KR101192568B1 - Branched polycarbonate resin and process for production thereof - Google Patents

Abstract

There is provided a branched polycarbonate resin obtained from a dihydric phenol, a carbonate precursor, a branching agent and a terminal terminator, wherein the branching agent consists of a trisphenol compound represented by the following general formula (I). By using the said branching agent, washing | cleaning property is good, there is little blowdown by a melt | melt at the time of shaping | molding, a fine sand phenomenon, etc., melt tension and moldability are high, productivity is excellent, and a favorable molded article can be produced efficiently. :

Formula I

Description

Branched polycarbonate resin and its manufacturing method {BRANCHED POLYCARBONATE RESIN AND PROCESS FOR PRODUCTION THEREOF}

The present invention relates to a branched polycarbonate resin and a method for producing the same. More specifically, the present invention relates to a branched polycarbonate resin having improved productivity, moldability and the like and a method for producing the same.

Generally, polycarbonate resins produced from bisphenol A and the like are used for a wide range of applications because of their excellent transparency, heat resistance and mechanical properties. However, when the polycarbonate resin is used for applications such as blow molding and extrusion molding, a satisfactory molded article having low melt tension is not obtained, and a polycarbonate having a relatively low molecular weight in order to improve transferability in injection molding or the like. In the case of using a resin, there is a drawback that a satisfactory molded article cannot be obtained due to stringiness or the like.

As a method for solving this, the method of using the branched polycarbonate resin obtained by adding the branching agent which has three functional groups is known (for example, refer patent document 1).

However, the branched polycarbonate resin obtained by this method certainly improves the melt tension and formability and has excellent properties in terms of physical properties. However, the branched polycarbonate resin includes an organic phase and a by-product containing the polymer in the cleaning process of the polymer solution during polymer production. There is a problem that the separation from the aqueous phase is poor, and the productivity is lowered. In particular, when a branching agent is added to the aqueous phase or a branching agent that is insoluble in an organic solvent, the semi-hydrophilic semi-lipophilic polycarbonate oligomer becomes creamy between the aqueous phase and the organic phase, which inhibits stable production or prolongs the separation time. There are problems such as need or multiple steps for separation operation.

Patent Document 1: Japanese Patent Application Laid-Open No. 1991-182524

DISCLOSURE OF INVENTION

An object of the present invention is to provide a branched polycarbonate resin which can not only have high melt tension and moldability but also have excellent productivity and can efficiently produce a good molded article.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the said objective can be achieved by using a trisphenol silane compound which has a specific structure as a branching agent in superposing | polymerizing a branched polycarbonate resin. Discovered and completed the present invention.

That is, this invention provides the following branched polycarbonate resin and its manufacturing method.

(1) A branched polycarbonate resin obtained from a dihydric phenol, a carbonate precursor, a branching agent and a terminal terminator, wherein the branching agent consists of a trisphenol compound represented by the following formula (I):

Where

R is represented by Formula II,

n is an integer from 1 to 100,

R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R "is a C2-C12 alkylene group.

(2) A branching agent comprising a trisphenol compound represented by the formula (I) is obtained by reacting with divalent phenol at 0.001 to 4 mol%, and has a viscosity number of 37 to 132 ml / g. Branched polycarbonate resins.

(3) The branched polycarbonate resin according to the above (1) or (2), wherein the branching agent is a compound in which R in formula (I) is represented by the following formula (III) wherein n is 1 and R 'represents a methyl group:

(4) A method for producing a branched polycarbonate, wherein a trisphenol compound represented by the following formula (I) is used as a branching agent in interfacial polycondensation of dihydric phenol and phosgene:

Formula I

(II)

Where

R is represented by Formula II,

n is an integer from 1 to 100,

R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R "is a C2-C12 alkylene group.

(5) A polycarbonate oligomer is prepared by reacting a divalent phenol with a branching agent and a phosgene composed of a trisphenol compound represented by the formula (I), and reacting the divalent phenol and terminal terminator with the obtained polycarbonate oligomer ( The manufacturing method of the branched polycarbonate of 4).

(6) The method for producing a branched polycarbonate according to the above (4) or (5), wherein the branching agent is dissolved in an organic solvent.

Best Mode for Carrying Out the Invention

Branched polycarbonate resins of the invention are made from dihydric phenols, carbonate precursors, branching agents, and end terminators.

As a dihydric phenol which is a raw material, hydroquinone, 4,4'- dihydroxy diphenyl, bis (4-hydroxyphenyl) alkanes, bis (4-hydroxyphenyl) cycloalkanes, bis (4-hydroxy) Phenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 9,9-bis (4-hydroxyphenyl) fluorene and the like and These halogen derivatives are mentioned, Especially, 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is used preferably. These dihydric phenols may be used independently and may be used together 2 or more types. It is also possible to use difunctional compounds other than dihydric phenols (e.g., divalent carboxylic acids such as decane dicarboxylic acid, etc.) together with the dihydric phenols.

As the carbonate precursor, phosgene or carbonate compound is used. As a carbonate compound, Diaryl carbonate, such as diphenyl carbonate; And dialkyl carbonates such as dimethyl carbonate or diethyl carbonate. These carbonate compounds may also be used alone or in combination of two or more thereof.

The present invention uses a compound represented by the following formula (I) as the branching agent:

Formula I

(II)

Where

R is represented by Formula II,

n is an integer from 1 to 100,

R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R "is a C2-C12 alkylene group.

Examples of the alkyl group having 1 to 10 carbon atoms for R 'include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like, and may be branched chain type. .

Examples of the alkylene group having 2 to 12 carbon atoms for R ″ include ethylene group, propylene group, trimethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, and the like, and may be branched chain. n is preferably 1 to 50.

Among the branching agents represented by the formula (I), in particular, R 'is a methyl group, R is represented by the following formula (III), and n is preferably used here.

(III)

The amount of branching agent used is preferably 0.001 to 4 mol%, more preferably 0.001 to 3 mol% with respect to dihydric phenol. When the branching agent is 0.001 mol% or more, the effect by the branching agent is obtained, and melt tension and moldability become sufficient. Moreover, if the branched chain is 4 mol% or less, the solubility of a polycarbonate will not fall and it is preferable at the point of productivity.

In addition, it is preferable to use the branching agent represented by General formula (I) in the state melt | dissolved in the organic solvent, The solvent etc. which are used for the interfacial polycondensation reaction mentioned later as this organic solvent are mentioned.

The terminal terminator may be any structure as long as it is monohydric phenol, and there is no particular limitation. For example, p-butylphenol, p-octylphenol, p-cumylphenol, p-amylphenol, p-nonylphenol, p-cresol, 2,4,6-tribromophenol, p-bromophenol, 4-hydroxybenzophenone, phenol, long chain alkyl phenol and the like are used. These terminal stoppers may be used alone or in combination of two or more thereof.

There is no restriction | limiting in particular in the branched polycarbonate resin of this invention, It can manufacture using said raw material. Specifically, for example, in producing a polycarbonate by interfacial polycondensation of dihydric phenol and phosgene, a trisphenol compound represented by the formula (I) is used as a branching agent. At this time, methylene chloride, chloroform, chlorobenzene, carbon tetrachloride, etc. are used as a solvent, the divalent phenol and phosgene are reacted by a well-known method, a polycarbonate oligomer is produced, and the obtained polycarbonate oligomer is obtained. In the method for producing a linear polycarbonate obtained by reacting a dihydric phenol and a terminal terminator, a branching agent composed of a trisphenol compound represented by the formula (I) is reacted with a divalent phenol and phosgene or a polycarbonate oligomer It is preferable to add and react before the process of making a bivalent phenol react.

The branched polycarbonate resin of the present invention thus obtained preferably has a viscosity number (VN) of 30 to 150 ml / g, more preferably 37 to 132 ml / g. If the viscosity number is 30 ml / g or more, the strength of the molded article is good, and if it is 150 ml / g or less, it has a suitable melt viscosity and solution viscosity, and handling is good.

Moreover, in manufacture of the branched polycarbonate resin of this invention, various additives, such as antioxidant, a mold release agent, a weathering agent, a coloring agent, a nucleating agent, can also be mix | blended in the range which does not impair a characteristic. When used as a building material use in a sheet | seat field, it is preferable to mix | blend a weathering agent, and it is preferable to mix | blend a nucleating agent in a foam sheet.

The branched polycarbonate resin of the present invention can produce a high quality molded article efficiently by using a specific branching agent soluble in an organic solvent, having high melt tension, good moldability, and excellent productivity.

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these Examples.

On the other hand, the properties of the polycarbonate were measured and evaluated as follows.

(1) Amount of branching agent (mol%): The polycarbonate flakes were alkali-decomposed and determined by liquid chromatography.

(2) Viscosity number (VN) (ml / g): It calculated | required based on ISO 1628-4.

(3) Melt tension: It measured as tension (g) which arises when temperature is 280 degreeC, extrusion rate 10 mm / min, take-out rate 157 mm / sec, and orifice L / D is 8 / 2.1.

(4) Separation time: For methylene chloride solution (before washing) and the solution of polycarbonate obtained in the reactor (1 l tank reactor with interruption plate, paddle type stirring blade and cooling jacket) used in the polymerization process A 15 volume% washing liquid (0.03 mol / l NaOH aqueous solution) was added, the mixture was stirred at a rotational speed of 500 rpm for 10 minutes and then left to stand, and the time for separating the aqueous phase and the organic phase (methylene chloride phase) was measured. If the separation time is less than 1 hour, it is indicated as S (short).

(5) Cheek sand phenomenon: After filling 5 g of the obtained polycarbonate flakes in the cylinder of 10 mm diameter heated at 280 degreeC, the strand was extruded from the nozzle whose L / D is 10/1 mm. After completion of the extrusion, it was evaluated whether the axon phenomenon due to the molten polycarbonate occurred between the solidified strand portion and the nozzle. Here, when the sand yarn phenomenon is seen, the sand yarn phenomenon occurs at the tip of a nozzle during injection molding, and it becomes easy to produce a molding defect.

Example 1

(Oligomer Synthesis Process)

To the bisphenol A to be dissolved in an aqueous solution of 5.6% by weight of sodium hydroxide, 2000 ppm of sodium disionite was added, and bisphenol A was dissolved so that the concentration of bisphenol A was 13.5% by weight to prepare an aqueous sodium hydroxide solution of bisphenol A.

40 L / hr of sodium hydroxide aqueous solution of this bisphenol A, 15 L / hr of methylene chloride, and 4.0 kg / hr of phosgene were continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m. The tubular reactor had a jacket portion, and the cooling water was passed through the jacket to maintain the temperature of the reaction solution at 40 ° C or lower.

The reaction liquid from the tubular reactor was continuously introduced into a 40 liter tank reactor with a retracting vane and a baffle plate, further comprising 2.8 L / hour aqueous sodium hydroxide solution of bisphenol A, 0.07 aqueous 25 wt% sodium hydroxide solution. The reaction was carried out by adding 1 liter / hour, 17 liters / hour of water, and 0.64 liters / hour of 1 wt% triethylamine aqueous solution.

The aqueous phase was separated and the methylene chloride phase was taken out by standing still with the reaction liquid overflowed from a tank type reactor. The polycarbonate oligomer obtained had a concentration of 346 g / l and a chloroformate group concentration of 0.73 mol / l.

(Polymerization process)

In a 1 L tank reactor equipped with a baffle plate, paddle stir blades and cooling jacket, 130 mL of the oligomer solution, 95 mL of methylene chloride, 53 μL of triethylamine and 230 mg of HU-055 B (Structure: [(CH ₃ ) ₂ (HOC ₆ H ₄ C ₃ H ₆ ) SiO] ₃ SiCH ₃ , Dow Corning Toray Co., Ltd.), and 178 g of a 6.4% by weight aqueous sodium hydroxide solution were added under stirring. The reaction was carried out for 20 minutes. In this reaction process, it controlled by cooling so that reaction temperature might not be 20 degreeC or more.

Next, 8.20 g of bisphenol A was dissolved in an aqueous solution of 889 mg of p-butylphenol (terminal terminator, PTBP) and an aqueous sodium hydroxide solution of bisphenol A (4.90 g of NaOH and 16 mg of sodium disionite) in 72 ml of water. ) Was added and the polymerization reaction was carried out for 1 hour.

600 ml of methylene chloride was added for dilution, followed by standing to separate the organic phase containing polycarbonate and the aqueous phase containing excess bisphenol A and NaOH to isolate the organic phase.

The methylene chloride solution of the obtained polycarbonate was washed sequentially with 15% by volume 0.03 mol / l NaOH aqueous solution and 0.2 mol / l hydrochloric acid with respect to this solution, and then the electrical conductivity of the aqueous phase after washing was 0.01 μS / m or less. The washing was repeated with pure water until

In each washing process, the organic phase and the water phase could be separated within 1 hour.

Flaking Process

The flake obtained by concentrating and grinding the methylene chloride solution of polycarbonate obtained by washing | cleaning was dried at 120 degreeC under reduced pressure. The properties of the polycarbonates are shown in Table 1.

Comparative Example 1

In Example 1, it carried out similarly to Example 1 except having used 105 mg of 1,1,1-tris (4-hydroxyphenyl) ethane (THPE) as a branching agent. However, since THPE had low solubility in methylene chloride, it was dissolved and added to a 6.4 weight% sodium hydroxide aqueous solution. The properties of the obtained polycarbonate are shown in Table 1. In the washing step, the separation of the aqueous phase and the organic phase was slow, and a foamy phase was formed between the aqueous phase and the organic phase and did not separate in one hour.

Comparative Example 2

It carried out similarly to Example 1 except not having used the branching agent in Example 1. The properties of the obtained polycarbonate are shown in Table 1.

Examples 2 to 5

In Example 1, the addition amount of the branching agent and the terminal terminator (PTBP) was changed and carried out in the same manner as in Example 1. The properties of the obtained polycarbonate are shown in Table 1.

Comparative Example 3

In Example 2, it carried out similarly to Example 2 except having used 221 mg of THPE instead of HU-055B. However, since THPE had low solubility in methylene chloride, it was dissolved and added to a 6.4 weight% sodium hydroxide aqueous solution. The properties of the obtained polycarbonate are shown in Table 1. In the washing step, the separation of the aqueous phase and the organic phase was slow, and a foamy phase was formed between the aqueous phase and the organic phase and did not separate in one hour.

Comparative Example 4

In Example 3, it carried out similarly to Example 3 except having used 273 mg of THPE instead of HU-055B. However, since THPE had low solubility in methylene chloride, it was dissolved and added to a 6.4 weight% sodium hydroxide aqueous solution. The properties of the obtained polycarbonate are shown in Table 1. In the washing step, the separation of the aqueous phase and the organic phase was slow, and a foamy phase was formed between the aqueous phase and the organic phase and did not separate in one hour.

Comparative Example 5

It carried out similarly to Example 4 except not having used the branching agent in Example 4. The properties of the obtained polycarbonate are shown in Table 1.

According to the present invention, by using a trisphenol compound having a specific structure for the polymerization of branched polycarbonate resin as a branching agent, the cleaning property is good, there is little blow down due to the melt during the molding, a tendon sand phenomenon, etc. It is possible to obtain a branched polycarbonate resin which is not only high in melt tension and moldability but also excellent in productivity and capable of efficiently producing a good molded article.

Claims (6)

Branched polycarbonate resins obtained from dihydric phenols, carbonate precursors, branching agents and end terminators, wherein the branching agents consist of trisphenol compounds represented by the formula Formula I

(II)

Where R is represented by Formula II, n is an integer from 1 to 100, R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R "is a C2-C12 alkylene group. The method of claim 1, A branched polycarbonate resin obtained by reacting a branching agent composed of a trisphenol compound represented by the formula (I) using 0.001 to 4 mol% with respect to divalent phenol, and having a viscosity number in the range of 37 to 132 ml / g. 3. The method according to claim 1 or 2, The branching agent is a branched polycarbonate resin wherein R in Formula I is represented by the following Formula III, wherein n is 1 and R 'represents a methyl group: (III)

In preparing a branched polycarbonate by interfacial polycondensation of dihydric phenol and phosgene, a process for producing a branched polycarbonate comprising using a trisphenol compound represented by the following formula (I) as a branching agent: Formula I

(II)

Where R is represented by Formula II, n is an integer from 1 to 100, R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R "is a C2-C12 alkylene group. The method of claim 4, wherein Of a branched polycarbonate in which a bicarbonate and a branching agent consisting of a trisphenol compound represented by the formula (I) and a phosgene are reacted to prepare a polycarbonate oligomer, and the resulting polycarbonate oligomer is reacted with a divalent phenol and a terminal terminator. Manufacturing method. The method according to claim 4 or 5, A method for producing a branched polycarbonate using a branching agent dissolved in an organic solvent.