CN103524722A - Fluorine-containing PBT (polybutylene terephthalate) random copolyester and preparation method thereof - Google Patents
Fluorine-containing PBT (polybutylene terephthalate) random copolyester and preparation method thereof Download PDFInfo
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- CN103524722A CN103524722A CN201310445644.7A CN201310445644A CN103524722A CN 103524722 A CN103524722 A CN 103524722A CN 201310445644 A CN201310445644 A CN 201310445644A CN 103524722 A CN103524722 A CN 103524722A
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- fluorine
- terephthalic acid
- esterification
- polycondensation
- containing pbt
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 98
- 239000011737 fluorine Substances 0.000 title claims abstract description 91
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001634 Copolyester Polymers 0.000 title abstract description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 title description 49
- -1 polybutylene terephthalate Polymers 0.000 title description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 119
- 238000005886 esterification reaction Methods 0.000 claims abstract description 100
- 229920000728 polyester Polymers 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 52
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims description 99
- 230000035484 reaction time Effects 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 13
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 10
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 4
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 101000877589 Homo sapiens Protein farnesyltransferase/geranylgeranyltransferase type-1 subunit alpha Proteins 0.000 description 48
- 102100035480 Protein farnesyltransferase/geranylgeranyltransferase type-1 subunit alpha Human genes 0.000 description 48
- 150000007520 diprotic acids Chemical class 0.000 description 23
- 239000000047 product Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 238000005453 pelletization Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 229920004935 Trevira® Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to fluorine-containing PBT random copolyester and a preparation method thereof. The preparation method comprises the steps as follows: tetrafluoroterephthalic acid, terephthalic acid and 1,4-butanediol are adopted as raw materials, and an esterification reaction is conducted at the temperature in a range of 160-220 DEG C under the negative pressure condition in a nitrogen atmosphere; a pre-polycondensation reaction is conducted at the temperature in a range of 260-270 DEG C under the condition of rough vacuum; and then vacuum pumping is conducted continuously till the absolute pressure is lower than 100Pa, and a final polycondensation reaction is conducted at the reaction temperature in a range of 270-275 DEG C, so that the fluorine-containing PBT random copolyester is prepared. According to the preparation method, the obtained fluorine-containing PBT random copolyester has the good heat stability and processibility and can be directly used for spinning, film formation, injection molding and the like. Fluorine atoms are introduced, so that super-hydrophobic, hydrophobic, oleophobic and stain-resistant properties of a polyester material are improved, and the fluorine-containing PBT random copolyester has great application prospects in manufacturing of water-proof clothes, stain-resistant work clothes and work clothes of certain particular industries.
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; as far back as twentieth century, just synthesized ethylene glycol terephthalate (PET) forties; and find that it has excellent performance, and be widely used in the fields such as weaving, packing, health care, automobile, electronic apparatus, safety precaution, environment protection.
Polybutylene terephthalate (PBT) is a kind of crystallinity line style saturated polyester, has that high temperature resistant, moisture-proof, electrical insulation capability are good, a feature such as oil resistant, resistance to chemical attack, moulding are fast.Its some application examples in industry demonstrate the superiority that it 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.Along with the research of PBT structure and performance is deepened constantly, not only develop different stage, dissimilar engineering plastics, as HI high impact, heat-resisting, fire-retardant etc., and its application aspect synthon is more and more paid attention to.PBT fibrous elasticity is superior, soft, and dyeing is convenient, has terylene, polyamide fibre, spandex three's advantage concurrently.
Along with social progress, the raising of living standards of the people, needs more and more higher to differential, the functionalization of trevira.Therefore also become particularly important of the modification of polyester, polyester modification object, except conventional polyester performance is optimized, is mainly to give 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 introduce fluorine atom in polymkeric substance, thereby improve the surface property of material, as hydro-oleophobicity and didirtresistance etc., and give polyester material various functions.Because fluoropolymer has low surface energy, low-friction coefficient and non-adhesivity conventionally, dust dirt such as is difficult to adhere at the characteristic, so the anti-soil wear resistance of fluoropolymer is good.And current fluoropolymer be take fluoroolefins base polymer as main (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. relatively lags behind.
Many scholars are studied fluorochemicals modified poly ester, and have obtained certain achievement.The mode of fluorochemicals modified poly ester is mainly by adding fluorine-containing end-capping reagent at present, or adds the fluorochemicalss such as Fluorinated dihydric alcohol, fluorine-containing diprotic acid to carry out modified poly ester as the 3rd monomer.In Chinese patent CN101139434A, adopt adding of fluorine-containing end-capping reagent, dimethyl isophthalate and butyleneglycol adopt ester-interchange method, add fluorine-containing end-capping reagent N-hydroxyethyl perfluor decoylamide, have prepared the low and polyester material that stain resistant performance 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.) utilize the principle of molecular designing, by adding the mode of Fluorinated dihydric alcohol copolymerization, p-phthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol terpolymer have been synthesized to the polyester of novel high fluorine content.This polyester has excellent performance and is applied to optical waveguide material.
Yet the polyester that these are contained to fluorine element is applied to there is certain limitation in weaving and wrapping material, subject matter is that the molecular weight of polyesters that contains fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art is mainly to give its water proof anti-soil function by the fluorine-containing rear Collator Mode of fabric at present, and the problem such as that the shortcoming of this class methods maximum is to be difficult to solve is ageing, weather resistance and wear resistance, and waste time and energy.
Therefore, develop fluorine-containing polyester for weave and super-hydrophobic, the hydrophobic and oil repellent of wrapping material, the modification of antifouling property will have important theory significance and using value.
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 has been introduced 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, the fluorine-containing PBT atactic polyester that process esterification and polycondensation obtain.This fluorine-containing PBT atactic polyester section can direct fabrics, film forming, injection moulding etc.And by copolymerization method, polyester is carried out to hydrophobic antifouling modification, can fundamentally solve the problems such as ageing, the weather resistance of hydrophobic antifouling polyester and wear resistance.
It is raw material that terephthalic acid, BDO, tetrafluoro terephthalic acid are take in the present invention, by certain proportioning, carries out esterification and polycondensation, thereby prepares fluorine-containing PBT atactic polyester.
A kind of fluorine-containing PBT atactic polyester of the present invention, is characterized in that described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester being 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, be divided into esterification and polycondensation two steps, and concrete steps are as follows:
The esterification stage: adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.In esterification without extra catalyst, nitrogen atmosphere, under condition of negative pressure, pressure-controlling is carried out being less than absolute pressure 1KPa, temperature is controlled at 160～220 ℃, the reaction times is 2～3 hours, what esterification water quantity of distillate reached theoretical value more than 90% is 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 is controlled at below absolute pressure 500Pa, and temperature is controlled at 260～270 ℃, and the reaction times is 40～60 minutes.
Polycondensation high vacuum stage of Fig:
Above-mentioned material is through rough vacuum after the stage, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, temperature of reaction is controlled at 270～275 ℃, 3～4 hours reaction times, with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
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 a kind of in tetrabutyl titanate, metatitanic acid four isopropyl esters, 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 a kind of 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 a kind of 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.On phenyl ring due to di-carboxylic acid used, there is fluorine atom, the electronegativity of fluorine atom is large, conjugative effect at esterification stage fluorine atom strengthens the acidity of di-carboxylic acid, 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, the end-blocking product that particularly generates alkene and aldehyde, has restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, has reduced side reaction, has improved the molecular weight of product, makes to meet spinning requirement.
Conventionally, in polyester esterification process, be that the hydrogen ion that ionizes out by di-carboxylic acid used is as the catalyzer of esterification, carry out self-catalyzed reaction, by regulating the temperature, pressure of esterification and micromolecularly ejecting the speed of controlling its esterification, yet the prerequisite of carrying out esterification is under certain temperature of reaction and pressure, just can carry out esterification.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby 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, conjugative effect due to 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 simultaneously, speed of response is accelerated, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the electron pair of oxonium ion is had to stronger magnetism, so just can make O-H key weaken, and is conducive to react dissociation; On the contrary, if the electronegativity of M is little, so just will generate alkali center.M-O-H is similar with amphoteric substance, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And when acidic substance exist, by the mode of alkali formula ionization, undertaken.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 relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, 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 just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the large oxide compound of electronegativity of metal ion is mainly acid, and what electronegativity was little is alkalescence.
Esterification of the present invention is in the stage, reaction end actual water quantity of distillate producing in esterification reach theoretical value 90% with on grasp.Theoretical value is the quantity of distillate of gained water while pressing chemical equation complete reaction.Due to esterification this as reversible reaction, moreover raw material has residually in transport pipe, and along with the carrying out of reaction, the viscosity of system increases, and can cause shipwreck that esterification produces 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 setting determining of numerical value can obtain by the analysis to polyester slice.
The fluorine-containing PBT atactic polyester of gained of the present invention is due to the introducing of fluorine atom, improved super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of trevira, at waterproof garment, in the working suit manufacture of the working suit bearing dirty and some special industry, has huge prospect.
The invention has the beneficial effects as follows:
1. the copolyesters contain fluorine atoms making; strong electronegativity due to fluorine; high C-F bond energy and the copolyesters that the shielding protection effect of carbochain makes to synthesize is also had except the performance of the traditional polyester of further lifting well heat-resisting, ageing-resistant, 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, have expanded range of application.
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 be controlled the speed of esterification by adding the 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, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of fluorine-containing PTT atactic polyester of the present invention, is characterized in that described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester being 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 steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1: 0.02; (PTA+FPTA): BG=1: 1.4.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 1KMa, and temperature is controlled at 220 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.01% the stablizer triphenylphosphate that adds 0.01% catalyzer metatitanic acid four butyl esters of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 500Pa, temperature is controlled at 265 ℃, 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 is controlled at 270 ℃, 4 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 2
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.04; (PTA+FPTA): BG=1: 1.5.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 900Pa, and temperature is controlled at 210 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.01% the stablizer triphenylphosphate that adds 0.01% catalyzer metatitanic acid four isopropyl esters of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 260 ℃, 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 is controlled at 270 ℃, 4 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 3
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.1; (PTA+FPTA): BG=1: 1.6.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 800Pa, and temperature is controlled at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.02% the stablizer trimethyl phosphite 99 that adds 0.02% catalyzer metatitanic acid tetra-ethyl ester of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 265 ℃, 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 is controlled at 275 ℃, 3.5 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 4
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.2; (PTA+FPTA): BG=1: 1.8.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 700Pa, and temperature is controlled at 180 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.02% the stablizer trimethyl phosphite 99 that adds the sub-tin of 0.02% catalyst acetic acid of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 260 ℃, 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 is controlled at 273 ℃, 3.5 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 5
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.4; (PTA+FPTA): BG=1: 2.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 600Pa, and temperature is controlled at 160 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.03% the stablizer trimethyl phosphite that adds 0.03% catalyzer dibutyltin diacetate of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 300Pa, temperature is controlled at 260 ℃, 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 is controlled at 270 ℃, 3 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 6
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopting terephthalic acid (PTA), BDO (BG) is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) carries out esterification after being made into uniform sizing material as the 3rd monomer.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.5; (PTA+FPTA): BG=1: 1.8.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 500Pa, and temperature is controlled at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.03% the stablizer triphenylphosphate that adds 0.03% catalyzer metatitanic acid four butyl esters of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 300Pa, temperature is controlled at 260 ℃, 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 is controlled at 275 ℃, 3 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 7
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as the 3rd monomer, adds 0.01% magnesium oxide of di-carboxylic acid gross weight used simultaneously, carries out esterification.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.5; (PTA+FPTA): BG=1: 1.4.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 1KMa, and temperature is controlled at 220 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.01% the stablizer triphenylphosphate that adds 0.01% catalyzer metatitanic acid four butyl esters of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 500Pa, temperature is controlled at 265 ℃, 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 is controlled at 270 ℃, 4 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 8
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as the 3rd monomer, adds 0.02% silicon oxide of di-carboxylic acid gross weight used simultaneously, carries out esterification.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.6; (PTA+FPTA): BG=1: 1.5.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 900Pa, and temperature is controlled at 210 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.01% the stablizer triphenylphosphate that adds 0.01% catalyzer metatitanic acid four isopropyl esters of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 260 ℃, 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 is controlled at 270 ℃, 4 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 9
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as the 3rd monomer, adds 0.03% calcium oxide of di-carboxylic acid gross weight used simultaneously, carries out esterification.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.8; (PTA+FPTA): BG=1: 1.8.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 800Pa, and temperature is controlled at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.02% the stablizer trimethyl phosphite 99 that adds 0.02% catalyzer metatitanic acid tetra-ethyl ester of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 265 ℃, 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 is controlled at 275 ℃, 3.5 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 10
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as the 3rd monomer, adds 0.04% zinc oxide of di-carboxylic acid gross weight used simultaneously, carries out esterification.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 0.8; (PTA+FPTA): BG=1: 2.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 700Pa, and temperature is controlled at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.03% the stablizer trimethyl phosphite 99 that adds the sub-tin of 0.03% catalyst acetic acid of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 400Pa, temperature is controlled at 260 ℃, 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 is controlled at 273 ℃, 3.5 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Embodiment 11
A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt terephthalic acid (PTA), 1,4-butyleneglycol (BG) is main raw material, fluorine-containing properties-correcting agent tetrafluoro terephthalic acid (FPTA) is made into uniform sizing material as the 3rd monomer, adds 0.05% manganese oxide of di-carboxylic acid gross weight used simultaneously, carries out esterification.Terephthalic acid in raw material (PTA), tetrafluoro terephthalic acid (FPTA), BDO (BG) mol ratio are: PTA: FPTA=1: 1; (PTA+FPTA): BG=1: 2.In esterification, without extra catalyst, in nitrogen atmosphere, under condition of negative pressure, pressure-controlling is being less than absolute pressure 500Pa, and temperature is controlled at 160 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is reaction end.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.03% the stablizer trimethyl phosphite that adds 0.03% catalyzer dibutyltin diacetate of diprotic acid weight used and diprotic acid weight used in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is controlled at absolute pressure and is less than 300Pa, temperature is controlled at 265 ℃, 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 is controlled at 275 ℃, 3 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing PBT atactic polyester section.
Claims (6)
1. a fluorine-containing PBT atactic polyester, is characterized in that: described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester being obtained by tetrafluoro terephthalic acid, terephthalic acid and butyleneglycol copolymerization; Described tetrafluoro terephthalic acid has following structural formula:
2. the preparation method of a kind of fluorine-containing PBT atactic polyester as claimed in claim 1, is characterized in that: the preparation method of described fluorine-containing PBT atactic polyester is divided into esterification and polycondensation two steps; Concrete steps are:
Described esterification:
Adopting terephthalic acid, BDO is main raw material, and fluorine-containing properties-correcting agent tetrafluoro terephthalic acid carries out esterification after being made into uniform sizing material as the 3rd monomer.In esterification without extra catalyst, nitrogen atmosphere, under condition of negative pressure, pressure-controlling is carried out being less than absolute pressure 1KPa, temperature is controlled at 160～220 ℃, the reaction times is 2～3 hours, what esterification water quantity of distillate reached theoretical value more than 90% is reaction end;
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, starts polycondensation, and described negative pressure refers to below absolute pressure 500Pa, and temperature is controlled at 260～270 ℃, 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 is controlled at 270～275 ℃, 3～4 hours reaction times, with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
3. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 2, it is characterized in that, the mol ratio of terephthalic acid and tetrafluoro terephthalic acid is 1: 0.02～1, and the total amount of terephthalic acid and tetrafluoro terephthalic acid and the mol ratio of 1.4-butyleneglycol are 1: 1.4～2.
4. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 2, it is characterized in that, described catalyzer is selected from a kind of in tetrabutyl titanate, metatitanic acid four isopropyl esters, tetraethyl titanate, stannous acetate, dibutyltin diacetate, and catalyst levels is 0.01%～0.03% of tetrafluoro terephthalic acid and terephthalic acid gross weight.
5. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 2, it is characterized in that, described stablizer is selected from a kind of 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.
6. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 2, it is characterized in that, when tetrafluoro terephthalic acid and terephthalic acid mol ratio are 0.5～1: in the time of 1, described esterification also 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.
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| CN112646147A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Weather-proof PBT copolyester with low dielectric constant and preparation method thereof |
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