RU2360798C2 - Method and device for production of moulded product - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: first version of the method consists in the fact that prepolymer in melted condition is continuously supplied from channel of prepolymer supply to polymerisation reactor. Further prepolymer is unloaded from holes of porous plate and is polymerised by reaction of polycondensation in melt in process of discharge on substrate at lower pressure. Produced resin in melt condition without hardening is transferred at least in one moulding machine. Pressure of transfer in moulding machine is controlled so that pressure is maintained at arbitrary level from 0.1 to 100 MPa (absolute pressure). Pressure is maintained by means of (I) control of discharged amount from unloading pump of polymerisation reactor at the level of 1-100 from value of prepolymer supply flow and by means of (II) return of resin unloaded from unloading pump to bottom of polymerisation reactor comprising pipeline connected to discharged flow from unloading pump of polymerisation reactor and bottom of polymerisation reactor, and system of pressure measurement at the outlet and control of opening extent of polymer return valve or return pressure valve installed in pipeline. Resin polymerised by reaction of polycondensation in melt represents polymer selected from group that contains aliphatic polyethers, aliphatic polyamides, aliphatic polycarbonates, aliphatic aromatic polyethers, aliphatic aromatic polyamides, aliphatic aromatic polycarbonates, aromatic polyethers and aromatic polyamides. According to the second version of the method, unloading of melt resin from reactor of polymerisation is realised with application of at least two unloading pumps, and resin transfer is realised at least into two moulding machines and/or granulating machines. Device for production of moulded product according to the first version includes channel of prepolymer supply in reactor of polymerisation having bottom and substrate, porous plate with holes, unloading pump, pipeline connected to discharged flow from unloading pump, system of pressure measurement at the inlet, valve of polymer return or return pressure valve installed in pipeline, and moulding machine. Device for production of moulded product according to the second version includes channel of prepolymer supply in reactor of polymerisation having bottom and substrate, porous plate with holes, at least two unloading pumps, pipeline connected to discharged flow from unloading pump, system of pressure measurement at the inlet, valve of polymer return or return pressure valve installed in pipeline, and at least two moulding machines and/or granulating machines.

EFFECT: high-quality molded product with high yield, good colour and lower content of side products.

19 cl, 14 tbl, 9 ex, 11 dwg

Description

FIELD OF THE INVENTION

The present invention relates to a method for producing a molded product consisting of a resin polymerized by a melt polycondensation reaction.

BACKGROUND OF THE INVENTION

It is known that various polycondensation polymers represented by a polyester resin such as polyethylene terephthalate (hereinafter “PET”) have such characteristics as excellent thermal and mechanical properties and, recently, also as environmentally acceptable reusable material and are widely used as fibers, magnetic tapes, packaging films, linens or injection molded products for various applications or blanks in the manufacture of beverage containers.

In particular, the production of a hollow product obtained by blow molding a preform having excellent characteristics, such as light weight, impact resistance and transparency, along with the recyclability suitable for various beverage containers such as carbonated beverage, is rapidly increasing. or juice, tea and mineral water, or liquid spices such as soy sauce, fruit puree and salad oil, cosmetic and liquid detergents, and such sales are expected will further expand in the future.

These containers require not only excellent strength, shock resistance and transparency, but also no effect on the taste of the contents. Thus, the polycondensation polymer used requires a high degree of polymerization, no staining and high quality with a low content of impurities formed by thermal decomposition, for example, acetaldehyde. In addition, such a polycondensation polymer requires strictly industrially stable production, with good productivity and low cost.

In the case of a hollow product obtained from polyethylene terephthalate resin, the preform is obtained by blow molding of granules of resin obtained by solid phase polymerization, which gives low coloring and a small content of acetaldehyde; however, recently, as a low-cost production method, a method has been proposed for producing a preform by pumping polyethylene terephthalate resin obtained by continuous melt polymerization into a preform molding machine in the molten state as it is (see, for example, patents 1-16).

To obtain a molded product with stable quality, it is necessary to regulate the quality and quantity of the molten resin pumped into the molding machine at a constant speed. However, the methods proposed to date, are not easy to maintain the quality of the molded product, since the polycondensed resin represented by a polyethylene terephthalate resin, during a long period of stay in the molten state leads to a thermal decomposition reaction, which leads to problems of reduced quality, such as depending on the residence time, the accumulation of a decomposition product such as acetaldehyde, molecular weight reduction and staining. In addition to the above, the molecular weight may decrease during the pumping of the resin dispatched from the polymerization reactor to the molding machine, which can lead to a variation in the melt viscosity and thus the pumped amount. The amount pumped to the molding machine can also vary with the viscosity of the molten resin dispatched from the polymerization reactor by a preliminary change in the polymerization system.

The methods typically proposed also have difficulty matching the “resin production rate” in the melt polymerization reactor and the “resin formation rate” in the molding machine. For example, when the molding machine breaks down or the molding machine is stopped to remove the oligomer and similar adherence to the mold, the “resin molding speed” in the molding machine is lower than the “resin producing rate” in the melt polymerization reactor. Conversely, the "resin production rate" in the melt polymerization reactor may be lower than the "resin formation rate" in the molding machine when the reaction in the polymerization system stalls. As described above, the mutual variation of the "resin production rate" and the "resin molding rate" leads to a variation in the quality of the resin due to a change in the residence time of the resin in the melt in the inlet stream longer than that of the molding machine.

In addition, an injection molding machine, such as a preform molding machine, has the problem that the flow of molten resin from the melt polymerization reactor is intermittent due to multiple molding of the resin doses and the casting cycle, which always causes a variation in the residence time of the resin in the melt .

Patent 2 for the first time describes a compensation method for intermittent flow into an injection molding machine by opening the feed channel of a molding machine in a specific sequence to achieve a substantially constant flow of material during molding using multiple molding machines in a practical method for producing the above-described molded product; however, this patent does not provide for varying the quality or melt viscosity of the resin fed to the molding machine. As described above, the mutual variation of the “resin production rate” and the “resin molding rate” leads to a variation in the quality of the resin. This method also has the problem of generating a large number of defective products or losses until the quality of the molded product is stably restored after a single accident occurs, since a complicated system or replacement sequence is required.

Patents 4, 6, 7, 9, 10, and 14 for the first time describe a method for transferring an aldehyde that is formed and accumulates in the resin during the polymer’s stay in the melt during polymerisation in the melt until it cools and solidifies after polymerisation in the melt and transfer to the molding machine, in harmless form by adding an acetaldehyde scavenger. However, this is not effective in relation to the problem of reducing the molecular weight of the resin, although it can be applied as a measure for acetaldehyde in the case of varying the quality of the resin and the pumped amount of resin supplied to the molding machine and also mutually varying the “resin production rate” and “molding speed resin. " In addition, there is also the problem of deterioration in the color tone of the resin under the action of the acetaldehyde absorber itself.

Other patents among patents 1-16 do not offer technology for completely eliminating changes in the quality of the molded product in the event of variations in the quality and pumped amount of resin supplied to the molding machine, and also mutually varying “resin production rate” and “resin molding rate”.

[Patent 1] JP No. 3345250

[Patent 2] JP-A-11-508836

[Patent 3] JP-A-11-511187

[Patent 4] USP No. 5656221

[Patent 5] JP-A-2000-506199

[Patent 6] JP-A-2002-514239

[Patent 7] JP-A-2001-516297

[Patent 8] WO 98/41559

[Patent 9] JP-A-2001-516389

[Patent 10] JP-A-2001-517164

[Patent 11] JP-A-2000-117819

[Patent 12] WO 2004/24577

[Patent 13] US-A-2005-29712

[Patent 14] DE-A-10356298

[Patent 15] JP-A-2005-171081

[Patent 16] JP-A-2005-193379

LIST OF PROBLEMS SOLVED IN THE INVENTION

The objective of the present invention is to create a technology by which it is possible to obtain a molded product with stable quality and weight during the period of action. The technology is a method of producing a high-quality molded product with a low price by pumping a resin continuously polymerized by a polycondensation reaction in a melt, in which the quality and magnitude of the feed flow of the molten resin supplied to the molding machine are easily controlled, and they are also easily regulated even in the case of mutual variation " resin production rate "and" resin formation rate "in the molten state as it is.

The authors intensively studied ways to solve the above problems and found that melt polycondensation is possible at a low temperature never achieved in a well-known polymerization device, in a method for producing a molded product characterized by continuous polymerization of a resin by a melt polycondensation, pumping the polymerized resin in the molten state in the molten state at least one molding machine, and melt molding. Namely, by applying a polymerization reactor based on a new principle, the prepolymer is continuously fed in a molten state from the feed channel of the prepolymer into the polymerization reactor, is discharged from the openings of the porous plate, followed by polymerization during discharge under reduced pressure on the substrate.

As a result, due to a small variation in the quality and viscosity of the molten molten resin fed into the molding machine, the feed flow and the quality of the resin fed into the molding machine can be kept constant by adjusting the transfer pressure to the molding machine so as to maintain an arbitrary pressure level from 0.1 to 100 MPa (absolute pressure) and also the residence time of the melt during pumping of the resin can be reduced by designing a smaller volume of the transfer pipe (dia emp pipeline) to the molten resin. According to the present invention, the problem of intermittent flow into the molding machine can be solved without a complex system or switching sequence; and the quality of the resin and the magnitude of the feed flow can also be normalized using multiple molding machines.

Due to the possibility of conducting polycondensation in the melt at low temperature, which provides a slight variation in the quality and viscosity of the melt of the molten resin fed into the molding machine, the quality of the resin and the amount of feed flow to multiple molding machines and / or granulating machines can also be stably established by applying the feeding method resin to each individual molding machine and / or granulating machine by installing at least two loading pumps on the floor reactor merizatsii of the present invention.

In addition, it was found that by installing a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine, at the bottom of said polymerization reactor or after a discharge pump of said polymerization reactor to control the output of said transfer pump, based on determining the level of the bottom of the polymerization reactor, and thus, keeping the polymer residence time constant at the bottom of the melt polymerization reactor, it is possible to avoid varying the time byvaniya polymer melt at the bottom of the polymerization reactor, even in case of mutual variation of "resin producing rate" and "resin molding rate", and during the period of action can be obtained a molded product with stable quality and weight.

Based on these findings, the authors created the present invention.

Thus, the present invention includes the following aspects:

1. A method of obtaining a molded product consisting of a resin polymerized by a melt polycondensation reaction, comprising continuously feeding the prepolymer in the molten state from the feed channel of the prepolymer into the polymerization reactor, unloading from the openings of the porous plate, followed by polymerization during discharge under reduced pressure on the substrate and molding by pumping to at least one molding machine in a molten state without curing, where the transfer pressure into said molding Ashina adjusted so that the pressure is maintained at arbitrary level between 0.1 to 100 MPa (absolute pressure).

2. The production method according to claim 1, wherein the transfer pressure to the molding machine is controlled so that the pressure is maintained at an arbitrary level from 0.1 to 100 MPa (absolute pressure) by adjusting the discharged amount from the discharge pump of said polymerization reactor.

3. The production method according to claim 1, in which the transfer pressure into the molding machine is controlled so that the pressure is maintained at an arbitrary level from 0.1 to 100 MPa (absolute pressure) by:

(I) adjusting the discharged amount from the discharge pump of said polymerization reactor at a level of 1-100 from the size of the prepolymer feed stream; and by

(II) a system for returning a resin dispensed from a discharge pump to the bottom of said polymerization reactor, consisting of a pipe connected to a discharge stream of a discharge pump of said polymerization reactor and a bottom of said polymerization reactor and a system for measuring the outlet pressure and controlling the degree of opening of the polymer return valve or the valve back pressure installed on said pipeline.

4. The production method according to claims 1 to 3, in which the transfer pressure into the molding machine is from 0.1 to 100 MPa and is adjusted to maintain a level that does not exceed ± 80% of the set pressure.

5. The production method according to any one of claims 1 to 4, in which the polymer is pumped into a granulating machine and / or an exhaust nozzle, so that the residence time of the polymer in the melt at the bottom is controlled within 0.1-120 minutes by installing said reactor at the bottom polymerization, or after the discharge pump of said polymerization reactor, a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine.

6. A method of obtaining a molded product consisting of a resin polymerized by a melt polycondensation reaction, which includes continuously feeding the prepolymer in the molten state from the feed channel of the prepolymer into the polymerization reactor, unloading from the openings of the porous plate, polymerization during discharge onto the substrate under reduced pressure, shipping said resin from at least two shipping pumps of said polymerization reactor, followed by molding by pumping into at least two ormovochnye machine and / or granulating machine in a molten state without solidification.

7. The production method according to claim 6, in which at least one molding machine and / or granulating machine are associated with each of the shipping pumps of said polymerization reactor.

8. The production method according to any one of claims 1 to 7, in which at least a portion of the polycondensation polymer obtained by said melt polycondensation reaction in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the stages obtaining said polycondensation polymer.

9. A method for producing a molded product according to any one of claims 1 to 8, wherein said prepolymer is reacted with an arbitrary amount of molecular weight regulator at an arbitrary stage before being introduced into said polymerization reactor.

10. A method of producing a molded product according to any one of claims 1 to 9, in which said molded product is at least one type selected from a blank for molding bottles, films, webs, containers and fibers.

11. The production method according to any one of claims 1 to 10, in which the resin polymerized by said melt polycondensation reaction is a polyester resin.

12. A device for producing a molded product, consisting of a resin polymerized by a melt polycondensation reaction, comprising continuously feeding the prepolymer in the molten state from the prepolymer feed channel into the polymerization reactor, unloading from the openings of the porous plate, followed by polymerization during discharge onto the substrate under reduced pressure and molding by pumping to at least one molding machine in a molten state without curing, where the transfer pressure into said molds the full-time machine is adjusted so that the pressure is maintained from 0.1 to 100 MPa (absolute pressure).

13. The device according to item 12, in which the transfer pressure to the molding machine is controlled so that the pressure is maintained from 0.1 to 100 MPa (absolute pressure) by adjusting the discharge amount from the discharge pump of said polymerization reactor.

14. The device according to item 12, in which the transfer pressure into the molding machine is controlled so that the pressure is maintained from 0.1 to 100 MPa (absolute pressure) by:

(I) adjusting the discharged amount from the shipping pump of said polymerization reactor at a level of 1-100 from the magnitude of the feed stream of the prepolymer; and

(II) a system for returning a resin dispensed from a discharge pump to the bottom of said polymerization reactor, consisting of a pipe connected to a discharge stream of a discharge pump of said polymerization reactor and a bottom of said polymerization reactor and a system for measuring the outlet pressure and controlling the degree of opening of the polymer return valve or the valve back pressure installed on said pipeline.

15. The device according to any one of paragraphs.12-14, in which the polymer is pumped into a granulating machine and / or exhaust nozzle, so that the residence time of the polymer in the melt is regulated at a level of from 0.1 to 120 minutes by installing on the bottom of the said polymerization reactor, or after the discharge pump of said polymerization reactor, a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine

16. A device for producing a molded product consisting of a resin polymerized by a melt polycondensation reaction, in which the prepolymer is continuously supplied in the molten state from the prepolymer feed channel into the polymerization reactor, is discharged from the openings of the porous plate, polymerized during discharge onto the substrate under reduced pressure, and the resin is dispatched from at least two shipping pumps of said polymerization reactor, then molded by pumping into at least two molding m machines and / or granulating machines in a molten state without curing.

By using the production method of the present invention in a method for producing a high-quality molded product with low cost by pumping in the molten state, as it is, a resin continuously polymerized by a melt polycondensation reaction, it is possible to easily and stably maintain the quality and magnitude of the feed flow of the molten resin supplied to a molding machine, and also it is easy to adjust them even if the "resin production speed" and the "resin molding speed" are mutually varied; and during the period of action can be obtained molded product with stable quality and weight.

DESCRIPTION OF THE BEST EMBODIMENT

Since the present invention uses a polymerization reactor based on the new principle, (a) the principle of the polymerization method, (b) the polycondensation polymer, (c) the polymerization reactor, (d) the polymerization method and (e) the method are specifically explained below in that order. molding.

(a) Principle of the polymerization process:

The polymerization method of the present invention is a method carried out by feeding the prepolymer resin, which can be polymerized by a melt polycondensation reaction, in the molten state from the prepolymer feed channel to the polymerization reactor, unloading from the openings of the porous plate and dumping by gravity to the substrate at a reduced pressure or inert gas atmosphere under reduced pressure.

As described below, by satisfying acceptable conditions regarding the characteristics of the prepolymer, the structure of the polymerization reactor and the polymerization method when dumped onto the substrate, the prepolymer can contain a large amount of foam and roll down in the polymerization reactor in the form of spherical (massive) structures from the resin as the polymerization proceeds.

This causes a significant increase in the contact area between the resin and the vapor phase, the effect of mixing the resin and the effective removal of the by-product of the polycondensation reaction (ethylene glycol in the case of polyethylene terephthalate) or impurities formed by thermal decomposition during polymerization (acetaldehyde in the case of polyethylene terephthalate) from the prepolymer.

Thus, the polymerization method of the present invention has the advantage of an impressively higher polymerization rate compared to conventional melt polymerization technology; as well as obtaining a resin having a very small residue of impurities and high quality at a low temperature, which is never achieved in a well-known polymerization device.

(b) Polycondensation polymer:

"A resin that can be polymerized by a melt polycondensation reaction" as used in the present invention means a polymer with a structure formed by at least one kind of monomer with two or more condensable functional groups linked through said functional groups. The aforementioned monomer may be either a monomer having said functional groups directly attached to an aliphatic hydrocarbon group, or a monomer having said functional groups directly attached to an aromatic hydrocarbon group.

Specific examples of polycondensed resins include polymers having a linked structure of an aliphatic hydrocarbon group with said functional groups, such as aliphatic polyesters, aliphatic polyamides and aliphatic polycarbonates; polymers having the associated structure of an aliphatic hydrocarbon group and an aromatic hydrocarbon group with the aforementioned functional groups, such as aliphatic aromatic polyesters, aliphatic aromatic polyamides and aliphatic aromatic polycarbonates; and polymers having a linked structure of an aromatic hydrocarbon group with said functional groups, such as aromatic polyesters and aromatic polyamides.

The polycondensed resins described above may be homopolymers or copolymers. They are also copolymers in which various bonds, such as ether bonds, amide bonds and carbonate bonds, may be present in a random or block order. Specific examples of these copolymers include polyether carbonates and polyether amides.

"Prepolymer" means a polymer in the initial stage of polymerization, with a lower degree of polymerization than the degree of polymerization of the final resin, and may include an oligomer, or a monomer and oligomer pre-polymerized to the desired degree of polymerization using a well-known device, such as a vertical mixing polymerization reactor , horizontal mixing polymerization reactor with monoaxial or biaxial mixing paddle, type of thin-film polymerization reactor with plates, with gravity-flowing down, a thin-film polymerization reactor with gravity-flowing downward on inclined planes, a tubular polymerization reactor and a tower with irrigated walls.

For example, a polyester prepolymer is produced by polycondensing a compound having a hydroxyl group and a compound having a carboxyl group, or a compound having an ester of a carboxyl group with a lower alcohol. A polyamide prepolymer is prepared by polycondensation of a compound having an amino group and a compound having a carboxyl group. A polycarbonate prepolymer is prepared by polycondensing a compound having a carbonyl group that is directly bonded to two groups, such as an aryloxy group or an alkoxy group on both sides, and a compound having a hydroxyl group.

Typically, for example, an aliphatic polyester prepolymer was prepared by polycondensation of a monomer having a hydroxyl group directly attached to an aliphatic hydrocarbon group having 1 to 30 carbon atoms, such as ethylene glycol, and a monomer having a carboxyl group directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as adipic acid; or a monomer having a hydroxyl group and a carboxyl group directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as glycolic acid.

An aliphatic aromatic polyester prepolymer is prepared by polycondensation of a monomer having a hydroxyl group directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2,6-naphthalenedicarboxylic acid, 1,6-hexamethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexane-dimethanol; and a monomer having a carboxyl group directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms, such as terephthalic acid, isophthalic acid, oxalic acid, succinic acid, adipic acid, dodecandioic acid, fumaric acid, maleic acid, 1, 4-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 3,5-dicarboxybenzenesulfonic acid in the form of tetramethylphosphonium salt and 1,4-cyclohexanedicarboxylic acid; or a monomer with such a carbon group esterified with a lower alcohol.

An aromatic polyester prepolymer was prepared by polycondensing a monomer having a hydroxyl group directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms, such as bisphenol A, and a monomer having a carboxyl group directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms such as terephthalic acid.

An aliphatic polyamide prepolymer was prepared by polycondensation of a monomer having an amino group directly attached to an aliphatic hydrocarbon group having from 2 to 30 carbon atoms, such as hexamethylene diamine, and a monomer having a carboxyl group directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms such as adipic acid.

An aliphatic aromatic polyamide prepolymer was prepared by polycondensation of a monomer having an amino group directly attached to an aliphatic hydrocarbon group having from 2 to 30 carbon atoms, such as hexamethylenediamine, and a monomer having a carboxyl group directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms such as terephthalic acid.

An aromatic polyamide prepolymer was prepared by polycondensation of a monomer having an amino group directly attached to an aliphatic hydrocarbon group having from 6 to 30 carbon atoms, such as para-phenylenediamine, and a monomer having a carboxyl group directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms such as terephthalic acid.

An aliphatic polycarbonate prepolymer was prepared by polycondensing a monomer having a hydroxyl group directly attached to an aliphatic hydrocarbon group having from 2 to 30 carbon atoms, such as 1,6-hexanediol, and a monomer having a carbonyl group that is directly linked to phenoxy groups with both sides, such as diphenyl carbonate.

An aliphatic aromatic polycarbonate prepolymer was prepared by polycondensing a monomer having a hydroxyl group directly attached to an aliphatic hydrocarbon group having from 2 to 30 carbon atoms, such as 1,6-hexanediol, and a monomer having a hydroxyl group directly attached to the aromatic hydrocarbon group, having from 6 to 30 carbon atoms, such as bisphenol A, and a monomer having a carbonyl group that is directly attached to phenoxy groups on both sides, such as diphenyl carbonate.

All of these prepolymers include those obtained by copolymerization to a polyalkylene glycol such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

By reference to a specific method for preparing the above-described prepolymers, for example, "Polymer Synthesis, vol. 1, second edition", 1992 (US, published by Academic Press, Inc) can be proposed.

The degree of polymerization of the prepolymer suitable for the present invention can be determined by the melt viscosity when tested under a shear rate of 1000 (s ^-1 ) at the polymerization temperature in the polymerization reactor of the present invention. The preferred range is 60-100000 (poise). By controlling at 60 (poise) or higher, powerful foaming and dispersion of the prepolymer dispensed from the openings of the porous plate of the polymerization reactor can be suppressed, and by controlling at 100,000 (poise) or less, by-products can be effectively removed from the system and such polymerization is fast. The degree of polymerization of the prepolymer of the present invention is preferably in the range from 100 to 50,000 (poise), more preferably in the range from 200 to 10,000 (poise), and particularly preferably in the range from 300 to 5000 (poise). The basis for a prepolymer with such a relatively high viscosity to be preferred in the present invention is to polymerize the resin in a state containing a greater amount of foam, as described above, and thus significantly increase the polymerization rate.

(c) Polymerization reactor:

The polymerization reactor of the present invention is a device characterized by introducing the above-described prepolymer in the molten state into the polymerization reactor, discharging from the openings of the porous plate, followed by polycondensation in the melt during discharge onto the substrate under reduced pressure or in an inert gas atmosphere under reduced pressure.

(c-1) Porous plate:

The porous plate is a plate substrate with multiple through holes. By using a porous plate, prepolymer dispersion can be suppressed and local buildup in the reactor can also be prevented, and thus a high quality and homogeneous resin can be obtained.

With respect to the structure of the porous plate, the thickness is not specifically limited, however, it is usually in the range of 0.1 to 300 mm, preferably in the range of 1 to 200 mm, more preferably in the range of 5 to 150 mm. The porous plate must withstand the pressure of the molten prepolymer feed stream and also, when the substrate of the polymerization vessel is fixed on the porous plate, it must have a strength sufficient to support the mass of the substrate and prepolymer casting, and reinforced by stiffeners, similar are also preferred.

The type of openings of the porous plate is usually selected from a circular, oval, triangular, slotted, polygonal and star-shaped species. The cross-sectional area of the hole is usually in the range from 0.01 to 100 cm ² , preferably in the range from 0.05 to 10 cm ^2, and particularly preferably in the range from 0.1 to 5 cm ² . It is also intended to mount an exhaust nozzle and the like attached to the hole.

The distance between the holes is usually, measured as the distance between the centers, from 1 to 500 mm, preferably from 10 to 100 mm. The openings of the porous plate may be through holes or may be tubes attached to the porous plate. They can be conical. It is preferable to determine the size and type of the hole so that the pressure loss when passing the prepolymer through the porous plate is from 0.1 to 50 kg / cm ² .

The number of openings of the porous plate is not specifically limited and depends on conditions such as reaction temperature or pressure, amount of catalyst and molecular weight range of polymerizable, however, it is usually necessary to equal 100 kg / h in polymer production, 10-10 ⁵ , more preferably 50 -10 ⁴ and even more preferably 10 ² -10 ³ .

As the material of the porous plate, a metal material such as stainless steel, carbon steel, Hastelloy, nickel, titanium, chromium and other alloys is usually preferred.

The method of discharging the prepolymer through such a porous plate includes a method of casting under the influence of a liquid head or its own mass, a method of pneumatic extrusion using a pump and the like, however, it is preferable to extrude using a weighing pump, such as a gear pump, to suppress variation in the quantity entrapping prepolymer.

It is preferable to install the filter in a stream passing from the outside of the porous plate. By applying a filter, foreign particles burdening the openings of the porous plate can be removed. The types of filter can be selected, respectively, in order to remove foreign particles larger than the diameter of the holes of the porous plate and do not break when passing through the prepolymer.

(c-2) Substrate:

The prepolymer dispatched from the openings of the porous plate drips onto the substrate. A typical substrate structure includes a “wire”, a “chain-like” combined with a wire material or a “lattice-like structure” (“metal mesh”), a “stereo-lattice-like structure” with a wire material like “jangle gym”, a “thin plate” with flat surface or curvature and a "porous lamellar" structure. In addition to this, to effectively remove reaction by-products or impurities resulting from thermal decomposition during polymerization, active mixing and surface renewal are preferred by increasing the surface area of the resin to be dumped, along with dropping the prepolymer onto the substrate with a stiffness with respect to discharge directions. Also preferred is a substrate with a structure for interrupting the discharge of the resin, such as a "wire structure with stiffness in relation to the direction of discharge." A combination of these substrates may also be used.

A “wire” substrate is a material with a very large ratio between the average cross-sectional size and the length in the perpendicular direction to said cross-section. The cross-sectional area is not specifically limited, however, it is usually in the range from 10 ⁻³ to 10 ² cm ² , preferably in the range from 10 ⁻³ to 10 ¹ cm ^2, and particularly preferably in the range from 10 ⁻² to 1 cm ² . The cross-sectional view is not specifically limited, however, it is usually selected from such species as circular, oval, triangular, square, polygonal and star-shaped. The cross-sectional view includes any of the same or different kinds in the length direction. Cavity wires are also included. A single type of wire or multiple wires combined by a twisting method and the like are also included. Wire with a smooth or rough surface or partial protrusions are also included.

A “chain-like” substrate is a material with rings made of the above-described bonded wire material. The type of ring includes such as circular, oval, rectangular and square. The binding method includes one-dimensional, two-dimensional and three-dimensional methods.

The substrate "lattice-like structure (metal mesh)" is the above-described wire material combined into a lattice. Combined wires include linear wires or curved wires and the angle of association can be chosen arbitrarily. The ratio of the areas between the material and the space where the material of the "lattice-like structure (metal mesh)" extends from the vertical direction to the surface is not specifically limited, however, it is usually in the range from 1: 0.5 to 1: 1000, preferably in the range from 1: 1 to 1: 500, and particularly preferably in the range of 1: 5 to 1: 100. The area ratio is preferably the same in the horizontal direction, while in the vertical direction it can be the same or the volume ratio, preferably larger in a smaller part.

The substrate of the “stereo lattice structure” is a wire material stereoscopically integrated only like a “jangle gym” in a 3D lattice. Combined wires include linear wires or curved wires and the angle of association can be chosen arbitrarily.

The substrate "wire structure with stiffness in relation to the direction of discharge" is a wire connected to transitions having a circular or polygonal cross section in the right corner, or wires connected to a disk-shaped or cylindrical material. The distance between the stiffeners is preferably not less than 5 mm. A typical example includes a wire with disks through which the wire passes, and the disks have a diameter larger than the wire diameter by at least 5 mm, but not greater than 100 mm and a thickness of 1 to 50 mm, and are connected in space through distance from 1 to 500 mm.

The volume ratio between the substrate installed in the reactor and the space in the reactor is not specifically limited, however, it is usually in the range from 1: 0.5 to 1:10 ⁷ , preferably in the range from 1:10 to 1:10 ⁶ and especially preferably in the range of 1:50 to 1:10 ⁵ . The volumetric ratio between the substrate and the space in the reactor is preferably the same in the horizontal direction, while in the vertical direction it can be the same or the spatial volumetric ratio in the reactor is preferably larger in a smaller part.

If a single substrate is installed or multiple substrates are installed, then they can be selected, respectively, depending on the type. A “wire” or “chain-like” substrate is usually composed of 1 to 10 ⁵ parts, preferably 3 to 10 ⁴ parts. A “sieve-like structure” or “chain-like, two-dimensionally bound”, “thin lamellar” and “porous lamellar” substrates are usually formed of 1-10 ⁴ parts, preferably 2-10 ³ parts. The "stereo-lattice-like structure" and the "chain-shaped, three-dimensionally connected" substrates can be installed singly or multiple in compartments, respectively, when discussing the size of the device or the space available for installation.

When multiple substrates are installed, it is preferred that they are separated without contacting each other using, respectively, dividers.

The substrate material is not specifically limited, however, it is usually selected from materials such as stainless steel, carbon steel, Hastelloy and titanium. Also included are wires after various surface treatments such as plating, lining, passivating treatment and acid cleaning.

In the present invention, the prepolymer is usually supplied from one or more holes of the porous plate, depending on one substrate, however, the number of holes can be selected, respectively, depending on the type of substrate. The prepolymer can also be dropped onto multiple substrates after passing through one hole.

The position of the substrate is not specifically limited as long as the prepolymer can be dropped onto the substrate and the method of attaching the substrate to the porous plate can be selected from, respectively, the case when it is installed with the passage through the hole of the porous plate and the case where it is installed without transmission through the hole of the porous plate, but below the hole of the porous plate.

The height for casting the prepolymer in accordance with the substrate after passing through the hole is preferably in the range of 0.5 to 50 m, preferably in the range of 1 to 20 m, and more preferably in the range of 2 to 10 m.

(c-3) Heating device:

The polymerization temperature can be conveniently set by adjusting the temperature of the heater or heat jacket located on the surface of the wall of the polymerization reactor covering the substrate, or by placing the heater or coolant inside the substrate to control these temperatures.

(c-4) Pressure Reducing Device:

The level of reduced pressure in the polymerization reactor can be conveniently set by linking the outlet channel for depressurizing, installed at any place in the polymerization reactor, with a vacuum line to control the level of reduced pressure. By-products of the polymerization, impurities generated during thermal decomposition during the polymerization, and an inert gas, optionally introduced into the polymerization reactor, are discharged from the exhaust channel for pressure relief.

(c-5) Inert gas supply device:

To carry out the reaction in an inert gas atmosphere under reduced pressure, and when the inert gas is directly introduced into the polymerization reactor, the gas can be supplied from a supply channel installed in an arbitrary position of the polymerization reactor. The inert gas supply channel is preferably located far from the porous plate and close to the resin discharge channel. It is also preferable that the supply is located away from the outlet for pressure relief.

It is also possible a method of pre-absorption and / or absorption of inert gas into the prepolymer, and in this case, the inert gas supply device is additionally installed on the inlet stream of the polymerization reactor of the present invention.

As the inert gas supply device, a known adsorption device is used, such as a packed column type adsorption device, a plate adsorption device and a spray column type adsorption device, as described, for example, in the Chemical Apparatus Design and Operation, series, No. 2, revised, "Gas Absorption", P.49-54 (Published 15, March, 1981 from Chemical Industry Co., Ltd.); or a method for injecting an inert gas into a prepolymer pumping line. The most preferred method is a method using an inert gas adsorption device during the discharge of a prepolymer onto a substrate in an inert gas atmosphere. In this method, an inert gas with a higher pressure than the pressure in the polymerization reactor was introduced into the inert gas adsorption device. The pressure here is preferably from 0.01 to 1 MPa, more preferably from 0.05 to 0.5 MPa, and even more preferably from 0.1 to 0.2 MPa.

(d) Polymerization Method:

The authors found that by polymerizing a prepolymer with a melt viscosity in the range described above, using the polymerization reactor described above, in the range of the polymerization temperature and the low pressure level, as described below, dispersion of the prepolymer during powerful foaming exactly under the porous plate is suppressed and the quality of the resin is also suppressed. by pollution on the surface of the nozzle or on the surface of the wall of the polymerization reactor, and unexpectedly there is a phenomenon of "increase in resin surface area" inclusion of more foam casting resin in accordance with the substrate and "rolling the resin into a circular foam on a substrate."

At the same time, a significant increase in the polymerization rate and an improvement in the color tone of the resin were confirmed.

A significant increase in the polymerization rate is assumed to be brought about by the combined action of the increasing effect of the surface area of the resin by including more foam and the effect of updating the surface area with the plasticizing effect of the foam. The plasticizing effect of the foam makes it possible to improve the color tone of the resin by reducing the residence time of the resin inside the polymerization reactor and easily removing the high viscosity resin from the polymerization reactor after polymerization to a high degree.

A thin film melt polymerization device with gravity discharge, such as a traditional column with irrigated walls, for producing a high-quality resin with a high degree of polymerization, is intended for polymerization of a prepolymer with a small degree of coloring obtained at an early stage of the reaction and a much lower degree of polymerization compared to with the method of the present invention, at a higher temperature and at a shorter residence time compared to the present invention. Based on traditional common sense, subsequent melt polymerization of a prepolymer with a high degree of polymerization and high melt viscosity, as in the method of the present invention, was considered to lead to significant progress in dyeing and an excessive, longer residence time during discharge into the polymerization reactor, and such production of high-quality resin was never intended.

Conversely, in the present invention, as described above, by setting the viscosity range of the prepolymer melt at a higher level than traditional common sense, or, as explained below, further, by setting the polymerization temperature at a lower level than traditional common sense, was found that the foamed state of the resin can be controlled, and the polymerization rate can be significantly increased despite the low temperature and the unexpected effect that the resin with a high degree of polymerization can easy to retract.

(d-1) Polymerization temperature:

The temperature of the polycondensation reaction is preferably not lower than the temperature lower by 10 ° C than the melting point of the crystal of the polycondensed resin, and not higher than the temperature higher than the melting point of the crystal by 60 ° C. By setting the temperature to not lower than the temperature, which is less than the melting point of the crystal by 10 ° C, curing of the reaction products or prolongation of the reaction time can be suppressed; and by setting the temperature to not higher than the melting point of the crystal at 60 ° C, thermal decomposition can be suppressed and a resin with excellent color tone can be obtained. This temperature is more preferably not lower than the temperature lower than the melting point of the crystal by 5 ° C, and not higher than the temperature higher than the melting point of the crystal by 40 ° C, and more preferably not lower than the melting point of the crystal and not higher than the temperature higher than the melting point of the crystal, at 30 ° C. The reason for the preference for such a relatively low reaction temperature in the present invention is the ease with which the resin absorbs more foam and the possibility of a significant increase in the rate of polymerization.

"Crystal melting point" here is the maximum temperature of the endothermic peak obtained by melting the crystal, as measured under the following conditions using Pyris 1 DSC from Perkin Elmer Co., Ltd. (differential scanning calorimeter with input compensation). Peak temperature was determined using the included software.

Measurement temperature: 0-300 ° C.

Temperature increase rate: 10 ° C / min.

(d-2) Polymerization pressure:

The melt polycondensation reaction of the present invention should be carried out under reduced pressure to guarantee the condition of a resin containing a large amount of foam. The level of reduced pressure is set, respectively, in response to the sublimation state of the prepolymer or polycondensation reaction products or the reaction rate. The reduced pressure level is preferably not higher than 50,000 Pa, more preferably not higher than 10,000 Pa, more preferably not higher than 1000 Pa, and particularly preferably not higher than 500 Pa. The lower limit is not specifically limited, however, it is preferably not less than 0.1 Pa from the point of view of the size of the device for creating reduced pressure inside the polymerization reactor.

Also preferred is a method in which, by introducing a small amount of an inert gas that does not adversely affect the polycondensation reaction in the polymerization reactor, polymerization by-products or impurities resulting from thermal decomposition during polymerization are removed with the gas.

The introduction of an inert gas into the polymerization reactor is usually considered a method mainly for the progress of the reaction by reducing the partial pressure of the polymerization by-products and the shift of equilibrium. However, the inert gas introduced in the present invention is sufficient in very small quantities and thus the accelerating effect on the polymerization rate due to the decreasing partial pressure effect is expected to be small, and thus, the role of the inert gas cannot be explained based on the traditional understanding.

As a result of the study, the authors unexpectedly observed that when an inert gas was introduced into the polymerization reactor, the phenomenon of foaming of the prepolymer when dumped onto the substrate in the molten state became powerful, which impressively increased the surface area of the mentioned prepolymer and provided very good renewable surface conditions. The reason has not been established, however, this change in the internal and surface state of this prepolymer was evaluated as causing a significant increase in the polymerization rate.

The introduced inert gas is preferably a gas that does not adversely affect the resin, such as coloring, metamorphism and decomposition, and includes nitrogen, argon, helium, carbon dioxide or a lower hydrocarbon, and a gas mixture thereof. As an inert gas, nitrogen, argon, helium and carbon dioxide are preferred, and nitrogen is particularly preferred among them in terms of easy availability.

A very small amount of inert gas introduced is sufficient in the present invention, such as preferably from 0.05 to 100 mg per 1 g of resin discharged from the polymerization reactor. By setting the amount of inert gas to not less than 0.05 mg per 1 g of resin discharged, foaming of the resin becomes sufficient and the increase in the effect of the degree of polymerization becomes high. At the same time, when installed no higher than 100 mg, it becomes easy to increase the level of reduced pressure. The amount of inert gas is more preferably 0.1 to 50 mg per 1 g of discharge resin, and particularly preferably 0.2 to 10 mg.

A method of introducing an inert gas includes a method of directly introducing into the polymerization reactor, a method of introducing into the polymerization reactor by adsorption and / or incorporating an inert gas into the prepolymer in advance and releasing said absorbed and / or included gas from the prepolymer under reduced pressure; as well as a method that combines them. “Adsorption” here means a case in which an inert gas dissolves in the resin and is not present as air bubbles, while “inclusion” means the presence of air bubbles . In the presence of air bubbles, the size of the air bubbles was preferably as small as possible, and the average diameter of the air bubbles was preferably not more than 5 mm, and more preferably not more than 2 mm.

(d-3) Polymerization time:

The polymerization time is the total of the time required for the resin to drip according to the substrate and the residence time at the bottom of the polymerization reactor, preferably in the range of 10 seconds to 100 hours, more preferably in the range of 1 minute to 10 hours, even more preferably in the range from 5 minutes to 5 hours, particularly preferably in the range from 20 minutes to 3 hours, and most preferably in the range from 30 minutes to 2 hours.

In the present invention, in order to suppress thermal decomposition, such as at the bottom of a polymerization reactor or a discharge pipe, it is preferable to reduce the residence time in these areas.

(d-4) Polymerization Rate:

The polymerization ability of the polymerization reactor of the present invention has features such as, in the case of using a wire substrate mounted inside the polymerization reactor, the increase is proportional to the numbers of the substrate, and the ease of scaling up the structure.

In the case of the use of a wire substrate, the flow rate of the prepolymer on the substrate is preferably from 10 ^-2 to 10 ² l / h and by setting the flow rate within this range, sufficient productivity can be guaranteed and the polymerization rate can also be impressively increased. More preferably, the flow rate is in the range from 0.1 to 50 l / h.

In the case of accepting a substrate from a combination of wires, such as a substrate of a lattice-like structure (metal mesh), the flow rate is preferably from 10 ^-2 to 10 ² l / h on a substrate of a wire structure installed in the vertical direction, more preferably in the range from 0.1 up to 50 l / h.

In the case of accepting a substrate without a structure obtained by combining wires, such as a thin plate substrate, the flow rate is preferably from 10 ^-2 to 10 ² l / h per opening of the porous plate for supplying the prepolymer to the substrate, more preferably in the range from 0.1 to 50 l / h

(d-5) Molecular Weight Regulator:

In the present invention, if necessary, at an arbitrary stage prior to supplying the prepolymer to the polymerization reactor of the present invention, the prepolymer can be reacted with an molecular weight regulator in an arbitrary amount. The authors found that by correcting the molecular weight of the prepolymer fed to the polymerization reactor of the present invention, the rate of discharge of the prepolymer onto the substrate can be impressively changed, whereby the residence time in the polymerization reactor and quality, such as the degree of polymerization of the resulting resin and productivity, can be easily controlled. adjustable over a wide range.

As a molecular weight regulator, a reagent for reducing molecular weight or a reagent for increasing molecular weight was used. In the present invention, by applying a molecular weight regulator, quality, such as the degree of polymerization of the polycondensation polymer and productivity, can be set in a wide range not achievable with the conventional polymerization process.

When a molecular weight reduction reagent is used, the polymerization degree of the polycondensation polymer obtained in the polymerization reactor of the present invention can be reduced over a wide range by adding only a relatively small amount of molecular weight reduction reagent. This is so because in addition to the initial reagent effect to reduce the molecular weight, there is also the effect of reducing the reaction time by increasing the rate of discharge of the prepolymer onto the substrate. The ability to significantly lower degree of polymerization of the resulting polycondensation polymer has the same meaning of significantly reducing productivity.

Conversely, in the traditional polymerization method, only the initial effect of the reagent to reduce the molecular weight is realized, and the degree of polymerization of the polycondensation polymer is reduced in response to only the added amount of the reagent to reduce the molecular weight and, therefore, to adjust over a wide range, it is necessary to add a larger amount, which poses a problem in terms of process, price and also the quality of the product. At the same time, when a reagent is used to increase the molecular weight, the degree of polymerization of the polycondensation polymer obtained in the polymerization reactor of the present invention can be significantly increased only by adding a relatively small amount of the reagent to increase the molecular weight. This is so because, in addition to the initial effect of the reagent for increasing the molecular weight, there is also the effect of increasing the reaction time by lowering the rate of discharge of the prepolymer onto the substrate. The ability to significantly increase the degree of polymerization of the resulting polycondensation polymer is of the same importance as the ability to make an impressive increase in productivity. Conversely, in the traditional polymerization method, only the initial effect of the reagent to increase the molecular weight is realized, and the polymerization degree of the polycondensation polymer increases only by adding the amount of reagent to increase the molecular weight, and in order to regulate in a wide range, it is necessary to add a larger amount, which poses a problem with the point of view of the process, price and also the quality of the product.

By varying the molecular weight of the prepolymer supplied from the prepolymer preparation step, the state variation was measured; based on this result, a molecular weight regulator was added to the prepolymer in the step prior to feeding the prepolymer to the polymerization reactor, whereby a change in molecular weight was achieved and the prepolymer can also be introduced into the polymerization reactor in a state of slight molecular weight change.

The molecular weight regulator can be reacted with the prepolymer at an arbitrary stage before the prepolymer is fed into the polymerization reactor. This reaction can be carried out by installing a separate reactor or in a pipeline by introducing a molecular weight regulator into the prepolymer feed line. A preferred method is that the mixing and reaction of the molecular weight regulator is activated by using a mixing device with a drive, such as an extruder, or a stationary mixing device.

As a reagent for reducing molecular weight, a known reagent can be used, such as that used to depolymerize or reduce the molecular weight of the polymer, respectively, and depending on the types of polymer. As a reagent for reducing molecular weight, it is also preferable to use the starting monomer as described above, or a prepolymer with a lower molecular weight, taken from a step closer to the feed, or a compound by-produced in the polycondensation reaction.

For example, in the case of a polyester resin, a mixture consisting of one or more kinds of compounds selected from compounds having two or less hydroxyl groups directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as ethylene glycol, 1 can be used. , 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexanediol, methanol, ethanol, propanol, butanol and benzyl alcohol; or alkylene glycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol; or water; or compounds having two or less carboxyl groups directly attached to an aromatic hydrocarbon group having from 6 to 30 carbon atoms, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid and 3,5-dicarboxybenzenesulfonic acid in the form of tetramethylphosphonium salts; or compounds having two or less carboxyl groups directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, succinic acid, adipic acid, dodecandioic acid fumaric acid, maleic acid and 1,4-cyclohexanedicarboxylic acid; or compounds having a hydroxyl group and a carboxyl group directly attached to an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, such as lactic acid and glycolic acid; or compounds having such a carboxylic acid group esterified with a lower alcohol.

Also, in the case of a polyamide resin or a polycarbonate resin, a starting monomer as described above, or a prepolymer with a lower molecular weight taken from a step closer to the feed, or a compound by-produced from the polycondensation reaction can be used as a reagent to reduce molecular weight . It is also possible that the above molecular weight reducing reagent for a polyester resin is used instead, as a molecular weight reducing reagent, for a polyamide resin or polycarbonate resin, or, conversely, the above molecular weight reducing reagent for these resins is used as a molecular weight reducing reagent masses of polyester resin. In addition, the following methods are possible;

- suppression of molecular weight gain: by suppressing the polycondensation reaction by adding a compound with the function of suppressing polymerization by a catalytic effect, such as water and trimethyl phosphate;

- reduction of molecular weight, as well as suppression of molecular weight gain: by adding a monofunctional group, which is a reagent for quenching the reaction or a little reactive compound;

- suppression of the polycondensation reaction: by reducing the temperature of the prepolymer by adding a prepolymer with a lower temperature or by mixing a portion of the prepolymer having a locally lower temperature with another portion.

The reagent for increasing molecular weight is not specifically limited in that it has the effect of increasing the molecular weight of the prepolymer. A method of increasing molecular weight is represented by one or more species selected from:

- adding, to increase the molecular weight by an exchange reaction, a higher molecular weight prepolymer selected from a step closer to the product or a product containing a high molecular weight polymer or a high molecular weight polymer obtained by another polymerization technology, such as solid phase polymerization;

- a partial cross-linking reaction by adding a compound having three or more functional groups that may be involved in the condensation reaction, such as glycerin, pentaerythrol, sorbitol, 1,2,4-benzene-tricarboxylic acid and citric acid;

- acceleration of the polycondensation reaction by adding, or by adding more than ordinary, the amount of hydrolyzate obtained by hydrolysis of titanium oxide, titanium tetrabutoxide, titanium tetraisopropoxide, titanium halide or titanium alkoxide; hydrolyzate obtained by hydrolysis of germanium oxide, germanium isopropoxide, germanium alkoxide; and compounds containing titanium, germanium, arsenic, tin, aluminum, cobalt and having a catalytic effect on the polymerization, such as arsenic oxide, tin acetate, tin 2-ethylhexanate, aluminum acetate, aluminum propionate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum carbonate, aluminum phosphate, aluminum ethoxide, aluminum isopropoxide, aluminum acetylacetonate and cobalt acetate;

- promoting the polycondensation reaction by adding a prepolymer heated to a higher temperature or by mixing a portion of the prepolymer heated locally to a higher temperature with another portion to increase the temperature of the prepolymer.

(d-6) Other additives:

The present invention includes the case where various additives, if necessary, were copolymerized or mixed, such as a matting agent, a heat stabilizer, a flame retardant, an antistatic agent, an anti-foaming agent, a normochromatic agent, an antioxidant, an UV absorber, a crystal-forming agent, a brightener and an absorber impurities. These stabilizers or various additives can be added at arbitrary stages prior to molding.

In particular, in the present invention, preferably a suitable stabilizer is added depending on the polymerisable polymer. For example, in the case of a polyester resin, a compound based on a compound of pentavalent and / or trivalent phosphorus or hindered phenol is preferred. The added amount of phosphorus compound is preferably 2-500 ppm, considering the mass ratio of elemental phosphorus to polymer, more preferably 10-200 ppm; as specific compounds, trimethylphosphite, phosphoric acid and phosphorous acid are preferred. A phosphorus-based compound is preferred since it not only inhibits the coloring of the polymer, but also has the effect of a crystal forming agent.

The hindered phenol compound is a derivative based on hindered phenol having a substituent with a steric barrier in a position adjacent to the phenolic hydroxyl group and a compound having at least one ether bond in the molecule. The added amount of hindered phenol compound is preferably from 0.001 to 1% by weight, based on the resulting polymer, more preferably from 0.01 to 0.2% by weight. Specific compounds include tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythrol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide). The combined use of these stabilizers is one of the preferred methods.

It is also preferable to add a crystal forming agent in the present invention, and in the case of a polyester resin, compounds such as a phosphorus-based compound, an organic acid metal salt and a powdered polyolefin, or other resins are preferred. The amount of crystal forming agent added is preferably from 2 to 1000 ppm of the polymer, more preferably from 10 to 500 ppm. Especially included are phosphates such as 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphoric acid sodium salt, bis (4-tert-butylphenyl) phosphoric acid sodium salt; and sorbitol, such as bis (para-methylbenzylidene) sorbitol; and metal-containing compounds, such as the hydroxyaluminium salt of bis-4-tert-butylbenzoic acid. In particular, for a preform used for a bottle of polyethylene terephthalate by heating in a throat portion for thermal crystallization, it is preferable to use it to promote crystallization and to reduce the temperature of thermal crystallization.

In the present invention, the addition of an absorber of volatile low molecular weight impurities is also one of the preferred methods. In the case of polyethylene terephthalate, the impurity is acetaldehyde and the scavenger for it includes a polymer or polyamide oligomer, or polyetheramide, or a low molecular weight compound having an amide group or amine group, such as 2-aminobenzamide. Specific examples of such compounds include polymers such as nylon-6,6 polyamide, nylon-6 and nylon-4,6 or polyethyleneimine, in addition, reaction products between N-phenylbenzylamine and 2,4,4-trimethylpentene, or Irganox -1098, Irganox-565 (registered trademark) manufactured by Ciba Specialty Chemicals Co. Ltd., and the like. These scavengers are preferably added at the stage between the shipment of the resin from the polymerization reactor and its transfer to the molding machine.

(E) Forming Method:

The polymer obtained by polymerization can be used in molding by re-melting after granulation, however, the polymer can be pumped to the molding machine in the molten state for molding. By these methods, not only the difficult stages to granule formation, such as transportation, storage and drying, and energy can be reduced, but also a much higher quality molded product can be obtained.

When the polymer obtained by polymerization was pumped in the molten state into a molding machine for molding, to obtain a molded product with a slight variation in quality and weight, the following methods were used: adjusting the pressure for pumping the resin into the molding machine to a constant value (E-1) and adjusting the time the stay of the polymer in the melt of the incoming stream of the molding machine to a constant value (E-2).

By means of a polymerization reactor based on the new principle of the present invention, melt polycondensation is possible at a much lower temperature than in conventional polymerization technology, which provides a slight variation in the quality and viscosity of the melt of the molten resin fed to the molding machine, and thus the molded product with a small variation in quality and mass and / or granules with a small variation in quality can be stably obtained by installing at least two ships lev els pumps in a polymerization reactor of the present invention and the resin supply separately to the molding machine and / or granulating machine (E-3). A naturally preferred method (E-3) is that methods (E-1) and (E-2) were used in combination.

In addition, by means of the polymerization reactor of the present invention, it is also possible that at least a portion of the polycondensation polymer obtained in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the steps for producing said polycondensation polymer (E-4) .

All methods (from E-1 to E-4) are explained below.

(E-1) A method for adjusting a resin transfer pressure into a molding machine.

In the method for producing the molded product of the present invention, in order to adjust the transfer pressure of the resin to the molding machine at a constant level, it is necessary to maintain the transfer pressure in the molding machine at an arbitrary pressure level from 0.1 to 100 MPa (absolute pressure).

When the transfer pressure to the molding machine varies, it is difficult to maintain a constant amount of resin feed flow into the molding machine. In particular, when an injection molding machine is used, the weighing step of the obtained resin and the injection step without producing the resin are repeated, which makes the resin flow intermittent and thus, varying the transfer pressure to the molding machine is unavoidable and creates the problem of varying the mass of the molded product.

The transfer pressure to the molding machine is preferably not less than 0.1 MPa for the precise injection of the high viscosity resin into the molding machine and preferably not more than 100 MPa, in terms of the size of the device or preventing the resin from leaking from the connecting part of the pipeline. Preferably, the pressure is in the range of 0.5 to 70 MPa, more preferably in the range of 1 to 50 MPa, and most preferably in the range of 2 to 30 MPa. By maintaining the transfer pressure at a high level, a smaller volume (smaller diameter) of the conveying conduit for the molten resin is possible, and the residence time in the melt when pumping the resin can preferably be shortened. A particularly preferred range is from 3 to 20 MPa.

When adjusting the transfer pressure to the molding machine at a constant level, it is preferable that the pressure variation is small and, to prevent variation in the mass of the molded product, it is preferable not to deviate more than ± 80% from the set pressure, more preferably not more than ± 50%, particularly preferably not more ± 30% and most preferably not more than ± 20%.

Using this method, it is possible to maintain a constant value of the resin feed stream to various molding machines, including an injection molding machine, and even if multiple the same or different types of molding machines are used, the resin feed stream can be kept constant without a complicated switching system and switching sequence. Also, when molding using multiple molding machines, even when part of the molding machines is shut off due to an accident, the production of a molded product with stable quality and weight may be possible on other molding machines.

As described above, methods for controlling the transfer pressure into the molding machine are not specifically limited and well-known methods can be applied; preferred control methods are specifically explained below (E-1-1 and E-1-2).

(E-1-1) A method for controlling the transfer pressure by adjusting the discharge amount from the discharge pump:

The transfer pressure is measured in the pipeline for transferring the molten resin from the polymerization reactor to the molding machine, and the discharge pump performance is controlled so that the transfer pressure is kept at an arbitrary level of 0.1 to 100 MPa (absolute pressure). In this case, it is preferable that the pressure variation is small and preferably does not deviate more than ± 80% of the set pressure to prevent variation in the mass of the molded product.

(E-1-2) A method for controlling the transfer pressure by returning a portion of the resin dispatched to the polymerization reactor while maintaining a constant amount of discharge of the discharge pump:

In this method, the discharge pump of the polymerization reactor is controlled so as to maintain the discharged amount at a selected level of 1.0-100 of the size of the prepolymer feed stream. The discharged amount of the discharge pump is preferably not less than 1.0 from the size of the feed stream of the prepolymer to prevent the resin from staying in the polymerization reactor, and preferably not more than 100 in terms of the size of the device; preferably in the range of 1.1-50, more preferably in the range of 1.15-20, and most preferably in the range of 1.2-5.

In addition to the pipeline for transferring the molten resin from the polymerization reactor to the molding machine, after the aforementioned discharge pump, a pipeline was installed to return a portion of the shipped resin to the bottom of the polymerization reactor and a system for determining the outlet pressure and controlling the degree of opening of the polymer return valve or backpressure valve in the pipeline for return the resin to the bottom.

The transfer pressure was measured in the pipeline for transferring the molten resin from the polymerization reactor to the molding machine, and the degree of opening of the outlet pressure detection system and the degree of opening of the polymer return valve or backpressure valve are controlled so that the transfer pressure is kept at an arbitrary level of 0.1 up to 100 MPa (absolute pressure). In this case, it is preferable that the pressure variation is small and preferably does not deviate more than ± 80% of the set pressure in order to prevent the mass variation of the molded product.

This method makes the discharge quantity of the discharge pump constant, leading to a small load of the discharge pump and a small risk of accident, and thus is preferred.

(E-2) The control method for the residence time of the polymer in the melt:

In the method for producing the molded product of the present invention, it is possible to carry out polymerization at a low temperature never achieved by well-known polymerization devices and even when the residence time of the polymer in the melt is varied in the inlet stream of the molding machine, the variation in the quality or mass of the molded product is small. As a way to further maintain a constant residence time of the polymer in the melt at the bottom of the polymerization reactor by installing a discharge pump connected to the granulation machine and / or an exhaust nozzle at the bottom of the polymerization reactor or after the discharge pump of the polymerization reactor, the polymer can be pumped to the granulation machine and / or an exhaust nozzle so that the residence time of the molten polymer at the bottom of the polymerization reactor is controlled at a selected time in the range of 0.1-120 minutes. By this, even in the case of the mutual variation of the “resin production rate” and the “resin molding rate”, the variation in the residence time of the molten polymer at the bottom of the polymerization reactor can be avoided, which otherwise leads to damage to the polymer quality, and possibly stable production over a period of a slight variation in the quality and mass of the molded product.

The residence time of the polymer in the melt at the bottom of the polymerization reactor is preferably not shorter than 0.1 minute from the point of view of maintaining the air tightness of the discharge pump and preferably not longer than 120 minutes from the point of view of suppressing thermal decomposition of the resin, more preferably in the range of 0.2 up to 60 minutes, further preferably in the range of 0.3 to 30 minutes, and particularly preferably in the range of 0.4 to 15 minutes.

When the residence time of the polymer in the melt at the bottom of the polymerization reactor varies significantly, the quality of the resin or the viscosity of the melt can vary and, thus, it is preferable to keep it constant, preferably not deviating more than ± 100% from a certain residence time of the polymer in the melt, more preferably not more than ± 80%, particularly preferably not more than ± 50%, particularly preferably not more than ± 30% and most preferably not more than ± 20%.

(E-3) A method for installing at least two loading pumps in a polymerization reactor of the present invention.

For stable production of a molded product with a small variation in quality and mass and / or granules with a small variation in quality by linking multiple molding machines and / or granulating machines to the polymerization reactor of the present invention, a method is preferred in which at least two discharge pumps are installed with said reactor polymerization and resin is fed into multiple molding machines and / or granulating machines.

It is preferable to create a production line where at least one or more molding machines and / or granulating machines are connected to each loading pump. These molding machines and / or granulating machines can be simultaneously molded and / or granulated and can also be molded or granulated using a single desired molding machine or granulating machine in a production line by installing a switching valve in a branched pipeline connecting the discharge pump and multiple molding or granulating machines cars.

As described above, by installing at least two off-loading pumps, at least two production lines are created, making the change in production or type of molded product with each line easy. In this way, even when at least one of the lines is stopped due to an accident or repair, production can be continued by adjusting the performance of other lines.

The discharge quantity of the discharge pump of each line can be set in accordance with the production planned by the molding machine or granulating machine and, in the case of injection molding machine, it can be synchronized with the weighing-injection cycle; or the discharged amount of the discharge pump can also be controlled so that the transfer pressure to the injection molding machine is held at an arbitrary pressure of 0.1 to 100 MPa (absolute pressure). The transfer pressure to the molding machine can also be controlled by returning a portion of the resin to be shipped to the bottom of the polymerization reactor or pumping it to an outlet nozzle or pelletizing machine installed separately from the molding machine while adjusting the discharge amount selected from 1.0-100 of the prepolymer feed flow.

(E-4) A method of returning to an arbitrary stage among the steps for producing said polycondensation polymer to recycle at least a portion of the polycondensation polymer obtained in an amount greater than the amount used in molding or granulation.

In the above method (E-2), losses can be minimized by returning the withdrawn resin from the exhaust nozzle or pelletizing machine, in order to avoid varying the residence time of the polymer in the melt of the inlet stream of the molding machine, to an arbitrary stage among the steps for producing said polycondensation polymer.

These polycondensation polymers, other than the amount used to form the products or granules that were originally the target, are hereinafter referred to as "excess polymers".

For recycling, "excess polymers" can be, for example, either introduced through a porous plate of a polymerization reactor based on the new principle of the present invention, or introduced by placing an outlet nozzle in an arbitrary position, such as the bottom of said polymerization reactor, or connected to the stream of said polycondensation polymer in the inlet stream of the aforementioned polymerization reactor from the prepolymer preparation device, or into the initial monomer tank, or at an arbitrary position of the pipeline binding these devices.

When the "excess polymers" are attached to the stream of said polycondensation polymer, in order to minimize variation in the residence time of the polymer in the polymerization system, a method is also preferred in which the feed rate of the feed stream of the starting monomer or prepolymer to the junction decreases in response to the number of "excess polymers" attached. When "excess polymers" are formed in large quantities, in order to minimize the increase in residence time at the inlet stream to the junction, a method for connecting the source monomer tank to the inlet stream, the first or second prepolymer production reactor, in particular, a reactor for forming the initial condensation product, is also preferred or a first polycondensation reactor. When the "excess polymers" are formed in small quantities, the method of addition to the final reactor closest to the shipped portion of the "excess polymers" is also preferred.

Also preferred is a method in which the “excess polymers” are combined with a small amount of a prepolymer having a low degree of polymerization or, previously, with the starting monomer to make mixing easy, before the polymers are attached to the stream of said polycondensation polymer. Also preferred for this purpose is a method of using a stationary mixer or pre-mixing tank of a stirred type, a kneading type or an extruding type.

All "excess polymers" can be attached to the stream of said polycondensation polymer for circulation, or only part can be circulated to stabilize the polymer system at an early stage and stop can be covered if the granules are either run out or rejected.

(E-5) Other molding conditions:

The polymer once granulated, in particular in the case of a highly crystalline polymer, requires heating at a high temperature during the melting process and, moreover, easily forms shear heat, which creates a problem of significant quality damage. However, the granules and molded product obtained by the polymerization method and the molding method of the present invention have slight quality damage before and after the melting process. It is believed that this is because the polymerization temperature is low in the polymerization method of the present invention and, in addition, the polymerization is completed in a short time, and due to the absence of a rotary drive or resin retention areas in the polymerization device itself, there is a small inlet air stream , splitting of molecular units during shear and resin damage when in the melt and, further, there is no effect of moisture adsorption or oxidative damage even when connected to devices from melting.

In order to transfer the polymer polymerized by the polymerization method of the present invention to the molded molding machine for molding, it is necessary to transfer the polymer withdrawn from the polymerization reactor to the molding machine at a temperature as low as possible and for a short time within the range of non-curing of the polymer . The "molten state" here means that the polymer is in a flow state by melting when heated and has a viscosity of about 500,000 Poise or less.

The temperature for transferring and molding the polymer obtained by polymerization into the molding machine is not lower than the temperature lower than the melting point of the crystal by 10 ° C, for stable transfer without a significant increase in viscosity or curing. By setting the temperature not higher than a temperature higher than the melting point of the crystal at 60 ° C, a high-quality molded product with a low level of staining or the formation of volatile impurities during thermal decomposition can be obtained. A temperature higher than the melting point of the crystal by 0-40 ° C is preferred, more preferred is a temperature above the melting point of the crystal by 0-30 ° C, even more preferred is a temperature above the melting point of the crystal by 0-20 ° C and especially a temperature above the melting point of the crystal of 1-15 ° C is preferred. These temperatures can be achieved by conveniently controlling the temperature with a heater or jacket covering the conveying pipe, transfer pump and molding machine.

The time required before molding is preferably within 40 minutes, more preferably within 20 minutes, and particularly preferably within 10 minutes. Naturally, a shorter time is best. "Time required before molding" here is a period from the point in time when the molten polymer exits the discharge pump of the polymerization reactor to the point in time when it is cooled to a temperature not higher than the crystallization temperature of said polymer, such as a molded product or granules. When the molten polymer is continuously pumped in the pipeline, etc., the average time calculated from the volume of the pipeline, etc., and the flow rate can be applied. When this time varies, it is necessary to set within the time described above.

As a molding machine, a commercial molding machine using granules as raw material can be used in the initial state or after modification. In particular, in the present invention, since the polymer in the molten state is directly fed from the polymerization reactor, a granule plasticization mechanism, such as a melt plasticization screw, can be simplified or omitted, which is necessary in a molding machine using traditional granules as raw materials. As a result, molding can be carried out under the conditions of a plasticizing mechanism of low heat generation during shear, whereby a much higher quality molded product can be obtained.

Molding can be carried out using a single molding machine or two or more molding machines of the same or different types. Since the molding machine is intermittently controlled when multiple molding machines are used, in order to stabilize at a constant level the flow rate of polymer withdrawn from the polymerization reactor, it is also preferable to apply a method in which the flow rate is averaged by switching the molding cycle in a given number of multiple molding machines.

When a polymer continuously withdrawn from the polymerization reactor is introduced into the intermittently controlled molding machine, a method in which the drive is separately mounted halfway to collect molten polymer is also preferred. This method is more preferable because the molding machine and the drive are synchronized to reduce the residence of the molten polymer.

This method is also preferable, since by installing separately from the molding machine an exhaust nozzle of a resin, or an extruder, or a granulating machine, a molded product and granules are simultaneously obtained.

Further, based on the drawings, the case of polymerization of polyethylene terephthalate is described as a preferred example of the present invention.

Figure 1 and others show embodiments of a preferred combination for implementing the method of the present invention, however, the present invention is not limited to them.

The digital symbols in the drawings have the following meanings:

1 - Transfer pump;

2 - Channel for summing the prepolymer;

3 - Porous plate;

4 - viewing window;

5 - Substrate;

6 - Inert gas supply channel;

7 - exhaust channel with reduced pressure;

8 - Discharge pump;

9 - Distributor;

10 - Forming machines A;

11 - Forming machines B;

12 - Forming machines C;

13 - Granulating machine;

14 - Transfer pump;

15 - System for determining the pressure at the outlet and control at the outlet of the discharge pump;

16 - System for determining the level and control at the outlet of the transfer pump;

17 - Polymerization reactor;

18 - System for determining the outlet pressure and controlling the degree of opening of the polymer return valve; or backpressure valve;

19 - Switch valve;

20 - Distributor;

21 - stirred polymerisation reactor;

22 - The mixing blade;

23 - Polymer return pipe;

N1 - Transfer pump;

N2 - Channel prepolymer;

N3 - Porous plate;

N5 - Substrate;

N6 - Inert gas supply channel;

N7 - outlet channel with reduced pressure;

N8 - Pumping and transfer pump;

N10 - Inert gas adsorption device;

P1 - Etherification Reactor;

P2 - The mixing blade;

P3 - exhaust channel with reduced pressure;

P4 - Transfer pump;

P5 — First stirred type polymerization reactor;

P6 - The mixing blade;

P7 - exhaust channel with reduced pressure;

P8 - Transfer pump;

P9 — Second stirred-type polymerization reactor;

P10 - The mixing blade;

P11 - Exhaust duct with reduced pressure;

E1 - The first transesterification reactor;

E2 - The mixing blade;

E3 - outlet channel with reduced pressure;

E4 - Transfer pump;

E5 - Second transesterification reactor;

E6 - The mixing blade;

E7 - exhaust channel with reduced pressure;

E8 - Transfer pump;

E9 — First stirred type polymerization reactor;

E10 - The mixing blade;

E11 - The outlet channel with reduced pressure;

E12 - Transfer pump;

E13 - Horizontal mixing polymerization reactor;

E14 - The mixing blade;

E15 - Exhaust duct with reduced pressure.

1, prepolymer A of a polycondensation polymer, such as polyethylene terephthalate, is introduced into the polymerization reactor from the prepolymer feed channel (2) by means of a transfer pump (1), if necessary, with molecular weight regulator B, and introduced into the polymerization reactor by passing through a porous plate (3) and is dumped onto the substrate (5). Inside, the polymerization reactor (17) is controlled at a certain level of reduced pressure; ethylene glycol by-products, etc., and the like, or an inert gas, such as nitrogen, supplied, if necessary, from the inert gas supply channel (6), are discharged through the outlet channel under reduced pressure (7). The polymer obtained by polymerization is discharged by means of a discharge pump (8). The performance of the discharge pump (8) was adjusted by means of a system (15) for determining the outlet pressure and controlling the discharge of the discharge pump. The polymer was removed and, after continuous shipment, by means of a discharge pump (8), it was fed to A-C molding machines (10-12) through a transport pipe and distributor (9), and molded. Three or more molding machines may also be attached.

The polymer polymerized during casting in accordance with the substrate (5) was discharged from the discharge channel by means of a discharge pump (8) after casting to the lower part of the polymerization reactor (17) and, in this case, it is preferable to make the amount accumulated in the lower part of the polymerization reactor as small as possible and as constant as possible. A method for controlling the accumulated amount includes adjusting the magnitude of the liquid feed stream of the transfer pump (1) and the discharge pump (8) by adjusting the accumulated amount through an inspection window (4) or using a level gauge such as a capacitance type level gauge. As a preferred example, FIG. 1 shows a control method by installing a transfer pump (14) connected to a granulating machine (13), and by pumping to a granulating machine simultaneously with a molding machine so that the residence time of the polymer at the bottom of the polymerization reactor ( 17) was regulated at the selected time value.

A transfer pump (1 and 14), a polymerization reactor (17), a discharge pump (8), a conveyor pipe and a distributor (9), A-C molding machines (10-12), a granulating machine (13), etc. heated with a heater or jacket and kept heated.

The polymerization reactor used in the present invention may be equipped with a stirrer, etc., at the bottom of the polymerization reactor, however, this is not particularly necessary. Therefore, it is possible to remove the rotary drive on the polymerization reactor itself, which guarantees polymerization under well-isolated conditions, even in high vacuum. Since the rotary drive of the discharge pump is coated with the resin to be shipped, such a reactor is much better sealed than a rotary drive polymerization reactor.

The method of the present invention can also be carried out in a single unit of a polymerization reactor. It can be carried out by two or more units of the polymerization reactor. In addition, a single unit of the polymerization reactor can be partitioned in vertical or horizontal type to create multi-stage polymerization reactors.

In the present invention, the step of increasing the molecular weight, from a prepolymer of a polycondensation polymer, such as polyethylene terephthalate, to a polycondensation polymer, such as a high polymerisation polyethylene terephthalate, which is the target polymer, can also be carried out by polymerization while dropping the entire prepolymer from the openings of the porous plate onto the substrate. However, it is preferable to combine with other methods, for example, polymerization in a stirred type polymerization reactor and in a horizontal mixing polymerization reactor.

The horizontal mixing polymerization reactor includes, for example, the polymerization reactor described in the fourth chapter of the "Research Report by Reaction Engineering Research Association: Reactive Processing, Part 2" (Society of Polymer Science, Japan; 1992), such as screw type, independent type blades, monoaxial type and diaxial type.

As the stirred type polymerization reactor, any of the mixed type reactors described, for example, in Chapter 11 of the Chemical Apparatus Handbook (Edited by Society of Chemical Engineers, Japan; 1989) can be used. The view of the reactor is not specifically limited. A cylindrical vertical view is usually used or horizontal type. The type of mixing blade is also not specifically limited. For example, the blade type, anchor type, turbine type, screw type, tape type and double-blade type are used.

The step of preparing the prepolymer from the feed can be carried out either in a batch system or a continuous system. In the case of a batch system, the entire amount of the feed or reaction products is fed into the reactor, reacted for several set hours, and then the entire amount of the reaction products is pumped to the next reactor. At the same time, in the case of a continuous system, the feed or reaction products are continuously fed into each reactor and the reaction products can be shipped continuously. A continuous system is preferred for producing a homogeneous and high quality polycondensation polymer, such as polyethylene terephthalate and its molded product in large quantities.

In the present invention, a molding machine means a device for casting molten resin into a specific form, including devices such as an extrusion machine, an injection molding machine, and a blow molding machine. The molded product obtained by the molding machine includes bottles, bottle blanks, films, linens, tubes, rods, fibers, and various kinds of products obtained by casting. The present invention is applicable, in particular, to obtain blanks for food bottles. This is because food bottles strictly require not only excellent strength and transparency, but also a reduced amount of low molecular weight volatile impurities represented by acetaldehyde in the case of polyethylene terephthalate, affecting the taste or smell of the contents, along with good performance and the ability to be produced with low cost.

Figure 2 presents a typical example of a polymerization reactor implementing the method of the present invention, in the case of using an inert gas adsorption device. Prepolymer A of a polycondensation polymer, such as polyethylene terephthalate, is introduced into the inert gas adsorption device (N10) from the prepolymer feed channel (N2) through the transfer pump (N1) and introduced into the inert gas adsorption device by passing through the porous plate (N3) and dumping onto the substrate ( N5). Inside, the inert gas adsorption device is controlled at a certain level of reduced pressure through the reduced pressure outlet (N7) and prepolymer A adsorbs, during casting, an inert gas such as nitrogen introduced from the inert gas inlet (N6). Prepolymer A is fed from the feed channel (2) to the polymerization reactor (17) by pumping and a transfer pump (N8), introduced into the polymerization reactor by passing through a porous plate (3) and dumped onto the substrate (5). Inside, the polymerization reactor is controlled at a certain level of reduced pressure and ethylene glycol by-products, etc. removed through the outlet channel with reduced pressure (7). The polymer obtained by polymerization is dispatched by means of a discharge pump (8) to a discharge channel through a distributor (9). The polymerization reactor (17) and other devices were heated with a heater or jacket and kept heated.

The polymer obtained by polymerization is continuously dispatched from the discharge pump (8) and then fed into the molding machines A-C (10-12) through the conveyor pipe and distributor (9) and formed. Three or more molding machines may be attached.

As a preferred example for maintaining the correct and constant residence time of the resin in the inlet stream of the molding machine and, thus, obtaining a molded product with always constant quality and weight, FIG. 2 shows a device having a connected transfer pump (14) connected to a granulating machine (13) simultaneously with molding machines. In the device, the resin is pumped into a granulating machine (13) in order to control the residence time of the polymer in the melt at the bottom of the polymerization reactor at a selected time value.

A transfer pump (1 and 14), an inert gas adsorption device (N10), a polymerization reactor (17), a discharge pump (8), a conveyor pipe and distributor (9), AC molding machines (10-12), and a granulating machine (13) etc. heated with a heater or jacket and kept heated.

Figure 3 represents an embodiment in a preferred combination for the practical implementation of the method of the present invention, by controlling the transfer pressure by returning a portion of the resin to be shipped to the bottom of the polymerization reactor while maintaining a constant discharge quantity of the discharge pump. However, the present invention is not limited to these embodiments.

A prepolymer A of a polycondensation polymer, such as polyethylene terephthalate, is introduced into the polymerization reactor from the prepolymer feed channel (2) through a transfer pump (1) and introduced inside the polymerization reactor (17) by passing through a porous plate (3), and dumped onto the substrate (5). Inside, the polymerization reactor (17) is regulated at a certain level of reduced pressure and ethylene glycol by-products, etc. or an inert gas, such as nitrogen, supplied, if necessary, through the inert gas supply channel (6) is discharged through the outlet channel with reduced pressure (7). The polymer obtained by polymerization is dispatched from a discharge pump (8). The discharge amount from the discharge pump (8) is adjusted at a level selected from 1.0 to 100 of the size of the feed stream of prepolymer A.

The polymer obtained by polymerization is continuously dispatched from the discharge pump (8) and then fed into the molding machines A-C (10-12) through the conveyor pipe and distributor (9) and formed. Three or more molding machines may be attached.

A pipeline for returning the resin to the bottom of the polymerization reactor was installed in addition to the molding machine, after the discharge pump (8) and the system for determining the outlet pressure and controlling the degree of opening of the polymer return valve; or a backpressure valve (18) was installed on said pipeline. The degree of opening of the outlet pressure detection system and the degree of opening of the polymer return valve or the backpressure valve (18) are controlled to maintain the transfer pressure in the molding machine at an arbitrary level.

The polymer polymerized during discharge onto the substrate was discharged from the discharge channel by means of a discharge pump (8) after casting to the lower part of the polymerization reactor. In this case, it is preferable to make the amount accumulated in the lower part of the polymerization reactor as small as possible and as constant as possible. The method for controlling the accumulated amount includes adjusting the magnitude of the liquid feed stream of the transfer pump (14) and the discharge pump (8) by adjusting the accumulated amount through the inspection window (4) or with a level gauge, such as a capacitance type level gauge.

As a preferred example, FIG. 3 represents a device having a connected transfer pump (14) connected to a granulating machine (13) simultaneously with the molding machines. In the device, the resin is pumped into a granulating machine (13) in order to control the residence time of the polymer in the melt at the bottom of the polymerization reactor at a selected time value.

A transfer pump (1 and 14), a polymerization reactor (17), a discharge pump (8), a transport pipe and a distributor (9), a system for determining the outlet pressure and controlling the degree of opening of the polymer return valve, or backpressure valve (18), molding machines AC (10-12), granulating machine (13), etc. heated with a heater or jacket and kept heated.

Figure 4 represents a typical example of a polymerization reactor for implementing the method of the present invention, in the case of using an inert gas adsorption device, by controlling the transfer pressure by returning a portion of the resin to be shipped to the bottom of the polymerization reactor while maintaining a constant discharge quantity of the discharge pump.

5 is an example of a preferred embodiment of a method for installing at least two loading pumps near the bottom of a polymerization reactor, however, the present invention is not limited to these embodiments.

A prepolymer A of a polycondensation polymer, such as polyethylene terephthalate, is introduced into the polymerization reactor (17) through the prepolymer feed channel (2) through a transfer pump (1) from the polymerization reactor, and introduced into the polymerization reactor by passing through a porous plate (3) and dumped onto the substrate ( 5). Inside, the polymerization reactor is controlled at a certain level of reduced pressure and ethylene glycol by-products, etc. or an inert gas, such as nitrogen, supplied, if necessary, through the inert gas supply channel (6), is discharged through the outlet channel with reduced pressure (7). The polymer obtained by polymerization is dispatched by multiple shipping pumps (8) through a distributor (9).

The polymer obtained by polymerization is continuously discharged by each shipping pump (8) and then fed into the A-C molding machines (10-12) or granulating machine (13) through a transport pipe equipped with a switching valve (19), and molded. Three or more molding machines and granulating machines can be attached.

The polymer polymerized during discharge to the substrate is discharged from the discharge channel by a discharge pump, after discharge to the bottom of the polymerization reactor. In this case, it is preferable to make the amount accumulated in the lower part of the polymerization reactor as small as possible and as constant as possible. The method for controlling the accumulated amount includes adjusting the magnitude of the liquid feed stream of the transfer pump (1) and the discharge pump (8) by adjusting the accumulated amount through the inspection window (4) or with a level gauge such as a capacitance type level gauge.

A transfer pump (1 and 14), a polymerization reactor (17), a discharge pump (8), a conveying pipe and distributor (9), a shift valve (19), AC molding machines (10-12), a granulating machine (13), and etc. heated with a heater or jacket and kept heated.

6 represents a specific example of a polymerization reactor for implementing the method of the present invention by installing at least two discharge pumps near the bottom of the polymerization reactor, in the case of using an inert gas adsorption device.

Fig. 9 is an example of a preferred embodiment, in the case of polymerization of polyethylene terephthalate, for recycling "excess polymers". However, the present invention is not limited to this.

Figure 9 presents a specific example of polymerization of polyethylene terephthalate and molding using high purity terephthalic acid as a raw material. Raw material S, which is high purity terephthalic acid and ethylene glycol, forms bis (hydroxyethyl terephthalate) and oligomer in the esterification reactor (P1), which is composed of only a few monomer units, which are condensates of initial stages polyethylene terephthalate. The products are pumped to the first stirred type polymerization reactor (P5) through a transfer pump (P4) and form a prepolymer with an ultimate viscosity [h] in the range of 0.04 to 2 dl / g by the polycondensation reaction. When the prepolymer with the desired ultimate viscosity [h] cannot be obtained immediately in the first stirred type polymerization reactor (P5), the prepolymer is then pumped to the second stirred type polymerization reactor (P9) through a transfer pump (P8) and subjected to further polycondensation to obtain a prepolymer with desired ultimate viscosity [h].

The polyethylene terephthalate prepolymer A thus obtained is fed into the polymerization reactor (17) through the prepolymer feed channel (2) through a transfer pump (1) and introduced into the polymerization reactor by passing through a porous plate (3) and collected in accordance with the substrate (5). Inside, the polymerization reactor is controlled at a certain level of reduced pressure and ethylene glycol by-products, etc. or an inert gas, such as nitrogen, supplied, if necessary, from the inert gas supply channel (6), is discharged through the outlet channel with a reduced pressure (7). The polymer obtained by polymerization is dispatched by means of a discharge pump (8) and fed into the molding machines A-C (10-12) through a conveyor pipe and distributor (9). Three or more molding machines may be attached. Polyethylene terephthalate resin, polymerized in excess over the amount processed by the molding machine, is returned through the polymer return line (23) to the first stirred type polymerization reactor (P5) through the transfer pump (14) and can be recycled.

The polymer polymerized during casting in accordance with the substrate (5) was discharged from the discharge channel by means of a discharge pump (8), moves by motor M after casting to the lower part of the polymerization reactor (17). In this case, it is preferable to make the amount accumulated in the lower part of the polymerization reactor (17) as small as possible and as constant as possible. The method for controlling the accumulated amount includes adjusting the magnitude of the liquid feed stream of the transfer pump (14) by adjusting the accumulated amount through the inspection window (4) or with a level gauge such as a capacitance type level gauge.

A transfer pump (1 and 14), a polymerization reactor itself (5), a first stirred type polymerization reactor (P5), a second stirred type polymerization reactor (P9), a transfer pump (P4), a discharge pump (8), a conveying pipeline and a distributor ( 9), polymer return pipe (23), AC molding machines (10-12), etc. heated with a heater or jacket and kept heated.

Figure 10 presents a specific example of polymerization of polyethylene terephthalate and molding using dimethyl terephthalate as a raw material. Feed S, which is dimethyl terephthalate and ethylene glycol, forms bis (hydroxyethyl terephthalate) and an oligomer formed from only a few monomer units, which are the early stages of polyethylene terephthalate condensates in the first transesterification reactor (E1) and the second transesterification reactor (E5). The products are pumped to the first stirred type polymerization reactor (E9) by means of a transfer pump (E8) and form a prepolymer with an ultimate viscosity [h] in the range of 0.04 to 2 dl / g by the polycondensation reaction. When the prepolymer with the desired ultimate viscosity [h] cannot be obtained immediately in the first stirred type polymerization reactor (E9), the prepolymer is then pumped to the horizontal mixing polymerization reactor (E13) using a transfer pump (E12) and then polycondensed to obtain the prepolymer with desired ultimate viscosity [h]. The polyethylene terephthalate prepolymer A thus obtained is introduced, similarly to Fig. 9, into the polymerization reactor (17) through the feed channel of the prepolymer (2) through a transfer pump (1), the polymerization reactor is introduced inside by passing through a porous plate (3) and dumped onto the substrate (5). Inside, the polymerization reactor (17) is regulated at a certain level of reduced pressure and ethylene glycol by-products, etc. or an inert gas, such as nitrogen, introduced, if necessary, from the inert gas supply channel (6), is discharged through the outlet channel with reduced pressure (7). The polymer obtained by polymerization is dispatched by means of a discharging pump (8) driven by motor M and fed into molding machines A-C (10-12) through a conveyor pipe and distributor (9), and molded. Three or more molding machines may be attached. Polyethylene terephthalate resin, polymerized in excess over the amount processed by the molding machine, is returned to the first stirred type polymerization reactor (E9) through the polymer recovery line (23) using a transfer pump (14) and can be recycled.

11 shows an example of a preferred embodiment in the polymerization of polyethylene terephthalate, in the case of using a molecular weight regulator B. However, the present invention is not limited to this embodiment. In this figure, polyethylene terephthalate prepolymer A is fed into the polymerization reactor (17) from the prepolymer production step by means of a transfer pump (1) through a pipeline. The molecular weight regulator B is mixed in the feed line and the molecular weight of prepolymer A is changed by the reaction between the prepolymer A and the molecular weight regulator B in the pipeline. Prepolymer A is fed into the polymerization reactor (17) through the prepolymer feed channel (2) and introduced into the polymerization reactor (17) by passing through the holes of the porous plate (3) and dumped onto the substrate (5).

Inside, the polymerization reactor (17) is regulated at a certain level of reduced pressure and ethylene glycol by-products, etc. or an inert gas, such as nitrogen, introduced, if necessary, from the inert gas supply channel (6), is discharged through the outlet channel with reduced pressure (7).

The polymer obtained by polymerization was discharged from the discharge channel (9) by means of a discharge pump (8) after casting into the lower part of the polymerization reactor. In this case, it is preferable to make the amount accumulated in the lower part of the polymerization reactor (17) as small as possible and as constant as possible. The method for controlling the accumulated amount includes adjusting the magnitude of the liquid feed stream of the transfer pump (14) and the discharge pump (8) by adjusting the accumulated amount through the inspection window (4) or with a level gauge, such as a capacitance type level gauge.

A transfer pump (1 and 14), a polymerization reactor (17), a discharge pump (8), a transport pipeline, etc. heated with a heater or jacket and kept heated.

The polycondensation polymer, dispatched from the polymerization reactor by means of a discharge pump (8), after adjusting the quality, such as the degree of polymerization and the quantity produced by the molecular weight regulator B, is pumped and can be molded or granulated in AC (10-12) or granulating molding machines machines (13) installed adjacent to the polymerization reactor, as shown.

EXAMPLES

The present invention is explained with reference to examples.

The main measured values in the examples were determined by the following methods.

(1) Ultimate viscosity [h]

The ultimate viscosity [h] was measured according to the following equation by extrapolating to a zero concentration of the ratio h _sp / C between the relative viscosity h _sp in o-chlorophenol at 35 ° C and the concentration C (g / 100 ml): using an Ostwald viscometer (Ostwald).

EXPRESSION 1

The degree of polymerization of the prepolymer can be investigated through the more generally applicable aforementioned ultimate viscosity [h] instead of melt viscosity in the case of polyethylene terephthalate.

For example, a melt viscosity at 260 ° C of a prepolymer of a polyethylene terephthalate resin with an ultimate viscosity [h] of 0.15 dl / g is about 60 poise, and a melt viscosity at 260 ° C of a prepolymer of a polyethylene terephthalate resin with an ultimate viscosity [h] of 1.2 dl / g is about 100,000 poise.

(2) Crystal melting point

The melting point of the crystal was determined from the maximum temperature of the endothermic peak obtained from the melting of the crystal, measured under the following conditions using a Pyris 1 DSC (Peripheral Compensation Differential Scanning Calorimeter) from Perkin Elmer Co., Ltd. Peak values were determined using the included analytical software.

Measurement temperature: 0 to 300 ° C.

Temperature set speed: 10 ° C / min.

(3) The number of carboxyl groups at the ends of the polymer chain

It was determined according to the following expression by dissolving 1 g of the sample in 25 ml of benzyl alcohol, and then adding 25 ml of chloroform for titration with 1/50 N potassium hydroxide alcohol solution, based on the value from titration V _A (ml) and the value from blank experiment V ₀ , without polyethylene terephthalate:

The number of carboxyl groups at the ends of the polymer chain:

(meq / kg) = (v _A -V ₀ ) × 20.

(4) The color tone of the resin (L value, B value)

Investigated according to the JIS-Z8730 method using the included analytical software, by dissolving 1.5 g of the sample in 10 g of 1,1,1,3,3,3-hexafluoro-2-propanol and transmittance analysis using UV-2500PC (UV-VIS spectrophotometer) from Shimadzu Corp.

(5) Impurity content

The sample was thoroughly ground and ground with cooling for 3-10 minutes while cooling in liquid nitrogen using a 6700 freeze mill (freezer) from SPEX Co., Ltd., resulting in a particle size of 850-1000 μm. 1 g of the above powder was placed in a glass ampoule with 2 ml of water and sealed after passing nitrogen, and heated at 130 ° C for 90 minutes to extract impurities such as acetaldehyde. The ampoule was opened after cooling for analysis in the following conditions using GC-14B (gas chromatograph) from Shimadzu Corp.

Column: VOCOL (60 m × 0.25 mm with a film thickness of 1.5 μm).

Temperature conditions: keeping at 35 ° C for 10 min, followed by an increase of 5 ° C / min to 100 ° C and then 20 ° C / min from 100 to 220 ° C.

The temperature in the injector is 220 ° C.

Injection method: separate method (separation ratio = 1: 30), injection volume 1.5 μl.

Registration Method: Fourier Transformation (FID).

EXAMPLE 1

Using the device shown in Fig. 1, a prepolymer of polyethylene terephthalate with a maximum viscosity [h] of 0.48 dl / g, the number of carboxyl groups at the ends of the polymer chain 32 meq / kg and a melting point of the crystal of 256 ° C, was introduced into the polymerization reactor (17 ) through the feed channel of the prepolymer (2) using a transfer pump (1), shipped at a speed of 15 g / min for each hole of the porous plate (3) in the molten state at 265 ° C, then polymerized under reduced pressure of 65 Pa during discharge to substrate at the same external temperature as in shipment, it was discharged from the polymerization reactor (17) by means of a discharge pump (8) and subjected to molding into a billet in a blow molding in series at a molding temperature of 280 ° C using a biaxial orientation blow molding machine (SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as the molding machine A (10). Dumbbell-shaped pieces were molded at a molding temperature of 280 ° C using an injection molding machine (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11). Instead of a molding machine, granulating machine C was installed as molding machine C (12).

The productivity of the discharge pump (8) from the bottom of the polymerization reactor (17) was controlled by determining the outlet pressure at the discharge stream of the discharge pump (8) and using a system (15) to determine the outlet pressure and control the exit of the discharge pump in order to maintain the level 20 MPa (absolute pressure) during molding. Thus, the variation of the outlet pressure during molding was always controlled within ± 20%.

A porous plate 50 mm thick was used, with 14 holes with a diameter of 1 mm, where each 7 holes aligned with a line with a distance of 10 mm between them formed 2 parallel lines with a distance of 70 mm. In the immediate vicinity of each hole, a substrate was used, connected vertically to wires having a diameter of 2 mm and a length of 8 m, where the wires were installed perpendicular to other wires having a diameter of 2 mm and a length of 100 mm in 100 mm space to form a lattice-like structure. Stainless steel was used as the substrate material.

As the prepolymer, a prepolymer was used, such as obtained by adding 0.04% by weight of dimisiac trioxide and 100 ppm of trimethyl phosphate, based on the mass fraction of elemental phosphorus. The residence time in the polymerization reactor was 70 minutes. Used the residence time, determined by the amount of polymer inside the polymerization reactor, divided by the magnitude of the feed stream. This caused a decrease in the powerful foaming of the prepolymer, shipped from the porous plate during polymerization, which led to very little contamination on the surface of the nozzle or the surface of the wall. The absorption of a large amount of foam discharged by the resin and the rolling of the resin onto the substrate in the form of a circular foam were observed.

First of all, the pipeline for transporting the polymer to the transfer pump (14) in FIG. 1 was closed so that the resin was fed only to the A-C molding machines (10-12) for continuous molding of the molded products for more than 5 hours. The molding cycles of molding machine A (10) and molding machine B (11), in particular, the timing of each weighing stage, were not set in a specific way, and thus molding by molding machine A (10) and molding machine B (11) was carried out independently. The molding machine C (12) also functioned under constant conditions without adjusting the initially set values.

The yield, appearance and quality of the molded products obtained by A-C molding machines (10-12) were examined once per hour and it was confirmed that molded products with stable quality can be obtained for more than 5 hours. The results are presented in table 1.

EXAMPLE 2

Polymerization and molding were carried out under the same conditions as in example 1, except that the outlet pressure during molding was controlled so that it remained at 5 MPa (absolute pressure) by means of a system (15) for determining the outlet pressure and control at the outlet of the discharge pump. The results are presented in table 2.

EXAMPLE 3

Polymerization and molding were carried out under the same conditions as in Example 1, except that the outlet pressure during molding was controlled so as to maintain 2 MPa (absolute pressure) by means of a system (15) for determining outlet pressure and control at the outlet of the discharge pump. The results are presented in table 3.

EXAMPLE 4

The polymerization and molding was carried out under the same conditions as in example 1 and the pipeline for transporting the polymer to the transfer pump (14) in figure 1 was opened; the amount of polymer accumulated at the bottom of the polymerization reactor was measured by a level detector mounted at the bottom of the polymerization reactor (17). The residence time at the bottom of the polymerization reactor was controlled so as to be maintained at a level of 2 minutes by means of a system (16) for determining the level and control at the outlet of the transfer pump and transfer pump (14), whose output was controlled by the system. The polymer shipped by the transfer pump was granulated in a granulating machine (13). Thus, the variation in the residence time at the bottom of the polymerization reactor (17) during molding was always controlled within ± 20%.

The resin was thus fed into the A-C molding machines (10-12) and the granulating machine (13) for continuously molding the molded products for more than 5 hours. After 1 hour as the simulation of the molding machine accident occurred, the molding machine B (11) was stopped and molding was continued only in the molding machines A and C (10 and 12) and the granulating machine (13).

The yield, type and quality of the molded products obtained by each molding machine was examined once an hour and confirmed that the molded products with stable quality can be obtained for more than 5 hours, in particular, even after the molding machine B is stopped (11) after 1 hours, by using other molding machines. The results are presented in table 4.

COMPARATIVE EXAMPLE 1

Polymerization and molding were carried out under the same conditions as in Example 1. However, the control of the discharge pump by means of the system (15) for determining the outlet pressure and exit control for the discharge pump was not performed; and the discharge amount was maintained at 12.6 kg / h. This led to always greater variation in outlet pressure during molding in the range from 0 to 220 MPa (absolute pressure).

The resin was thus fed only to A-C molding machines (10-12) for the continuous molding of molded products for more than 5 hours.

The yield, appearance and quality of the molded products obtained by each molding machine was examined once an hour and a low quality of all molded products was found and the variation was also large. The results are presented in table 5.

COMPARATIVE EXAMPLE 2

Polymerization and molding were carried out under the same conditions as in Example 1, except that the outlet pressure during molding was controlled to maintain 0.05 MPa (absolute pressure) by means of a system (15) for determining the outlet pressure and control at the outlet of the discharge pump. However, in this case, feeding the molten resin could not be completed within the weighing period of the molding machine, and further molding was not possible.

EXAMPLE 5

Using the device shown in FIG. 3, a prepolymer of polyethylene terephthalate with a maximum viscosity [h] of 0.46 dl / g, the number of carboxyl groups at the ends of the polymer chain 32 meq / kg and a melting point of the crystal of 256 ° C, was fed at a rate of 12.6 kg / h to the polymerization reactor (17) through the prepolymer feed channel (2) using a transfer pump (1), shipped at a speed of 15 g / min for each hole of the porous plate (3) in the molten state at 265 ° C, then polymerized at reduced pressure of 65 Pa during casting in accordance with paragraph with a pad at the same external temperature as in the shipment, it was discharged from the polymerization reactor (17) by means of a discharge pump (8) and was subjected to molding into a billet in a blow molding in series at a molding temperature of 280 ° C using a biaxial orientation blow molding machine (SBIII-100H -15 from Aoki Technical Laboratory, Inc.) as the molding machine A (10).

Dumbbell-shaped pieces were molded at a molding temperature of 280 ° C using an injection molding machine (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11).

Instead of a molding machine, a granulating machine was installed as molding machine C (12). In addition, a pipeline was installed to return the polymer from the midpoint of the pipeline connecting the discharge pump (8) and the transfer pump (14) to the bottom of the polymerization reactor (17). A system for determining the outlet pressure and a control of the degree of opening of the polymer return valve to control the flow rate were installed on this pipeline for polymer return.

The discharge amount of the discharge pump (8) from the bottom of the polymerization reactor was maintained at 20.0 kg / h. Also, by measuring the pressure of the discharge stream of the discharge pump (8) so as to maintain a pressure of 20 MPa (absolute pressure) during molding, the degree of opening of the polymer return valve installed on the polymer return pipe was controlled by the outlet pressure detection and control system the degree of opening of the polymer return valve (18). Thus, the variation in outlet pressure during molding was always controlled within ± 20%.

A porous plate 50 mm thick was used, with 14 holes with a diameter of 1 mm, where each 7 holes aligned with a line with a distance of 10 mm between them formed 2 parallel lines with a distance of 70 mm. In the immediate vicinity of each hole, a substrate was used, connected vertically to wires having a diameter of 2 mm and a length of 8 m, where the wires were installed perpendicular to other wires having a diameter of 2 mm and a length of 100 mm in 100 mm space to form a lattice-like structure. Stainless steel was used as the substrate material.

As the prepolymer, a prepolymer was used, such as obtained by adding 0.04% by weight of dimisiac trioxide and 100 ppm of trimethyl phosphate, based on the mass fraction of elemental phosphorus. The residence time in the polymerization reactor was 70 minutes. Used the residence time, determined by the amount of polymer inside the polymerization reactor (17), divided by the magnitude of the feed stream. This caused a decrease in the powerful foaming of the prepolymer, shipped from the porous plate during polymerization, which led to very little contamination on the surface of the nozzle or the surface of the wall. The absorption of a large amount of foam discharged by the resin and the rolling of the resin onto the substrate in the form of a circular foam were observed.

First of all, the pipeline for transporting the polymer to the transfer pump (14) in FIG. 3 was closed in order to supply resin only to A-C molding machines (10-12) for continuous molding of molded products for more than 5 hours. The molding cycles of molding machine A (10) and molding machine B (11), in particular, the timing of each weighing stage, were not set in a specific way, and thus molding by molding machine A (10) and molding machine B (11) was carried out independently. The molding machine C (12) was also controlled under constant conditions without adjusting the initial values.

The yield, type and quality of the molded products obtained by each molding machine was examined once per hour and confirmed that the molded products with stable quality can be obtained for more than 5 hours. The results are presented in table 6.

EXAMPLE 6

Polymerization and molding were carried out under the same conditions as in Example 5. In this case, the amount of polymer accumulated at the bottom of the polymerization reactor (17) was measured by a level detector mounted on the bottom of the polymerization reactor (17). The residence time at the bottom of the polymerization reactor (17) was controlled so as to be maintained at a level of 2 minutes, by means of a system (16) for determining the level and control at the outlet of the transfer pump, by means of the transfer pump (14), whose output was controlled by the system. The polymer shipped from the transfer pump (14) was granulated in a granulating machine (13). Thus, the variation in the residence time at the bottom of the polymerization reactor during molding was always controlled within ± 20%.

The resin was thus fed into A-C molding machines (10-12) and a granulating machine (13) to continuously produce molded products for more than 5 hours. In this case, after 1 hour, as a simulation of the accident of the molding machine, the molding machine B (11) was stopped and molding continued only in the molding machines A and C (10 and 12) and the granulating machine (13).

The yield, type and quality of the molded products obtained by each molding machine was examined once an hour and confirmed that the molded products with stable quality can be obtained for more than 5 hours, in particular, even after the molding machine B is stopped (11) after 1 hours, by using other molding machines. The results are presented in table 7.

COMPARATIVE EXAMPLE 3

The polymerization and molding were carried out under the same conditions as in Example 5. However, the discharged amount of the discharge pump (8) was held at 12.6 kg / h and the pipeline for transporting the polymer to the transfer pump (14) in FIG. 1 was closed so that supply resin only to AC molding machines (10-12). This led to always greater variation in outlet pressure during molding in the range from 0 to 220 MPa (absolute pressure).

Thus, molded products were continuously produced for more than 5 hours. The yield, appearance and quality of the molded products obtained by each molding machine was examined once an hour and low quality of all molded products was found, and the variation was also large. The results are presented in table 8.

EXAMPLE 7

Using the device shown in FIG. 5, a prepolymer of polyethylene terephthalate with an ultimate viscosity [h] of 0.48 dl / g, the number of carboxyl groups at the ends of the polymer chain 32 meq / kg and a melting point of the crystal of 256 ° C, was introduced into the polymerization reactor (17 ) through the feed channel of the prepolymer (2) using a transfer pump (1), shipped at a speed of 15 g / min for each hole of the porous plate (3) in the molten state at 265 ° C, then polymerized under reduced pressure of 65 Pa during casting matching with the substrate at the same at the same temperature as in the shipment, it was discharged from the polymerization reactor (17) by means of a discharge pump (8) installed near the bottom of the polymerization reactor and was subjected to sequential molding at a molding temperature of 280 ° C using a blow molding machine with biaxial orientation ( SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as molding machine A (10).

While the molding machine A (10) was stopped, the resin was allowed to be introduced into the granulating machine (13) by a switching valve (19). Dumbbell-shaped pieces were molded at a molding temperature of 280 ° C. using an injection molding machine (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11). While the molding machine B (11) was stopped, the resin was allowed to enter the granulating machine (13) using a switching valve (19). Molding machine C (12) was not connected. Granules were produced only by installing a granulating machine (13).

A porous plate (3) with a thickness of 50 mm was used, with 14 holes with a diameter of 1 mm, where each 7 holes aligned with the line with a distance of 10 mm between them formed 2 parallel lines with a distance of 70 mm. In the immediate vicinity of each hole, a substrate (5) was used, then attached vertically to wires having a diameter of 2 mm and a length of 8 m, where the mentioned wires were installed perpendicular to other wires having a diameter of 2 mm and a length of 100 mm in 100 mm space for formation sieve-like structure. Stainless steel was used as the substrate material. The discharge pump was controlled by regulation through the inspection window (4) so that the polymer did not accumulate much at the bottom of the polymerization reactor (17).

As the prepolymer, a prepolymer was used, such as obtained by adding 0.04% by weight of dimisiac trioxide and 100 ppm of trimethyl phosphate, based on the mass fraction of elemental phosphorus. The residence time in the polymerization reactor was 70 minutes. Used the residence time, determined by the amount of polymer inside the polymerization reactor, divided by the magnitude of the feed stream. This caused a decrease in the powerful foaming of the prepolymer shipped from the porous plate (3) during polymerization, which led to very little pollution on the surface of the nozzle or on the wall surface. The absorption of a large amount of foam discharged by the resin and the rolling of the resin onto the substrate in the form of a circular foam were observed.

First of all, through the switching valve, the resin was fed into the molding machine A (10), the molding machine B (11) and the granulating machine (13) and by adjusting the capacity of the unloading pump at any value of 5.0 kg / h, 4.5 kg / h and 3.1 kg / h, molded products and granules were continuously produced for more than 5 hours. The yield, appearance and quality of the molded products obtained by each molding machine were examined once per hour. According to the present invention can be obtained high-quality molded products and granules having a high degree of polymerization, good color tone and low acetaldehyde content. The results are presented in table 9.

COMPARATIVE EXAMPLE 4

Using the device shown in Fig. 7, the polymerization was carried out similarly to Example 7. The polymer was discharged from the polymerization reactor (17) with a single discharge pump (8) installed near the bottom of the polymerization reactor (17) and guided by a distributor (20). Biaxial Oriented Blow Molding Machine (SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as A (10) molding machine, Injection Molding Machine (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11) and granulating machine (13) were connected with the same type of pipeline and internal volume, suitable for simultaneous molding of molded products.

Then, by adjusting the discharged amount of the discharge pump (8) to 12.6 kg / h, molded products were continuously produced for more than 5 hours. The yield, appearance and quality of each of the molded products was examined once per hour. By the method of distributing the resin through such a distributor, the quality and mass of the molded products were varied during the period of action, which reduced the final parameters of the molded products. The results are presented in table 10.

COMPARATIVE EXAMPLE 5

Using the device shown in FIG. 8, a prepolymer of polyethylene terephthalate with an ultimate viscosity [h] of 0.48 dl / g, a number of carboxyl groups at the ends of the polymer chain of 32 meq / kg and a melting point of 256 ° C was fed into a stirred polymerisation reactor ( 21) through the feed channel of the prepolymer (2) using a transfer pump (1), polymerized under the conditions: polymerization temperature 285 ° C, reduced pressure 50 Pa, residence time 60 minutes and polymerization rate 12.6 kg / h, was discharged from the polymerization reactor (17) three shipment pumps (8) installed at the bottom of the polymerization reactor (21), and was subjected to the simultaneous production of molded products and pellets using a biaxial orientated blow molding machine (SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as the molding machine A (10), injection molding machines (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11) and granulating machine (12), and the output of the pumps was adjusted to 5.0 kg / h, 4 5 kg / h and 3.1 kg / h.

Molded products and granules were continuously produced for more than 5 hours. The yield, appearance and quality of the molded products was examined once per hour. When such a conventional stirred type polymerization reactor was used, quality such as degree of polymerization, color tone, and acetaldehyde content were insufficient, and these quality and mass of molded products varied significantly during the period of action. Thus, the final parameters of such molded products were low. The results are presented in table 11.

EXAMPLE 8

Using the device shown in Fig. 9 and using high purity terephthalic acid and ethylene glycol (EG) as raw material, polyethylene terephthalate was polymerized by a continuous polymerization process at an average of 10.0 kg / h. Using a vertical mixing polymerization reactor having paddle-shaped mixing blades, such as an esterification reactor (P1), and a first and second stirred type polymerization reactor (P5, P9), the polymerization was carried out under reduced pressure during the prepolymer casting in accordance with a substrate protruding from holes of the porous plate (3) into the final polymerization reactor (17).

The polymerization was carried out by continuously loading a suspension-like mixture of terephthalic acid and ethylene glycol (EG) in a molar ratio of 1: 1.2 into the esterification reactor under the conditions shown in table 12. In this case, to the prepolymer obtained in the first stirred-type polymerization reactor was added 0.04% by weight of dimisiac trioxide and 20 ppm trimethylphosphate, based on the mass fraction of elemental phosphorus. Arsenic trioxide and trimethyl phosphate were added as 2% by weight solutions in ethylene glycol. The polymerization results are presented in table 12. The prepolymer fed to the final polymerization reactor had a limit viscosity [h] of 0.47 dl / g and a melting point of the crystal of 255 ° C.

The mentioned prepolymer of polyethylene terephthalate was fed into the polymerization reactor (17) through the feed channel of the prepolymer (2) using a transfer pump (1), shipped at a speed of 10 g / min for each hole of the porous plate (3) in the molten state at 260 ° C, then polymerized at a reduced pressure of 65 Pa during casting in accordance with the substrate (5) at the same external temperature as in the shipment, it was diverted by means of a discharge pump (8) and then through the transport pipe and distributor (9) entered the mold injection into the preform in blow molding sequentially at a molding temperature of 280 ° C using a biaxial orientation blow molding machine (SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as molding machine A (10). Dumbbell-shaped pieces were molded using an injection molding machine (MJEC-10 from MODERN MACHINERY CO., LTD) as molding machine B (11). Continuous molding was carried out using only molding machine A (10) and molding machine B (11) without connecting the injection molding machine C (12). The performance of the discharge pump from the bottom of the polymerization reactor (17) was controlled by measuring the outlet pressure of the discharge flow of the discharge pump and by means of a system (15) to determine the outlet pressure and control the outlet of the discharge pump, so as to maintain a level of 20 MPa (absolute pressure) during molding. Thus, the variation in outlet pressure during molding was always controlled within ± 20%. Additionally, by installing a polymer return pipe (23) to bind the distributor (9) and the first stirred type polymerization reactor (P5), an excess of polyethylene terephthalate resin polymerized above the capacity of the molding machine was recycled using a transfer pump (14).

A porous plate 50 mm thick was used, with 14 holes with a diameter of 1 mm, where each 7 holes aligned with a line with a distance of 10 mm between them formed 2 parallel lines with a distance of 70 mm. In the immediate vicinity of each hole, a substrate was used, connected vertically to wires having a diameter of 2 mm and a length of 8 m, where the wires were installed perpendicular to other wires having a diameter of 2 mm and a length of 100 mm in 100 mm space to form a lattice-like structure. Stainless steel was used as the substrate material.

The discharge pump by regulation through the inspection window was controlled so that the polymer accumulated in small quantities at the bottom of the polymerization reactor. The residence time in the polymerization reactor was 65 minutes. Used the residence time, determined by the amount of polymer inside the polymerization reactor (17), divided by the magnitude of the feed stream. This caused a decrease in the powerful foaming of the prepolymer, shipped from the porous plate during polymerization, which led to very little contamination on the surface of the nozzle or the surface of the wall. Observed the absorption of a large amount of foam discharged by the resin, and rolling onto the substrate in the form of a round foam.

First of all, polyethylene terephthalate was stably and continuously polymerized at 10.0 kg / h under the above conditions, then it was subjected to continuous molding at 5 kg / h using an injection molding machine A and using an injection molding machine B at 4.5 kg / hours At the same time, an excess of polymer of 0.5 kg / h was recycled to the first stirred type polymerization reactor (P5) through the polymer recovery line and, also, the amount of feed continuously loaded into the esterification reactor was reduced to 95% of the initial reaction start stage . After reaching such a state (indicated by the starting state), polymerization and blow molding were carried out continuously for more than 24 hours. During this period, the quality of the molded products obtained by each molding machine was examined once an hour and found that all molded products can be obtained within more than 24 hours with stable quality. The results are presented in table 13.

EXAMPLE 9

After setting the initial state to the conditions as in example 8, as a simulation of the accident of the molding machine, the injection molding machine B was stopped and the excess polymer 5.0 kg / h was returned to the first stirred type polymerization reactor (P5) through the polymer recovery line and also the amount of feed continuously charged into the esterification reactor was reduced to 50% of the initial stage of the start of the reaction. After setting this state, polymerization and blow molding was carried out continuously for more than 24 hours using only the injection molding machine A. During this period, the quality of the obtained molded product was examined once per hour and it was found that all molded products could be obtained within more than 24 hours with stable quality. The results are presented in table 14.

Examples 10-11

Using the device shown in FIG. 1, a PET prepolymer with an ultimate viscosity [η] of 0.48 dl / g, a number of carboxyl groups at the ends of the polymer chain of 32 meq / kg and a melting point of 256 ° C was fed into the polymerization reactor (17) through the feed channel of the prepolymer (2) with a transfer pump (1), dispatched at a speed of 15 g / min for each hole of the porous plate (3) in the molten state at 265 ° C, then polymerized under reduced pressure of 65 Pa when dropped onto the substrate at the same ambient temperature, as during unloading, was blown out of the polymerization reactor (17) by a discharge pump (8), and then a blank was formed for blow molding at a molding temperature of 280 ° C. using a blow molding machine with a biaxial orientation (SBIII-100H-15 from Aoki Technical Laboratory, Inc.) as molding machine A (10).

The quantity exiting from the discharge pump (8) to the bottom of the polymerization reactor (17) was controlled by determining the outlet pressure in the discharge stream of the discharge pump (8) using the system (15) to determine the outlet pressure and control the exit of the discharge pump, so in order to maintain the outlet pressure (absolute pressure) indicated in table 15 during molding. By the indicated means, the variations in the outlet pressure during molding were always controlled within ± 20%.

A porous plate with a thickness of 50 mm and 14 holes with a diameter of 1 mm was used, where every 7 holes occupied a space of 10 mm and were linearly aligned in the form of 2 straight lines parallel to each other at a distance of 70 mm. A guide substrate was used, vertically connected to wires having a diameter of 2 mm and a length of 8 m near each hole, where the wires were perpendicular to other wires having a diameter of 2 mm and a length of 100 mm in 100 mm space to create a lattice structure. Stainless steel was used as the material of the guide substrate.

As the prepolymer, a prepolymer was used, such as obtained by adding 0.04% by weight of dimisiac trioxide and 100 ppm trimethyl phosphate, based on the mass fraction of elemental phosphorus. The residence time in the polymerization reactor was 70 minutes. The residence time was determined by the amount of polymer inside the polymerization reactor, divided by the amount of load. This leads to a decrease in the powerful foaming of the prepolymer discharged from the porous plate during polymerization, which leads to very little contamination on the surface of the nozzle or the surface of the walls. Observed the absorption of a large amount of foam discharged resin and rolling onto a substrate in the form of a round foam.

First, the pipeline transferring the polymer in the direction of the transfer pump (14) in FIG. 1 was closed; for the receipt of resin only in molding machine A (10) for continuous molding of molded products for 5 hours. The molding cycles of molding machine A (10), especially the timing of each weighing stage, were not set at all, and molding was carried out in molding machine A (10) in this way.

The yield, shape and quality of the molded products obtained by molding machine A (10) were examined every hour and it was confirmed that molded products with stable quality can be obtained within 5 hours. The results are presented in table 15.

Table 1
Example 1: Varying the molded product for 5 hours (outlet pressure 20 MPa) View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. Product A Hollow product 5.0 ± 0.0 0.76 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 11.4 ± 0.5 0.17 ± 0.1 Forms. Product B Dumbbell 4,5 ± 0,0 0.76 ± 0.0 78.00 ± 0.05 99.4 ± 0.1 14.1 ± 0.6 0.18 ± 0.1 Granule C Granule 3.1 ± 0.0 0.77 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.6 ± 0.3 0.15 ± 0.1 table 2
Example 2: Varying the molded product for 5 hours (discharge pressure 5 MPa) View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. Product A Hollow product 5.0 ± 0.0 0.76 ± 0.0 24.60 ± 0.11 99.6 ± 0.1 11.4 ± 0.5 0.18 ± 0.1 Forms. Product B Dumbbell 4,5 ± 0,0 0.76 ± 0.0 78.00 ± 0.09 99.4 ± 0.1 14.1 ± 0.6 0.18 ± 0.2 Granule C Granule 3.1 ± 0.1 0.77 ± 0.1 0.050 ± 0.014 99.8 ± 0.1 3.9 ± 0.6 0.16 ± 0.1 Table 3
Example 3: Varying the molded product for 5 hours (discharge pressure 2 MPa) View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. Product A Hollow product 5.0 ± 0.0 0.76 ± 0.0 24.60 ± 0.23 99.6 ± 0.2 11.8 ± 1.5 0.19 ± 0.2 Forms. product B Dumbbell 4,5 ± 0,1 0.76 ± 0.1 77.99 ± 0.14 99.4 ± 0.2 14.5 ± 1.9 0.19 ± 0.3 Granule C Granule 3.1 ± 0.1 0.77 ± 0.1 0.051 ± 0.022 99.8 ± 0.1 4.2 ± 1.5 0.16 ± 0.2 Table 4
Example 4: Varying the molded product before and after stopping the molding machine B View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. Product A (Hollow Product) To stop B 5,0 0.76 24.61 99.6 11.7 0.16 4 hours after stopping 5.0 ± 0.0 0.76 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 11.4 ± 0.5 0.17 ± 0.1 Granule C To stop B 3,1 0.77 0,052 99.7 3,7 0.15 4 hours after stopping 3.1 ± 0.0 0.77 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.6 ± 0.3 0.15 ± 0.1 Table 5
Comparative Example 1: Variation of the molded product for 5 hours (without adjusting the outlet pressure) View Yield (kg / h) Limit. viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. product A Hollow product 5.0 ± 0.2 0.76 ± 0.2 24.52 ± 0.90 98.6 ± 0.3 17.4 ± 2.4 0.29 ± 0.3 Forms. product B Dumbbell 4,5 ± 0,2 0.76 ± 0.2 77.84 ± 0.20 97.9 ± 0.3 20.1 ± 3.3 0.31 ± 0.4 Granule C Granule 3.1 ± 0.2 0.77 ± 0.1 0,053 ± 0,044 97.8 ± 0.4 7.6 ± 3.2 0.34 ± 0.3 Table 6
Example 5: Varying the molded product for 5 hours (discharge pressure 20 MPa) View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Molded Product A Hollow product 5.0 ± 0.0 0.75 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 10.5 ± 0.5 0.17 ± 0.1 Molded Product B Dumbbell 4,5 ± 0,0 0.75 ± 0.0 78.00 ± 0.05 99.4 ± 0.1 13.2 ± 0.6 0.18 ± 0.1 Granule C Granule 3.1 ± 0.0 0.76 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.5 ± 0.3 0.15 ± 0.1 Table 7
Example 6: Variation of the molded product before and after stopping the molding machine In View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Molded Product A To stop B 5,0 0.75 24.61 99.6, 0.16 10,4 4 hours after stopping 5.0 ± 0.0 0.75 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 10.5 ± 0.5 (Hollow product) 0.17 ± 0.1 Granule C To stop B 3,1 0.76 0,052 99.7, 0.15 3.4 4 hours after stopping 3.1 ± 0.0 0.76 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.5 ± 0.3 0.15 ± 0.1 Table 8
Comparative example 3: variation of the molded product within 5 hours View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. product A Hollow product 5.0 + 0.2 0.75 ± 0.2 24.52 ± 0.90 98.6 ± 0.3 16.4 ± 2.2 0.30 ± 0.3 Forms. product B Dumbbell 4,5 ± 0,2 0.75 ± 0.2 77.84 ± 0.20 97.8 ± 0.3 20.3 ± 3.7 0.30 ± 0.4 Granule C Granule 3.1 ± 0.2 0.76 ± 0.1 0,053 ± 0,044 97.9 ± 0.4 7.2 ± 3.2 0.34 ± 0.3 Table 9
Example 7: variation of the molded product within 5 hours View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. product A Hollow product 5.0 ± 0.0 0.75 ± 0.0 24.60 ± 0.04 99.6 ± 0.1 10.5 ± 0.5 0.17 ± 0.1 Forms. product B Dumbbell 4,5 ± 0,0 0.75 ± 0.0 78.00 ± 0.04 99.4 ± 0.1 13.2 ± 0.6 0.18 ± 0.1 Granule C Granule 3.1 ± 0.0 0.76 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.5 ± 0.3 0.15 ± 0.1 Table 10
Comparative example 4: variation of the molded product within 5 hours View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. product A Hollow product 5.0 ± 0.2 0.75 ± 0.2 24.50 ± 1.0 98.6 ± 0.2 13.4 ± 3.2 0.27 ± 0.3 Forms. product B Dumbbell 4,5 ± 0,2 0.75 ± 0.2 77.79 ± 0.40 98.3 ± 0.2 17.6 ± 3.9 0.26 ± 0.2 Granule C Granule 3.1 ± 0.2 0.76 ± 0.1 0,053 ± 0,048 98.4 ± 0.2 6.2 ± 3.8 0.21 ± 0.3 Table 11
Comparative example 5: variation of the molded product within 5 hours View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Forms. Hollow 5.0 ± 0.2 0.62 ± 0.3 24.59 ± 94.3 ± 0.8 56.4 ± 7.2 product A product 1.3 0.77 ± 0.6 Forms. product B Dumbbell 4,5 ± 0,1 0.62 ± 0.4 78.01 ± 0.30 95.5 ± 0.9 50.1 ± 6.9 0.98 ± 0.5 Granule C Granule 3.1 ± 0.2 0.62 ± 0.3 0.052 ± 0.010 94.7 ± 1.0 48.1 ± 8.3 0.82 ± 0.5 Table 12 Pace. (° C) Duration of stay (min) Vacuum Level (Pa) Marginal
viscosity (dl / g) Esterification reactor 260 180 normal - First stirred type polymerization reactor 280 80 20000 0.20 Second stirred type polymerization reactor 285 60 one hundred 0.47 Table 13
Example 8: Variation of the molded product within 24 hours View Yield (kg / h) Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Forms. product A (hollow product) Start Status 0.75 24.61 99.6 0.16 10,4 1-12 hours after launch 0.75 ± 0.0 24.6 ± 0.05 99.6 ± 0.1 10.5 ± 0.5 0.17 ± 0.1 13-24 hours after launch 0.75 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 10.5 ± 0.5 0.17 ± 0.1 Forms. product B (dumbbell) Start Status 0.76 0,052 99.7, 0.15 3.4 1-12 hours after start 0.76 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.5 ± 0.3 0.15 ± 0.1 13-24 hours after starting t 0.76 ± 0.0 0.050 ± 0.003 99.8 ± 0.1 3.5 ± 0.3 0.15 ± 0.1

Table 14
Example 9: Variation of the molded product within 24 hours View Ultimate Viscosity (dl / g) Mass (g) Color tone (L value, b value) Acetaldehyde Content (ppm) Molded Product A (Full Product Start Status 0.75 24.61 99.6 10,4 0.16 1-12 hours after start 0.75 ± 0.0 24.60 ± 0.05 99.6 ± 0.1 10.5 ± 0.5 0.17 ± 0.1 13-24 hours after launch 0.75 ± 0.0 24.60 ± 0.05 99.6 ± 0.2 10.5 ± 0.5 0.17 ± 0.1 Table 15.
Examples 10-11: changing the molded product within 5 hours. View Outlet pressure Exit Ultimate viscosity Weight Color tone resin Acetaldehyde content (MPa) (kg / h) (dl / g) (g) (L - value, b - value) hour / million Molded Product A Hollow product 0.5 5.0 ± 0.0 0.76 ± 0.0 24.60 + 0.20 99.6 ± 0.2. 12.5 ± 1.5 0.19 ± 0.2 Molded Product A Hollow product 80.0 5.0 + 0.0 0.76 ± 0.0 24.60 ± 0.20 99.6 ± 0.2. 11.1 ± 0.5 0.17 ± 0.2

INDUSTRIAL APPLICABILITY

The present invention provides a method for producing a high-quality molded product with low cost by pumping a resin continuously polymerized by a melt polycondensation reaction, in the molten state as it is, in which it is easy to control the quality and amount of feed flow of the molten resin fed to the molding machine, and also it is easy to adjust them even if the “resin production rate” and the “resin formation rate” are mutually varied, and may be A molded product with stable quality and weight is produced.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

Figure 2. A schematic diagram showing an inert gas adsorption apparatus, a polymerization reactor, and a molding apparatus used in the present invention.

Figure 3. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

Figure 4. A schematic diagram showing an inert gas adsorption apparatus, a polymerization reactor, and a molding apparatus used in the present invention.

Figure 5. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

6. A schematic diagram showing an inert gas adsorption apparatus, a polymerization reactor, and a molding apparatus used in the present invention.

7. A schematic diagram showing an example of a polymerization reactor and a molding device used in a comparative example.

Fig. 8. A schematic diagram showing an example of a polymerization reactor and a molding device used in a comparative example.

Fig.9. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

Figure 10. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

11. A schematic diagram showing an example of a polymerization reactor and molding apparatus used in the present invention.

Claims (19)

1. A method of obtaining a molded product consisting of a resin polymerized by a melt polycondensation reaction, comprising continuously feeding the prepolymer in the molten state from the feed channel of the prepolymer into the polymerization reactor, unloading from the openings of the porous plate, followed by polymerization during discharge under reduced pressure onto the substrate and molding by transferring to at least one molding machine in a molten state without curing, where the transfer pressure into said molding machine is reg can be adjusted in such a way that the pressure is maintained at an arbitrary level from 0.1 to 100 MPa (absolute pressure) by (I) adjusting the discharged amount from the discharge pump of the aforementioned polymerization reactor at a level of 1-100 from the size of the prepolymer feed flow and by (II) returning resin dispensed from the discharge pump to the bottom of said polymerization reactor, consisting of a pipe connected to a discharge stream from the discharge pump of said polymerization reactor and the bottom of said polymerization reactor and, and systems for measuring outlet pressure and controlling the degree of opening of a polymer return valve or a back pressure valve installed on said pipeline, the resin polymerized by the melt polycondensation reaction being a polymer selected from the group consisting of aliphatic polyesters, aliphatic polyamides, aliphatic polycarbonates, aliphatic aromatic polyesters, aliphatic aromatic polyamides, aliphatic aromatic polycarbonates, aromatic polyesters and aro mate polyamides. 2. The method according to claim 1, in which the transfer pressure to the molding machine is controlled so that the pressure is maintained at an arbitrary level from 0.1 to 100 MPa (absolute pressure) by adjusting the discharged amount from the discharge pump of said polymerization reactor. 3. The method according to claim 1 or 2, in which the transfer pressure into the molding machine is from 0.1 to 100 MPa and is adjusted to maintain a level that does not exceed ± 80% of the set pressure. 4. The method according to claim 1 or 2, in which the polymer is transferred to a granulating machine and / or an exhaust nozzle, so that the residence time of the polymer in the melt at the bottom is regulated in the range from 0.1 to 120 minutes by installing said polymerization reactor at the bottom, or after the discharge pump of said polymerization reactor, a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine. 5. The method according to claim 3, in which the polymer is transferred to a granulating machine and / or an exhaust nozzle, so that the residence time of the polymer in the melt at the bottom is controlled in the range from 0.1 to 120 minutes by installing on the bottom of the said polymerization reactor, or after a discharge pump of said polymerization reactor, a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine. 6. A method of obtaining a molded product consisting of a resin polymerized by a melt polycondensation reaction, comprising continuously feeding the prepolymer in the molten state from the prepolymer feed channel into the polymerization reactor, unloading from the openings of the porous plate, polymerization during discharge onto the substrate under reduced pressure, shipping said resins from at least two shipping pumps of said polymerization reactor, followed by molding by transfer to at least two molding machines and / or granulating machines in a molten state without curing, where the transfer pressure into the said molding machine is controlled so that the pressure is maintained at an arbitrary level from 0.1 to 100 MPa (absolute pressure) by (I) adjusting the discharge quantity from the discharge pump said polymerization reactor at a level of 1-100 of the magnitude of the feed stream of the prepolymer and by (II) returning the resin shipped from the loading pump to the bottom of said polymerization reactor, consisting of a pipeline connected to the discharge stream from the discharge pump of said polymerization reactor and the bottom of said polymerization reactor, and a system for measuring the outlet pressure and controlling the degree of opening of the polymer return valve or the back pressure valve installed on said pipeline, the resin being melt polymerized by a polycondensation reaction a polymer selected from the group consisting of aliphatic polyesters, aliphatic polyamides, aliphatic polycarbonates, aliphatic aromas iCal polyesters, aliphatic aromatic polyamides, aliphatic aromatic polycarbonates, aromatic polyesters and aromatic polyamides. 7. The method according to claim 6, in which at least one molding machine and / or granulating machine are associated with each of the shipping pumps of said polymerization reactor. 8. The method according to claim 1 or 2, in which at least a portion of the polycondensation polymer obtained by said melt polycondensation reaction in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the steps for producing said polycondensation polymer. 9. The method according to claim 3, in which at least a portion of the polycondensation polymer obtained by said melt polycondensation reaction in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the steps for producing said polycondensation polymer. 10. The method according to claim 4, in which at least a portion of the polycondensation polymer obtained by said melt polycondensation reaction in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the steps for producing said polycondensation polymer. 11. The method according to claim 5, in which at least a portion of the polycondensation polymer obtained by said melt polycondensation reaction in an amount greater than the amount used in molding or granulation is returned for recycling to an arbitrary stage among the steps for producing said polycondensation polymer. 12. The method according to claim 6 or 7, in which at least a portion of the polycondensation polymer obtained by the said polycondensation reaction in the melt in an amount greater than the amount used in molding or granulation, is returned for recycling to an arbitrary stage among the stages of obtaining said polycondensation polymer. 13. The method according to claim 1, wherein said prepolymer is reacted with an arbitrary amount of a molecular weight regulator at an arbitrary stage before being introduced into said polymerization reactor. 14. The method according to claim 1, wherein said molded product is at least one type selected from a blank for molding bottles, films, webs, containers and fibers. 15. The method according to claim 1, in which the resin polymerized by the aforementioned polycondensation reaction in the melt, is a polyester resin. 16. A device for producing a molded product consisting of a resin polymerized by a melt polycondensation reaction, comprising continuously feeding the prepolymer in the molten state from the prepolymer feed channel into the polymerization reactor, unloading from the openings of the porous plate, followed by polymerization during discharge onto the substrate under reduced pressure and molding by transferring to at least one molding machine in a molten state without curing, where the transfer pressure into said molding The machine is controlled in such a way that the pressure is maintained from 0.1 to 100 MPa (absolute pressure), by (I) adjusting the discharged amount from the shipping pump of the aforementioned polymerization reactor at a level of 1-100 from the size of the prepolymer feed stream and (II) resin dispensed from the discharge pump to the bottom of said polymerization reactor, consisting of a pipe connected to a discharge stream from the discharge pump of said polymerization reactor and the bottom of said polymerization reactor, and a system we measure the pressure at the outlet and regulate the degree of opening of the polymer return valve or the back pressure valve installed on the said pipeline. 17. The device according to clause 16, in which the transfer pressure into the molding machine is controlled so that the pressure is maintained from 0.1 to 100 MPa (absolute pressure) by adjusting the discharge amount from the discharge pump of said polymerization reactor. 18. The device according to clause 16 or 17, in which the polymer is transferred to a granulating machine and / or exhaust nozzle, so that the residence time of the polymer in the melt is regulated at a level of from 0.1 to 120 minutes by installing on the bottom of the said polymerization reactor, or after a discharge pump of said polymerization reactor, a transfer pump connected to a granulating machine and / or additionally an exhaust nozzle in a molding machine. 19. A device for producing a molded product consisting of a resin polymerized by a melt polycondensation reaction, in which the prepolymer is continuously supplied in the molten state from the prepolymer feed channel to the polymerization reactor, unloaded from the openings of the porous plate, polymerized during discharge onto the substrate under reduced pressure, and the resin is dispatched from at least two dispensing pumps of said polymerization reactor, then molded by transfer to at least two molding machines and / or granulating machines in a molten state without curing, where the transfer pressure into said molding machine is controlled in such a way that the pressure is maintained from 0.1 to 100 MPa (absolute pressure), by (I) controlling the discharge amount from the discharge pump of said polymerization reactor at a level of 1-100 of the magnitude of the feed stream of the prepolymer and by (II) returning the resin dispatched from the discharge pump to the bottom of said polymerization reactor, consisting of a pipeline connected to a discharge the flow from the discharge pump of said polymerization reactor and the bottom of said polymerization reactor, and a system for measuring outlet pressure and controlling the degree of opening of the polymer return valve or back pressure valve installed on said pipeline.

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