CN103467723B - A kind of fluorine-containing PBT polyester and preparation method thereof - Google Patents
A kind of fluorine-containing PBT polyester and preparation method thereof Download PDFInfo
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- CN103467723B CN103467723B CN201310447175.2A CN201310447175A CN103467723B CN 103467723 B CN103467723 B CN 103467723B CN 201310447175 A CN201310447175 A CN 201310447175A CN 103467723 B CN103467723 B CN 103467723B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 69
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000032050 esterification Effects 0.000 claims abstract description 70
- 238000005886 esterification reaction Methods 0.000 claims abstract description 70
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 67
- 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 31
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 7
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-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
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 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 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
- 239000003054 catalyst Substances 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
- 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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 1
- -1 alcohol ester Chemical class 0.000 abstract description 11
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002940 repellent Effects 0.000 abstract description 3
- 239000005871 repellent Substances 0.000 abstract description 3
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 3
- 150000002221 fluorine Chemical class 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 37
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 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
- 238000005453 pelletization Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000032683 aging Effects 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
- 229920002647 polyamide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003063 flame retardant Substances 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
- 238000011160 research Methods 0.000 description 2
- 239000002699 waste material Substances 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
- 229920001634 Copolyester Polymers 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
- 229920004935 Trevira® 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
- 230000015572 biosynthetic process 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
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 150000007520 diprotic acids Chemical class 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
- 239000000835 fiber Substances 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000178 monomer Substances 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
- 238000004806 packaging method and process 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
- 230000001737 promoting effect Effects 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
- 238000007493 shaping process Methods 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
- 238000003786 synthesis reaction Methods 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
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of fluorine-containing PBT polyester and preparation method thereof, this fluorine-containing PBT polyester refers to polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester.Adopt tetrafluoro terephthalic acid and BDO as raw material, add inhibitor, in nitrogen atmosphere, carry out esterification under certain temperature and pressure and obtain esterification products; Again catalyzer and stablizer are joined in esterification products, under certain temperature and pressure, carry out polycondensation, obtain fluorine-containing PBT polyester through polycondensation rough vacuum stage and high vacuum stage of Fig.The fluorine-containing PBT 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 PBT polyester material, at waterproof garment, in the working suit manufacture of the working suit born dirty and some special industry, have huge prospect.
Description
Technical field
The present invention relates to a kind of fluorine-containing PBT polyester and preparation method thereof, particularly relate to fluorine-containing PBT 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, the fluorine-containing polyester of development of new, for weaving and the modification of super-hydrophobic, hydrophobic and oil repellent, antifouling property of wrapping material, will have important theory significance and using value.At waterproof garment, in the working suit manufacture of the working suit born dirty and some special industry, there is huge prospect.
Summary of the invention
The object of this invention is to provide a kind of fluorine-containing PBT polyester and preparation method thereof, particularly relate to fluorine-containing PBT polyester that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.Fluorine-containing PBT polyester of the present invention introduces fluorine atom on the main chain of polymkeric substance, and the fluorine-containing PBT polyester section of preparing can be directly used in spinning, film forming, injection moulding etc., therefore can well solve this kind of problem that wastes time and energy.Fluorine-containing PBT polyester described in the present invention is terephthalic acid by contain fluorine atoms on phenyl ring and BDO, through the fluorine-containing PBT polyester that over-churning and polycondensation obtain.This fluorine-containing PBT polyester section can direct fabrics, film forming, injection moulding.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 invention provides a kind of preparation method of fluorine-containing PBT polyester, be divided into esterification and polycondensation two step; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid and BDO as raw material, add inhibitor, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is carried out being less than under absolute pressure 1KPa, and temperature is at 160 ~ 220 DEG C, and the time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described inhibitor is the one in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom in the phenyl ring due to di-carboxylic acid used, the electronegativity of fluorine atom is large, in the conjugative effect of esterification stage fluorine atom, the acidity of di-carboxylic acid is strengthened, cause the activity of carboxyl in di-carboxylic acid to increase simultaneously, speed of response is accelerated, and speed of response increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation, particularly generate the end-cap product of alkene and aldehyde, constrain the increase of molecular weight of product; From experimental result, if do not add inhibitor, the molecular weight of polyesters of synthesis is on the low side, can not meet the demand of spinning and film forming; The speed added for controlling the esterification stage of inhibitor, decreases side reaction, improves the molecular weight of product, make to meet spinning requirement.
Usually, it is the hydrogen ion that ionized out by the di-carboxylic acid used catalyzer as esterification in polyester esterification process, carry out self-catalyzed reaction, by regulating the temperature of esterification, pressure and the micromolecular speed ejecting its esterification of control, but the prerequisite of carrying out esterification under certain temperature of reaction and pressure, just will can carry out esterification.When temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thus affect follow-up technique.If the small molecules in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, due to the conjugative effect of fluorine, at esterification stage fluorine atom, the acidity of di-carboxylic acid is strengthened, cause the activity of carboxyl in di-carboxylic acid to increase, speed of response is accelerated, and side reaction increases simultaneously, be difficult to control, and then affect the growth of molecular weight of product, therefore add inhibitor, namely by selecting metal oxide used to regulate.Described metal oxide can dissociate by the following two kinds mode:
Here M is metal ion, if the electronegativity of M is quite large, has stronger magnetism, O-H key so just can be made to weaken to the electron pair of oxonium ion, is conducive to reacting dissociation; On the contrary, if the electronegativity of M is little, so just alkali center will be generated.M-O-H is similar with amphoteric substance, when there being alkaline matter to exist, reacting and the mode by acid dissociation being carried out; And when acidic substance exist, then undertaken by the mode of alkali formula ionization.The M-O of reversed reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid sites, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in O ion then relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, and intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and metal ion electronegativity is less, and negative charge density is larger.So, acidity and the alkalescence of metal oxide have just all connected with the electronegativity of metal ion, and the oxide compound that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is then alkalescence.
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 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, 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 ~ 275 DEG C, 3 ~ 4 hours reaction times.Polycondensation 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 polyester as above, the mol ratio of described butyleneglycol and tetrafluoro terephthalic acid is 1.4 ~ 2.0:1.
The preparation method of a kind of fluorine-containing PBT 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% ~ 0.05% of described tetrafluoro terephthalic acid weight.
The preparation method of a kind of fluorine-containing PBT polyester as above, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid weight.
The preparation method of a kind of fluorine-containing PBT polyester as above, the add-on of described inhibitor is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid weight.
The fluorine-containing PBT polyester of one of the present invention, refers to the polybutylene terephthalate that benzene ring hydrogen replaced by fluorine, and be polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester, its general structure is
Wherein n=70 ~ 150.
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 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 polyester material, at waterproof garment, has huge prospect in the working suit manufacture of the working suit born dirty and some special industry.
Beneficial effect:
1, obtained fluorine-containing PBT polyester contain fluorine atoms; due to the strong electronegativity of fluorine; high C-F bond energy and make the copolyesters synthesized also have well heat-resisting, ageing-resistant except promoting the performance of conventional polyester further to the shielding protection effect of carbochain, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction, also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, extend range of application.
2, the speed of esterification can be controlled in polyester esterification process by inhibiting, reduce the generation of side reaction.
3, the fluorine-containing PBT polyester section of gained can direct fabrics, film forming, injection moulding etc.
4, the fluorine-containing PBT polyester of gained has good thermostability and workability.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The fluorine-containing PBT polyester of one of the present invention, refers to the polybutylene terephthalate that benzene ring hydrogen replaced by fluorine, and be polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester, its general structure is
Wherein n=70 ~ 150.
Embodiment 1
A preparation method for fluorine-containing PBT polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the BDO of 1.4:1 and tetrafluoro terephthalic acid as raw material, add the magnesium oxide of 0.01% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and pressure-controlling is at below 1KPa, and temperature controls at 220 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
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 tetrafluoro terephthalic acid weight and 0.01% of tetrafluoro terephthalic acid weight is added in esterification products, polycondensation is started under the condition of negative pressure, described negative pressure refers to that absolute pressure is less than 500Pa, 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 polyester section.
Embodiment 2
A preparation method for fluorine-containing PBT polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the BDO of 1.6:1 and tetrafluoro terephthalic acid as raw material, add the silicon oxide of 0.02% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and pressure-controlling is at below 900Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
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 0.02% of tetrafluoro terephthalic acid weight and 0.02% of tetrafluoro terephthalic acid weight is added in esterification products, polycondensation is started under the condition of negative pressure, described negative pressure refers to that absolute pressure is less than 400Pa, 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 80Pa, 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 polyester section.
Embodiment 3
A preparation method for fluorine-containing PBT polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the BDO of 1.8:1 and tetrafluoro terephthalic acid as raw material, add the calcium oxide of 0.03% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and pressure-controlling is at below 800Pa, and temperature controls at 180 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
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 0.03% of tetrafluoro terephthalic acid weight and 0.03% of tetrafluoro terephthalic acid weight is added in esterification products, polycondensation is started under the condition of negative pressure, described negative pressure refers to that absolute pressure is less than 300Pa, 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 60Pa, 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 polyester section.
Embodiment 4
A preparation method for fluorine-containing PBT polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the BDO of 1.9:1 and tetrafluoro terephthalic acid as raw material, add the zinc oxide of 0.04% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and pressure-controlling is at below 700Pa, and temperature controls at 170 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
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 0.04% of tetrafluoro terephthalic acid weight and 0.04% of tetrafluoro terephthalic acid weight is added in esterification products, polycondensation is started under the condition of negative pressure, described negative pressure refers to that absolute pressure is less than 300Pa, temperature controls at 270 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 60Pa, 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 polyester section.
Embodiment 5
A preparation method for fluorine-containing PBT polyester, is divided into esterification and polycondensation two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the BDO of 2.0:1 and tetrafluoro terephthalic acid as raw material, add the manganese oxide of 0.05% of tetrafluoro terephthalic acid weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and pressure-controlling is at below 600Pa, and temperature controls at 160 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
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 0.05% of tetrafluoro terephthalic acid weight and 0.05% of tetrafluoro terephthalic acid weight is added in esterification products, polycondensation is started under the condition of negative pressure, described negative pressure refers to that absolute pressure is less than 300Pa, 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 polyester section.
Claims (5)
1. a preparation method for fluorine-containing PBT polyester, is characterized in that: the preparation method of described fluorine-containing PBT polyester is divided into esterification and polycondensation two step; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid and BDO as raw material, add inhibitor, the add-on of described inhibitor is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid weight; Carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is in nitrogen atmosphere, and pressure-controlling is being less than absolute pressure 1KPa, and temperature is at 160 ~ 220 DEG C, and the time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described inhibitor is the one in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide;
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 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, 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 ~ 275 DEG C, 3 ~ 4 hours reaction times.
2. the preparation method of a kind of fluorine-containing PBT polyester according to claim 1, is characterized in that.
3. the preparation method of a kind of fluorine-containing PBT polyester according to claim 1, is characterized in that, the mol ratio of described BDO and tetrafluoro terephthalic acid is 1.4 ~ 2.0:1.
4. the preparation method of a kind of fluorine-containing PBT 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% ~ 0.05% of described tetrafluoro terephthalic acid weight.
5. the preparation method of a kind of fluorine-containing PBT polyester according to claim 1, it is characterized in that, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid weight.
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