CN103524722B - A kind of fluorine-containing PBT atactic polyester and preparation method thereof - Google Patents
A kind of fluorine-containing PBT atactic polyester and preparation method thereof Download PDFInfo
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- CN103524722B CN103524722B CN201310445644.7A CN201310445644A CN103524722B CN 103524722 B CN103524722 B CN 103524722B CN 201310445644 A CN201310445644 A CN 201310445644A CN 103524722 B CN103524722 B CN 103524722B
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Abstract
The present invention relates to a kind of fluorine-containing PBT atactic polyester and preparation method thereof, this fluorine-containing PBT atactic polyester adopts tetrafluoro terephthalic acid, terephthalic acid and BDO as raw material, in nitrogen atmosphere, under condition of negative pressure, temperature controls to carry out esterification at 160 ~ 220 DEG C; Rough vacuum, 260 ~ 270 DEG C of conditions carry out prepolymerization reaction; Then continue to be evacuated to absolute pressure and be less than 100Pa, temperature of reaction controls to carry out whole polycondensation at 270 ~ 275 DEG C, thus obtained fluorine-containing PBT atactic polyester.The fluorine-containing PBT atactic polyester of gained of the present invention has good thermostability and workability, can be directly used in spinning, film forming, injection moulding etc.Due to the introducing of fluorine atom, improve super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, in the working suit manufacture of the working suit born dirty and some special industry, have huge application prospect.
Description
Technical field
The present invention relates to a kind of fluorine-containing PBT atactic polyester and preparation method thereof, particularly relate to fluorine-containing PBT atactic polyester that a kind of benzene ring hydrogen replaced by fluorine 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 polyamide (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.
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 PBT atactic polyester and preparation method thereof, particularly relate to fluorine-containing PBT atactic polyester that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.Fluorine-containing PBT atactic polyester of the present invention introduces fluorine atom on the main chain of polymkeric substance, and the fluorine-containing PBT atactic polyester section of preparing can be directly used in spinning, film forming, injection moulding etc.Fluorine-containing PBT atactic polyester described in the present invention is by tetrafluoro terephthalic acid, terephthalic acid and butyleneglycol, through the fluorine-containing PBT atactic polyester that esterification and polycondensation obtain.This fluorine-containing PBT atactic polyester section can direct fabrics, film forming, injection moulding etc.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.
The present invention for raw material, by certain proportioning, carries out esterification and polycondensation with terephthalic acid, BDO, tetrafluoro terephthalic acid, thus prepares fluorine-containing PBT atactic polyester.
The fluorine-containing PBT atactic polyester of one of the present invention, is characterized in that described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester obtained by tetrafluoro terephthalic acid, terephthalic acid and butyleneglycol copolymerization; Described tetrafluoro terephthalic acid has following structural formula:
Realizing concrete technical scheme of the present invention is: a kind of fluorine-containing copolyesters and preparation method thereof, and be divided into esterification and polycondensation two step, concrete steps are as follows:
The esterification stage: employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.Without the need to extra catalyst in esterification, nitrogen atmosphere, under condition of negative pressure, pressure-controlling is carried out being less than absolute pressure 1KPa, and temperature controls at 160 ~ 220 DEG C, and the reaction times is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
The polycondensation stage comprises polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage:
In esterification products, add catalyzer and stablizer, under the condition of negative pressure, start polycondensation, this staged pressure controls at below absolute pressure 500Pa, and temperature controls at 260 ~ 270 DEG C, and the reaction times is 40 ~ 60 minutes.
Polycondensation high vacuum stage of Fig:
Above-mentioned material is after the rough vacuum stage, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, temperature of reaction controls at 270 ~ 275 DEG C, in 3 ~ 4 hours reaction times, to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PBT atactic polyester as above, described starting monomer is terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG).Its mol ratio is: PTA:FPTA=1: 0.02 ~ 1; (PTA+FPTA): BG=1: 1.4 ~ 2.
The preparation method of a kind of fluorine-containing PBT atactic polyester as above, described catalyzer is selected from the one in tetrabutyl titanate, metatitanic acid four isopropyl ester, tetraethyl titanate, stannous acetate, dibutyltin diacetate, and catalyst levels is 0.01% ~ 0.03% of di-carboxylic acid gross weight used.
The preparation method of a kind of fluorine-containing PBT atactic polyester as above, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99, trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of di-carboxylic acid gross weight used.
The preparation method of a kind of fluorine-containing PBT atactic polyester as above, when tetrafluoro terephthalic acid and terephthalic acid mol ratio are 0.5 ~ 1:1, described esterification also adds the one in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide, as inhibitor, add-on is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid and terephthalic acid gross weight.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
In polycondensation high vacuum stage of Fig of the present invention, the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value is 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 PBT atactic polyester 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 trevira, at waterproof garment, has huge prospect in the working suit manufacture of the working suit born dirty and some special industry.
The invention has the beneficial effects as follows:
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 fluorine-containing copolyester section of gained can direct fabrics, film forming, injection moulding etc.
3. the fluorine-containing copolyesters of gained has good thermostability and workability.
4. esterification process can control the speed of esterification by adding agent of drawing up, and reduces the generation of side reaction.
5. preparation method of the present invention is simple, is easy to control, favorable reproducibility.
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 PTT atactic polyester of one of the present invention, is characterized in that described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester obtained by tetrafluoro terephthalic acid, terephthalic acid and butyleneglycol copolymerization; Described tetrafluoro terephthalic acid has following structural formula:
Embodiment 1
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1: 0.02; (PTA+FPTA): BG=1: 1.4.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 1KMa, and temperature controls at 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer triphenylphosphate of the catalyzer tetrabutyl titanate of 0.01% of diprotic acid weight used and 0.01% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 500Pa in absolute pressure, temperature controls at 265 DEG C, and the reaction times is 60 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction controls at 270 DEG C, 4 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 2
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.04; (PTA+FPTA): BG=1: 1.5.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 900Pa, and temperature controls at 210 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer triphenylphosphate of catalyzer metatitanic acid four isopropyl ester of 0.01% of diprotic acid weight used and 0.01% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 60 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 90Pa, and temperature of reaction controls at 270 DEG C, 4 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 3
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.1; (PTA+FPTA): BG=1: 1.6.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 800Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite 99 of the catalyzer tetraethyl titanate of 0.02% of diprotic acid weight used and 0.02% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 265 DEG C, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and temperature of reaction controls at 275 DEG C, 3.5 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 4
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.2; (PTA+FPTA): BG=1: 1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 700Pa, and temperature controls at 180 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite 99 of the sub-tin of catalyst acetic acid of 0.02% of diprotic acid weight used and 0.02% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and temperature of reaction controls at 273 DEG C, 3.5 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 5
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.4; (PTA+FPTA): BG=1: 2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 600Pa, and temperature controls at 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite of the catalyzer dibutyltin diacetate of 0.03% of diprotic acid weight used and 0.03% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 40 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and temperature of reaction controls at 270 DEG C, 3 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 6
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.5; (PTA+FPTA): BG=1: 1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 500Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer triphenylphosphate of the catalyzer tetrabutyl titanate of 0.03% of diprotic acid weight used and 0.03% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 40 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 30Pa, and temperature of reaction controls at 275 DEG C, 3 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 7
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as Third monomer, adds the magnesium oxide of 0.01% of di-carboxylic acid gross weight used simultaneously, carries out esterification.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.5; (PTA+FPTA): BG=1: 1.4.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 1KMa, and temperature controls at 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer triphenylphosphate of the catalyzer tetrabutyl titanate of 0.01% of diprotic acid weight used and 0.01% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 500Pa in absolute pressure, temperature controls at 265 DEG C, and the reaction times is 60 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction controls at 270 DEG C, 4 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 8
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as Third monomer, adds the silicon oxide of 0.02% of di-carboxylic acid gross weight used simultaneously, carries out esterification.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.6; (PTA+FPTA): BG=1: 1.5.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 900Pa, and temperature controls at 210 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer triphenylphosphate of catalyzer metatitanic acid four isopropyl ester of 0.01% of diprotic acid weight used and 0.01% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 55 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 90Pa, and temperature of reaction controls at 270 DEG C, 4 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 9
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as Third monomer, adds the calcium oxide of 0.03% of di-carboxylic acid gross weight used simultaneously, carries out esterification.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.8; (PTA+FPTA): BG=1: 1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 800Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite 99 of the catalyzer tetraethyl titanate of 0.02% of diprotic acid weight used and 0.02% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 265 DEG C, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and temperature of reaction controls at 275 DEG C, 3.5 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 10
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as Third monomer, adds the zinc oxide of 0.04% of di-carboxylic acid gross weight used simultaneously, carries out esterification.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.8; (PTA+FPTA): BG=1: 2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 700Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite 99 of the sub-tin of catalyst acetic acid of 0.03% of diprotic acid weight used and 0.03% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and temperature of reaction controls at 273 DEG C, 3.5 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Embodiment 11
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as Third monomer, adds the manganese oxide of 0.05% of di-carboxylic acid gross weight used simultaneously, carries out esterification.In raw material, terephthalic acid (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 1; (PTA+FPTA): BG=1: 2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 500Pa, and temperature controls at 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, the stablizer trimethyl phosphite of the catalyzer dibutyltin diacetate of 0.03% of diprotic acid weight used and 0.03% of diprotic acid weight used is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 265 DEG C, and the reaction times is 40 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and temperature of reaction controls at 275 DEG C, 3 hours reaction times.Polycondensation to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PBT atactic polyester section.
Claims (4)
1. a preparation method for fluorine-containing PBT atactic polyester, is characterized in that: the preparation method of described fluorine-containing PBT atactic polyester is divided into esterification and polycondensation two step; Concrete steps are:
Described esterification:
Employing terephthalic acid, BDO are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid carries out esterification after being made into uniform sizing material as Third monomer; Without the need to extra catalyst in esterification, nitrogen atmosphere, under condition of negative pressure, pressure-controlling is carried out being less than absolute pressure 1KPa, temperature controls at 160 ~ 220 DEG C, and the reaction times is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end; Tetrafluoro terephthalic acid and terephthalic acid mol ratio are 0.5 ~ 1:1; Described esterification adds magnesium oxide, silicon oxide, calcium oxide, zinc oxide or manganese oxide, and add-on is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid and terephthalic acid gross weight;
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
In the described polycondensation rough vacuum stage, add catalyzer and stablizer in described esterification products, under the condition of negative pressure, start polycondensation, described negative pressure refers to below absolute pressure 500Pa, and temperature controls at 260 ~ 270 DEG C, and the reaction times is 40 ~ 60 minutes;
Described polycondensation high vacuum stage of Fig, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, temperature of reaction controls at 270 ~ 275 DEG C, in 3 ~ 4 hours reaction times, to be as the criterion judgement reaction end with reactor agitator motor power or in-line viscometer reading;
Described tetrafluoro terephthalic acid has following structural formula:
2. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 1, it is characterized in that, the total amount of terephthalic acid and tetrafluoro terephthalic acid and the mol ratio of BDO are 1:1.4 ~ 2.
3. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 1, it is characterized in that, described catalyzer is selected from the one in tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, stannous acetate, dibutyltin diacetate, and catalyst levels is 0.01% ~ 0.03% of tetrafluoro terephthalic acid and terephthalic acid gross weight.
4. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 1, it is characterized in that, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99, trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of tetrafluoro terephthalic acid and terephthalic acid gross weight.
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| CN113151927B (en) * | 2021-05-24 | 2023-01-20 | 太仓市洪宇新材料科技有限公司 | Colored fluorine-containing antibacterial parallel composite PBT (polybutylene terephthalate) fiber and preparation method thereof |
| CN113604900A (en) * | 2021-05-24 | 2021-11-05 | 太仓市洪宇新材料科技有限公司 | Production process method of fluorine-containing antibacterial PBT fiber |
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