EA022372B1 - Continuous process for the production of branched polycarbonate - Google Patents

Abstract

The invention relates to a continuous process for the production of branched polycarbonate, which includes a step (A) of producing a low-molecular polycarbonate having a number-average molecular weight of 1000 to 10000 from an aromatic dihydroxyl compound and a carbonic diester via transesterification; a step (B) of adding the polyfunctional compound in a liquid state to the low-molecular polycarbonate, and mixing the resulting system; and a step (C) of conducting the polymerization of the mixture successively until the melt index and melt index ratio of the low-molecular polycarbonate reach 10 g/10 min or less and 14 or more respectively, and thus producing a branched polycarbonate.

Description

The present invention relates to a method for the continuous production of branched polycarbonate by transesterification reaction.

Prior art

Polycarbonates are structural plastics with high transparency and heat resistance, as well as high mechanical strength, including impact resistance, and they are widely used in industry, including for the production of optical lenses, in the electrical and electronic industries, automobiles, etc. Owing to their constructional properties and rigidity, which determine resistance to cracking during falling, large injection molded large bottles have become widespread in recent years for transporting drinking water to countries with insufficient drinking water production capacities and for transporting mineral water from specific places of its production .

Stable blow molding of these large-sized bottles requires a high melt viscosity and high melt tension compared to conventional polycarbonates. Therefore, there was a need to increase the stretching of the polycarbonate melt by increasing the degree of high molecular weight and introducing branched structures into the molecule. In the phosgene method, which has been used for a long time as a method for producing polycarbonates, this is achieved by using a multifunctional compound as a branching agent with the introduction of a branched structure into polycarbonate, as proposed in patent document 1. However, the phosgene method involves the use of highly toxic phosgene or large quantities of chlorine solvents and therefore poses a great threat to the environment. Due to the growing concern about the state of the environment in recent years, methods for producing polycarbonates have moved toward transesterification methods that do not use phosgene or large quantities of chlorine-containing solvents. However, continuous industrial production of branched polycarbonates based on transesterification are still under development, and numerous improvements have been proposed.

Upon transesterification, an aromatic dihydroxy compound, diphenyl carbonate and a polyfunctional compound as a branching agent can be melt-reacted in the presence of a catalyst to form a branched polycarbonate. However, a simple reaction does not provide an easy yield of branched polycarbonates that meets the requirements of industrial production, and therefore the following methods [1] - [3] have been proposed as improvements.

[1] Methods involving the use of specific catalysts to reduce the branched Kolbe-Schmitt structures (Co1Be-8cncr1y), which spontaneously form during the reaction from the melt (patent documents 2-4), methods that improve the color tone through the use of specific catalysts ( patent document 5), and methods that use multifunctional compounds of specific structures as branching agents (patent documents 6-8).

[2] Methods in which a branching agent comprising a polyfunctional compound is added to the obtained polycarbonate together with a transesterification catalyst for reaction in an extruder to produce a branched polycarbonate (patent documents 9-11).

[3] Methods in which the formation of branched structures that spontaneously form during the polymerization reaction is actively accelerated without the use of branching agents that can contaminate the system when branched polycarbonates are obtained (patent documents 12 and 13).

List of cited references

Patent Literature.

[Patent document 1] Japanese patent DR 47-23918 Century

[Patent document 2] Japanese patent DR 05-271400 A.

[Patent document 3] Japanese patent DR 05-271402 A.

[Patent document 4] Japanese patent DR 05-295101 A.

[Patent document 5] Japanese patent DR 04-89824 A.

[Patent document 6] Japan patent DR 2001-302780 A.

[Patent Document 7] Japanese Patent DR 2002-508801 U.

[Patent document 8] Japan patent DR 2006-131910 A.

[Patent document 9] Japanese patent DR 02-245023 A.

[Patent document 10] Japan patent DR 11-209469 A.

[Patent document 11] Japanese patent DR 2000-290364 A.

[Patent document 12] Japanese patent DR 2002-308976 A.

[Patent document 13] Japanese patent DR 2004-002831 A.

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SUMMARY OF THE INVENTION Technical Problem Solved by the Invention

The polycarbonates obtained by the method [1] have an improved shade, but also have a high content of defects such as fisheye and poor resistance to the action of hot water. In addition, since the branching agent is charged with the aromatic dihydroxy compound and diphenyl carbonate in the linear polycarbonate formation step, fish-eye defects occur in the subsequently formed linear polycarbonate, after the transition from the branched polycarbonate to linear polycarbonate. This creates major problems, such as the need for a significant period of time during the transition to eliminate this negative effect, or the production must be suspended for cleaning production equipment.

The production method [2] avoids the above problem when switching from the production of one product variety to another, since no branching agent is added at the polymerization stage, but the resulting branched polycarbonate has numerous defects such as fish eye and reduced resistance to hot water, which often makes the implementation of a stable process for the production of satisfactory polycarbonate is impossible.

The production method [3] also has the advantage that a branching agent is not added, but a stable production process is difficult, as side reactions of rearrangement are actively accelerated, as well as undesirable side reactions that worsen the color and contribute to the formation of defects such as fish eye, and resistance exposure to hot water is also reduced and problems arise, such as losses during the transition from production of one variety of a product to another variety.

The present invention was carried out in the light of these circumstances, and its task is to develop a method for the continuous production of branched polycarbonates, in which transesterification results in branched polycarbonates having low losses when switching from production of one variety of a product to another variety, excellent shade, resistance to hot water and low level of formation of defects such as fisheye.

Solution

The invention relates to a method for the continuous production of branched polycarbonate, where the method includes (A) a step for producing a low molecular weight polycarbonate with a number average molecular weight of 1000-10000 from an aromatic dihydroxy compound and a carbonic diester by transesterification reaction, (B) a step for adding and mixing a polyfunctional compound with a low molecular weight in the liquid state and (C) the stage of the subsequent polymerization reaction until the melt index of low molecules polycarbonate molecular weight exceeds 10 g / 10 min, and the branching index does not reach at least 14, to obtain a branched polycarbonate. According to this method, it is possible to continuously obtain branched polycarbonates with low losses during the transition from one product grade to another, excellent shade and resistance to hot water, as well as a low level of formation of defects such as fish eyes, according to the transesterification reaction.

According to this invention, the interval ΔΤ (° C) determined by the following formula (1) is preferably between -20 and 20 ° C. This will allow a more significant effect of the invention.

LT-T _? -T- (1) where Τ ₁ represents the temperature (° C) of low molecular weight polycarbonate introduced into the final polymerization reactor in step (C);

T ₂ represents the temperature (° C) of a branched polycarbonate polymerized in the final polymerization reactor in step (C), where T ₂ is 285 ° C or less.

The multifunctional compound is preferably added to the melt mixer mounted on the line between the device used in step (A) and the device used in step (C) as a solution in a solvent. This will allow a more significant effect of the invention.

The solvent is preferably at least one solvent selected from the group consisting of phenols, carbonic acid diesters, ketones, ethers, mixtures and reaction products of aromatic dihydroxy compounds and carbonic acid diesters, as well as low molecular weight polycarbonates with a number average molecular weight of 5000 or less . This will allow a more significant effect of the invention.

The solvent is preferably a depolymerization solvent. This will allow a more significant effect of the invention. As used herein, the term “depolymerization solvent” refers to a solvent that induces the depolymerization of polycarbonate.

The invention may further include (Ό) a polymerization reaction step until the melt index exceeds 100 g / 10 min to produce polycarbonate after step (A). By this method, it is possible to carry out continuous production of various types of polycarbonates, including branched polycarbonates, with a low loss when switching from the production of one variety of product to another grade, as well as with excellent shade and resistance to hot water and a reduced level of formation of defects such as fish eye according to transesterification reaction.

The device used in stage (A) is connected to the device used in stage (C) and the device used in stage (Ό), a line having a branching section that is divided in such a way that passes through the device used in stage (C), and the device used in stage (Ό), and the multifunctional connection can be introduced into the melt mixer installed on the line between the branching sections and the device used in stage (C). This will allow a more significant effect of the invention.

The invention also relates to branched polycarbonate obtained by the above method. The branched polycarbonate obtained by this method has an excellent shade and resistance to hot water, as well as a low level of formation of defects such as fish eye.

Benefits of the invention

According to the invention, it is possible to provide a process for the continuous production of branched polycarbonates, in which branched polycarbonates are formed, having low losses when switching from the production of one variety of product to another grade, excellent shade and resistance to hot water, and a low level of formation of defects such as fisheye, according to the reaction interesterification.

Brief Description of the Drawings

In FIG. 1 is a diagram of a branched polycarbonate production system according to one embodiment of the invention.

In FIG. 2 is a diagram of a production system for various types of polycarbonates according to one embodiment of the invention.

Description of Embodiments

Further, the present invention will be discussed in more detail. In the process for the continuous production of the branched polycarbonate of the present embodiment, the branched polycarbonate can be obtained by transesterification from an aromatic dihydroxy compound, a carbonic acid diester and a polyfunctional compound.

According to this embodiment, the aromatic dihydroxy compound is a compound represented, for example, by the formula HO-Ar-OH (where Ar is a divalent aromatic residue and may be, for example, phenylene, naphthylene, biphenylene, pyridylene or a divalent aromatic residue represented by the formula-Ag ¹ -Υ-Ar ² - wherein each of Ar ¹ and Ar ² independently represents a C5 _- 7odvuhvalentnuyu carbocyclic or heterocyclic aromatic group, and Υ is C _1- s ₀ divalent alkylene group y).

In the divalent aromatic group (Ar ¹ , Ar ² ), one or more hydrogen atoms connected to the aromatic ring can be replaced by another substituent that does not adversely affect the course of the reaction, such as C _1-10 alkyl, C _5-10 cycloalkyl a group comprising a ring, C _1-10 alkoxy, phenyl, phenoxy, vinyl, cyano, ester, amide or nitro. Specific examples of preferred heterocyclic aromatic groups include heterocyclic aromatic groups containing one or more nitrogen atoms, oxygen atoms, or sulfur atoms including a ring.

As the groups Ag ¹ and Ag ² , substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene and substituted or unsubstituted pyridylene are preferred.

A divalent alkylene group Υ is an organic group represented by any of the following general formulas:

[Chemical formula 1]

where each K ¹ , K ² , K ³ and K ⁴ independently represents a hydrogen atom, C _1-10 alkyl, C _1-10 alkoxy, C5-10 cycloalkyl group comprising a ring, C5-10 carbocyclic aromatic group comprising a ring, or C _{6 -10} carbocyclic aralkyl group including a ring;

k represents an integer of 3-11;

K ⁵ and K ^{6 are} independently selected for each X and each independently represents a hydrogen atom or a C _1-6 alkyl group;

X represents carbon;

one or more hydrogen atoms in K ¹ , K ² , K ³ , K ⁴ , K ⁵ and K ⁶ may optionally be substituted with another substituent that does not adversely affect the course of the reaction, such as C _1-10 alkyl,

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C _1-10 alkoxy, phenyl, phenoxy, vinyl, cyano, ester, amide or nitro group.

Examples of a divalent aromatic residue Ar containing these substituents include groups represented by the following general formulas:

[Chemical formula 2]

where each K ⁷ and K ⁸ independently represents a hydrogen atom, C _1-10 alkyl, C1_1 ₀ alkoxy, C ₅ _1 ₀ cycloalkyl group including a ring, or phenyl group;

each of the symbols m and η represents an integer 1-4, when m is 2-4, each of the radicals K ⁷ may be the same or different from the other, and when η is 2-4, each of the radicals K ⁸ may be the same or different from the other.

The divalent aromatic residue Ar may be a residue represented by the formula -Ατ ¹ -Ζ-Ατ ² - (where Ar ¹ and Ag ² have the meanings indicated above, Ζ represents a single bond or a divalent group such as -0-, -CO-, -δ-, -δΟ ₂ -, -80-, -COO- or -ΟΟΝ / Κ ¹ ) -, and K ¹ has the meanings indicated above).

Examples of such a divalent aromatic residue Ar include groups represented by the following general formulas:

[Chemical formula 3] ev ⁷ ). (nn sn ⁷ ). svl sn. (c ') n <"')„ <k '> „

-® - © (B ⁷ ). (n '> l <B ^Γ ). <n ') n (B ^7), CB') "(V ⁷⁾ of θ '·) n CH _and D of removal, Art SAEs

I sn, where K ⁷ , K ⁸ t and η have the same definitions as described above.

The aromatic dihydroxy compound used in this embodiment of the invention may be of one type or two or more different types. A typical example of an aromatic dihydroxy compound is bisphenol A, and when used in conjunction with another aromatic

- 4,022,372 by the dihydroxy compound, bisphenol A is preferably used in a ratio of at least 85 mol% relative to the total amount of aromatic dihydroxy compounds. These aromatic dihydroxy compounds preferably have a low content of chlorine and alkali or alkaline earth metals, and, if possible, they preferably do not contain these elements.

The carbonic acid diester used in this embodiment is a compound represented, for example, by the following general formula:

[Chemical formula 4]

Oh, and.

Ar ³ —O — C — O — Ag ⁴ where each Ar ³ and Ar ⁴ represents a monovalent aromatic group.

Aromatic monovalent groups of Ag ³ and Ag ⁴ are preferably phenyl, naphthyl, biphenyl or pyridyl groups. In Ag ³ and Ag ^4, one or more hydrogen atoms connected to the aromatic ring may optionally be substituted with another substituent that does not adversely affect the course of the reaction, such as Syoalkyl, Sy ₀ alkoxy, phenyl, phenoxy, vinyl, cyano, complex ether, amide or nitro group. Ar ³ and Ar ⁴ may be the same or different.

More preferred examples for Ag ³ and Ag ⁴ include groups represented by the following formulas:

[Chemical formula 5]

Typical examples of carbonic acid diesters include substituted or unsubstituted diphenyl carbonates represented by the following general formula:

[Chemical formula 6] (n ') p O CB ¹⁰ ),' © -L-® 'where each K ⁹ and K ¹⁰ independently represents a hydrogen atom, Sy ₀ alkyl, Sy ₀ alkoxy, C _{5-1 0} cycloalkyl group, comprising a ring or phenyl group;

each of the characters p and s. | represents an integer 1-5, when p is 2 or more, each of the radicals K ⁹ may be different from the other, and when S. | equal to 2 or more, each of the radicals K ¹⁰ may be different from the other.

Of these carbonic acid diesters, symmetric diaryl carbonates, including unsubstituted diphenyl carbonates, and lower alkyl substituted diphenyl carbonates, such as ditolyl carbonate and di-tert-butyl phenyl carbonate, are preferred, diphenyl carbonate is more preferred. These carbonic acid diesters can be used individually or in combination of two or more of them. The carbonic acid diesters preferably have a low content of chlorine and alkali or alkaline earth metals, and, if possible, they preferably do not contain these elements.

The proportion of aromatic dihydroxy compound and carbonic acid diester (feed ratio) will depend on the type of aromatic dihydroxy compound and carbonic acid diester used, given molecular weight, fraction of hydroxyl terminal groups and polymerization conditions, and is not particularly limited. The carbonic acid diester can be used in an amount of preferably 0.9-2.5 mol, more preferably 0.95-2.0 mol, and even more preferably 0.98-1.5 mol per 1 mol of aromatic dihydroxy compound. Aromatic monohydroxy compound can also be used to convert end groups or change molecular weight.

The multifunctional compound used in the manufacturing process of this embodiment is a compound containing at least 3 functional groups in the molecule that are reactive with respect to the carbonic acid diester, and it is preferably a compound containing at least 3 phenolic hydroxyl and / or carboxyl groups. Examples of multifunctional compounds include the following compounds:

1,1,1-tris- (4-hydroxyphenyl) ethane,

4- [4- [1,1-bis- (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl] phenol,

2,2 ', 2-tris- (4-hydroxyphenyl) diisopropylbenzene,

- 5 022372 a, a ', a-tris- (4-hydroxyphenyl) triisopropylbenzene, fluoroglycine,

4.6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane-2,

1,3,5-tri (4-hydroxyphenyl) benzene,

2,2'-bis- [4,4- (4,4'-dihydroxydiphenyl) cyclohexyl] propane, a-methyl-a, a, a-tris- (4-hydroxyphenyl) -1,4-diethylbenzene, tri- (4-hydroxyphenyl) phenylmethane,

2.4- bis- (4-hydroxyphenylisopropyl) phenol,

2.6- bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol,

2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenyl) terephthalic acid ester, tetra- (4-hydroxyphenyl) methane, tetra- (4- (4-hydroxyphenylisopropyl) phenoxy) methane,

1.4- bis- (4 ', 4-dihydroxytriphenyl) methylbenzene,

2.4- dihydroxybenzoic acid, trimesinic acid,

3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, trimesine trichloride, a, a ', a-tris- (4-hydroxyphenol) -1,3,5- triisopropylbenzene, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid,

SbN5-81- (O-81 (CH3) 2-C3Nb-SbN4-OH) 3,

CH ₃ -81- (O-81 (CH3) ₂ -C ₃ H ₆ -C ₆ H ₄ -OH) s and the like, of which 1,1,1-tris- (4-hydroxyphenyl) are most preferred ) ethane and 4- [4- [1,1-bis- (4hydroxyphenyl) ethyl] -α, α-dimethylbenzyl] phenol.

The amount of polyfunctional compound used relative to the aromatic dihydroxy compound may be preferably 0.1-0.95 mol%, more preferably 0.2-0.8 mol%, and most preferably 0.3-0.6 mol%. If it does not exceed 0.95 mol.%, This will not lead to an increase in the formation of defects such as fisheye, while the stretching of the melt increases with an increase in the amount of at least 0.1 mol.%.

Transesterification is a process in which a compound undergoes polycondensation by a transesterification reaction in a melt state in the presence or absence of a catalyst, when heated under reduced pressure and / or in an inert gas stream, while the polymerization process does not have any limitations from the point of view of the device used. For example, the device used can be a stirred reactor, a thin-film reactor, a centrifugal thin-film evaporation reactor, a biaxial kneading reactor with an updated surface, a biaxial horizontal stirred reactor, a reactor with wettable walls, and a perforated plate reactor in which droplet polymerization proceeds under free-fall conditions. or a reactor with perforated plates connected by a wire, in which polymerization proceeds under the conditions of dropping drops to e wire. According to an embodiment of the invention, they can also be used in combination to produce the desired polycarbonate by a stepwise polycondensation reaction. For example, it is preferable that the production process is carried out in a stirred vessel reactor until a molten prepolymer of low molecular weight appears, and the resulting molten prepolymer is then polymerized using a perforated plate reactor in which drop polymerization proceeds or a fluidized bed polymerization reactor zone of the contact wire, in which polymerization proceeds with the free flowing of droplets along the wire. To reduce losses during the transition from the production of one product grade to another grade, it is particularly preferable to use a fluidized bed polymerization reactor in the contact wire region with excellent displacement efficiency, as a polymerization reactor installed downstream of the melt mixer. These manufacturing processes can be carried out, for example, subject to US Pat. No. 5,589,564. There are no particular restrictions on the materials of these reactors, but at least the surface material of the inner wall of the reactor is usually stainless steel, nickel, glass, or the like.

The temperature for melt polymerization by transesterification reaction is preferably 50-320 ° C. The aromatic monohydroxy compound is formed as the reaction proceeds, and the reaction rate increases when the reaction product is withdrawn from the reaction system. Thus, it is preferable to use a method in which an inert gas is introduced that does not adversely affect the course of the reaction, such as nitrogen, argon, helium, carbon dioxide or gaseous lower hydrocarbon, and the aromatic monohydroxy compound formed is withdrawn together with the gas, or a method in which the reaction is carried out under reduced pressure. The preferred reaction pressure will vary depending on the molecular weight of the product, but preferably it is between 10 mm Nd and normal pressure in the first polymerization step, preferably not more than 20 mm Nd, most preferably not more than 10 mm Nd in the last polymerization step and preferably not more 5 mm Nd in the final reactor.

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Next, step (A), step (B) and step (C) of an embodiment of the invention will be explained. A detailed explanation will be given with reference to FIG. 1, but the manufacturing process of this embodiment is not limited to it.

The continuous production method of a branched polycarbonate according to this embodiment of the invention includes (A) a step for producing a low molecular weight polycarbonate with a number average molecular weight of 1000-10000 from an aromatic dihydroxy compound and a carbonic acid diester by transesterification, (B) a step for adding and mixing a polyfunctional compound with a low molecular weight low molecular weight and (C) a step for the subsequent polymerization reaction until the melt index (ΜΙ) -molecular polycarbonate does not exceed 10 g / 10 min, and ΜΙΚ be at least 14, to obtain a branched polycarbonate.

The branched polycarbonate production system shown in FIG. 1 includes a first polymerization step with stirring with the first stirred polymerisation reactors 3A, 3B, a second polymerization step with stirring with a second stirred tank polymerisation reactor 3C and a third polymerization process with stirring with a third stirred tank reactor 3Ό, as well as a first polymerization step with fluidization in the area of the contact wire with the first polymerization reactor 108A with fluidization in the area of the contact wire and the second stage of polymerization with fluidization in the region of stroke wire to a second polymerization reactor 108B fluidisation in the contact wire.

Stage (A) is stage 3A and 3B to 3C, 3, and 108A.

Each of the 3Λ-3Ό stirred tank polymerization reactors includes inlet channels 1A, 1B for the product to be polymerized or inlet channels 1C, 1Ό for the prepolymer, ventilation holes 2 отверстия-2Ό, exhaust channels 5 выпуск-5Ό and mixers 6алки-6Ό with fixed mixing paddles. The first stage of polymerization with stirring is carried out in a batch system with the loading of polymerizable products, aromatic dihydroxy compound and carbonic acid diester into the first polymerization reactor 3A and 3B with a stirrer, which are installed in parallel. The polymerization catalyst is usually added at this stage, but it can be added at a later stage. The resulting molten prepolymers 4A and 4B are charged via a conveying pipe to a second casing polymerization reactor 3C with a mixer through an input channel 1C for the prepolymer. During this period of time, a priming pump 8 installed on the product transfer line can, if necessary, be used to transfer molten prepolymers 4A and 4B. In addition, the molten prepolymer 4C, subjected to polymerization in the second stage of polymerization with stirring, is pushed by a pumping pump 7C installed on the outlet channel 5C from the second shell polymerisation reactor 3C with a stirrer and loaded through the input channel 1Ό for the prepolymer into the third tank polymerisation reactor 3 реак with agitator along the conveying pipe. Thus, the second and third stages of polymerization proceed continuously.

The molten prepolymer 4Ό, formed in the third stage of polymerization with stirring, is pushed from the outlet channel 5Ό from the third casing polymerization reactor 3ал with a stirrer by a pump 7Ό and moves through the transport pipe to the first fluidization polymerization reactor 108A in the contact wire region.

After this, the first and second stages of polymerization on a contact wire with fluidization proceed continuously in the first and second reactors 108A and 108B of polymerization with fluidization on a contact wire. The first and second contact bed fluidized bed polymerization reactors 108A and 108B are equipped with input channels 101A, 101B for the prepolymer, perforated plates 102A, 102B, guide wires 103A, 103B, openings 104A, 104B for gas supply, ventilation ducts 105A, 105B and outlet channels 107A, 107B, respectively.

The molten prepolymer 4Ό entering through the prepolymer feed port 101A is polymerized by the dripping of the drops in contact with the wire, and the molten prepolymer 109A is collected at the bottom of the first fluidized bed polymerisation reactor 108A. The polymerization reaction proceeds until the number average molecular weight (Mp) of the molten prepolymer 109A reaches 1000-10000. The number average molecular weight is preferably 1500-8000, and more preferably 2000-7000. If Mn is at least 1000, then losses during the transition from the production of one product variety to another will decrease, and if it does not exceed 10,000, the formation of defects such as fish eye will decrease, and the resistance to hot water can be improved. The molten prepolymer 109A is pushed from the outlet channel 107A by a pumping pump 106A and moves through a conveying pipe to the input channel 101B for the prepolymer of the second fluidized bed polymerisation reactor 108B. Measurement of number average molecular weight and weight average molecular weight according to this embodiment of the invention can be carried out by gel permeation chromatography (OPC).

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Step (B) is a step in which a polyfunctional compound is added and mixed with the low molecular weight polycarbonate obtained in step (A) in a liquid state. In FIG. 1, a conveying pipe from the outlet channel 107A to the prepolymer input channel 101B, a melt mixer (linear mixer) 110 mounted on the conveying pipe, and a supply line 111 of the multifunctional compound correspond to step (B). In this case, the multifunctional compound in liquid state is loaded into the melt mixer 110 through the multifunctional compound supply line 111 and mixed with the molten prepolymer 109A, which is transported from the first contact wire fluidized bed polymerization reactor 108A. When the depolymerization reaction proceeds at a given point in time, it can proceed to equilibrium inside the melt mixer or proceed until it is completed inside the transport pipe. Since this is followed by step (C), there is no need for the depolymerization reaction to reach equilibrium at this stage. For a more uniform mixture, a mixing zone, such as a static mixer, may be provided in the conveying pipe.

Stage (B) may be located in the system of FIG. 1 between the outlet channel 5Ό and the inlet channel 101A of the prepolymer or in the pipe between the outlet channel 5C and the inlet channel 1Ό of the prepolymer. In step (B, according to this embodiment of the invention, the reaction (including the depolymerization reaction when depolymerization takes place) can be carried out by directly introducing the multifunctional compound into the conveying pipe without using a melt mixer, either in the conveying pipe or in a fixed mixing zone, such as a static mixer A plasticizer such as a twin screw extruder can also be used as a melt mixer. In this case, a multifunctional compound can be added It is present in a molten state or dissolved in a solvent for administration, if it is in powder form. In order to reduce the number of fish-eye defects and improve the resistance to hot water, the multifunctional compound is preferably added in the molten state or dissolved in the solvent, and most preferably added to dissolved in a solvent.

According to an embodiment of the invention, the multifunctional compound can also be introduced into the melt mixer in a state dissolved in a solvent. The solvent used to dissolve the polyfunctional compound is preferably a commercially available compound, such as phenol, an aromatic dihydroxy compound, a carbonic acid diester, a mixture or a reaction product of an aromatic dihydroxy compound and a carbonic diester, or a low molecular weight polycarbonate with a weight average 5000. These solvents may be used individually or in combination of two or more of them. Using these compounds as solvents can reduce the number of fish-eye defects in the resulting branched polycarbonate. Although the reason for this is not entirely clear, it is believed that the use of these compounds as solvents can cause the depolymerization of polycarbonate and, thus, further accelerate the dispersion of the polyfunctional compound. In this case, the molecular weight of the polycarbonate will temporarily decrease due to depolymerization, and since it is undesirable from the point of view of achieving too large a decrease in molecular weight, the amount of solvent is preferably determined so that the percentage reduction in molecular weight is below 50% and more preferably below 30%. A solvent for dissolving the multifunctional compound may be added as a solution of methanol, ethanol, acetone, methylene chloride or the like. in a general purpose solvent.

According to an embodiment of the invention, the term multifunctional compound in a liquid state refers either to a state in which the multifunctional compound itself is molten, or to a state in which the multifunctional compound is dissolved in a solvent.

In addition, a multifunctional compound in a liquid state according to this embodiment of the invention relates to the dissolved state of a multifunctional compound due to interaction with a solvent and / or other components. Other components may include a catalyst that accelerates the reaction between the polyfunctional compound and the solvent. The catalyst used may be selected as desired, depending on the solvent, and may be the catalyst used in the polymerization.

Stage (C) is the stage at which the polymerization of low molecular weight polycarbonate proceeds until ΜΙ of the polycarbonate exceeds 10 g / 10 min and the branching index ΜΙΚ is at least 14. This corresponds to the second fluidization polymerization reactor 108B in the region the contact wire shown in FIG. 1. There are no specific restrictions on the number of polymerization reactors in step (C), but an increased number of polymerization reactors can increase the transition time from production of one product grade to another grade and increase losses, and therefore one polymerization reactor is preferred.

The molten prepolymer 109A, which was loaded into the second fluidization polymerization reactor 108B in the contact wire region, polymerizes during runoff and contact with

- 8 022372 by wire, as in the first fluidized bed polymerization reactor 108A, and the molten polymer 109B is collected at the bottom of the second fluidized bed polymerization reactor 108B. The molten polymer 109B is withdrawn through the outlet channel 107B by a suction pump 106B and is recovered as a branched polycarbonate.

To obtain a higher molecular weight polymer, molten prepolymer 109A, loaded into a second fluidization polymerization reactor 108B in the contact wire region, should be fed in a smaller amount to provide sufficient polymerization time, although this will depend on the temperature in the polymerization reaction apparatus. Therefore, the performance of high molecular weight polymer is reduced. In addition, low prepolymer loading can also lead to quality problems besides performance. If the feed rate is too low, part of the residual prepolymer may remain on the wire and may increase the formation of defects such as fish eye.

Productivity tends to decrease in conventional methods when M1 <5, and when M1 <4, in addition to reduced productivity, there is a risk of increased formation of defects such as fisheye.

In the method of the present embodiment, a fixed amount of prepolymer can be loaded onto each wire to increase productivity and improve quality. In conventional methods, high molecular weight polymers are prepared at a limited feed rate of the prepolymer into the second contact wire fluidized bed polymerization reactor 108B. In the method of the present embodiment, however, it is possible to obtain an unexpected effect in which loading the prepolymer containing the added branching agent increases the residence time on the wire during the dropping of the droplets through the wire.

In particular, the feed rate of the prepolymer into the second contact wire fluidized bed polymerization reactor 108B as the final polymerisation reactor using 8 m of wire is preferably 0.3-3.0 kg / (h-wire), more preferably 0.4- 2.5 kg / (h-wire) and even more preferably 0.5-2.0 kg / (h-wire) as the mass (kg) per unit time (h) per wire. The prepolymer feed rate to the wire is proportional to the length of the wire.

If the feed rate is less than 0.3 kg / (h-wire), then the productivity will decrease, and some phenomena associated with the residual polymer on the wire may occur (increased number of defects such as fish eye, for example). At a feed rate exceeding 3.0 kg / (h-wire), the residence time or contact time of the prepolymer with the wire will decrease, making it difficult to obtain a sufficient molecular weight.

From the point of view of obtaining a sufficient value of M1 and M1K and a satisfactory color cast and number of fish eye defects for this embodiment, the reaction temperature from step (A) to step (C) is preferably 50-320 ° C., more preferably 100300 ° C., even more preferably 130-280 ° C. and most preferably 150-270 ° C. Stage (C) is preferably carried out at a temperature of 250-320 ° C, more preferably 250-300 ° C, even more preferably 255-280 ° C and most preferably 260-270 ° C.

According to this embodiment of the invention, the interval Δ С (° C) determined by the following formula (1) is preferably between -20 and 20 ° C, from the point of view of impact strength, tint and formation of defects such as fish eyes of the obtained branched polymer

LT-T -.- T- (1) where T ₁ represents the temperature (° C) of low molecular weight polycarbonate introduced into the final polymerization reactor in step (C);

T ₂ represents the temperature (° C) of a branched polycarbonate polymerized in the final polymerization reactor in step (C), wherein T ₂ is 285 ° C or less.

T _{2 is} preferably 250-285 ° C., More preferably 260-275 ° C.

The term final polymerization reactor means a polymerization reactor in which the reaction proceeds until M1 of the branched polycarbonate exceeds 10 g / 10 min.

In traditional melt polymerization processes, the viscosity of the polymer in the final polymerization reactor corresponding to step (C) of this embodiment of the invention increases with increasing molecular weight, which makes it necessary to significantly increase the temperature in the reactor to reduce viscosity. The use of a vertical polymerization reactor as the final polymerization reactor for the method according to this embodiment of the invention allows to obtain a branched polycarbonate with excellent physical properties and quality while maintaining a high viscosity, which previously could not be achieved.

According to this embodiment of the invention, the value of M1 is measured in accordance with standard L8TM ,1238, at a temperature of 300 ° C and a load of 1.2 kg. The branching index M1K means a value measured under a load of 12 kg in the same way divided by M1. According to this embodiment, the branched polycarbonate obtained in step (C) has an M1 of not more than 10 g / 10 min, preferably 0.5-8 g / 10 min, more preferably 1-6 g / 10 min and

- 9,022,372 most preferably 2-4 g / 10 min when using a large bottle, such as a 5 gallon bottle (approximately 20 L). If it is less than this range, formability will deteriorate, whereas if it is more than 10 g / 10 min, formability will also deteriorate. The branching index ΜΙΚ is in the range of 14 or more, and it is preferably 15-30, more preferably 16-25. If this value is less than 14, then the blow molding cannot be improved sufficiently and defects in molding or unevenness can form, whereas if it is greater than 30, defects in molding and unevenness will be formed and a larger number of defects such as fish eyes will be seen.

After step (C), the resulting branched polycarbonate is usually granulated, but a molding machine can be directly attached to form molded articles, such as a sheet or bottle. To reduce or remove defects such as fisheye, a polymer filter can be installed to filter out particles of approximately 1-50 microns.

As a separate mode, an embodiment of the invention may further include a step (Ό), in which the polymerization reaction proceeds to produce polycarbonate until a melt index of not more than 100 g / 10 min after step (A) is reached. This scheme will allow the production of various types of polycarbonates. A circuit including step (Ό) will now be discussed with reference to FIG. 2.

In FIG. 2 shows a diagram of a system for the production of various types of polycarbonates. The production system is similar to the system shown in FIG. 1 in that it includes a first polymerization step with stirring with the first stirred polymerisation reactors 3A, 3B, a second polymerization step with stirring with a second stirrer polymerization reactor 3C and a third polymerization step with stirring with a third stirred tank polymerization reactor 3Ό, and a first fluidized bed polymerization stage on a contact wire with a first contact wire fluidized bed polymerization reactor 108A and a second fluidized bed polymerization stage a bed on a wire with a second fluidized bed polymerization reactor 108B on a contact wire. For a method of producing various types of polycarbonates according to this embodiment, a third polymerization step on a contact wire with a third contact wire fluidization polymerization reactor 108C is additionally provided, conveying pumps 106A, 106Ό and a branching section 120.

The molten prepolymer 109A obtained in step (A) is discharged through an outlet channel 107A and sent to a conveying pipe. The conveying pipe has a branching section 120, which branches it into a device for stage (B) and a device for stage (Ό). The stream of molten prepolymer 109A, which flows from the outlet channel 107A, is bifurcated in the branching section 120 and forced into each branched stream by a suction pump 106Ό at the inlet to stage (B) and / or a transfer pump 106A at the inlet to stage (Ό) and moves along a transport pipe to the input channel 101B of the prepolymer of the second fluidized bed polymerisation reactor 108B and / or to the input channel 101C of the prepolymer of the third fluidized bed polymerisation reactor 108C.

When the transfer pump 106Ό is operating, a branched polycarbonate is formed in step (A), step (B), and step (C) in the same manner as in the above embodiment. The transfer pipe from the transfer pump 106Ό to 101B, the melt mixer (linear mixer) 110 mounted on the transfer pipe, and the multifunctional connection conduit 111 shown in FIG. 2 correspond to stage (B), while the process from the second fluidized bed polymerisation reactor 108B to the contact wire to the output channel 107B corresponds to stage (C).

When the priming pump 106A is operating, the first and third polymerisations with fluidization on the contact wire proceed continuously in the first and third reactors 108A, 108C of polymerisation with fluidization on the contact wire.

Stage (Ό) corresponds to the process from the transfer pump 106A through the third fluidized bed polymerization reactor 108C to the contact wire to the outlet channel 107C. In step (Ό), the molten prepolymer 109A, which moves from the outlet channel 107A of the first fluidized bed polymerisation reactor 108A through a transfer pipe when the transfer pump 106A is operating, passes to the feed channel 101C for the prepolymer of the third fluidized bed polymerisation reactor 108C.

The molten prepolymer 109A, which was loaded into the third contact wire fluidized polymerization reactor 108C, undergoes polymerization by run-off in contact with the wire, as in the first contact wire fluidized polymerization reactor 108A, and the molten polymer 109C is collected at the bottom of the third reactor 108C contact wire fluidization polymerization. The molten polymer 109C is discharged through a discharge channel 107C by a transfer pump 106C and collected as polycarbonate.

The polycarbonate obtained in step (Ό) has ΜΙ not more than 100 g / 10 min, preferably 1-90 g / 10 min, and more preferably 5-80 g / 10 min, and is determined by the type of product obtained. Ec-10 022372, if its value exceeds this interval, then the mechanical properties will deteriorate, and if it is less, the formability of the polymer will deteriorate.

In the production system shown in FIG. 2, a branched polycarbonate can be obtained in step (B), which has a melt mixer 110 for introducing a multifunctional compound and a subsequent step (C), and polycarbonate can be obtained in step (Ό). By adjusting the operating states of the transfer pumps 106A, 106Ό, it is possible to control the amount of branched polycarbonate formed in step (B) and in step (C), and the amount of polycarbonate formed in step (Ό). If any of the transfer pumps 106A, 106Ό is turned off, only the desired polycarbonate can be obtained, which is formed in stage (B) and stage (C) or stage (Ό). Thus, this embodiment of the invention allows to minimize losses during the transition from the production of one variety of product to another variety. Furthermore, although FIG. 2 shows only one stage (B), stage (C) and stage (Ό) for each stage (A), more than one of these stages can be used.

From the point of view of achieving sufficient ΜΙ and ΜΙΚ values and a satisfactory color cast and number of fish eye defects for this embodiment, the reaction temperature in each of step (A), step (B), step (C) and step (Ό) is preferably 50-320 ° C, more preferably 100-300 ° C, even more preferably 130-280 ° C and most preferably 150-270 ° C. Stage (C) and stage (Ό) are preferably carried out at a temperature in the range of 250-320 ° C, more preferably 250-300 ° C, even more preferably 255-280 ° C and most preferably 260-270 ° C.

In order to obtain a branched polycarbonate composition comprising additives such as stabilizers, antioxidants, dyes or pigments, ultraviolet absorbers and flame retardants or stiffening agents such as fiberglass and fillers, according to the method of this embodiment, preferably branched polycarbonate is fed into the molten state from stage (C) of the final reactor and stage (Ό) into an extruder, static mixer or the like, and the above additives are introduced and mixed with it for zeroing.

A polymerization catalyst may also be used, as in the introduction of step (A), in the process of this embodiment. The polymerization catalyst used is not particularly limited, as it is the catalyst used in the art, and examples include catalysts comprising alkali or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal salts, alkaline earth metal salts and quaternary ammonium salts of boron or aluminum hydroxides such as lithium aluminum hydride, sodium borohydride or tetramethylammonium borohydride; alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride and calcium hydride; alkali metal or alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide and calcium methoxide; alkali metal or alkaline earth metal aryloxides such as lithium phenoxide, sodium phenoxide, magnesium phenoxide, NO-At-OH and ΝαΟ-ΑΓ-ΟΝα (where Ar represents an aryl group); salts of organic acids and alkali metals or alkaline earth metals such as lithium acetate, calcium acetate and sodium benzoate; zinc compounds such as zinc oxide, zinc acetate and zinc phenoxide; boron compounds such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate, ammonium borates represented by (Κ ¹ Κ ² Κ ³ Κ ⁴ ) ΝΒ (Κ ¹ Κ ² Κ ³ Κ ⁴ ), phosphonium borates represented by (K ¹ K ² K ³ K ⁴ ) RV (K ¹ K ² K ³ K ⁴ ) (where each K ¹ , K ² , K ³ and K ⁴ independently represents a hydrogen atom, Sy ₀ alkyl, Sy ₀ alkoxy, C _{5 -} 1 ₀ cycloalkyl constituting the ring, C _{5-1 0} carbocyclic aromatic group constituting the ring, or C _{6-1 0} carbocycloalkyl group); silicon compounds such as silicon oxide, sodium silicate, tetraalkyl silicones, tetraaryl silicones and diphenylethylethoxysilicone; germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide and germanium phenoxide; tin compounds, including tin compounds joined by alkoxy or aryloxy groups, or organic tin compounds such as tin oxide, dialkyl tin oxide, dialkyl tin carboxylate, tin acetate and ethyl tin butoxide; lead compounds such as lead oxide, lead acetate, lead carbonate and basic carbonate, and organic tin alkoxides or aryloxides; onium compounds such as quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium salts; antimony compounds such as antimony oxide and antimony acetate; manganese compounds such as manganese acetate, manganese carbonate and manganese borate; titanium compounds such as titanium oxide and alkoxide or titanium aryloxide; and zirconium compounds such as zirconium acetate, zirconium oxide, zirconium alkoxides or aryloxides, and zirconium acetylacetone. When a catalyst is used, it may be of the same type or a combination of two or more types. The amount of these catalysts will usually be selected in the range between 10 ^-8 and 1 wt.h. and preferably between 10 ^-7 and 10 ^-1 parts by weight per 100 parts by weight by weight of the original aromatic dihydroxy compound.

- 11 022372

The branched polycarbonate obtained by the technological method according to this embodiment of the invention has a repeating unit represented by the general formula (1) in the main chain and branched chains:

[Chemical formula 7]

Ϊ

-O — Ah — O C— (1)

The branched polycarbonate obtained by the method of this embodiment of the invention may include a branched structure (a) formed by a multifunctional compound directly connected to the main chain and branched chains, and a branched structure (b) comprising at least one structure selected from the group consisting of branched structures represented by general formulas (2) - (4).

In a branched polycarbonate obtained by the method according to this embodiment of the invention, the total amount of a substance with a branched structure (a) formed by a multifunctional compound and a branched structure (b) represented by general formulas (2) to (4), relative to the amount of substance of the repeating unit, represented by the general formula (1) is preferably 0.2-1.0 mol%, more preferably 0.3-0.9 mol%, and even more preferably 0.3-0.8 mol%. An amount in excess of 1.0 mol.% Will lead to an increase in defects such as fish eye and a decrease in impact strength or mechanical strength, while an amount of less than 0.2 mol.% Will reduce the positive effect of improving moldability. As used herein, the term “amount of substance” refers to the amount of substance of a component formed by each structure obtained by hydrolysis of a branched polycarbonate.

[Chemical formula 8]

[Chemical formula 10]

where Ar is a divalent aromatic residue and Ag ¹ is a trivalent aromatic residue.

Ar in the general formulas (1) and (3) have the same meanings as Ar in HO-Ar-OH. In addition, each Ar ¹ in the general formulas (2) - (4) represents a trivalent aromatic residue with an additional hydrogen atom or the like removed from Ar to attach a substituent (e.g., -COO-), which should be present as a branching center .

In addition, the ratio of the amount of a substance with a branched structure (b) to the total amount of a substance with a branched structure (a) and a branched structure (b) in the branched polycarbonate obtained by the method according to this embodiment of the invention is 0.1-0.6, preferably 0.2-0.6 and even more preferably 0.3-0.6. If it exceeds 0.6, then the resistance to the action of hot water will tend to decrease, and if it is less than 0.1, the MTO value will tend to decrease and the increase in melt tension will decrease.

The ratio of the amount of a substance with a branched structure represented by the general formula (2) to the amount of a substance with a branched structure (b) represented by the general formulas (2) - (4) is 0.5 or more, preferably 0.85 or more and still more preferably 0.9 or more. If it is below 0.5, then the impact resistance and mechanical strength may decrease, and the number of defects such as fish eye may increase.

As used herein, the term “backbone” refers to a polymer chain formed by the condensation of an aromatic dihydroxy compound and a carbonic acid diester used as starting materials from a transesterification reaction. In particular, in areas branched by a multifunctional compound (branched structure (a)), the branched chain with the longest part at the branched end is repeatedly selected from among

- 12,022,372 branched chains that are present, and this is defined as the main chain.

As used herein, the term branched structure (a) refers to a branched structure due to branching by a polyfunctional compound. For example, when 1,1,1-tris- (4-hydroxyphenyl) ethane is used as a multifunctional compound, the structure represented by the following formula is branched structure (a) and the hydrolyzed 1,1,1-tris- (4-hydroxyphenyl ) ethane is quantified as the amount of a substance with a branched structure (a):

As used herein, the term branched structure (b) refers to a branched structure that spontaneously forms on the main chain during a process for producing branched polycarbonate (e.g., Fries rearrangement (Ppec)).

The branched polycarbonate obtained according to this embodiment is preferably substantially free of chlorine. As described in International Patent Publication No. \ νϋ 2005/121210, when a branched polycarbonate is prepared from an aromatic dihydroxy compound, a carbonic acid diester and a polyfunctional compound substantially free of chlorine in this transesterification process, a branched polycarbonate with a chlorine content of not more than 10 ppm, preferably not more than 1 ppm, since no other chlorine compounds were added.

When forming a film with a thickness of 50 μm and a width of 30 cm, the branched polycarbonate obtained according to the present embodiment had no more than 100, preferably not more than 80, even more preferably not more than 50 fish-eye defects larger than 300 μm per 1 m of random length plot.

The color cast (b * value) of the branched polycarbonate obtained in the present embodiment is 0-3.0, preferably 0-2.5, and even more preferably 0-1.5. If this range is exceeded, the branched polycarbonate will become yellowish and will have a poor appearance. If necessary, yellowness can be compensated for by a color agent, such as a bluing agent, but also transparency should be taken into account.

The color shade of the branched polycarbonate obtained according to the present embodiment of the invention can be measured by injection molding a flat plate 3.2 mm thick at a cylinder temperature of 300 ° C and a mold temperature of 90 ° C and placing it on a white calibration plate SK-400 from Cots Μίηοΐΐα Ηο16ίη§5, 1ps. for measurement by reflection with a measured diameter of 8 mm, determining the difference in the value of b * relative to the white calibration plate (b * value of the flat plate = measured value of the flat plate on the white calibration plate - measured value of the white calibration plate).

The branched structures (a) and (b) in the branched polycarbonate obtained in the present embodiment can be determined by complete hydrolysis of the branched polycarbonate and reverse phase liquid chromatography. Hydrolysis of the polycarbonate can be carried out by hydrolysis at ordinary temperature, as described in the publication Poluteg Edentababop apb Alpnu. 45 (1994), 127-137, which is preferred since this procedure is simple and does not involve secondary reactions during decomposition, providing complete hydrolysis of the polycarbonate, and according to an embodiment of the invention, it can be carried out at room temperature (25 ° C.).

If necessary, a coloring agent, a heat-resistant stabilizer, an antioxidant, a weatherproofing agent, an ultraviolet absorber, a separating agent, a softener, an antistatic agent, a plasticizer or the like can be used in the continuous production process of the branched polycarbonate of this embodiment. Such additives can be introduced after the polymerization is completed, while the polycarbonate-based resin is in the molten state or the polycarbonate can be granulated first and the additives introduced later before re-melting and mixing.

The spontaneous formation of branched structures (b) represented by the general formulas (2) - (4) during transesterification is also known. According to the present embodiment, a branched structure may be present in the branched polycarbonate. In this case, the amount obtained from the polyfunctional compound can be reduced in accordance with the number of branched structures (b). In this case, the total amount of a substance with a branched structure (a) formed by a functional compound and a substance with a branched structure (b) of any of the general formulas (2) - (4), formed spontaneously during transesterification, is

- 13 022372

0.2-1.0 mol%, preferably 0.2-0.9 mol%, and more preferably 0.3-0.8 mol%, based on the amount of a substance having a repeating unit represented by the general formula (1). If the amount exceeds 1.0 mol%, the number of defects such as fisheye will tend to increase, and if it is less than 0.2 mol%, the value of the ICBM will tend to decrease, and the growth of the melt extension will decrease.

When a typical bisphenol A is used as an aromatic dihydroxy compound, the general formulas (2) - (4) become formulas (9) - (11):

These branched structures can be determined by complete hydrolysis of the branched polycarbonate and reverse phase liquid chromatography. The ratio of the amount of a substance with a branched structure (b) to the total amount of a substance with a branched structure (a) and a branched structure (b) in the branched polycarbonate obtained in the present embodiment is 0.1-0.6. In addition, the ratio of the amount of a branched substance represented by the general formula (2) to the amount of a branched structure (b) is 0.85 or more, more preferably 0.9 or more.

Examples

The present invention will be explained in more detail using examples and comparative examples. However, the present invention is not limited to the examples below.

The evaluated properties were measured by the following methods.

(1) Molecular mass.

(1-a). Srednekamennogo molecular weight: it was measured by gel permeation chromatography (HLC-8320OPC from р050Ι1 Comp., 2 columns ΤδΚ-ОЬ §iret MiShrote ΗΖ-Μ, ΡΙ detector) with tetrahydrofuran as an eluent at a temperature of 40 ° С. Molecular weight was determined from the calibration curve for standard monodispersed polystyrene (EabaU1a1, product Wapap 1ps.) Using the equivalent molecular weight calibration curve according to the following formula:

M _RS = 0.3591 M _P3 ¹ · ⁰³⁸⁸ , where M _RS is the molecular weight of polycarbonate;

M _RE is the molecular weight of polystyrene.

(1-b). Mass-average molecular weight: it was measured by gel permeation chromatography (HLC-8320ORC from Τ050Ι1 Co., 2 columns ΤδΚ-ОЕ 8 and MiShrote ΗΖ-М, ΡΙ detector), eluent = tetrahydrofuran, injection volume = 5 μl, measurement temperature = 40 ° С detector = ΡΙ detector.

Obtaining a sample for measurements: a portion of a branched polycarbonate weighing 10 mg was dissolved in 10 ml of methylene chloride. Molecular weight was determined from the calibration curve for standard monodispersed polystyrene (Ea81U1a1 (REE, UEBBOKHOU, ΟΡΕΕΝ), product Wapap 1ps.) Using the equivalent calibration curve for the molecular weight according to the following formula:

M _RS = 0.3591M _P3 ¹ · ⁰³⁸⁸ , where MPC is the molecular weight of polycarbonate;

M _P8 is the molecular weight of polystyrene.

(2) MB, ICBM: M1 (melt index) was measured according to the ΑδΤΜ Ό1238 standard at a temperature of 300 ° C and a load of 1.2 kg. ICBMs, (branching index) was determined as a value measured at a load of 12 kg in the same way and divided by MB.

(3) Color shade: a flat plate of 15 cmx15 cmx3.2 mm thick was obtained by injection molding at a cylinder temperature of 300 ° C and a molding temperature of 90 ° C and the CP-400 instrument

- 14,022,372

Cotza Μίηοΐΐα Ηο1άίη§8, 1ps. used to determine the deviation (b) from the b value of the standard white plate.

(4) Fisheye-type defect: a film 50 μm thick and 30 cm wide was formed using a Tapapé P1a8Jc8 MasYpetu Co., ID film machine. (single-screw extruder with a diameter of 30 mm, screw rotation speed of 100 rpm, productivity 10 kg / h, cylinder temperature 280 ° C, temperature of the T-shaped extrusion head 260 ° C, roll temperature 120 ° C) and the number of defects such as fish was visually counted an eye of at least 300 microns in size within an arbitrarily selected area of 1 m length.

(5) Time until completion of the transition from the production of one variety of product to another variety: the supply of the multifunctional compound was stopped after the formation of branched polycarbonate and after the transition to the production of polycarbonate with M1 10 g / 10 min, the number of fish-eye defects in the obtained polycarbonate was measured every hour and determined the time until the measured value falls below 1.

(6) Degree of branching structure: after dissolving 55 mg of polycarbonate in 2 ml of tetrahydrofuran, 0.5 ml of 5N was added. a solution of potassium hydroxide in methanol and the mixture was stirred at 25 ° C for 2 hours until the completion of hydrolysis. Then, 0.3 ml of concentrated hydrochloric acid was added, and measurements were carried out by reverse phase liquid chromatography (KS-1100, product LdPeS). Reverse-phase liquid chromatography was carried out using a 1ep8Y8-8 column (registered trademark СБЫepsek, 1ps.) With a mixed eluent containing methanol and 0.1% aqueous phosphoric acid, at a column thermostat temperature of 40 ° С, methanol / A 0.1% aqueous phosphoric acid solution with a gradient ranging from 20/80 to 100/0 and detection using a UV detector with a wavelength of 300 nm.

(7) Resistance to the action of hot water: a flat plate, molded as described in paragraph (3) above, was removed after 300 hours of immersion in hot water at a temperature of 95 ° C and kept in a chamber with a constant temperature and humidity at 23 ° C, 50% ΚΗ. The degree of cracking was visually evaluated after 24 hours. A: no cracks, B: 1-9 cracks, C: 10 or more cracks.

(8) Shock resistance.

A 5 gallon water bottle (approximately 20 L) (approximately 25 cm diameter, approximately 50 cm high) was molded by injection molding using a pressure molding press of Α8Β-650ΕΧΗ8 of No. 88е1 ΑδΒ MasYpe Co., ID, at a temperature cylinder 295 ° C, the temperature of the molding rod 60 ° C and the temperature of the cavity of the mold 30 ° C.

(8-a) Bottle strength: the water bottle molded above was filled with water, and the bottle was thrown from a height of 1.5 m in 4 directions (vertically, inverted, oblique vertically and obliquely inverted), and then evaluated the presence or absence of cracks (good (A): no cracks, bad (C): cracks).

(8-b) Charpy strength: a specimen was prepared for injection molding tests according to ISO 306 at a cylinder temperature of 300 ° C and a mold temperature of 90 ° C and tests were performed on notched specimens.

Example 1

The production system shown in FIG. 1, used to obtain branched polycarbonate. The first stirred tank polymerization reactors 3A and 3B with an internal volume of 100 L were equipped with mixers 6A, 6B, each having a rigid mixing paddle. The second stirred tank polymerization reactor 3C and the third 50l tank polymerization reactor 3Ό each were equipped with 6C, 6Ό stirrers having a rigid mixing paddle. The first and second fluidized bed polymerization reactors 108A, 108B on the contact wire had a perforated plate 102A with 5 holes and a perforated plate 102B with 3 holes and §§ 316B guide wires 103A, 103B with a diameter of 1 mm and a length of 8 m. The first case reactors 3A and 3B stirred polymerization was used in alternate switching mode, and further from the second shell reactor, 3C stirred polymerization was used continuously.

kg of a polymerizable product comprising bisphenol A as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic acid diester (in a molar ratio of 1.06 relative to bisphenol A) and a disodium salt of bisphenol A as a catalyst (75 ppm by weight relative to bisphenol A in the polymerisable product, calculated on the number of sodium atoms), was loaded into the first case polymerization reactor 3A with stirring through the input channel 1A for the product to be polymerized. Stirring was continued at a temperature of the reaction mixture of 180 ° C., a pressure of the reaction mixture equal to atmospheric pressure, and a nitrogen gas feed rate of 1 l / h. The outlet channel 5A was opened after 4 hours and the molten prepolymer 4A was sent to a second stirred polymerisation reactor 3C with a flow rate of 7 l / h.

Further, the first stirred tank polymerization reactor 3B was operated in the same manner as the first stirred tank polymerization reactor 3A to obtain a molten prepolymer 4B. After the first stirred tank polymerization reactor 3A was empty, the outlet duct 5A of the first capacitive polymerization reactor

- 15 022372

BAT with stirring was closed and the outlet channel 5B of the first ZV stirred tank polymerization reactor was opened and the molten prepolymer 4B was fed from the first stirred tank polymerization reactor 3B with stirring into the second stirred tank polymerization reactor ZS with a flow rate of 7 l / h. This operation was repeated to alternately continuously feed the molten prepolymers 4A and 4B into the second stirred tank polymerization reactor ZS.

The second stirred tank polymerization reactor ZS with stirring was maintained at a reaction temperature of 2 ° C and a reaction pressure of 1 ° C, 0 kPa to obtain a molten prepolymer 4 ° C. After the volume of the molten prepolymer 4C reached 20 L, a portion of the molten prepolymer 4C was continuously withdrawn and fed into the third stirred reaction tank polymerization reactor ZE to maintain a constant internal volume of 20 L.

The third stirred reaction vessel of the WE polymerization was maintained at a reaction temperature of 265 ° C and a reaction pressure of 2.6 kPa to obtain a 4Ό molten prepolymer. After the volume of the 4Ό molten prepolymer reached 20 L, a portion of the 4Ό molten prepolymer was continuously withdrawn and fed into the first contact wire fluidized bed polymerisation reactor 108A to maintain a constant internal volume of 20 L.

The first contact wire polymerization reactor 108A was maintained at a reaction temperature of 265 ° C. and a reaction pressure of 400 Pa to obtain a molten prepolymer 109A. After the volume of molten prepolymer 109A reached 10 L, a portion of the molten prepolymer 109A was continuously withdrawn and fed through a linear in-line mixer 110 to a second contact wire fluidized bed polymerisation reactor 108B to maintain a constant volume of 10 L. The number average molecular weight of the molten prepolymer 109A was 7500.

A homogeneous solution of the polyfunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane in phenol as a solvent (mixture in the mass ratio polyfunctional compound / phenol = 1 / 1.5) was fed to a linear mixer 110, maintained at a temperature of 265 ° C and a rotational speed of 15 rpm in an amount providing a molar ratio of the polyfunctional compound of 0.004 relative to the structure of bisphenol A in the molten prepolymer 109A, through conduit 111 at a temperature of 180 ° C. The number average molecular weight of the molten prepolymer, measured immediately before being fed to the second fluidized bed polymerisation reactor 108B, was 4000.

The second contact wire polymerization reactor 108B was maintained at a reaction temperature of 265 ° C. and a reaction pressure of 118 Pa to obtain a branched polycarbonate. After the volume of the branched polycarbonate reached 10 L, a suction pump 106B was used to continuously withdraw the polymer in the form of a bundle from the outlet channel 107B to maintain a constant volume of 10 L, and after cooling it was cut to obtain a granular branched polycarbonate. The results of evaluating the properties of the obtained branched polycarbonate are presented in table. 1. In the table. 1-3 in the formula, Τ1 represents the temperature (° C) of the low molecular weight polycarbonate introduced into the final polymerization reactor, and T ₂ represents the temperature (° C) of the branched polycarbonate polymerized in the final polymerization reactor. The temperature difference (ΔΤ) was 0 ° C.

Example 2

The solvent of example 1 was replaced with a homogeneous mixture of acetone and phenol (mixture in the mass ratio polyfunctional compound / acetone / phenol = 1 / 2.5 / 0.1). A homogeneous solution was supplied to a linear mixer 110 through a pipe 111 at a temperature of 40 ° C. The second contact wire polymerization reactor 108A was maintained at a reaction temperature of 265 ° C. and a reaction pressure of 790 Pa to give a molten prepolymer 109A. The measured number average molecular weight of the molten prepolymer was 5500. The number average molecular weight of the molten prepolymer measured immediately before entering the second contact wire fluidized bed polymerisation reactor 108B was 4200. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers was per wire in the final polymerization reactor was the value shown in table. 1. The rest of the operation was carried out in the same manner as in example 1. The results of the evaluation of the obtained branched polycarbonate are presented in table. 1. It was found that ΔΤ was 0 ° C.

Example Z.

The solvent of example 2 was replaced by a number average molecular weight prepolymer of 2500. The ratio in the mixture of the branching agent and the prepolymer was 1: 2 by weight. A homogeneous solution was supplied to a linear mixer 110 through a pipe 111 at a temperature of 180 ° C. The number average molecular weight of the molten prepolymer 109A was 5700. The number average molecular weight of the molten prepolymer measured directly before entering the second fluidized bed polymerisation reactor 108B 108B was 4900. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the diluted 16 022372 fused prepolymers per wire in the final polymerization reactor was the value shown in the table. 1. The rest of the operation was carried out in the same manner as in example 2. The evaluation results of the obtained branched polycarbonate are presented in table. 1. It was found that ΔΤ was 0 ° C.

Example 4

The solvent of Example 2 was replaced with diphenyl carbonate (EPC) and bisphenol A (BPA). A homogeneous solution was supplied to a linear mixer 110 through a pipe 111 at a temperature of 180 ° C. The ratio in the mixture of the branching agent, OPC and BPA was 1.5: 0.5: 1 by weight. Disodium salt of bisphenol A was added as a catalyst (75 ppm by weight relative to bisphenol A in the polymerisable product, calculated on the number of sodium atoms). The number average molecular weight of the molten prepolymer 109A was 5700. The number average molecular weight of the molten prepolymer was measured directly before entering the second fluidized bed polymerisation reactor 108B 108B. The molar prepolymer molecular weight was 4200. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers was per wire in the final polymerization reactor was the value shown in table. 1. The rest of the operation was carried out in the same manner as in example 2. The evaluation results of the obtained branched polycarbonate are presented in table. 1. It was found that ΔΤ was 0 ° C.

Example 5

The solvent of Example 2 was replaced with diphenyl carbonate (ERS). The ratio in the mixture of branching agent and OPC was 1: 0.67 by weight. A homogeneous solution was supplied to a linear mixer 110 through a pipe 111 at a temperature of 180 ° C. The number average molecular weight of the molten prepolymer 109A was 5700. The number average molecular weight of the molten prepolymer measured directly before entering the second fluidized bed polymerisation reactor 108B 108B was 4000. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers per wire in the final polymerization reactor was the value shown in table. 1. The rest of the operation was carried out in the same manner as in example 2. The evaluation results of the obtained branched polycarbonate are presented in table. 1. It was found that ΔΤ was 0 ° C.

Example 6

Acetone was used as a solvent of the multifunctional compound, and the mixture was fed into the third 3Ό polymerization reactor with stirring instead of the linear mixer 110. The feed rates of the molten prepolymers in stage (A) were controlled so that the flow rate of each of the molten prepolymers to the wire in the final polymerization reactor was shown in the table. 1. Otherwise, the operation was carried out in the same manner as in Example 2. A slight change in ΜΙ was observed, but the production of branched polycarbonate remained stable. The evaluation results of the obtained branched polycarbonate are presented in table. 1. It was found that ΔΤ was 0 ° C.

Example 7

The polyfunctional compound of Example 2 was 4- [4- [1,1-bis- (4-hydroxyphenyl) ethyl] -a, adimethylbenzyl] phenol, and the solvent was replaced with acetone. The first contact wire polymerization reactor 108A was maintained at a temperature of 265 ° C. and a reaction pressure of 1000 Pa to obtain a molten prepolymer 109A. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers to the wire in the final polymerization reactor was as shown in Table 1. 1. The rest of the operation was carried out in the same manner as in example 2. The evaluation results of the obtained branched polycarbonate are presented in table. 2. It was found that ΔΤ was -0.2 ° C.

Example 8

This example was carried out in the same manner as example 2, except that phenol was used as a solvent (polyfunctional compound / phenol = 6/4 mass ratio) and that a twin screw extruder with gas extraction (product 1ked1 1gop Wogks, PCM = 30 mm, L / O = 30, temperature = 265 ° C) was placed after the outlet channel 107B from the second fluidized bed polymerization reactor on the contact wire of FIG. 1, and the polyfunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane (molar ratio of 0.004 relative to the structure of bisphenol A) was not supplied through a linear mixer 110, but was loaded in powder form from the ventilation hole of a twin-screw extruder. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers to the wire in the final polymerization reactor was as shown in Table 1. 1. The evaluation results of the obtained branched polycarbonate are presented in table. 2. It was found that ΔΤ was 25 ° C.

- 17 022372

Comparative example 1.

This example was carried out in the same manner as example 2, except that a twin-screw extruder with a gas outlet (product 1ked1 1gop Aogkz. PCM = 30 mm, L / O = 30, temperature = 265 ° C) was placed after the output channel 107B from the second contact wire polymerization reactor of FIG. 1, and the polyfunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane (molar ratio of 0.004 relative to the structure of bisphenol A) was not supplied through a linear mixer 110, but was loaded in powder form from the ventilation hole of a twin-screw extruder. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers to the wire in the final polymerization reactor was as shown in Table 1. 1. The evaluation results of the obtained branched polycarbonate are presented in table. 3. It was found that ΔΤ was 0 ° C.

Comparative Example 2

In FIG. 1 linear mixer 110 was replaced by a single-screw extruder with a gas outlet, and a pipe from 107A was connected to the feed channel to the single-screw extruder, while the outlet channel from the single-screw extruder was connected by a pipe with 101B. The operation was carried out in the same manner as in example 2, except that the multifunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane (molar ratio = 0.004 relative to the structure of bisphenol A) was loaded in powder form from the vent single screw extruder. The feed rates of the molten prepolymers in step (A) were controlled so that the flow rate of each of the molten prepolymers to the wire in the final polymerization reactor was as shown in Table 1. 1. The evaluation results of the obtained branched polycarbonate are presented in table. 3. It was found that ΔΤ was 0 ° C.

Comparative example 3.

In FIG. 1 linear mixer 110 was replaced by a twin-screw extruder with a gas outlet (product 1ked1 1Gop Aogkz, PCM = 30 mm, L / O = 30, temperature = 265 ° C), and a pipe from 107A was connected to the feed channel of the twin-screw extruder, while the output channel from a twin screw extruder was connected to a feed channel of a horizontal polymerization reactor (not shown). The polyfunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane (molar ratio = 0.004 relative to the structure of bisphenol A) was charged at ordinary temperature from the vent of the twin-screw extruder. For the final polymerization reactor connected to the twin-screw extruder, a horizontal polymerization reactor was installed instead of the polymerisation reactor 108B for the final polymerization. The temperature in the horizontal polymerization reactor was set to 320 ° C. The remaining operations were carried out as in example 2. The results of the evaluation of the obtained branched polycarbonate are presented in table. 3. It was found that ΔΤ was 30 ° C.

Comparative example 4.

In FIG. 1 linear mixer 110 was replaced by a twin-screw extruder with a gas outlet (product 1ked1 1Gop Aogkz, PCM = 30 mm, L / O = 30, temperature = 265 ° C), and a pipe from 107A was connected to the feed channel of the twin-screw extruder, while the output channel from a twin screw extruder was connected to an input channel into a horizontal polymerization reactor (not shown). The multifunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane (molar ratio = 0.004 with respect to the structure of bisphenol A) and EMF were charged at ordinary temperature through the ventilation hole of a twin-screw extruder. The mass ratio of the branching agent and the OCP was 1: 0.6. For the final polymerization reactor connected to the twin-screw extruder, a horizontal polymerization reactor was installed instead of the polymerisation reactor 108B for the final polymerization. The temperature in the horizontal polymerization reactor was set to 320 ° C. The remaining operations were carried out as in example 2. The results of the evaluation of the obtained branched polycarbonate are presented in table. 3. It was found that ΔΤ was 25 ° C.

Comparative example 5.

No polyfunctional compound or solvent was added in Example 2. In order to obtain a high molecular weight polymer with M1 = 3, the feed rate to the final polymerization reactor 108B was minimized and the feed rate to the wire was 0.2 kg / h-wire. By increasing the residence time at 103 V, it was possible to obtain a high molecular weight polymer with M1 = 3, but the resulting polymer had numerous fish-eye defects. Productivity was also significantly lower than in example 2.

Example 9

For the production of branched polycarbonate, the production system shown in FIG. 2. The first stirred tank polymerization reactors 3A and 3B with an internal volume of 100 L were each equipped with mixers 6A, 6B having a rigid mixing paddle. The second stirred tank polymerization reactor 3C and the third 50L stirred polymerization reactor were each equipped with 6C, 6Ό stirrers having a rigid mixing paddle. The first and second contact wire polymerization reactors 108A, 108B have a perforated plate 102A with 5 holes and a perforated plate

- 18 022372 wires have a perforated plate 102A with 5 holes and a perforated plate 102B with 3 holes and §§ 316B guide wires 103A, 103B with a diameter of 1 mm, a length of 8 m. The first stirred tank polymerization reactors 3A and 3B were used in alternating mode switching further continuously from the second polymerization reactor 3C.

kg of a polymerizable product comprising bisphenol A as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic acid diester (in a molar ratio of 1.07 relative to bisphenol A) and a disodium salt of bisphenol A as a catalyst (50 pbw by weight relative to bisphenol A in the polymerisable product, calculated on the number of sodium atoms), was loaded into the first stirred polymerisation reactor 3A 3A. Stirring was continued at a temperature of the reaction mixture of 185 ° C, a pressure of the reaction mixture equal to atmospheric pressure, and a feed rate of gaseous nitrogen of 1 l / h. The outlet channel 5A was opened after 4 hours and the molten prepolymer 4A was fed into a second stirred polymerisation reactor 3C with a flow rate of each molten prepolymer to the wire in the final polymerization reactor, the values of which are given in Table 1. 2.

Further, the first stirred tank polymerization reactor 3B was operated in the same manner as the first stirred tank polymerization reactor 3A to obtain a molten prepolymer 4B. After the first stirred tank polymerization reactor 3A was empty, the outlet channel 5A of the first stirred tank polymerisation reactor 3A was closed and the lead channel 5B of the first stirred tank polymerisation reactor 3B was opened, and the molten prepolymer 4B was fed from the first stirred tank polymerisation reactor 3B in a second stirred polymerisation reactor 3C with a flow rate of each molten prepolymer per wire in the final polymerisation reactor, in the value of which is presented in table. 2. This operation was repeated to alternately continuously feed the molten prepolymers 4A and 4B into the second stirred stirred tank polymerisation reactor 3C.

The second stirred stirred tank polymerisation reactor 3C was maintained at a reaction temperature of 232 ° C. and a reaction pressure of 12.8 kPa to obtain a molten 4C prepolymer. After the volume of the molten prepolymer 4C reached 20 L, a portion of the molten prepolymer 4C was continuously withdrawn and fed into the third stirred polymerization reactor 3Ό with stirring to maintain a constant internal volume of 20 L.

The third stirred 3Ό polymerization reactor was maintained at a reaction temperature of 266 ° C and a reaction pressure of 2.5 kPa to give a 4Ό molten prepolymer. After the volume of the 4Ό molten prepolymer reached 20 L, a portion of the 4Ό molten prepolymer was continuously withdrawn and fed into the first contact wire fluidized bed polymerisation reactor 108A to maintain a constant internal volume of 20 L.

The first contact wire polymerization reactor 108A was maintained at a temperature of the reaction mixture of 266 ° C. and a pressure of the reaction mixture of 770 Pa to obtain a molten prepolymer 109A. After the volume of molten prepolymer 109A reached 10 liters, a portion of the molten prepolymer 109A was diverted to maintain a volume of 10 liters. The number average molecular weight of the molten prepolymer 109A was 5000. The withdrawn molten prepolymer 109A was continuously fed 1/2 volume into the second fluidized bed polymerisation reactor 108B through a linear mixer 110 and continuously fed 1/2 volume into the third fluidized polymerisation reactor 108C contact wire.

A homogeneous solution of the polyfunctional compound 1,1,1-tris- (4-hydroxyphenyl) ethane in phenol as a solvent in a mass ratio of 6: 4 was fed to a linear mixer 110, maintained at a temperature of 266 ° C and a rotational speed of 15 rpm, in an amount providing a molar ratio of the polyfunctional compound of 0.003 relative to the structure of bisphenol A in the molten prepolymer 109A, via conduit 111 at a temperature of 185 ° C. The number average molecular weight of the molten prepolymer, measured immediately before being fed to the second fluidized bed polymerisation reactor 108B, was 4400.

The second contact wire polymerization reactor 108B was maintained at a temperature of the reaction mixture of 266 ° C. and a pressure of the reaction mixture of 122 Pa to obtain a branched polycarbonate. After the volume of the branched polycarbonate reached 10 L, a suction pump 106B was used to continuously withdraw the polymer in the form of a bundle from the outlet channel 107B to maintain a constant volume of 10 L, and after cooling it was cut to obtain a granular branched polycarbonate. The results of evaluating the properties of the obtained branched polycarbonate are presented in table. 3.

The third contact wire polymerization reactor 108C was maintained at a temperature of the reaction mixture of 266 ° C. and a pressure of the reaction mixture of 135 Pa to obtain polycarbonate. After the polycarbonate volume reached 10 L, a suction pump 106C was used to continuously withdraw it from the outlet channel 107C in the form of a tow to maintain a constant internal volume of 10 L, and the tow was cooled and cut to obtain a granular linear polycarbonate having M1 10 g / 10 min , hue 0.6 and the measured number of defects such as fish

- 19,022,372 eyes 0. After continuous operation for 50 hours, the flow ratio of 106A and 106B was set to 50:50 to change the output of branched polycarbonate and linear polycarbonate in order to control production without loss when switching from production of one product variety to another grade, by Thus, the simultaneous production of various types of polycarbonates. The evaluation results of the obtained branched polycarbonate are presented in table. 2.

Table 1

Example one Example 2 Example 3 Example 4 Example 5 Example 6 The amount of polyfunctional compounds (molar ratio relative to the structure of bisphenol A) 0, CU4 0.004 0.004 0.004 0, 004 0, 004 MP polycarbonate at the point of addition of a multifunctional compound 7500 5500 5700 5700 5700 2300 Mm branched polycarbonate 36000 36000 36000 36000 36000 36000 Solvent PH Acetone, PH Fore- polymer OPC VRA ϋΡΟ Acetone MT (g / 10 min) thirty 3.0 3.0 thirty 3.0 3.0 ΜΙΕ 19, 9 19.5 19.0 19.3 19, 0 19, 0 Hue (b value) 0.5 0.6 0, 6 0, 6 0.6 0.5 Fisheye defects 0 0 0 0 0 0 Time before moving to another product 2 2 2 2 2 10 Resistance to hot water BUT BUT BUT BUT BUT BUT Branched structure (a) + branched structure (b) (mol%) 0, 57 0, 59 0, 58 0, 56 0, 56 0, 59 The relative content of each branched structure (B) / [(a) + (b)] 0.29 0, 32 0, 31 0.29 0, 29 0, 32 [The branched structure of the formula (2) / (b)] 0, 98 0, 96 0, 94 0, 95 0, 95 0, 96 Impact resistance Strength bottle BUT BUT BUT BUT BUT BUT Charlie Strength (kJ / ^mg ) 77 75 75 75 75 75 ΔΤ (Tg-Τϊ) 0 0 0 0 0 0 Feed prepolymer to the final reactor (kg / hour) 1/4 1,5 1,6 sixteen 1,5 1,6

table 2

Example 7 Example 8 Example 9 The amount of polyfunctional compounds (molar ratio 0.004 0.004 0.003 relative to the structure of bisphenol A) MP polycarbonate at the point of addition of a multifunctional compound 3200 5500 5500 Mm branched polycarbonate 36000 36000 36000 solvent Acetone PH PH ΜΙ (g / 10 min) thirty thirty 3,5 ΜΙΚ 19, 6 18.9 18, 9 Hue (b value) 1/1 0, 9 0.7 Fisheye defects 0 one 0 Time before moving to another product 2 2 - Resistance to hot water BUT IN BUT Branched structure (a) + branched structure (b) (mol%) 0, 58 0, 68 0.57 Relative content (b) / [(a) + (b)] 0.31 0.41 0.35 each branched _g structure [Branched structure of the formula (2) / (b)] 0.93 0.85 0.92 Strength bottle BUT BUT BUT impact resistance _, _. ?, Charlie Strength (kJ / m ') 77 70 75 ΔΤ (Τ ₂ -Τι) -0.2 25 0 Feed prepolymer to the final reactor (kg / h-wire) 1/5 fifteen 14

Table 3

Comp. example one Comp. example 2 Comp. example 3 Comp. example 4 Comp. example 5 The amount of polyfunctional compounds (molar ratio relative to the structure of bisphenol A) 0.004 0.004 0.004 0.004 - MP polycarbonate at the point of addition of a multifunctional compound 14000 5100 5100 5100 - Mm branched polycarbonate 34000 35,000 36000 36000 35,000 Solvent - - - Cattle - ΜΙ (g / 10 min) 3, 8 2,5 twenty 2.0 3.0 ΜΙΚ 13, 9 18, 9 20, 0 19, 0 13.0 Hue (b value) 1/6 1,2 fifteen 1,5 0, 6 Fisheye defects 42 28 thirty 28 47 Time before moving to another product one 4 > 2 0 > 20 - Resistance to hot water FROM IN FROM FROM IN Branched structure (a) + branched structure (b) (mol,%) 0.55 0.55 0, 90 0, 90 0.25 Relative content (b) / [(a) + (b)] 0.27 0.27 0.56 0.56 1.00 each branched [Branched structure of the formula structures (2) / (b)] 0.95 0.92 0.40 0.40 0, 95 „Durability of the bottle FROM FROM FROM FROM FROM Charopie Strength (kJ / m ^) 65 65 60 60 75 ΔΤ (Τ2-Ί4) 0 0 thirty 25 0 Feed prepolymer to the final reactor (kg / h-wire) sixteen fifteen - - 0.2

- 20 022372

Industrial applicability

The production method according to the invention provides the production of branched polycarbonates having reduced losses when switching production to a different product grade, resistance to hot water and low formation of fish-eye defects by transesterification, and it can provide branched polycarbonates having a high M1K value, excellent suitability for use in extrusion and high formability by blow molding.

List of reference positions:

1A, 1B: input channels for polymerizable material,

1C, 1Ό: input channels for prepolymers,

2A, 2B, 2C, 2Ό, 105A, 105V, 105C: ventilation ducts,

3A, 3B: first stirred polymerization reactors,

3C: second stirred polymerization reactor,

3Ό: third stirred polymerization reactor,

4A, 4B, 4C, 4Ό, 109A: molten prepolymers,

5A, 5V, 5C, 5Ό, 107A, 107V, 107C: output channels,

6A, 6B, 6C, 6Ό: mixers,

7C, 7Ό, 8, 106A: transfer pumps,

101A, 101B, 101C: input channels for prepolymers,

102A, 102B, 102C: perforated plates,

103A, 103B, 103C: guide wires,

104A, 104B, 104C: gas inlets,

106B, 106C: evacuation pumps,

108A: first contact wire fluidized bed polymerization reactor,

108B: a second contact wire polymerization reactor,

108C: third contact wire polymerization reactor,

109B, 109C: polymer melts,

110: melt mixer (polymer mixer),

111: multifunctional connection supply pipe,

120: pipe branching section.

Claims (7)

1. A method for the continuous production of branched polycarbonate, comprising the following steps: (A) obtaining a low molecular weight polycarbonate with a number average molecular weight of 100010000 from an aromatic dihydroxy compound and a carbonic acid diester by transesterification; (B) adding a multifunctional compound in a liquid state and mixing it with a low molecular weight polycarbonate, wherein the multifunctional compound is a compound containing at least 3 functional groups in the molecule that are reactive with respect to the carbonic acid diester; and (C) subsequently carrying out the polymerization reaction until the melt index of the low molecular weight polycarbonate exceeds 10 g / 10 min and the branching index becomes at least 14, to obtain a branched polycarbonate. 2. The method according to claim 1, where the interval ΔΤ (° C), determined by the following formula (1), is between -20 and 20 ° C: DT = T ₂ -T! (1) where T ₁ represents the temperature (° C) of low molecular weight polycarbonate introduced into the polymerization reactor in step (C); T ₂ represents the temperature (° C) of the branched polycarbonate obtained in the polymerization reactor in step (C), wherein T ₂ is 285 ° C or less. 3. The method according to claim 1 or 2, where the multifunctional compound is introduced into the melt mixer installed on the line between the device used in stage (A) and the device used in stage (C), in the form of a solution in a solvent. 4. The method according to claim 3, where the solvent is at least one substance selected from the group consisting of phenols, carbonic acid diesters, ketones, ethers, mixtures and reaction products of aromatic dihydroxy compounds with carbonic acid diesters and low molecular weight polycarbonates with number average molecular weight of 5000 or less. 5. The method according to any one of claims 1 to 4, where the solvent is a depolymerization solvent that induces the depolymerization of polycarbonate. 6. The method according to any one of claims 1 to 5, further comprising a step (Ό) following the step - 21 022372 (A) and carried out separately from stages (B) and (C), where the polymerization reaction is carried out until the melt index is not more than 100 g / 10 min, to obtain a polycarbonate different from the branched polycarbonate obtained in stage (C) . 7. The method according to claim 6, where the device used in stage (A) is connected to the device used in stage (C) and the device used in stage (Ό) using a pipeline having a branch section that bifurcates such in a way that passes through both the device used in step (C) and the device used in step (Ό), and the multifunctional connection is introduced into the melt mixer mounted on the line between the branching section and the device used in step (C). 101A 101V FIG. one FIG. 2