CN1192047C - Process for preparing copolyester used for bottle with low content of acetaldehyde - Google Patents
Process for preparing copolyester used for bottle with low content of acetaldehyde Download PDFInfo
- Publication number
- CN1192047C CN1192047C CNB011038330A CN01103833A CN1192047C CN 1192047 C CN1192047 C CN 1192047C CN B011038330 A CNB011038330 A CN B011038330A CN 01103833 A CN01103833 A CN 01103833A CN 1192047 C CN1192047 C CN 1192047C
- Authority
- CN
- China
- Prior art keywords
- copolyesters
- acetaldehyde
- bottle
- polyester
- pet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a method for preparing copolyester used for a bottle with low content of acetaldehyde. Polymers of polyethylene terephthalate (PET) are added with a right amount of modifying agent to reduce the amount of acetaldehyde generated by thermal cracking side reaction in a bottle manufacturing process; the modifying agent comprises a stabilizing agent and a first stage antioxidant, wherein the stabilizing agent is an inorganic phosphorus compound, and the added amount of which is based on the weight of all copolyester and is within the range of 0.003 to 0.5 wt%; the first stage antioxidant is the hindered phenolic antioxidant containing Ca<+2>, and the added amount of which is based on the weight of the all copolyester and is within the range of 0.005 to 5.0 wt%. compared with the side acetaldehyde generating amount of the copolyester preparation without the modifying agent, the present invention has the improving effect that the side acetaldehyde generating amount is reduced for 30%.
Description
The present invention system is about using the manufacture method of copolyesters for the polyester with low content of acetaldehyde bottle.Major technique is in polyethylene terephthalate polymer and the made PET polymer of multipolymer thereof, adds the stablizer of inorganic phosphorous compound and contains Ca
+ 21 grade of antioxidant of hindered phenol (hindered phenol) type so that reduce the acetaldehyde generating capacity that generates because of the side reaction of PET polymer thermo-cracking.Than the PET polyester bottles acetaldehyde that does not add properties-correcting agent, can reach at least and reduce by 30% effect.
Polyethylene terephthalate grain (PET) adds man-hour through the spraying machine bottle blowing, be subjected to the heat of spraying machine and the effect of screw rod mechanism shearing, the PET polymer takes place once again because of thermo-cracking causes side reaction acetaldehyde, when PET polyester bottles acetaldehyde is higher, can influence the smell of beverages such as mineral water, cola, thereby be rejected use.
Polyethylene terephthalate (PET) polyester bottles, because of having light weight, characteristic such as transparent, safe, replace containers such as traditional glass, aluminium, iron flask in a large number, and the PVC Plastic Bottle is also when incinerating burn processing, easily cause environmental issues such as dioxin (Dioxin) poisonous substance and acid rain, replaced by the PET polyester bottles gradually.
The manufacturing process that polyethylene terephthalate in the known technology (PET) polyester bottles is produced mainly is divided into three big steps:
(1) melt phase polycondensation operation
(2) solid state polycondensation operation
(3) spray the bottle blowing machine manufacturing operation
Below be respectively described below with regard to each step of above-mentioned known technology:
▲ step (1) indication melt phase polycondensation operation flow process can be divided into two kinds again:
(A) continous way-melt phase polycondensation operation
(B) intermittently (groove time) formula-melt phase polycondensation operation
In step (1A) continous way PET melt phase polycondensation operation program, behind terephthalic acid (PTA) and ethylene glycol (EG) furnishing slurry shape, after 0～10 mole of % of adding m-phthalic acid (IPA) sizes mixing in the lump, enter the esterification groove, carry out the direct esterification reaction, the esterification service temperature between 220 to 265 ℃, the esterification working pressure at normal pressure to 2.0Kg/cm
2, carry out in the process and water and the alcohols that generates must be distilled out, proceeding to conversion rate of esterification in the direct esterification reaction is 95% between 98% the time, promptly finishes esterification and enters polycondensation; Before polycondensation, must add catalyzer to quicken polycondensation speed, shorten polycondensation reaction time, this terephthalic acid ethylene glycol (PET) and multipolymer thereof, usually can use antimony acetate or antimonous oxide or germanium dioxide or titanium or above mixed form as catalyzer, the acceleration polycondensation is finished, add stablizer in addition, for example phosphoric acid, phosphorous acid, trimethyl phosphate, triphenylphosphate, triethyl phosphate etc.
Polyethylene terephthalate (PET) and multipolymer thereof are when carrying out polycondensation, be divided into prepolymerization reaction and main polyreaction, the prepolymerization temperature of reaction is between 270 to 280 ℃ of scopes, operation vacuum tightness is between 250 to 15mmHg, main polyreaction service temperature is between 275 to 285 ℃ of scopes, operation vacuum tightness is lower than under the high vacuum of 1mmHg, carry out polycondensation, when the reaction of PET melt phase polycondensation finishes, PET polymer limiting inherent viscosity IV value is brought up to 0.5～0.7dl/g, again polymer is unloaded quick cooling in the water coolant, and be cut into columned ester grain (chip), at the PET of this stage manufacturing polyester grain, its remaining acetaldehyde is not suitable for being directly used in injection bottle blowing machine processing and manufacturing polyester bottles more than 50ppm.
In step (1B) intermittently in (groove time) formula PET melt phase polymerization schedule of operation, by dimethyl terephthalate (DMT) DMT with after ethylene glycol (EG) mixes, after adding transesterification catalyst such as manganese acetate or zinc acetate or titanium catalyst, carry out transesterification reaction, the transesterification reaction service temperature is between 140 to 260 ℃ of scopes, in the process of carrying out, methyl alcohol must be distilled out, proceed to conversion rate of esterification between 95% to 98% o'clock in transesterification reaction, after adding 0～10 mole of % m-phthalic acid (IPA) formation multipolymer, promptly finish transesterification reaction, and before entering the melt phase polycondensation reaction, must add polycondensation catalyst again, to quicken polycondensation speed, shorten polycondensation reaction time.This ethylene glycol terephthalate (PET) and multipolymer thereof, can use antimony acetate or antimonous oxide or germanium dioxide or titanium or above mixed form as catalyzer, the acceleration polycondensation is finished, add stablizer in addition, for example phosphoric acid, phosphorous acid, trimethyl phosphate, triphenylphosphate, triethyl phosphate etc.
Polyethylene terephthalate (PET) and multipolymer thereof are when carrying out polycondensation, be divided into prepolymerization reaction and main polyreaction, the prepolymerization temperature of reaction is between 270 to 280 ℃ of scopes, operation vacuum tightness is between 250 to 15mmHg, main polyreaction service temperature is between 275 to 285 ℃ of scopes, operation vacuum tightness is lower than under the high vacuum of 1mmHg, carry out polycondensation, when the PET melt phase polymerization finishes, PET polymer limiting inherent viscosity IV value (IntrinsicViscosity) is increased to 0.5-0.7dl/g, again polymer is unloaded quick cooling in the cold water, and be cut into columned ester grain (chip), at the PET of this stage manufacturing polyester grain, its remaining acetaldehyde is unsuitable for being directly used in injection bottle blowing machine processing and manufacturing production polyester bottles more than 50ppm.
No matter for solving in continous way (being step 1A) or the intermittently still too high problem of remaining acetaldehyde in the PET polyester grain that obtains with the melt phase polycondensation reaction of (groove) formula (being step 1B) of above-mentioned known technology, the present invention adds inorganic Phosphorus stablizer before polycondensation phase, add antioxidant in addition again, as contain Ca
+ 2Hindered phenol type or phosphorous acid ester or thioether or carbodiimide or dibutyl sulfide for the amine zinc formate; Add toning agent in addition again, for example four hydration Cobaltous diacetates, cobalt chloride, Xiao Suangu etc.
Major technique of the present invention is in polyethylene terephthalate polymer and the made PET polymer of multipolymer thereof, adds the stablizer of inorganic phosphorous compound and contains Ca
+ 21 grade of antioxidant of hindered phenol (hindered phenol) type, to reduce the acetaldehyde generating capacity that generates because of the side reaction of PET polymer thermo-cracking; Than the acetaldehyde of the PET polyester bottles of not adding properties-correcting agent, can reach at least and reduce by 30% effect.
Above-mentioned limiting inherent viscosity (Intrinsic Viscosity) IV analytical method: be to measure with the Ubelohde viscosmeter, under 25 ℃, phenol and tetrachloroethane are measured with the mixed solvent of 3: 2 weight ratios.
▲ step (2) solid state polycondensation schedule of operation
Through the obtained polyethylene terephthalate of step (1) melt phase polymerization process (pET) grain, its limiting inherent viscosity IV value is between 0.5 to 0.7dl/g, when its suitable molecular weight sprays the operation of bottle blowing machine manufacturing polyester bottles in step (3), still belong on the low side, intensity is also not enough, and the acetaldehyde that PET polyester intragranular is remaining at this moment is higher, be not suitable for the manufacturing production of polyester bottles, event needs to handle through the solid state polycondensation of step (2) again, is worth between 0.72～1.2dl/g with the limiting inherent viscosity (IV) that improves polyethylene terephthalate (PET) grain; Obtaining enough to be suitable for being blow molded into thereafter the required molecular weight of moulding of bottle, and reduce the remaining acetaldehyde of PET intragranular and be lower than 1ppm.
In this used solid phase polycondensation mode of production, a kind of mode is with intermittently (groove) formula production, at turning slot internal heating PET polyester grain, and carries out under the environment that vacuumizes; Another kind of mode is with continous way production, and the PET grain in the solid state polycondensation groove, feeds rare gas element (for example nitrogen) with the raising limiting inherent viscosity again, and reduces the remaining acetaldehyde of PET intragranular to being lower than below the 1ppm after crystallizing and drying is handled.
Solid state polycondensation is to carry out in inert gas flow or carry out in vacuumizing, its service temperature is between 180 to 240 ℃, generally all be lower than polyethylene terephthalate and react below the multipolymer fusing point, to avoid caking to take place, under the normal circumstances, in the continous way method, PET grain solid state polycondensation is to carry out in the presence of inert gas flow, this rare gas element comprises nitrogen, carbonic acid gas, helium, argon, krypton, xenon-133 gas, also can use the mixture of various combinations or different inert gas, general most use nitrogen is as rare gas element, continous way solid state polycondensation device, can comprise fluidized-bed or moving-bed, under most of situation, the preferably is for using cylindrical polycondensation reactor, polyethylene terephthalate (PET) grain wherein, with this reactor of flowing through of required reaction times, this class cylindrical reactor possesses enough height, allow that the PET grain is because of under the action of gravity, the autoreactor top is to the bottom, with required reaction time, reach the final limiting inherent viscosity IV value of expectation, the control of this reaction time, can be controlled via the discharging of conditioned reaction device bottom, general preferable use rare gas element, its speed is lower than turbulent flow point (turbulentpoint), with the convection current reactor of upwards flowing through, make the PET grain can be by fluidization; The PET grain is at the solid state polycondensation action method, and whole process maintains the identical physical form of essence.
The representative look-ahead technique of this class solid state polycondensation is listed below:
United States Patent (USP) 4,161 has been described the PET grain in continous way solid state polycondensation manufacture method in 578, stir pre-crystallization reactor by mechanical force, improve PET grain degree of crystallinity, caking takes place during with the solution solid state polycondensation, and solid state polycondensation device discharging speed is minimum greater than 0.25ft/hr simultaneously.
United States Patent (USP) 4,374 has been described the PET grain in continous way solid state polycondensation manufacture method in 975, by pre-crystallization, dry pre-treatment, and at solid state polycondensation device feeding rare gas element, the solid state polycondensation actuator temperature is between 200 to 225 ℃, to improve PET grain limiting inherent viscosity (IV) value.
United States Patent (USP) 5,708 has been described the PET grain in continous way solid state polycondensation manufacture method in 124, in the moving bed type reactor, feed nitrogen or rare gas element, the solid state polycondensation service temperature is between 180 to 230 ℃, to improve PET grain limiting inherent viscosity (IV) value.The PET grain enters before the solid state polycondensation, and enough degree of crystallinity need be arranged, and just can avoid caking to take place, and come the crystalline PET grain with fluid bed.
▲ step (3) is sprayed bottle blowing machine and is processed into the PET polyester bottles
After the operation of step (2) solid state polycondensation is finished, make the polyethylene terephthalate grain of high IV, reach the required enough limiting inherent viscosities of bottle blowing machine (IV) value, again through spraying machine and bottle blowing machine processing and manufacturing, can make transparent polyester bottles, the spraying machine service temperature is between 260 to 285 ℃, and under this high temperature and mechanical shearing action, polyethylene terephthalate grain regenerated acetaldehyde can generate again rapidly.
Below be set forth in the prior art that step (3) reduces acetaldehyde in the PET bottle:
United States Patent (USP) the 5th, 597 has been described by improved injection board in 891, directly feeds clean-out system N in spraying machine
2Or vacuumize handling procedure, and reducing the polyester bottles acetaldehyde, but need injections board is made amendment, difficultly like this to be accepted by polyester bottles bottle blowing manufacturer, this patent be can't help polyethylene terephthalate (PET) polymer modification processing.
United States Patent (USP) 4,223, described in 128 by traditional solid state polycondensation program, with the PET polyester grain behind the solid state polycondensation, analyze acetaldehyde generating capacity again, and reckon without the cracking generation of spraying machine screw rod mechanism fail in shear, analytical results does not more have essential meaning, and be not according to Coca-Cola standard method of analysis: the polyester bottles after finishing with bottle blowing, analyze the regeneration acetaldehyde.
United States Patent (USP) 5,573, described in 820 without the solid state polycondensation program,, directly imported the spraying machine bottle blowing by the reacted polymer of melt phase polycondensation, emphasize bottle blowing machine mould hot water crystallization treatment program, reduce the polyester bottles acetaldehyde, can be lower than the polyester bottles of 10ppm content, but this 10ppm acetaldehyde numerical value, for charges such as filling mineral water, colas, still belong to higher.
United States Patent (USP) 5,656 has been described without the solid state polycondensation program in 719, directly when melt phase polymerization, feeds rare gas element such as CO
2, N
2After the processing, extract the polymer after volatile matter is handled again through finding time, directly import and spray bottle blowing machine manufacturing polyester bottles, can be lower than the polyester bottles of 10ppm content, but this 10ppm acetaldehyde numerical value for charges such as filling mineral water, colas, belongs to still higher.
United States Patent (USP) 4,391 has been described in 971 between in 230 to 300 ℃ of polyethylene terephthalate (PET) polymers, by the molecular sieve absorbents adsorption treatment, to reduce its acetaldehyde.
United States Patent (USP) 5,874, described in 517 in melt phase ethylene glycol terephthalate (PET) polymer and multipolymer thereof, add 1 grade of antioxidant Irganox-1010 and 2 grades of antioxidant PEPQ (the Clariant trade name is Sandostab PEPQ) to reduce the acetaldehyde amount that produces, but PEPQ does not does not check and approve by united States food and drug administration (FDA) as yet, so be unsuitable for being used in the interpolation of PET polyester bottles.
Aspect the acetaldehyde of above method in step (3) reduction PET bottle, still dislike not enough, in order to make secondary acetaldehyde reduction of giving birth to, the present invention adds an amount of stablizer and contains Ca
+ 2The hindered phenol type antioxidant, reduce the acetaldehyde generating capacity of step (3) because of the thermo-cracking by-product, can reduce the effect more than 30% at least.
Coca-Cola is to polyester bottles acetaldehyde standard method of test:
After PET polyester bottles bottle blowing is finished, with nitrogen N
2Fill blow 20 seconds after, bottleneck sealing places under 22 ± 1.5 ℃ of environment of room temperature, after 24 hours, extract the gas in the PET polyester bottles, analyze (GC) through gas phase chromatographic analysis instrument, area when measuring acetaldehyde and spike (Peak) occurring with respect to the respective value of standard baseline, is obtained acetaldehyde.
Measurement acetaldehyde analytical instrument type used herein is:
Perkin-Elmer Auto System XL Gas Chromatography HeadspaceInjector model.
Polyethylene terephthalate of the present invention and multipolymer thereof, system utilizes general known PET polyester production facility and production stage to make prepolymer, this manufacturing flow process comprises with terephthalic acid (PTA) or is initial reactant with dimethyl terephthalate (DMT) (DMT) and ethylene glycol, in addition, the m-phthalic acid (IPA) that adds 0 to 10 mole of % again carries out continous way or the production method of (groove) formula intermittently.Again aforementioned resulting prepolymer is carried out solid-phase polymerization, improve limiting inherent viscosity to the 0.72～1.2dl/g of copolyesters thing (copolymer).The used solid phase polycondensation mode of production of the present invention, a kind of is to add PET polyester grain with (groove) formula intermittently in turning slot, and under vacuum environment, carry out solid-phase polymerization, another kind is in a continuous manner, PET polyester grain is after crystallizing and drying is handled, in the solid state polycondensation groove, feed rare gas element (for example nitrogen), improve PET multipolymer limiting inherent viscosity between 0.72～1.2dl/g.
The invention provides a kind of manufacture method that has for polyester with low content of acetaldehyde polyester for bottle grain: form by dicarboxylic acid and dibasic alcohol in essence, under enough temperature of carrying out esterification or transesterification, react, and conversion rate of esterification is reached between 95%～98%, and before polycondensation, add catalyzer, toning agent, stablizer, contain Ca
+ 2The hindered phenol type antioxidant, and under the state of vacuumizing, carry out the melt phase polycondensation reaction, PET polyester grain limiting inherent viscosity (IV) value is controlled between 0.50 to 0.72dl/g.
According to foregoing:
(1) dicarboxylic acid comprises terephthalic acid (PTA), m-phthalic acid (IPA), dimethyl terephthalate (DMT) (DMT), naphthalene dicarboxylic acids (DNA) 2,6-naphthalenedicarboxylic acid, naphthalene diformic acid dimethyl ester (NDC) dimethy1 2,6-naphthalenedicarboxylate.
(2) dibasic alcohol comprises ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,4 cyclohexane dimethanol (CHDM).
(3) as described in (1) (2), amount ratio between dicarboxylic acid and the dibasic alcohol was preferably mol ratio 1: 1, in addition in order to make the copolyesters multipolymer, also can add above-mentioned other dicarboxylic acid or dibasic alcohol, at least 80 moles of % of its composition are terephthalic acid or naphthalene dicarboxylic acids or dimethyl terephthalate (DMT) or naphthalene diformic acid dimethyl ester.
(4) catalyzer comprises antimony acetate, antimonous oxide, germanium dioxide, titanium, manganese acetate, zinc acetate, is benchmark with copolyesters thing weight, and its catalyst metal element is 0～300ppm manganese, or 0～80ppm titanium, or 0～300ppm antimony, or 0～200ppm germanium.
(5) stablizer comprises phosphoric acid, phosphorous acid, trimethyl phosphate, triphenylphosphate, triethyl phosphate, is benchmark with copolyesters thing weight, and wherein phosphorus element content is in 5～100ppm scope, and phosphoric is preferably 37.6ppm.
(6) contain Ca
+ 2The hindered phenol type antioxidant is Irganox-1425 (the business-like product of Ciba), is benchmark with copolyesters thing weight, and calcium Ca constituent content is in 5～100ppm scope, and it is preferable that calcium Ca element is preferably 17.3ppm.
(7) toning agent is four hydration Cobaltous diacetates, cobalt chloride, Xiao Suangu, salicyl salicylic acid cobalt, is benchmark with copolyesters thing weight, and wherein cobalt Co constituent content is in 0～100ppm scope.
Embodiment
Below list some embodiment, will further specify the present invention, but need to understand its illustrative purpose, and the scope that does not limit the present invention in any way.
Embodiment 1
Behind terephthalic acid (PTA) and ethylene glycol (EG) furnishing slurry shape, enter the esterification groove, at absolute pressure 2.0kg/cm
2Down slurries are heated to 260 ℃, carry out esterification, reach more than 95% to conversion rate of esterification, before polycondensation, add polycondensation catalyst antimony acetate and toning agent four hydrations and touch sour cobalt in reactive tank, next vacuumize, make in the reactor to be decompressed to below the 1mmHg, and carry out the fs polycondensation for 270 ℃, then under 280 ℃, carry out the subordinate phase polycondensation again in temperature of reaction, manufacture prepolymer, its limiting inherent viscosity is controlled in 0.60 to the 0.64dl/g scope.In polyethylene terephthalate polymer, be benchmark with the polymer weight, the antimony element of catalyst acetic acid antimony accounts for 183.15ppm (umbers in per 1,000,000 parts), and the cobalt element of toning agent four hydration Cobaltous diacetates accounts for 34.27ppm.
With the above prepolymer pelletizing that obtains, be lower than under 180 ℃ the temperature earlier, carry out drying and crystallization after 6 hours, enter the solid state polycondensation device, admittedly for phase polycondensation temperature is 225 ℃, in 20 hours reaction times, the limiting inherent viscosity after solid state polycondensation is finished (IV) is controlled in 0.76～0.86dl/g scope.
Polyester grain after solid state polycondensation finished is processed into polyester bottles through 280 ℃ of spraying machines, with nitrogen N
2After blowing 20 seconds, the bottleneck sealing places under 22 ± 1.5 ℃ of environment of room temperature, after 24 hours, extracts the gas in the PET polyester bottles, and measuring acetaldehyde at gas phase chromatographic analysis instrument is 6.50ppm.
Embodiment 2
Repeating embodiment 1, in terephthalic acid (PTA) and ethylene glycol (EG) furnishing slurry liquid, is benchmark with multipolymer (copolymer), adds 2.7 moles of % of m-phthalic acid (IPA), adds stablizer phosphoric acid (H before polycondensation
3PO
4), be benchmark with multipolymer (copolymer) weight, phosphoric accounts for 37.6ppm, and measuring acetaldehyde at gas phase chromatographic analysis instrument is 3.95ppm.
Embodiment 3
Repeat embodiment 1, in terephthalic acid (PTA) and ethylene glycol (EG) furnishing pulpous state body fluid, with multipolymer (copolymer) is benchmark, add 2.7 moles of % of m-phthalic acid (IPA), before polycondensation, add 1 grade of antioxidant Irganox-1425, with multipolymer (copolymer) weight is benchmark, and calcium constituent accounts for 17.3ppm, and measuring acetaldehyde at gas phase chromatographic analysis instrument is 5.60ppm.
Embodiment 4
Repeating embodiment 1, in terephthalic acid (PTA) and ethylene glycol (EG) furnishing slurry liquid, is benchmark with multipolymer (copolymer), adds 2.7 moles of % of m-phthalic acid (IPA), adds stablizer phosphoric acid (H before the polycondensate reaction
3PO
4) and 1 grade of antioxidant Irganox-1425, (copolymer) is benchmark with multipolymer, phosphoric accounts for 37.6ppm.With multipolymer (copolymer) weight is benchmark, and calcium constituent accounts for 17.3ppm, and measuring acetaldehyde at gas phase chromatographic analysis instrument is 2.75ppm.
Claims (7)
1. one kind for the polyester with low content of acetaldehyde bottle manufacture method with copolyesters, it is characterized in that this method is in the repeating unit that is made up of dicarboxylic acid composition and dibasic alcohol composition, add m-phthalic acid in addition again based on 0 to 10 mole of % of this copolyesters mole number, make this dicarboxylic acid composition and dibasic alcohol composition be enough to finish conversion rate of esterification and reach more than 95%, add catalyzer, stablizer, toning agent then and contain Ca
+ 2The hindered phenol type antioxidant, to form described copolyesters, wherein Ca
+ 2Content be 2 to 200ppm based on the gross weight of copolyesters.
2. the manufacture method that supplies the polyester with low content of acetaldehyde bottle with copolyesters as claimed in claim 1 is characterized in that the mole number based on this copolyesters, and at least 80 moles of % of this copolyesters are terephthalic acid or naphthalene dicarboxylic acids.
3. the manufacture method that supplies the polyester with low content of acetaldehyde bottle with copolyesters as claimed in claim 1 is characterized in that the mole number based on this copolyesters, and at least 80 moles of % of this copolyesters are dimethyl terephthalate (DMT) or naphthalene dicarboxylic acids dimethyl ester.
4. as claimed in claim 1ly it is characterized in that for the polyester with low content of acetaldehyde bottle manufacture method with copolyesters described stablizer is a phosphoric acid, its phosphorus element content is 5 to 100ppm based on the gross weight of described copolyesters.
5. as claimed in claim 1 for the manufacture method of polyester with low content of acetaldehyde bottle with copolyesters, it is characterized in that the described Ca of containing
+ 2The hindered phenol type antioxidant be Irganox-1425.
6. as claimed in claim 1ly it is characterized in that for the polyester with low content of acetaldehyde bottle manufacture method with copolyesters described toning agent is four hydration Cobaltous diacetates, wherein the content of cobalt element is 0 to 100ppm based on the gross weight of described copolyesters.
7. as claimed in claim 1 for the manufacture method of polyester with low content of acetaldehyde bottle with copolyesters, it is characterized in that the gross weight of the metal element content of described catalyzer based on described copolyesters, it is 0 to 300ppm manganese element, or 0 to 80ppm titanium elements, or 0 to 300ppm antimony element, or 0 to 200ppm element Ge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011038330A CN1192047C (en) | 2001-02-22 | 2001-02-22 | Process for preparing copolyester used for bottle with low content of acetaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011038330A CN1192047C (en) | 2001-02-22 | 2001-02-22 | Process for preparing copolyester used for bottle with low content of acetaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1317507A CN1317507A (en) | 2001-10-17 |
| CN1192047C true CN1192047C (en) | 2005-03-09 |
Family
ID=4653503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011038330A Expired - Fee Related CN1192047C (en) | 2001-02-22 | 2001-02-22 | Process for preparing copolyester used for bottle with low content of acetaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1192047C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835333B2 (en) * | 2002-05-07 | 2004-12-28 | Milliken & Company | Combinations for use as toners in polyesters |
| US8557950B2 (en) * | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| BRPI0912455A2 (en) * | 2008-08-07 | 2018-10-16 | Invista Tech Sarl | "process for the production of a polyester and article" |
| CN101955582B (en) * | 2010-09-30 | 2012-07-25 | 南亚塑胶工业股份有限公司 | Titanium-containing copolyester used fro producing large volume polyester bottles and products thereof |
| CN102146157B (en) * | 2011-03-21 | 2013-01-09 | 浙江万凯新材料有限公司 | Iso propyl alcohol (IPA) esterification bottle grade polyester production equipment and method |
| CN104017189B (en) * | 2014-05-28 | 2016-03-23 | 浙江理工大学 | A kind of preparation method without antimony polyester for bottle |
| CN104017191B (en) * | 2014-05-28 | 2016-09-28 | 浙江理工大学 | A kind of preparation method of polyester for bottle |
| CN114874421B (en) * | 2022-05-30 | 2024-01-23 | 上海华峰新材料研发科技有限公司 | Polyester polyol with low aldehyde ketone content and preparation method and application thereof |
-
2001
- 2001-02-22 CN CNB011038330A patent/CN1192047C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1317507A (en) | 2001-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI288155B (en) | Manufacturing method of copolyester for PET bottles comprising low acetaldehyde content | |
| EP1373395B1 (en) | Process for preparing a stabilized polyester | |
| CN1196728C (en) | Process for production polyester with low content of free aldehyde | |
| EP0661326B1 (en) | Process for preparing polyester | |
| JP5288676B2 (en) | Catalyst for producing polyester, method for producing polyester, and polyester | |
| US6392005B1 (en) | Manufacturing method for decreasing the cyclic oligomer content in polyester | |
| CN1192047C (en) | Process for preparing copolyester used for bottle with low content of acetaldehyde | |
| JP5598162B2 (en) | Copolyester molded product | |
| JPH08283393A (en) | Polyethylene terephthalate and production thereof | |
| CN1218982C (en) | Copolyester with high carboxyl end groups and a method for making | |
| JPH0347830A (en) | Production of polyethylene terephthalate | |
| JP5045216B2 (en) | Method for producing polyester polycondensation catalyst, and method for producing polyester using the catalyst | |
| JP3357489B2 (en) | Polyester production method | |
| CN1210326C (en) | Prepn of copolyester containing glycol naphthalendicarboxylate | |
| US6783827B2 (en) | Method or decreasing the cyclic oligomer content in polyester product | |
| JP3357488B2 (en) | Polyester production method | |
| JP5251789B2 (en) | Copolyester | |
| JP3275649B2 (en) | Method for producing modified polyester resin | |
| JP2004307597A (en) | Method for producing polyethylene terephthalate | |
| EP1433806A1 (en) | Method for decreasing the cyclic oligomer content in polyester product | |
| JP4086983B2 (en) | Polyester manufacturing method | |
| JP4624590B2 (en) | Method for producing metal compound-containing polyester resin composition, preform for hollow molded article, and method for producing hollow molded article | |
| JP5320891B2 (en) | Polyester molding | |
| JP3365687B2 (en) | Method for producing polyester resin and polyester resin | |
| CN109666136B (en) | Preparation method of polyester injection molding with low acetaldehyde content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050309 Termination date: 20100222 |