CN104017189B - A kind of preparation method without antimony polyester for bottle - Google Patents
A kind of preparation method without antimony polyester for bottle Download PDFInfo
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- CN104017189B CN104017189B CN201410229500.2A CN201410229500A CN104017189B CN 104017189 B CN104017189 B CN 104017189B CN 201410229500 A CN201410229500 A CN 201410229500A CN 104017189 B CN104017189 B CN 104017189B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920000728 polyester Polymers 0.000 title claims description 25
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000007791 liquid phase Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000012071 phase Substances 0.000 claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 93
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- 150000003608 titanium Chemical class 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- 230000001965 increasing effect Effects 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 3
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 3
- 229910011212 Ti—Fe Inorganic materials 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000000048 melt cooling Methods 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 97
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 97
- 238000000034 method Methods 0.000 abstract description 20
- -1 polyethylene terephthalate Polymers 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 42
- 239000011552 falling film Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910004339 Ti-Si Inorganic materials 0.000 description 2
- 229910010978 Ti—Si Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000012539 chromatography resin Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 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
- 239000007789 gas Substances 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention is open a kind of without the preparation method of antimony bottle with polyethylene terephthalate (PET) resin, adopt esterification, melt phase polycondensation, liquid phase increase glutinous single stage method to prepare limiting viscosity be 0.70 ~ 1.00? the bottle PET resin of dL/g, polycondensation catalyst is Titanium series catalyst, high to human safety, and eliminate the operations such as solid phase polycondensation, decrease facility investment, shorten technical process, reduce production energy consumption.
Description
Technical field
The invention belongs to polyester for bottle production technical field, particularly a kind of preparation method of polyethylene terephthalate (PET) material of heavy metal free antimony.
Background technology
Polyester particularly polyethylene terephthalate (PET), because of its excellent physical and mechanical properties, the advantage such as inexpensive, recyclable, is widely used in food packaging applications.At present, the preparation of bottle PET resin generally adopts two-step approach, namely elder generation is the PET resin of 0.60 ~ 0.65dL/g through over-churning, melt phase polycondensation (generally comprise precondensation, final minification gathers) obtained limiting viscosity, and then make through solid phase polycondensation (temperature 180 ~ 230 DEG C) the bottle PET resin that limiting viscosity is 0.70 ~ 0.90dL/g, another effect of solid phase polycondensation is that acetaldehyde in PET resin is down to below 1ppm from 50 ~ 120ppm.This preparation method's facility investment is large, technical process is long, production energy consumption is high.The whole batch condensation polymerization reactor of above-mentioned melt phase polycondensation generally adopts Horizontal stirring reactor, mainly contain disc type and cage, rely on bottom to be immersed in the dish in melt layer or to net when rotating and melt is taken up film forming, small molecule by-product is taken away by vacuum system, final minification gathers temperature of reaction and is generally 275 ~ 290 DEG C, this kind of reactor is successful for the PET melt preparing below limiting viscosity 0.65dL/g, but along with the increase melt coefficient of dynamic viscosity of limiting viscosity sharply increases, mobility is deteriorated, small molecules devolatilization is also more and more difficult, so the space will improving limiting viscosity is further little.Although there has been report to stick about adopting esterification, melt phase polycondensation, liquid phase increasing and save the single stage method polyester industrial yarn production technology of solid phase polycondensation, but the requirement of bottle PET resin and polyester industrial yarn have very large difference, particularly bottle PET resin has very high requirement to acetaldehyde, the transparency, colourity b value, national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003 specifies, food packaging bottle PET resin acetaldehyde must be less than 1ppm, and colourity b value must be less than 2.0.And the limiting viscosity that horizontal whole batch condensation polymerization reactor obtains is in the PET base melt of 0.60 ~ 0.65dL/g, acetaldehyde is general up to 50 ~ 120ppm, if continue time expand to carry out melt phase polycondensation raising limiting viscosity, acetaldehyde will certainly increase further, and colourity b value also can raise because of polyester thermal destruction.In order to reduce the acetaldehyde in PET melt, being reported in PET polymerization process and adding acetaldehyde remover, but economically consideration can increase production cost, reality is not necessarily desirable.Bottle PET resin also needs to make bottle base through the injection moulding of screw rod heating and melting, acetaldehyde can regenerate again in this process, general acetaldehyde rises to about 10 ~ 15ppm bottle base from the 1ppm that is less than of bottle resins, if so adopt esterification, melt phase polycondensation, liquid phase to increase glutinous and direct injection moulding and make bottle base, liquid phase increases in the glutinous melt of PET height be sticked that acetaldehyde must lower than 10ppm, and this is the inaccessiable requirement of ordinary skill.
On the other hand, the polycondensation process of PET uses antimony (Sb) series catalysts usually, makes in container store food beverage process the antimony element having trace and separates out, produce threaten human health.Titanium series catalyst is the environmentally friendly catalyzer being hopeful to replace antimony-based catalyst most, do a large amount of research work both at home and abroad, but effect is still not ideal enough with the face of popularization, major cause is that Titanium series catalyst catalytic activity is higher, catalytic selectivity is poor, and side reaction is obvious, and melt form and aspect are partially yellow, current research and development mainly concentrates on the improvement to Titanium series catalyst itself, there is not yet and solves the partially yellow report of Titanium series catalyst PET hue from the change of batch condensation polymerization reactor.
Prepare the glutinous melt of PET height due to melt phase polycondensation single stage method and originally easily produce the form and aspect problem such as Huang and acetaldehyde height partially, and Titanium series catalyst is because catalytic activity is high, poor selectivity, Huang and acetaldehyde raise, so it is generally acknowledged that melt phase polycondensation single stage method is prepared the glutinous melt of PET height and can not be used Titanium series catalyst partially to increase the weight of again the glutinous melt form and aspect of PET height.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of polyester for bottle, can solve the synthtic price index that form and aspect are prepared, reduce costs, do not use antimony-based catalyst, reduce acetaldehyde and ensured to the glutinous melt of PET height preferably.
For this reason, the present invention by the following technical solutions: describedly formed by terephthalic acid (PTA), ethylene glycol (EG), copolymer components polycondensation without antimony polyester for bottle, limiting viscosity is 0.70 ~ 1.00dL/g; Polycondensation catalyst is Titanium series catalyst; Preparation section does not have solid phase polycondensation, to carry out liquid phase without cooled and solidified through the obtained PET base melt of esterification, melt phase polycondensation to increase and be sticked the glutinous melt of standby PET height, the glutinous melt of described PET height without cooled and solidified direct injection moulding make bottle base or sheet material, or the glutinous melt cooling cast bar pelletizing of described PET height is obtained PET resin, and then de-acetaldehyde obtains the bottle PET resin of acetaldehyde≤1ppm, colourity b value≤2.0; The PET base melt that described liquid phase Zeng Nianshiqian road melt phase polycondensation obtains relies on Gravitational sliding film forming to carry out falling liquid film reaction raising molecular weight at film supplying tube outer wall vertically downward.
On the basis adopting technique scheme, the present invention also can adopt following further technical scheme:
Described esterification: the molar ratio of terephthalic acid and ethylene glycol is 1:1 ~ 1.5, and copolymerization component addition is 0.1 ~ 15% of PTA weight, and esterification reaction temperature is 230 ~ 270 DEG C, and relative pressure is 0 ~ 0.3MPa, and conversion rate of esterification is 96 ~ 98%;
Described melt phase polycondensation: above-mentioned esterification products is vacuumized and carries out melt phase polycondensation, catalyzer is Titanium series catalyst, and condensation temperature is 250 ~ 280 DEG C, and absolute pressure is 0.1 ~ 25kPa, and obtained limiting viscosity is the PET base melt of 0.20 ~ 0.65dL/g;
Described liquid phase increases glutinous: increase in glutinous reactor in liquid phase and carry out, PET base melt is dispensed to liquid phase and increases in glutinous reactor each film supplying tube upper end vertically downward, then Gravitational sliding is relied on to carry out polycondensation in pipe outer wall film forming, falling liquid film temperature of reaction is 250 ~ 269 DEG C, absolute pressure is 25 ~ 200Pa, small molecule by-product is taken away by vacuum system, melt falls after pipe and converges to bottom reactor, after stirring homogenizing material, initiatively go out still fast with spiral pump, obtained limiting viscosity is the glutinous melt of PET height of 0.70 ~ 1.00dL/g;
Described de-acetaldehyde: heating medium is air or nitrogen, and temperature is 130 ~ 200 DEG C, obtains the bottle PET resin of acetaldehyde≤1ppm, colourity b value≤2.0.
Falling liquid film temperature of reaction 250 ~ 269 DEG C, every root film supplying tube PET base melt flow is 1 ~ 50kg/ hour.
Further optimization, falling liquid film temperature of reaction 255 ~ 265 DEG C, every root film supplying tube PET base melt flow is 2 ~ 30kg/ hour.
PET height sticks acetaldehyde≤10ppm in melt or PET resin.
Titanium series catalyst comprises inorganic salt, titanium isopropylate, titanium ethylene glycolate, tetraphenyl titanate, titanium acetylacetone, the oxygen acid compound of titanium, titanium dioxide, the TiO of titanium
2/ SiO
2, titanium complex, Ti-Si catalyzer, Ti-P catalyzer, Ti-Mg catalyzer, Ti-Zr catalyzer, Ti-Al catalyzer, Ti-Mn catalyzer, Ti-Ge catalyzer, Ti-Fe catalyzer, Ti-Co catalyzer, load-type Titanium compound, titanium compound catalyst, addition counts 1 ~ 100ppm of PTA weight with titanium elements.
Film supplying tube is pipe, or is steel tubing in different shapes, or is spiral tube, or is corrugated tube, or is bellows tube, or is the pipe of axial diameter change, or is the pipe connecting of pipe and steel tubing in different shapes.
Titanium series catalyst, toning agent, thermo-stabilizer, antioxidant is added before esterification or polycondensation.
Liquid phase increase glutinous can phase in, increase in glutinous reactors in 2 liquid phases of series connection and carry out.
Adopt the mode of production of tail more than, i.e. a set of polyester for bottle production line, end can have the glutinous reactor of multiple liquid phases increasings in parallel to prepare the glutinous melt of PET height.
Described copolymerization component comprise in m-phthalic acid (IPA), glycol ether (DEG), new penta tetrol (NPG), 1,4 cyclohexane dimethanol (CHDM) any one, or any two kinds, or any three kinds, or these four kinds.
As described in background, prepare the glutinous melt of PET height due to melt phase polycondensation single stage method and originally easily produce the form and aspect problem such as Huang and acetaldehyde height partially, and Titanium series catalyst is because catalytic activity is high, poor selectivity, Huang and acetaldehyde raise, so be generally difficult to imagine that melt phase polycondensation single stage method is prepared bottle PET resin and uses Titanium series catalyst partially to increase the weight of again the glutinous melt form and aspect of PET height.The melt phase polycondensation single stage method that the present invention adopts melt phase polycondensation to add vertical extratubal falling film prepares the glutinous melt of bottle PET height, and coordinate melt phase polycondensation with the reasonable cutting of the polymerization degree of vertical extratubal falling film and optimize the processing condition such as falling liquid film temperature of reaction, vacuum tightness, falling liquid film flow, break titanium catalyst and not easily met the usual view not only having obtained full-bodied PET melt but also ensured low acetaldehyde content and low colourity b value simultaneously, achieve beyond thought effect.The present invention finds through deep research, and increase the structural parameter of glutinous reactor by appropriate design liquid phase and control the melt flow of every root film supplying tube, falling liquid film reaction melt specific surface area (surface-area that unit volume melt has) can reach 100m like a cork
2/ m
3, be far longer than 40 ~ 50m of horizontal disc reactor or cage-like finishers
2/ m
3, be extremely conducive to small molecules devolatilization, inhibit Titanium series catalyst poor selectivity, easily produce the shortcoming that the partially yellow and acetaldehyde of PET hue raises.PET vertical extratubal falling film melt phase polycondensation process is the coupling process of a heat transfer, mass transfer, flowing and reaction, and liquid phase increases glutinous processing condition has complicated impact to reaction process and quality product.As high in falling liquid film temperature of reaction, melt coefficient of dynamic viscosity reduces, and mobility improves, and thickness is thinning, and acetaldehyde devolatilization is easy, but acetaldehyde formation speed is accelerated simultaneously; Otherwise falling liquid film temperature of reaction is low, melt coefficient of dynamic viscosity increases, and mobility is deteriorated, and thickness is thickening, and acetaldehyde is not easy to remove, but acetaldehyde formation speed is slack-off simultaneously.And for example falling liquid film melt flow is large, and thickness increases, and specific surface area reduces, and acetaldehyde is not easy devolatilization, but melt residence time shortens simultaneously, and acetaldehyde growing amount reduces; Otherwise falling liquid film melt flow is little, and thickness is thinning, specific surface area increases, and acetaldehyde devolatilization is easy, but melt residence time extends simultaneously, and acetaldehyde growing amount increases, and throughput reduces.After falling liquid film reaction terminates, the melt pipe that falls converges to liquid phase and increases bottom glutinous reactor, with agitator homogenizing material, and initiatively goes out still fast with spiral pump, shortens the residence time of melt bottom reactor as far as possible, reduce generation and the increase of colourity b value of acetaldehyde.The present invention is just on the basis of large quantity research, adopt Titanium series catalyst, abandon the two-step process route of solid phase polycondensation after existing first melt phase polycondensation, the melt phase polycondensation single stage method adopting melt phase polycondensation to add vertical extratubal falling film prepares the glutinous melt of PET height, and break through PET final minification and gather the common process condition that temperature of reaction is generally 275 ~ 290 DEG C, adopt the very low temperature technique (close to PET fusing point) of 250 ~ 269 DEG C, coordinate the falling liquid film flow optimized, the processing condition such as vacuum tightness, the glutinous melt preparation of final breakthrough PET height and technical barrier such as reduction acetaldehyde and colourity b value etc., PET height sticks acetaldehyde≤10ppm in melt or PET resin, bottle PET resin acetaldehyde≤1ppm that PET resin is obtained after de-acetaldehyde, colourity b value≤2.0, indices meets the requirement of national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.
Polyester for bottle prepared by the present invention is not containing heavy metal antimony, high to human safety, and eliminates the operations such as solid phase polycondensation, decreases facility investment, shortens technical process, reduce production energy consumption.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited to embodiment.
The present invention with terephthalic acid, ethylene glycol and copolymerization component for raw material, the molar ratio of terephthalic acid and ethylene glycol is 1:1 ~ 1.5, copolymerization component at least comprises m-phthalic acid (IPA), glycol ether (DEG), new penta tetrol (NPG), 1, one in 4-cyclohexanedimethanol (CHDM) four kinds, total addition level is 0.1 ~ 15% of PTA weight.Esterification reaction temperature 230 ~ 270 DEG C, relative pressure 0 ~ 0.3MPa, 2 ~ 8 hours time, as required, esterification generally can be divided into esterification 1,2 two stages of esterification, is not restricted.After conversion rate of esterification reaches 96 ~ 98%, enter polycondensation phase, condensation temperature 250 ~ 280 DEG C, absolute pressure 0.1 ~ 25kPa, 2 ~ 6 hours time, according to polycondensation desired characteristic viscosity size, can complete by a polycondensation vessel, also can be divided into precondensation 1, precondensation 2 two polycondensation vessels complete, be not restricted.In addition, before esterification or polycondensation, Titanium series catalyst, toning agent, thermo-stabilizer, antioxidant is added; Described Titanium series catalyst is inorganic salt, titanium isopropylate, titanium ethylene glycolate, tetraphenyl titanate, titanium acetylacetone, the oxygen acid compound of titanium, titanium dioxide, the TiO of titanium
2/ SiO
2, titanium complex, Ti-Si catalyzer, Ti-P catalyzer, Ti-Mg catalyzer, Ti-Zr catalyzer, Ti-Al catalyzer, Ti-Mn catalyzer, Ti-Ge catalyzer, Ti-Fe catalyzer, Ti-Co catalyzer, load-type Titanium compound, titanium compound catalyst, addition counts 1 ~ 100ppm of PTA weight with titanium elements; Described toning agent is red and blue toner, and addition is 0 ~ 50ppm of PTA weight; Described thermo-stabilizer is phosphoric acid, polyphosphoric acid, phosphorous acid, trimethyl phosphite 99, triphenylphosphate or triethyl phosphate, and addition counts 0 ~ 100ppm of PTA weight with phosphoric; Described antioxidant is the composite antioxidant of hindered phenol type antioxidant or hindered phenol and phosphorous acid ester, monothioester, carbon free radical trapers, as antioxidant 1010, or the mixture of antioxidant 1010 and irgasfos 168, addition is 0 ~ 1% of PTA weight.Limiting viscosity obtained after melt phase polycondensation is the PET base melt of 0.20 ~ 0.60dL/g, be dispensed to each film supplying tube upper end vertically downward in the glutinous reactor of liquid phase increasing, then Gravitational sliding is relied on to carry out polycondensation in pipe outer wall film forming, small molecule by-product is taken away by vacuum system, melt falls after pipe and converges to bottom reactor, initiatively still is gone out fast with spiral pump after stirring homogenizing material, obtained limiting viscosity is the glutinous melt of PET height of 0.70 ~ 1.00dL/g, every root film supplying tube PET base melt flow is 1 ~ 50kg/ hour, falling liquid film temperature of reaction 250 ~ 269 DEG C, absolute pressure 25 ~ 200Pa, 20 ~ 180 minutes time.Film supplying tube is pipe, or is steel tubing in different shapes, or is spiral tube, or is corrugated tube, or is bellows tube, or is the pipe of axial diameter change, or is the pipe connecting of pipe and steel tubing in different shapes.Acetaldehyde (AA) content≤10ppm in the obtained glutinous melt of PET height, directly injection moulding can make bottle base; Or sheet material is made in injection moulding; Or cast bar pelletizing, then take off acetaldehyde through dealdehyder tower, make the bottle PET resin of acetaldehyde≤1ppm, colourity b value≤2.0.Dealdehyder tower preferentially adopts vertical moving-bed type, and heating medium is air or nitrogen, temperature 130 ~ 200 DEG C.Liquid phase increase glutinous can phase in, increase in glutinous reactors in 2 liquid phases of series connection and carry out.The preparation method of above-mentioned a kind of polyester for bottle, the mode of production of tail more than can be adopted, i.e. a set of polyester for bottle production line, end can have the glutinous reactor of multiple liquid phases increasings in parallel to prepare the glutinous melt of PET height, both the scale effect of Large Copacity esterification and polycondensation had been played, meet again the demand that multiple product is produced, form the production line of flexibility.
embodiment 1
The molar ratio of PTA and EG is 1:1.3, add the IPA of PTA the weight 2.0% and DEG of 0.8%, add and be equivalent to the Ti-Mg catalyzer of PTA weight 10ppm, the blue toner of 1.8ppm in titanium elements, carry out esterification, esterification reaction temperature 240 ~ 250 DEG C, relative pressure 0 ~ 0.2MPa, deviates from water byproduct, generates ethylene glycol terephthalate (BHET) and oligopolymer thereof; After conversion rate of esterification reaches 97%, vacuumize and carry out polycondensation, add the antioxidant 1010 in the phosphoric acid of phosphoric 9ppm and 30ppm, condensation temperature 255 ~ 265 DEG C, absolute pressure 0.1 ~ 20kPa; When limiting viscosity reaches about 0.35dL/g, PET base melt is dispensed to liquid phase and increases in glutinous reactor each film supplying tube upper end vertically downward, then Gravitational sliding is relied on to carry out polycondensation in pipe outer wall film forming, falling liquid film temperature of reaction 255 ~ 265 DEG C, absolute pressure 25 ~ 150Pa, every root film supplying tube PET base melt flow is 15kg/ hour, and melt falls after pipe and converges to bottom reactor, with spiral pump initiatively quickly discharging after stirring homogenizing material; The pelletizing of cooling cast bar obtains PET resin, then takes off acetaldehyde by warm air beating, temperature 150 ~ 190 DEG C, obtained bottle PET resin.
embodiment 2
Proportioning raw materials and esterification are with embodiment 1, after conversion rate of esterification reaches 97%, vacuumize and carry out polycondensation, condensation temperature 250 ~ 260 DEG C, absolute pressure 0.1 ~ 20kPa, when limiting viscosity reaches about 0.25dL/g, PET base melt is delivered to the glutinous reactor of the 1st liquid phase increasing and carries out falling liquid film reaction, falling liquid film temperature of reaction 255 ~ 265 DEG C, absolute pressure 50 ~ 200Pa, every root film supplying tube PET base melt flow is 20kg/ hour, the melt characteristic viscosity that 1st liquid phase increases glutinous reactor discharging is about 0.50dL/g, then be delivered to the glutinous reactor of the 2nd liquid phase increasing and carry out falling liquid film reaction, falling liquid film temperature of reaction 255 ~ 265 DEG C, absolute pressure 25 ~ 150Pa, every root film supplying tube PET base melt flow is 15kg/ hour, melt falls after pipe and converges to bottom reactor, with spiral pump initiatively quickly discharging after stirring homogenizing material, pelletizing and de-acetaldehyde condition are with embodiment 1.
embodiment 3
Catalyzer changes to C-94(Germany Acordis product), addition is equivalent to the 10ppm of PTA weight in titanium elements, and all the other are with embodiment 1.
reference examples 1
Increase in glutinous reaction in liquid phase, falling liquid film temperature of reaction changes to 280 ~ 285 DEG C, and all the other are with embodiment 1.
reference examples 2
Increase in glutinous reaction in liquid phase, every root film supplying tube PET base melt flow is 60kg/ hour, and all the other are with embodiment 1.
reference examples 3
Preparation of raw material and esterification, melt phase polycondensation are identical with embodiment 1, but do not adopt vertical extratubal falling film to react, when melt after limiting viscosity reaches 0.35dL/g continues to react in former stirring-type melt polycondensation reaction still, gas clean-up is to absolute pressure 50 ~ 100Pa, condensation temperature 255 ~ 265 DEG C, discharging when no longer continuing to increase to viscosity, pelletizing and de-acetaldehyde condition are with embodiment 1.
Acetaldehyde measures: adopt acetaldehyde in Headspace Gas Chromatography resin, perform according to national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.
Limiting viscosity measures: measure with capillary viscosimetry, solvent adopts phenol and 1, and 1,2, the mixed solvent of the mass ratio of 60:40 pressed by 2-tetrachloroethane, performs according to national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.
Colourity b pH-value determination pH: measure with automatic colour difference meter, perform according to national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.
Embodiment and reference examples resin test result are in table 1.Embodiment 1, Ti-Mg catalyzer is adopted to prepare bottle PET resin with the method for vertical extratubal falling film, and adopting the processing condition optimized, obtained bottle PET resin acetaldehyde and colourity b value meet the requirement of national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.Embodiment 2, the PET base melt limiting viscosity that melt phase polycondensation obtains is lower, liquid phase increases glutinous point two stages enforcements, obtained bottle PET resin colourity b value is more lower slightly than embodiment 1, and acetaldehyde and colourity b value meet the requirement of national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.Embodiment 3, antimony catalyst changes to C-94, all the other are with embodiment 1, obtained bottle PET resin acetaldehyde and colourity b value slightly higher than embodiment 1, but meet the requirement of national standard " bottle polyethylene terephthalate (PET) resin " GB17931-2003.Reference examples 1, liquid phase increases glutinous falling liquid film temperature of reaction and is increased to 280 ~ 285 DEG C, and all the other are with embodiment 1, and PET resin acetaldehyde and b value increase substantially, and the glutinous melt of PET height directly injection moulding can not make bottle base.Reference examples 2, liquid phase increases glutinous film supplying tube PET base melt flow and is increased to 60kg/ hour, and all the other are with embodiment 1, and because the falling liquid film reaction times is not enough, PET resin limiting viscosity is lower, and acetaldehyde is very high, and the glutinous melt of PET height directly injection moulding can not make bottle base.Reference examples 3, owing to not adopting vertical extratubal falling film to react, proceeds reaction in former stirring-type melt polycondensation reaction still, but no matter how long PET resin limiting viscosity does not reach high value, and acetaldehyde increases substantially, and form and aspect are very yellow the reaction times.
Table 1 results contrast
Claims (10)
1. without a preparation method for antimony polyester for bottle, it is characterized in that: describedly to be formed by terephthalic acid (PTA), ethylene glycol (EG), copolymer components polycondensation without antimony polyester for bottle, limiting viscosity is 0.70 ~ 1.00dL/g; Polycondensation catalyst is Titanium series catalyst; Preparation section does not have solid phase polycondensation, to carry out liquid phase without cooled and solidified through the obtained PET base melt of esterification, melt phase polycondensation to increase and be sticked the glutinous melt of standby PET height, the glutinous melt of described PET height without cooled and solidified direct injection moulding make bottle base or sheet material, or the glutinous melt cooling cast bar pelletizing of described PET height is obtained PET resin, and then de-acetaldehyde obtains the bottle PET resin of acetaldehyde≤1ppm, colourity b value≤2.0; The PET base melt that described liquid phase Zeng Nianshiqian road melt phase polycondensation obtains relies on Gravitational sliding film forming to carry out falling liquid film reaction raising molecular weight at film supplying tube outer wall vertically downward, and described dependence Gravitational sliding carries out the temperature of reaction 250 ~ 269 DEG C of polycondensation in pipe outer wall film forming; Described esterification: the molar ratio of terephthalic acid and ethylene glycol is 1:1 ~ 1.5, and copolymerization component addition is 0.1 ~ 15% of PTA weight, and esterification reaction temperature is 230 ~ 270 DEG C, and relative pressure is 0 ~ 0.3MPa, and conversion rate of esterification is 96 ~ 98%;
Described melt phase polycondensation: above-mentioned esterification products is vacuumized and carries out melt phase polycondensation, catalyzer is Titanium series catalyst, and condensation temperature is 250 ~ 280 DEG C, and absolute pressure is 0.1 ~ 25kPa, and obtained limiting viscosity is the PET base melt of 0.20 ~ 0.65dL/g;
Described liquid phase increases glutinous: increase in glutinous reactor in liquid phase and carry out, PET base melt is dispensed to liquid phase and increases in glutinous reactor each film supplying tube upper end vertically downward, then Gravitational sliding is relied on to carry out polycondensation in pipe outer wall film forming, its temperature of reaction is 250 ~ 269 DEG C, absolute pressure is 25 ~ 200Pa, small molecule by-product is taken away by vacuum system, melt falls after pipe and converges to bottom reactor, after stirring homogenizing material, initiatively go out still fast with spiral pump, obtained limiting viscosity is the glutinous melt of PET height of 0.70 ~ 1.00dL/g;
Described de-acetaldehyde: heating medium is air or nitrogen, and temperature is 130 ~ 200 DEG C, obtains the bottle PET resin of acetaldehyde≤1ppm, colourity b value≤2.0; Described dependence Gravitational sliding carries out the temperature of reaction 250 ~ 269 DEG C of polycondensation in pipe outer wall film forming, and every root film supplying tube PET base melt flow is 1 ~ 50kg/ hour.
2. the preparation method of a kind of polyester for bottle according to claim 1, is characterized in that: PET height sticks acetaldehyde≤10ppm in melt or PET resin.
3. a kind of preparation method without antimony polyester for bottle according to claim 1, it is characterized in that: Titanium series catalyst comprises inorganic salt, titanium isopropylate, titanium ethylene glycolate, tetraphenyl titanate, titanium acetylacetone, the oxygen acid compound of titanium, titanium dioxide, titanium complex, the titanium compound catalyst of titanium, and addition counts 1 ~ 100ppm of PTA weight with titanium elements.
4. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: Titanium series catalyst comprises TiO
2/ SiO
2, Ti-P catalyzer, Ti-Mg catalyzer, Ti-Zr catalyzer, Ti-Al catalyzer, Ti-Mn catalyzer, Ti-Ge catalyzer, Ti-Fe catalyzer, Ti-Co catalyzer, load-type Titanium compound, addition counts 1 ~ 100ppm of PTA weight with titanium elements.
5. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: film supplying tube is pipe, or is steel tubing in different shapes.
6. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: film supplying tube is spiral tube, or is corrugated tube, or be bellows tube, or is the pipe of axial diameter change, or is the pipe connecting of pipe and steel tubing in different shapes.
7. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: before esterification or polycondensation, add Titanium series catalyst, toning agent, thermo-stabilizer, antioxidant.
8. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: liquid phase increases glutinous phase in, increases in glutinous reactor carry out in 2 liquid phases of series connection.
9. a kind of preparation method without antimony polyester for bottle according to claim 1, is characterized in that: the mode of production adopting tail more than, i.e. a set of polyester for bottle production line, and end has the glutinous reactor of multiple liquid phases increasings in parallel to prepare the glutinous melt of PET height.
10. a kind of preparation method without antimony polyester for bottle according to claim 1, it is characterized in that: described copolymerization component comprises m-phthalic acid (IPA), glycol ether (DEG), new penta tetrol (NPG), 1, any one in 4-cyclohexanedimethanol (CHDM), or any two kinds, or any three kinds, or these four kinds.
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| CN109897171A (en) * | 2019-03-29 | 2019-06-18 | 新凤鸣集团股份有限公司 | A kind of method that ecological efficient compounding polycondensation catalyst prepares polyester |
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| CN1275147A (en) * | 1998-10-26 | 2000-11-29 | 东丽株式会社 | Polyester composition, method for producing the same and polyester film |
| CN1317507A (en) * | 2001-02-22 | 2001-10-17 | 南亚塑胶工业股份有限公司 | Process for preparing copolyester used for bottle with low content of acetaldehyde |
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