Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
  • C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent

Definitions

• 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 and moldability, and a method for producing the same.
• polycarbonate resins that also produce bisphenol A or the like are widely used because of their excellent transparency, heat resistance, and mechanical properties.
• the polycarbonate resin is used for applications such as blow molding and extrusion molding, satisfactory molded products cannot be obtained due to low melt tension, and transferability and the like are improved in injection molding and the like.
• a polycarbonate resin having a relatively low molecular weight is used, there is a drawback that a satisfactory molded product cannot be obtained by stringing or the like.
• the branched polycarbonate resin obtained by this method has improved melt tension and moldability and has excellent properties in terms of physical properties, it has a great advantage in the polymer solution washing step in polymer production.
• the separation between the organic phase containing water and the aqueous phase containing by-products is poor, and the productivity decreases.
• the semi-hydrophilic and semi-lipophilic polycarbonate oligomer accumulates in a creamy state between the aqueous phase and the oil phase and is stable.
• problems such as hindering efficient production, requiring a long separation time, and requiring multiple steps in the separation operation.
• Patent Document 1 JP-A-3-182524
• An object of the present invention is to provide a branched polycarbonate resin which has high melt tension and moldability, is excellent in productivity, and can efficiently produce good molded products.
• the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that The present inventors have found that the above object can be achieved by using a trisphenol silane compound having a specific structure as a branching agent in the polymerization of -ponate resin, and completed the present invention.
• the SR R of the present invention II provides the following branched polycarbonate resin and a method for producing the same.
• branching agent is a trisphenol conjugate compound represented by the following general formula (I). Branched polycarbonate resin.
• n is an integer of 1 to: LOO
• R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• R ′′ is a carbon atom having 2 to It is an alkylene group of 12.
• the branched polycarbonate resin having a viscosity number in the range of 37 to 132.
• R is represented by the following general formula (II), n is an integer of 1 to: L00, R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ′′ is a carbon atom having 2 to It is an alkylene group of 12.
• a polycarbonate oligomer is produced by reacting a divalent phenol, a branching agent composed of a trisphenol conjugate represented by the general formula (I), and phosgene to obtain a polycarbonate oligomer.
• a branching agent composed of a trisphenol conjugate represented by the general formula (I)
• phosgene phosgene
• the branched polycarbonate resin of the present invention is produced from a divalent phenol and a carbonate precursor, a branching agent, RRRII and a terminal stopper.
• a difunctional conjugate other than divalent phenol for example, a divalent carboxylic acid such as decanedicarboxylic acid
• Yo it is used to together.
• phosgene or a carbonate ester conjugate is used as a carbonate precursor.
• carbonate compound examples include diaryl carbonate such as diphenyl carbonate, and dialkyl carbonate such as dimethyl carbonate and getyl carbonate. These carbonated ester conjugates may be used alone or in combination of two or more.
• the present invention uses a compound represented by the following general formula (I) as a branching agent.
• R is represented by the following general formula (II), n is 1 to: an integer of LOO, R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ′′ is a carbon atom having 2 to It is an alkylene group of 12.
• Examples of the alkyl group having 1 to 10 carbon atoms for R ′ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like. And a branched one may be used.
• Examples of the alkylene group having 2 to 12 carbon atoms for R include an ethylene group, a propylene group, a trimethylene group, a hexamethylene group, an otatamethylene group, a decamethylene group, and a dodecamethylene group.
• N is preferably 1 to 50.
• branching agents represented by the general formula (I) those in which R 'is a methyl group, R is represented by the following general formula (III), and n is 1 are preferably used.
• the amount of the branching agent to be used is preferably 0.001 to 4 mol%, more preferably 0.001 to 3 mol%, based on the divalent phenol.
• the amount of the branching agent is 0.001 mol% or more, the effect of the branching agent is obtained, and the melt tension and the formability are sufficient.
• the content is 4 mol% or less, the solubility of the polycarbonate is not reduced, which is preferable in production.
• the branching agent represented by the general formula (I) is preferably used in a state of being dissolved in an organic solvent.
• organic solvent include a solvent used in an interfacial polycondensation reaction described below. .
• the terminal terminator may have any structure as long as it is a monovalent phenol. There is no limit. For example, p-tert-butylphenol, p-tert-octylphenol, p-cuminolephenol, p-tert-amylphenol, p-norphenol, p-cresol, 2,4,6-tribromo Phenol, p-bromophenol, 4-hydroxybenzophenone, phenol, and long-chain alkylphenol are used. These terminal stoppers may be used alone or in combination of two or more.
• the branched polycarbonate resin of the present invention can be produced using the above-mentioned raw materials which are not particularly limited. Specifically, for example, in producing a polycarbonate by interfacial polycondensation of divalent phenol and phosgene, a trisphenol compound represented by the general formula (I) is used as a branching agent. At this time, using a solvent such as methylene chloride, chloroform, benzene, tetrachlorocarbon, and the like, a divalent phenol and phosgene were reacted by a known method to produce a polycarbonate oligomer.
• a solvent such as methylene chloride, chloroform, benzene, tetrachlorocarbon, and the like
• Polycarbonate oligomer According to a method for producing a linear polycarbonate obtained by reacting a divalent phenol and a terminal terminator with a dihydric phenol, a branching agent having a trisphenol-containing compound represented by the general formula (I) is It is preferable to add and react before the step of reacting a divalent phenol with phosgene or the step of reacting a divalent phenol with a polycarbonate oligomer.
• the thus obtained branched polycarbonate resin of the present invention preferably has a viscosity number (VN) of 30 to 150, more preferably 37 to 132.
• VN viscosity number
• the strength of the molded product is good, and when it is 150 or less, the molded product has an appropriate melt viscosity and a solution viscosity, and the handling is good.
• various additives such as an antioxidant, a release agent, a weathering agent, a colorant, and a nucleating agent are compounded within a range not to impair the properties. It is good.
• a weathering agent When used as a building material in the field of sheets, it is desirable to incorporate a weathering agent.
• a nucleating agent In the case of foamed sheets, it is desirable to incorporate a nucleating agent.
• the branched polycarbonate resin of the present invention has a high melt tension, good moldability, excellent productivity, and high quality molded articles by using a specific branching agent soluble in an organic solvent. Can be produced efficiently.
• the properties of the polycarbonate were measured and evaluated as follows.
• Amount of branching agent (mol%) The flakes were alkali-decomposed and determined by liquid chromatography.
• Viscosity number (VN) Performed according to ISO 1628-4.
• This bisphenol A aqueous sodium hydroxide solution of 40 liters Zhr, methylene chloride of 15 liters of Zhr and phosgene 4.OkgZhr were continuously passed through a tubular reactor having an inner diameter of 6 mm and a length of 30 m.
• the tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C or lower by passing cooling water through the jacket.
• the reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffle-type reactor equipped with a baffle equipped with swept wings, and further added bisphenol A aqueous sodium hydroxide solution with 2.8 liters
• the reaction was carried out by adding Zhr, 25 wt% aqueous sodium hydroxide solution 0.07 liter Zhr, water 17 liter Zhr and 1 wt% triethylamine aqueous solution at 0.64 liter / hr.
• the reaction solution overflowing from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by standing, and the methylene chloride phase was collected.
• the obtained polycarbonate oligomer had a concentration of 346 gZl and a chromate formate group concentration of 0.73 molZl.
• the obtained methylene chloride solution of the polycarbonate is washed successively with a 15% by volume aqueous solution of 0.03 mol Zl'NaOH and 0.2 mol Zl hydrochloric acid, and then the electric conductivity in the aqueous phase after washing is 0.01 ⁇ m. Washing with pure water was repeated until the water content became SZm or less.
• the organic phase and the aqueous phase could be separated within one hour.
• Example 1 was repeated, except that 105 mg of 1,1,1-tris (4-hydroxyphenyl) ethane (THPE) was used as a branching agent.
• THPE 1,1,1-tris (4-hydroxyphenyl) ethane
• Table 1 shows the properties of the obtained polycarbonate.
• Example 1 was repeated except that no branching agent was used. Table 1 shows the properties of the obtained polycarbonate.
• Example 1 was repeated in the same manner as in Example 1 except that the amounts of the branching agent and the terminal terminator (PTBP) were changed.
• Table 1 shows the properties of the obtained polycarbonate.
• Example 2 was carried out in the same manner as in Example 2 except that 221 mg of THPE was used instead of HU-055B. However, since THPE has low solubility in methylene chloride, it was added by dissolving it in a 6.4% by weight aqueous sodium hydroxide solution. Table 1 shows the properties of the obtained polycarbonate. During the washing process, the separation of the aqueous phase and the organic phase was delayed, and a foamy phase was formed between the aqueous phase and the organic phase.
• Example 3 was carried out in the same manner as in Example 3, except that 273 mg of THPE was used instead of HU-055B. However, since THPE has low solubility in methylene chloride, it was added by dissolving it in a 6.4% by weight aqueous sodium hydroxide solution. Table 1 shows the properties of the obtained polycarbonate. During the washing process, the separation of the aqueous phase and the organic phase was delayed, and a foamy phase was formed between the aqueous phase and the organic phase.
• Example 4 was carried out in the same manner as in Example 4 except that no branching agent was used. Table 1 shows the properties of the obtained polycarbonate. Cost me.
• a branched polycarbonate resin in polymerizing a branched polycarbonate resin, by using a trisphenol conjugate having a specific structure as a branching agent, dripping (blowdown) due to melting at the time of molding having good cleaning properties. It is possible to obtain a branched polycarbonate resin which has a high melt tension and a low moldability with a small amount of stringing and the like, and is excellent in productivity and capable of efficiently producing a good molded product.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyesters Or Polycarbonates (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=35428383

Family Applications (1)

Country Status (7)

Cited By (1)

Families Citing this family (3)

Citations (5)

Family Cites Families (8)

• 2004
  • 2004-05-24 JP JP2004152758A patent/JP4644442B2/ja not_active Expired - Fee Related
• 2005
  • 2005-05-19 EP EP05741485A patent/EP1749848B1/en not_active Expired - Lifetime
  • 2005-05-19 CN CNB2005800165747A patent/CN100558788C/zh not_active Expired - Fee Related
  • 2005-05-19 WO PCT/JP2005/009133 patent/WO2005113637A1/ja not_active Ceased
  • 2005-05-19 US US11/547,280 patent/US7541419B2/en not_active Expired - Fee Related
  • 2005-05-19 DE DE602005021778T patent/DE602005021778D1/de not_active Expired - Lifetime
  • 2005-05-23 TW TW094116780A patent/TW200613365A/zh not_active IP Right Cessation

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events