6)
1. a preparation method for fluorine-containing PET-PBT copolyesters, is characterized in that: the preparation method of described fluorine-containing PET-PBT copolyesters, is 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, and add inhibitor, the add-on of described 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 BDO as raw material, after being made into uniform sizing material, carry out esterification; Esterification is carried out under condition of negative pressure, and pressure-controlling is being less than absolute pressure 1KPa, and temperature is at 180 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Add catalyzer, continue to vacuumize, pressure-controlling is at below absolute pressure 500Pa, and temperature controls, at 260 ~ 270 DEG C, to carry out prepolymerization reaction, and 2 ~ 3 hours reaction times was prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.5dL/g ~ 0.6dL/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 ~ 6 hour, being as the criterion with reactor agitator motor power or in-line viscometer reading judges that final minification gathers reaction end;
Described inhibitor is the one in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide.
2. the method prepared of a kind of fluorine-containing PET-PBT copolyesters according to claim 1, it is characterized in that, described fluorine-containing terephthalic acid is tetrafluoro terephthalic acid or 2,5-difluoro terephthalic acid.
3. the preparation method of a kind of fluorine-containing PET-PBT copolyesters according to claim 1, it is characterized in that, described fluorine-containing terephthalic acid and ethylene glycol mol ratio are 1:1.4 ~ 2.0; Described terephthalic acid and BDO mol ratio are 1:1.4 ~ 2.0; Described step 3) in, step 1) obtained precondensation product and step 2) weight ratio of precondensation product that obtains is 0.1 ~ 0.9:0.9 ~ 0.1.
4. the preparation method of a kind of fluorine-containing PET-PBT copolyesters according to claim 1, it is characterized in that, 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; Described step 2) in catalyzer be selected from one in tetrabutyl titanate, titanium isopropylate and tetraethyl titanate, catalyst levels is 0.01% ~ 0.03% of described terephthalic acid weight; Described step 3) in catalyzer be selected from one in tetrabutyl titanate, titanium isopropylate and tetraethyl titanate, catalyst levels is step 3) in added precondensation total product weight 0.01% ~ 0.05%.
5. the preparation method of a kind of fluorine-containing PET-PBT copolyesters according to claim 1, 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%.
6. the fluorine-containing PET-PBT copolyesters that obtains of preparation method as claimed in claim 1, is characterized in that: described fluorine-containing PET-PBT copolyesters refers to the copolyesters that main chain is made up of fluorine-containing PET and PBT structure, and the general structure of its products therefrom is:
Or
Wherein m=50 ~ 90, n=40 ~ 80.
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| CN102816320A (en) * | 2012-08-24 | 2012-12-12 | 常州乐凯高性能材料有限公司 | Preparation method of polyester chip for optical film |
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| CN102816320A (en) * | 2012-08-24 | 2012-12-12 | 常州乐凯高性能材料有限公司 | Preparation method of polyester chip for optical film |
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