CN1217002A - Process for forming articles directly from melt polymerization - Google Patents
Process for forming articles directly from melt polymerization Download PDFInfo
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- CN1217002A CN1217002A CN97194115A CN97194115A CN1217002A CN 1217002 A CN1217002 A CN 1217002A CN 97194115 A CN97194115 A CN 97194115A CN 97194115 A CN97194115 A CN 97194115A CN 1217002 A CN1217002 A CN 1217002A
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- volatile matter
- polyester
- acetaldehyde
- ihv
- glycol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/18—Feeding the material into the injection moulding apparatus, i.e. feeding the non-plastified material into the injection unit
- B29C2045/1883—Feeding the material into the injection moulding apparatus, i.e. feeding the non-plastified material into the injection unit directly injecting moulding material from the chemical production plant into the mould without granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
Abstract
The present invention provides a process comprising the steps of a) melt reacting at least one glycol and at least one dicarboxylic acid to form a polyester having an IhV of at least about 0.5 dl/g, wherein said at least one glycol is selected from the group consisting of glycols having up to 10 carbon atoms and mixtures thereof and said dicarboxylic is selected from the group consisting of alkyl dicarboxylic acids having 2 to 16 carbon atoms, aryl dicarboxylic acids having 8 to 16 carbon atoms and mixtures thereof; and b) forming said polyester into shaped articles directly from step a). Thus, the present invention provides a 'direct melt to mold' process for forming polyester articles.
Description
Background of invention
Polyester is widely used in the production of fiber, moulded parts, film, sheet material, food disc and food and drink container.These polymkeric substance are generally by the prepared in reaction of melt polycondensation in batches or continuously for those skilled in the art were familiar with.Then with described polymkeric substance pelletizing and be used for various extruding and molded operation.Need in the application of high-molecular weight polymer at some, made pellet is placed under " solid-state " polycondensation condition that significantly improves limiting viscosity (IhV) value.The reaction of this solid state condensation needs, because be quite high for the melt viscosity of IhV value polyester polymers greater than 0.6 polymkeric substance.
In the preparation or the course of processing of the polyester of melt phase, form some byproduct.Wherein a kind of byproduct is an acetaldehyde, and its existence is extremely harmful to mouthfeel in moulded parts such as food product containers, beverage bottle, water bottle etc.Particularly for responsive beverage as can happy water, it would be desirable that producing acetaldehyde is lower than 10ppm, preferably is lower than the prefabrication of 5ppm.It is very difficult reaching so low acetaldehyde level, and still, because as well known by the skilled person in the art, acetaldehyde is to form continuously as a kind of byproduct in the polymerization of PET and similar polymkeric substance and melting process subsequently.
Therefore, before the present invention occurs, generally adopt a kind of three-step approach to provide always and be applicable to the polyester polymers that reduces the significant purposes of acetaldehyde.This method generally comprises the preparation of the relative lower molecular weight precursor polymer with IhV value of 0.6 that is undertaken by the melt polymerization technology known in this area.The acetaldehyde of this precursor is according to the difference of selected reaction conditions, scope can be from 30ppm to 150ppm more than.Then with this precursor cooling, granulating, crystallization with carry out solid-state polymerization.In general, use a kind of rare gas element to come from made pellet, to propose ethylene glycol, acetaldehyde and other byproducts of reaction, thus when described solid state reaction finishes, IhV value brought up to 0.70 or more than, acetaldehyde has been reduced to below the 1ppm or still less.For goods such as the beverage bottle prefabrication of making useful shape, so the product of preparation also must be heated in the 3rd step and melt, this process generally can cause acetaldehyde from pellet be lower than 1ppm be raised to 8 in the moulded products or 10ppm or more than.Although moulding process is finished in less than one or two minute usually, so big rising still takes place in acetaldehyde.We have found a kind of method now, polyester such as PET and similarly polymkeric substance can the molten state preparation, as if purifying falls excessive acetaldehyde and other by products and directly be molded as all beverage bottle prefabrication of useful moulded products from melting charge according to this, described moulded products has low unexpectedly acetaldehyde.The inventive method has not only avoided using the height of ordinary method to expend additional step as cooling, chopping, drying, crystallization, solid-state polymerization with melt etc. again, and the moulded products that is prepared by this law also has other good characteristics except that low acetaldehyde content, such as better color, still less because the loss of molecular weight that causes of fracture, and do not have the what is called " bubble " that forms sometimes during conventional crystallization/solid-state polymerization and/or the processed molding and the fault of " not fusant ".In the narration below, various advantages of the present invention will be conspicuous.
U.S.'s sequence number 08/498,404 has been described the apparatus and method of molten polymer distribution to many mould machines.
The acetaldehyde that U.S.'s sequence number 08/501,114 has been described by using a kind of inert gas purge agent to contact with molten polyester fusion PET is reduced to the modification method that is suitable for the direct level of using in the food product pack goods are provided.
Japanese patent application 53-71162 (1978) has described again the molten polyester sheet and has kept described molten polymer to reduce the method for acetaldehyde concentration under vacuum.
U.S.4,263,425 have described the PET of the polymkeric substance with low acetaldehyde concentration are provided the solid stated of pellet.The document discloses the elimination of the part acetaldehyde that reaches by the processing of stirring melting charge under the comparatively high temps under the vacuum.
U.S.4,064,112 has described the method that overcomes adhesion problems in solid-state processing.It discloses the molten state that does not have solid stated and has handled and to make that acetaldehyde concentration raises in the molten polyester.
U.S.4,154,920 solid stated of having described the melt polymerization of the polymkeric substance that IhV=0.4-0.6 is provided and the polymkeric substance of the IhV of tool more than 0.7 being provided.It has also narrated the use film to finish rapid polymerization, as the polymerization in the Luwa thin-film evaporator.
U.S.4,372,910 have described the method and apparatus of molding hollow plastic articles.It has been described in a forcing machine again the fusion pellet and the plasticizing resin of heat is extruded into parison in proper order and then parison directly is transferred to the blowing moulding process from a continuous fusion stream.
U.S.4,836,767 reduce the method for acetaldehyde when having described molding.It has been stated the linear in time increase of acetaldehyde and has increased with humidity index.
Japanese patent application 57-191320 (1982) has described just before the fiber melt-spun method of the acetaldehyde concentration in the pet polymer being reduced to below the 300ppm.
Japanese patent application 55-069618 (1980) has stated by melt polymerization, then has been extruded into fiber or film and subsequently fiber or film obtained the PET that acetaldehyde is lower than 20ppm by a kind of fluid or vacuum.Used fluid comprises air, nitrogen, water and steam.
U.S.5,270,444 and U.S.5,241,046 have described the amount that reduces acetaldehyde and cyclic oligomer in the described polymkeric substance with water treatment PET.
U.S.5,262,513 have set forth that oligomer is 1-2% in molten polymer, and oligomer is 0.5-1.0% in solid-state pet polymer.
U.S.5,169,582 have described the vented extruder that vacuum is applied to connection to remove monomer methods from nylon-6 (hexanolactam) polymkeric substance.U.S.3,183,366 and 3,578,640 disclose directly spinning of nylon-6.U.S.3,657,195 disclose by in the presence of steam in an exhaust screw extrusion press continuous condensed lower molecular weight nylon-6, the production of 6 high molecular weight nylons that carry out 6,6.
Following patent disclosure all respects of solid stated: U.S.4,963,644,4,223,128,4,591,629,4,395,222,4,374,97 and 5,119,170 and U.S.5,090,134, they disclose the solid stated pet polymer to obtaining the necessity of low acetaldehyde concentration.
U.S.4,820,795 have stated by molten polyester and melting charge have been injected mould and prepared a kind of container.Acetaldehyde concentration is selected crystalline with polymkeric substance to make up by catalyzer to reduce.
U.S.5,246,992 provide about being formed the background of the mechanism of acetaldehyde by PET, and have stated that the thermolysis of PET is subjected to the influence of temperature of reaction level, residence time and the influence that may be subjected to polycondensation catalyst character.
U.S.4,237,261 have described the straight spinning method of PET fiber.The IhV of this polymkeric substance must only be 0.6, does not mention the content that moulded parts, minimizing degraded product or acetaldehyde form.
U.S.4,230,819 have described with the acetaldehyde in dry inert gas (air under 170-250 ℃ or nitrogen) the removal crystalline PET.And stated by the decompression heating and can not remove acetaldehyde fully.
U.S.4,142,040 have stated to reducing acetaldehyde and form get rid of gaseous oxygen before the PET fusion He in the melting treatment.
Following patent relates to the volatile matter that removes of PET:
U.S.5,102,594 (powdered thermoplasticity condensation polymer being provided to vented extruder) for removing volatile matter and fusion; U.S.4,980,105 (in forcing machine, polycarbonate being removed volatile matter to remove volatile matter (particularly cyclic dimer) and to force described melting charge to pass through die head); U.S.4,362,852 (molten polymer such as nylon and PET being removed volatile matter) with a rotating disk treater; U.S.3,486,864 (fusion one solid-state prepolymer is also removed the polymerization reactor of volatility diol product then as early as possible with vacuum); U.S.3,913,796 (can effectively remove exhaust injector) as the gas of moisture, air and other volatile matters; And U.S.4,060,226 (having the exhaust injection molding screw extrusion press of discharging gas and steam and producing plastifying material (as nylon and other degradation materials) instrument that removes volatile matter) from spiro rod machine tube
The description of the drawings
Fig. 1 is a schema of the present invention.
Fig. 2 is the methodical schema of elder generation.
Explanation of the present invention
The invention provides the method for producing moulded parts, comprise the following steps:
A) frit reaction at least a two pure and mild at least a dicarboxylic acid are to form the polyester that a kind of IhV is at least 0.5dl/g, wherein said at least a glycol is selected from two pure and mild its mixtures of 10 carbon atoms of tool as many as, and described dicarboxylic acid is selected from the alkyl dicarboxylic aid of tool 2-16 carbon atom, aryl dicarboxylic acid and its mixture of tool 8-16 carbon atom; With
B) will directly make moulded products from the described polyester of step a.
Used term " IhV " is meant the limiting viscosity of polymkeric substance in this, by standard method with the measured in solution of 0.5g polymer dissolution in the mixture of 100ml phenol [60% (volume)] and tetrachloroethane [40% (volume)].
Specifically, the method that the inventive method provides a kind of " being molten to molding (melt to mold) ", wherein polyester polymers or multipolymer are prepared into the IhV value greater than 0.5 in molten state, and melting charge is directly delivered at least one mould machine or the shaper 6 from polycondensation reactor 1 then.Any conventional melt polymerization process that can produce required IhV can be used for described polycondensation, and reactor can comprise one or more reaction vessel or the reaction zones that can produce the polyester of the required IhV of tool.In general, described molten polyester is to import to 6 from 1 by a kind of rheid pump such as forcing machine, toothed gear pump or diskpac pump.Only show a mould machine among Fig. 1 although should understand, can use many mould machines.
Preferably polymkeric substance is removed volatile matter to remove acetaldehyde and other bad volatile matters.The described volatile matter step of removing can coexist as polycondensation reactor 1 or coexist as carrying out except that in the volatile matter device (not shown) separately of mould machine 6.
Fig. 2 has shown the method that prior art is used.The numbering of conventional equipment is identical with Fig. 1.With shown in Figure 1 the same, ordinary method also is to form polymkeric substance earlier in melt polymerization device 1.Molten polymer imported in the dicing machine (2) be extruded into solid grain.After the pelletizing, institute's pelletizing material can store or directly send into crystallization apparatus 3.After the crystallization, pellet is directed in the solid stated device 4, and the IhV of pellet and molecular weight are enhanced desired level and acetaldehyde is removed there.Crystallization apparatus and solid stated device in certain methods, have been merged.After the solid stated, described pellet is stored (in warehouse or railcar (railcar) 5), is transported to shaper (passing through railcar), stores (railcar or warehouse) and drying alternatively again.At last, described shaper imports forcing machine or other molded device 6 with described pellet, makes the finished product.Dicing machine, crystallization apparatus, solid stated device, drying machine, forcing machine and molded device all are to be generally those skilled in the art to be familiar with.
Therefore, from Fig. 1 and Fig. 2 more as can be seen.The inventive method has been eliminated the needs of fused again to pelletizing, crystallization, solid stated, drying and molded device prepolymer.A large amount of expenses (because reduced equipment claimed and can need) have not only been saved in the omission of these steps, and have reduced bad pollutent such as the acetaldehyde in the polymkeric substance of producing and the concentration of other volatile matters.
Described moulding-forming equipment 6 can be the device that any those skilled in the art of being generally are familiar with.For example, injection mould can be used for forming and is used for the parison of bottle blowing, food container, dish or other desired shapes.The polymer melt material also can be used in the extrusion blow molded operation so that bottle, food product containers etc. to be provided.Described polymer melt material can be delivered in the forcing machine equally to produce film, sheet material, section bar, pipe etc.
Under the situation that acetaldehyde is low in requiring final moulded parts, found that acetaldehyde can easily use a kind of rheid treater such as forcing machine, thin-film evaporator or place under the vacuum condition (the special sequence number 08/501,114 of the U.S.) to remove with the diskpac of inert gas purge or with melting charge from molten polymer.Any rheid treater that can produce the melting charge surface of big surface area per unit volume and/or fast rapid regeneration exposure all can be used for this step.Like this, the acetaldehyde level can easily drop to below the 10ppm.Before this is handled, from the typical concentration of acetaldehyde in the polymkeric substance of end reaction device normally 30ppm to surpassing 150ppm.
After removing acetaldehyde, the time span that restriction molded operation prepolymer is in molten state is important, because may produce other acetaldehyde in the molten polymer.The experience of conventional molded operation shows that this other acetaldehyde accumulation rate is exceedingly fast.For example, less than in 1 or 2 minute treatment time, the content of free aldehyde of polymkeric substance can be from pellet brings up to more than the 8-10ppm in bottle parison less than 1ppm in conventional mould machine.The acetaldehyde accumulation of this fast speed has seemed to get rid of the hands-on approach of any distribution and molding quantity-produced molten polymer, and anyway removes acetaldehyde well.
Yet, find unexpectedly to be starkly lower than by the pellet speed in the polyester melting charge that provides of fusion again at our acetaldehyde regeneration rate in the molding methods of being molten to.Like this, the molten polymer of being produced by our method can remain on the much longer time of molten state and not have undue acetaldehyde accumulation when handling.But, our being molten in the molding methods, the time limitation that is in molten state after preferably acetaldehyde is removed is being less than 8-10 minute.
Preferred practice of the present invention comprises: 1) melt polymerization; 2) molten state is removed volatile matter; With 3) directly polyester is made moulded products from molten state.For feasible hands-on approach is described, the selection that provide polymerization, removes volatile matter and molded aspect.
Described polymerization best incorporated polymer filtration step is carried out together.This filtration step should be finished in suitable processing as early as possible, so that the blackspot in keeping polymkeric substance utilizes than the low viscosity level in acceptable level.For example, if used two polycondensation reactors,, preferably filter is placed between them in order under lower melting charge viscosity, to filter.
Two embodiments of polymeric part partly are:
A) behind high IhV (＞0.68) the molten state reactor that filter is followed in routine.These reactors can be reactors well known in the art, such as being disclosed in U.S.5, and 055,273 or U.S.5,207,991 reactor, described patent is incorporated in this by reference.
B) prepare behind the conventional molten state reactor of polyester of IhV=0.4-0.65 and then polymkeric substance filter by any currently known methods, high-viscosity polyester that more and then can continuous condensed generation IhV＞0.68 behind the filter and produce another devices of a large amount of liquid surface area.This can finish by the reactor and the device that use known type, such as exhaust list screw rod or twin screw extruder (as U.S.4,107,787), thin-film evaporator (U.S.3,678,983), whereabouts thin wire (U.S.3,161,710), film (U.S.4,647,650) device (U.S.3 that, has the agitator of band metallic sieve, 256,484) or have device (U.S.3,279 of the agitator that the porous cage makes, 895), all these patents are all incorporated in this by reference.
The possible embodiment of removing volatile matter and molding function is:
A) in a device, whole polymer flow is removed volatile matter, then polymer distribution is arrived many multimembrane-cavity mould machines.
B) polymer distribution is removed in the volatile matter device to many, every table apparatus all will hang down acetaldehyde polymer and directly deliver in the coupled multimembrane-cavity mould machine.
C) polymer distribution is removed in the volatile matter device to many, the polymkeric substance that will remove volatile matter then is assigned to two or many mould machines from respectively removing the volatile matter device.
Described can be the device well known in the art on the melting charge surface of big per unit volume surface-area of any generation and/or fast rapid regeneration exposure except that the volatile matter device.This volatile matter device that removes should be able to or apply vacuum by inert gas purge and makes and have only low acetaldehyde dividing potential drop on the described fluid surface.This volatile matter device that removes can be exhaust single screw extrusion machine (U.S.4,107,787), exhaust twin screw extruder (U.S.3,619,145), rotating disk treater (U.S.4,362,852) or produce the device of polymkeric substance thin wire, all described patents are all incorporated in this by reference.
Under the situation of high-performance final polymerization reactor, equipment design, productivity and set of operating conditions can promote to improve the molecular weight of polyester and take off acetaldehyde in same equipment.In this embodiment preferred, described polymkeric substance is assigned in many multimembrane-cavity mould machines apace by the toothed gear pump that is directly connected to reactor outlet.In this embodiment, must SC reduce polymkeric substance at reactor outlet with lead to bridging in the distributing pipelines of mould machine.
Concerning poly-(ethylene glycol terephthalate) polymkeric substance, the melting treatment temperature that is fit to generally is 260-310 ℃.Certainly, for the polyester of other types, treatment temp can wait and regulate according to fusing point, IhV value.
Our advantage that is molten to molding methods is as follows:
1. operation is gone up than pelletizing, solid stated, drying and is melted considerably cheaper again.
2. energy-conservation.
3. type embryo or moulded parts have the transparency, color preferably, do not have not fusant or other defect, lower bad by-product concentration.
4. do not use additive just to reach the lower concentration of acetaldehyde.
5. it is lower that the acetaldehyde regeneration rate of the polymer melt material that provides is lower than the polymer melt material of using again the fusion pellet to obtain.
6. lower capital requirement.
The polymkeric substance that specifically can be used for the inventive method comprises poly-(ethylene glycol terephthalate), gathers ((ethylene naphthalate)) and contains the modification diprotic acid of as many as 50% (mole) and/or the copolyesters of glycol.The modification diprotic acid can comprise 2-40 carbon atom, and comprise m-phthalic acid, hexanodioic acid, pentanedioic acid, nonane diacid, sebacic acid, fumaric acid, dipolymer, along or anti-1, the various isomer of 4-cyclohexyl dicarboxylic acid, naphthalic acid etc.Polyester more preferably of the present invention comprises terephthalic acid, naphthalic acid or its mixture of at least 80% (mole).
Highly useful naphthalene diacid comprises 2,6-, and 1,4-, 1,5-, or 2, the 7-isomer, but 1,2-, 1,3-, 1,6-, 1,7-, 1,8-, 2,3-, 2,4-, 2,5-and/or 2, the 8-isomer also can use.Described diprotic acid can acid use or use like an elephant the form of dimethyl ester with its ester.
Typical modification glycol can comprise 3-10 carbon atom, comprises propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, Diethylene Glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol etc.Described cyclohexanedimethanol can be a cis or trans, also can be suitable/back mixing compound.Polyester more preferably of the present invention comprises the ethylene glycol of at least 80% (mole).
Particularly preferred polyester comprises the mixture of terephthalic acid and 60-99% (mole) ethylene glycol and 40-1% (mole) cyclohexanedimethanol.
In general, the IhV of the polyester of producing in the first step of the present invention is at least 0.5dl/g, more preferably is at least 0.65dl/g and 0.65-0.85dl/g most preferably.
Polyester of the present invention is easy to polycondensation condition preparation well known in the art.Typical available polyesterification reaction catalyzer comprises alcoholization titanium, dibutyl tin dilaurate and weisspiessglanz or nitrilotriacetic antimony, and they can use separately or mix use with acetate or benzoic zinc, manganese or magnesium salts and/or other this catalystic materials well known to those skilled in the art alternatively.Phosphorus or cobalt compound also can exist alternatively.Although we preferably use the continuous polycondensation device, the batch reactor of sequential operation also can use.
Although we preferably use the polyester of unmodified form in the method, also can use other components such as nucleator, branching agent, tinting material, pigment, filler, antioxidant, UV-light and thermo-stabilizer, impact modifying agent etc. if desired.
Embodiment
The following example further specifies the present invention.However, it should be understood that they only are used to furnish an explanation, and do not want to limit scope of the present invention.Residual acetaldehyde is meant the built-in acetaldehyde of pet polymer parent after fusion course the preceding necessarily.The measuring process of residual acetaldehyde is at first sample to be placed-40 ℃ of refrigeratores up to being ready to analysis.At this moment take out sample and place liquid nitrogen also to wear into less than 20 purpose pellets from refrigerator with little laboratory scale Wiley mill low temperature.The abrasive dust samples of about 50 grams are packed in the metal GC desorption tube of analyzing for AA.Each sample carries out two parallel laboratory tests and averages.Described sample hose is stored in-40 ℃ of refrigeratores analyzes up to GC.
For the GC desorption condition of analyzing be 150 ℃ following 10 minutes, at this moment between in AA sweep in the trap and under liquid nitrogen temperature by desorb and by means of rare gas element and collect.Subsequently AA is separated from trap and be drawn onto on the GC post, and come quantitatively by cold-trap being heated to 300 ℃.
The result that this result and 24 hours acetaldehyde are separated the head space that is drawn onto a bottle comparison shows that in the 2L bottle head space AA of l μ g/L is equivalent to the residual AA of about 3ppm of above-mentioned experimental measurement.Embodiment 1
Will be after filtration, with 3.5% (mole) 1, (suitable, the back mixing compound of a kind of 30/70% (mole)) modification of 4-cyclohexanedimethanol and IhV are that 0.64 Polyethylene Terephthalates (PET) is sent in the exhaust double-screw reactor.After being detained 25 minutes under the pressure of 275 ℃ temperature and 0.75 holder, the IhV of polymkeric substance is a residual acetaldehyde 0.75 and that contain 5ppm.Then the distribution piping valve system of polymkeric substance by about 2 minutes average retention times of tool is pumped in four independent mould machines.Every mould machine is cooled to be lower than before 200 ℃ at polymkeric substance all to have about 40 seconds residence time.The amount of residual acetaldehyde is 9ppm in the 0.75IhV of this molding prefabrication.Embodiment 2
PET is prepared into IhV is 0.74 under 285 ℃ whole melt temperature, after the filtration with described diverting flow be assigned to four and remove in the volatile matter degassing extruder.The flow velocity of per share stream equals a multicavity mold machine capacity.Enter the residual acetaldehyde that the polymkeric substance that removes the volatile matter forcing machine contains 210ppm.With the described volatile matter equipment that removes of nitrogen purge.Average delay in removing volatile matter equipment is in 15 minutes, and polymkeric substance is cooled to 280 ℃.Have the residual acetaldehyde of 5ppm from the described polymkeric substance that comes out except that volatile matter equipment, and directly eject the multimembrane-cavity mould machine.The prefabrication that is produced has 0.77 IhV and the acetaldehyde of 8ppm.Embodiment 3
Present embodiment adopts the equipment layout identical with embodiment 2.PET is prepared into 0.67 IhV at 270 ℃ in the molten state reactor, and it contains the 60ppm residual acetaldehyde after filtering and deliver to vented extruder.Under nitrogen purge each remove be detained 10 minutes in the volatile matter equipment after, polymkeric substance is molded as the IhV of tool 0.70 and the prefabrication of 3.5ppm residual acetaldehyde.Embodiment 4
Present embodiment adopts the equipment layout identical with embodiment 2.PET is prepared into 0.75 IhV at 270 ℃ in the molten state reactor, and it contains the 80ppm residual acetaldehyde after filtering and deliver to vented extruder.Under nitrogen purge each remove be detained 5 minutes in the volatile matter equipment and spent be cooled in about 2 minutes before be input in the mould after, the IhV of polymkeric substance tool 0.75 and 10ppm residual acetaldehyde.Transport except that the volatile matter device with by during mould machine is in the mould at polymkeric substance, record acetaldehyde again generation rate be per minute 1ppm.Embodiment 5
Temperature at 275 ℃ is prepared into IhV=0.71 with PET, and the PET pump is crossed a filter pump remove volatile matter device/reactor to what operate under the pressure of 275 ℃ temperature and 0.75 holder.After residence time residual acetaldehyde at 10 minutes is lowered to 6ppm, described polymer pump is crossed a distribution system to four a multimembrane-cavity mould machine with a toothed gear pump.The prefabrication that obtains has 0.75 IhV and the residual acetaldehyde of 10ppm.Embodiment 6
Temperature at 275 ℃ is prepared into IhV=0.5 with PET, and the PET pump is crossed a filter to another polycondensation reactor that operates under the pressure of 275 ℃ temperature and 0.75 holder.This reactor produce a large amount of surface-area and in 30 minutes described polymkeric substance reach 0.75 IhV.Then the molten polymer pump of tool 20ppm acetaldehyde is crossed a porous mouth mould and formed thin wire, the fell open container of a usefulness inert gas purge of described thin wire.Collect molten polymer then in the bottom of described container and be assigned in four mould machines.The prefabrication that obtains has 0.75 IhV and the residual acetaldehyde of 10ppm.Embodiment 7
PET is prepared into IhV=0.64 by common process under 285 ℃ whole melt temperature.After pump was crossed a filter and distribution system, the polymkeric substance that will contain the 100ppm residual acetaldehyde was delivered to two except that in the volatile matter reactor.Described reactor/remove volatile matter equipment operates under 0.75 backing pressure power and polymkeric substance is cooled to 275 ℃.After 20 minutes residence time, will be from every polymkeric substance that removes volatile matter equipment by in a toothed gear pump pump to the two multimembrane-cavity mould machine.The storing die cavity of filling every mould machine in proper order by a switch-valve that is fit to and distribution pipeline.Keep like this from the steady flow that removes volatile matter equipment/forcing machine.The prefabrication that obtains has 0.75 IhV and the residual acetaldehyde content of 9ppm.
Claims (12)
1. produce the method for moulded parts, comprise the following steps:
A) frit reaction at least a two pure and mild at least a dicarboxylic acid are to form the polyester that IhV is at least 0.5dl/g, wherein said at least a glycol is selected from two pure and mild its mixtures of 10 carbon atoms of tool as many as, and described dicarboxylic acid is selected from the alkyl dicarboxylic aid of tool 2-16 carbon atom, aryl dicarboxylic acid and its mixture of tool 8-16 carbon atom; With
B) will directly make moulded products from the described polyester of step a.
2. the method for claim 1 also is included in the preceding step of described polyester being removed volatile matter removal acetaldehyde of described forming step (b).
3. the process of claim 1 wherein that the IhV of described polyester from step a is at least 0.65dl/g.
4. according to the process of claim 1 wherein that described dicarboxylic acid comprises at least 80% (mole) terephthalic acid or naphthalic acid.
5. the process of claim 1 wherein that described glycol comprises the ethylene glycol of at least 80% (mole).
6. claim 1 or 4 method, wherein said glycol is the mixture of ethylene glycol and cyclohexanedimethanol.
7. the method for claim 2 is wherein reacted and is removed the volatile matter step and carry out on single device.
8. the method for claim 2 is wherein saidly removed carrying out except that the volatile matter device of the melting charge surface of volatile matter step by producing a large amount of surface area per unit volume and/or fast rapid regeneration exposure.
9. the process of claim 1 wherein that step b) carries out in one or more multimembrane-cavity mould machine.
10. the process of claim 1 wherein that step a) carries out in following a kind of device: exhaust single screw extrusion machine, twin screw extruder, thin-film evaporator, whereabouts fine rule material and have the film of the agitator of making by the porous cage.
11. the method for claim 2, the wherein said volatile matter that removes is undertaken by a following method: whole polymer flow is removed volatile matter in a device, then polymer distribution is arrived many multimembrane-cavity mould machines;
Described polyester is assigned to a plurality of removing in the volatile matter device, and each device all will hang down the acetaldehyde polyester and directly deliver in the multimembrane-cavity mould machine; With
With described polyester be assigned to a plurality of remove to form in the volatile matter device remove the volatile matter polyester, and will be assigned in two or many mould machines from each volatile matter polyester that removes that removes the volatile matter device.
12. the method for claim 1 or 2, wherein said polyester has the acetaldehyde that is less than 10ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60919796A | 1996-03-01 | 1996-03-01 | |
| US08/609,197 | 1996-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1217002A true CN1217002A (en) | 1999-05-19 |
Family
ID=24439751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97194115A Pending CN1217002A (en) | 1996-03-01 | 1997-02-27 | Process for forming articles directly from melt polymerization |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0883643A1 (en) |
| JP (1) | JP2000506199A (en) |
| CN (1) | CN1217002A (en) |
| AR (1) | AR006022A1 (en) |
| AU (1) | AU1977797A (en) |
| CA (1) | CA2248268A1 (en) |
| CO (1) | CO4560470A1 (en) |
| ID (1) | ID16094A (en) |
| PL (1) | PL328606A1 (en) |
| WO (1) | WO1997031968A1 (en) |
| ZA (1) | ZA971744B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6099778A (en) * | 1996-10-28 | 2000-08-08 | Eastman Chemical Company | Process for producing pet articles with low acetaldehyde |
| DE10045719B4 (en) * | 2000-09-15 | 2018-01-11 | Inventa-Fischer Gmbh & Co. Kg | Process for the preparation of polyesters with reduced content of acetaldehyde |
| US6762275B1 (en) | 2003-05-27 | 2004-07-13 | The Coca-Cola Company | Method to decrease the acetaldehyde content of melt-processed polyesters |
| US20050029712A1 (en) * | 2003-08-05 | 2005-02-10 | Nahill Thomas E. | Continuous production of container preforms |
| MXPA06003846A (en) * | 2003-10-10 | 2006-07-03 | Asahi Kasei Chemicals Corp | Process for producing polyalkylene terephthalate, process for producing polyalkylene terephthalate molding and polyalkylene terephthalate molding. |
| TWI316525B (en) | 2004-11-30 | 2009-11-01 | Asahi Kasei Chemicals Corp | Method and apparatus for producing molded product |
| JP4744450B2 (en) | 2004-11-30 | 2011-08-10 | 旭化成ケミカルズ株式会社 | POLYESTER RESIN, MOLDED ARTICLE THEREOF, AND METHOD FOR PRODUCING THEM |
| JP4770265B2 (en) * | 2005-05-18 | 2011-09-14 | 東洋製罐株式会社 | Melt polymerization / compression molding system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3654231A (en) * | 1970-06-29 | 1972-04-04 | Eastman Kodak Co | Manufacture of extruded superpolyester products |
| US4675378A (en) * | 1986-05-19 | 1987-06-23 | Celanese Corporation | Process control system |
-
1997
- 1997-02-26 ID IDP970576A patent/ID16094A/en unknown
- 1997-02-27 WO PCT/US1997/003037 patent/WO1997031968A1/en not_active Application Discontinuation
- 1997-02-27 EP EP97907893A patent/EP0883643A1/en not_active Withdrawn
- 1997-02-27 ZA ZA9701744A patent/ZA971744B/en unknown
- 1997-02-27 CA CA002248268A patent/CA2248268A1/en not_active Abandoned
- 1997-02-27 PL PL97328606A patent/PL328606A1/en unknown
- 1997-02-27 AU AU19777/97A patent/AU1977797A/en not_active Abandoned
- 1997-02-27 CN CN97194115A patent/CN1217002A/en active Pending
- 1997-02-27 JP JP9531102A patent/JP2000506199A/en active Pending
- 1997-02-27 AR ARP970100787A patent/AR006022A1/en unknown
- 1997-02-28 CO CO97010919A patent/CO4560470A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ID16094A (en) | 1997-09-04 |
| CO4560470A1 (en) | 1998-02-10 |
| WO1997031968A1 (en) | 1997-09-04 |
| CA2248268A1 (en) | 1997-09-04 |
| JP2000506199A (en) | 2000-05-23 |
| AU1977797A (en) | 1997-09-16 |
| ZA971744B (en) | 1997-09-04 |
| PL328606A1 (en) | 1999-02-01 |
| AR006022A1 (en) | 1999-07-21 |
| EP0883643A1 (en) | 1998-12-16 |
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