WO2002038647A1 - Polycarbonate lineaire - Google Patents

Polycarbonate lineaire Download PDF

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Publication number
WO2002038647A1
WO2002038647A1 PCT/JP2001/009392 JP0109392W WO0238647A1 WO 2002038647 A1 WO2002038647 A1 WO 2002038647A1 JP 0109392 W JP0109392 W JP 0109392W WO 0238647 A1 WO0238647 A1 WO 0238647A1
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WO
WIPO (PCT)
Prior art keywords
long
chain
polycarbonate
same manner
molecular weight
Prior art date
Application number
PCT/JP2001/009392
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English (en)
Japanese (ja)
Inventor
Yasuhiro Ishikawa
Original Assignee
Idemitsu Petrochemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2002038647A1 publication Critical patent/WO2002038647A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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 linear polycarbonate, and more particularly, to a linear polycarbonate having improved fluidity, free of deposits on a mold when injection molding is performed, and having a good appearance of a molded product.
  • Polycarbonate resin has excellent mechanical properties (especially impact resistance), electrical properties, transparency, etc., and is used as an engineering plastic in the fields of OA equipment, electrical and electronic equipment, and construction. It is widely used in various fields such as fields.
  • the present invention has been made under such a circumstance, and is a linear polycarbonate having improved fluidity, no adhesion to a mold when injection molding is performed, and a good appearance of a molded product. It provides a bond.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, obtained a polycarbonate using a long-chain monoalkylphenol having a specific number of carbon atoms as a terminal stopper. It has been found that by adjusting the amount of unreacted long-chain monoalkyl phenol therein, the object of the present invention can be met.
  • the present invention has been completed based on such findings. That is, the gist of the present invention is as follows.
  • a long-chain monoalkyl phenol having an alkyl group having an average carbon number of 19 to 35 is used as a terminal stopper, and the amount of unreacted long-chain monoalkyl phenol is 300.
  • straight-chain polycarbonate of the present invention include the general formula (I)
  • a polymer having a repeating unit having a structure represented by the following formula is preferable.
  • X 1 and X 2 each represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, —Propyl, isopropyl, n-butyl, isoptyl, tetrat —butyl, n-amyl, isoami / re, n-hexyl, isohexyl, pentyl And cyclohexyl groups.
  • X 1 and X 2 may be the same or different.
  • a and b represent the number of substitutions of X 1 and X 2 , respectively, and are integers of 0 to 4. When plural X 1, a plurality of X 1 may be the same as or different from each other, if X 2 is plural, X 2 may be the same with or different from each other.
  • Y is a single bond, an alkylene group having 1 to 8 carbon atoms (eg, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group), an alkylidene group having 2 to 8 carbon atoms (eg, an ethylidene group).
  • an alkylene group having 1 to 8 carbon atoms eg, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group
  • an alkylidene group having 2 to 8 carbon atoms eg, an ethylidene group
  • the linear polycarbonate is manufactured without using a branching agent.
  • the above polymer has a general formula ( ⁇ ⁇ )
  • divalent phenol represented by the general formula ( ⁇ ) various ones can be mentioned.
  • 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol II) is preferred.
  • divalent phenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl).
  • Bis (4-hydroxyphenyl) cycloanolecan 4, 4 , Zihydroxydifu-nore, bis (4-hydroxyfujinore) oxide, bis (4-hydoxyfujinore) sulphide, bis (4-hid oxipheninole) snorehon, bis (4hydroxyfifenole) Binore) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
  • examples of the divalent phenol include a quinone having a hide opening. These divalent phenols may be used alone or in combination of two or more.
  • Examples of the carbonate ester include dialkyl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethinole carbonate, and jetinole carbonate.
  • the terminating agent when a polycarbonate is produced by reacting the divalent phenol with a carbonate precursor, the terminating agent (also referred to as a molecular weight regulator) has an average carbon number of 19 to 35. It is essential to use long-chain monoalkylphenols with alkyl groups. If it is less than 19, the improvement of the fluidity is insufficient, and if it exceeds 35, the reactivity is poor, and the loss of the long-chain monoalkylphenol increases accordingly. Preferably, it has an average carbon number of 21 to 35, and more preferably, it has an average carbon number of 21 to 25.
  • the average carbon number of the above-mentioned alkyl group is the sum of [product of ((carbon number of alkyl group)) and (molar fraction thereof)].
  • the above long-chain monoalkylphenols may be used alone or in combination of two or more.
  • the carbon number of the alkyl group is represented by the average carbon number.
  • long-chain monoalkyl phenols include ortho-form, meta-form and para-form as isomers, and any of them may be used.
  • long chain al The kill group may be linear or branched.
  • the linear polycarbonate of the present invention must have a viscosity average molecular weight in the range of 13,500 to 30,000, from the viewpoint of mechanical strength and moldability. Preferably, it is in the range of 14, 000 to 25, 000, more preferably in the range of 14,500 to 21, 000.
  • the viscosity-average molecular weight (Mv) was determined by measuring the viscosity of the methylene chloride solution at 20 ° C using an Ubbelohde viscometer, and calculating the intrinsic viscosity [7?]. . 2 3 X 1 0- 5 MV 0. is a value calculated by 83 expression.
  • the unreacted long-chain monoalkylphenol of the linear polycarbonate of the present invention must be 300 ppm or less, preferably 200 ppm or less, and more preferably less than 100 ppm.
  • a force that is not particularly limited as a method of reducing the pressure to 300 ppm or less For example, in a solution method, a polycarbonate precipitate generated in a poor solvent may be separated by filtration. If it exceeds 300 ppm, deposits are observed on the injection mold and the appearance of the molded product is not good, which is not preferable.
  • additives such as an antioxidant, a lightness improver, a lubricant (a mold release agent), a flame retardant, and an anti-drip may be added to the direct-melted polycarbonate according to the present invention, as long as the object of the present invention is not impaired.
  • Agents, other inorganic fillers and the like may be appropriately contained.
  • a composition can be prepared by mixing and kneading various additives with the polycarbonate of the present invention.
  • a method applied to a usual resin composition can be applied as it is, such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw or a multi-screw screw of two or more screws.
  • a method using an extruder, a kneader or the like is preferable.
  • the kneading temperature is not particularly limited, but is usually suitably selected from the range of 240 to 34 ° C.
  • the resin composition thus obtained can be molded by a usual molding method, for example, a spray molding method or a compression molding method, to obtain a molded product.
  • a usual molding method for example, a spray molding method or a compression molding method
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
  • a reactor equipped with baffles and stirring blades, phenol 3 0 0 parts by weight of 1 - eicosene, a mixture of 1 one docosenoic and 1 tetracosene [Composition ratio (mol 0/0); 5 3.3: 4 0.2 : 6.5] 105 parts by mass [phenol Zolefin 9 Zl (molar ratio)] and a strongly acidic polystyrene sulfonic acid-type cation resin (Amberlystl 5; manufactured by Rohm and Haas Company) as a catalyst 10
  • the reaction raw materials and the catalyst were charged at a charging ratio of 2.5 parts by mass, and the reaction was carried out at 120 ° C. for 3 hours with stirring.
  • purification was performed by distillation under reduced pressure to obtain a long-chain monoalkylphenol (a).
  • the alkyl group of the long-chain monoalkylphenol (a) thus obtained had an average carbon number of 21.
  • phosgene is supplied at a flow rate of 4 ⁇ O kg / hr and an inner diameter of 6 mm and a pipe length.
  • the feed was continuously fed to a 30 m tubular reactor.
  • 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 tank reactor equipped with a baffle with a swept wing and having an inner volume of 40 liters, and further added with an aqueous sodium hydroxide solution of bisphenol A 2 .8 liter Zhr, 25% by mass aqueous sodium hydroxide solution 0.07 liter Z hr, 17 liters of water / hr, 1% by mass triethylamine aqueous solution 0.32 liter / hr The reaction was performed with the addition of hr.
  • 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 concentration of the polycarbonate oligomer obtained in this way was 3.55 g Z liter, and the concentration of the clog mouth home group was 0.80 mol / litre / re.
  • the polycarbonate thus obtained in methylene chloride solution was sequentially added to the solution by 15 volumes. /. Each with 0.03 mol Z sodium hydroxide aqueous solution and 0.2 mol Z little hydrochloric acid, and then the electric conductivity in the aqueous phase after washing becomes 0.12 SZm or less. Washing was repeated with pure water until it was complete.
  • Temperature pattern Hold at 40 ° C for 1 minute ⁇ Raise temperature by 40 ° CZ ⁇ 120. C / 7 min hold ⁇ 10 ° C / min temperature rise ⁇ 330 ° C / 5 min hold
  • Carrier gas Helium (40 cm 3 / s, constant flow)
  • Injection Splitless (2.0 ⁇ liter)
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 365 g of long-chain monoalkylphenol (b) was used instead of long-chain monoalkylphenol (a).
  • the viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 instead of the long-chain monoalkylphenol (a), Polycarbonate flakes were prepared in the same manner except that 198 g of lauric chloride was used. Its viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 249 g of palmitic acid mouth glass was used instead of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • a polycarbonate flake was prepared in the same manner as in Example 1, except that 270 g of stearic acid chloride was used instead of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that octadecylphenol (314 g) was used instead of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • a polycarbonate flake was prepared in the same manner as in Example 1 except that the amount of the long-chain monoalkylphenol (a) was changed to 292 g.
  • the viscosity average molecular weight, Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 is the same as Example 1 except that long-chain monoalkylphenol (b) (303 g) was used instead of long-chain monoalkylphenol (a). To prepare a polycarbonate flake. Its viscosity average molecular weight,
  • a polycarbonate flake was prepared in the same manner as in Example 1, except that 234 g of p-hydroxybenzoic acid dodecyl was used in place of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 210 g of palmitic acid mouthride was used instead of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 262 g of octadecylphenol was used instead of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • a polycarbonate flake was prepared in the same manner as in Example 1, except that the addition amount of the long-chain monoalkylphenol (a) was changed to 2666 g.
  • the viscosity average molecular weight, Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results. (Example 6)
  • Example 1 is the same as Example 1 except that long-chain monoalkylphenol (b) (276 g) was used instead of long-chain monoalkylphenol (a) Thus, a polycarbonate flake was prepared. Its viscosity average molecular weight,
  • a poly-carbonate flake was prepared in the same manner as in Example 1, except that 146 g of lauric chloride was used instead of the long monoalkylphenol (a). Its viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 184 g of palmitic acid mouthride was used in place of the long-chain monoalkylphenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Polycarbonate flakes were prepared in the same manner as in Example 1, except that 199 g of stearic acid chloride was used in place of the long-chain monoanolequinolephenol (a).
  • the viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 polycarbonate flakes were prepared in the same manner except that after adding n-hexane, the mixture was concentrated without filtration and the obtained solid was dried.
  • the viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results.
  • Comparative Example 1 After adding n-hexane, Polycarbonate flakes were prepared in the same manner, except that the resulting solids were dried. The viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Unreacted lauric chloride was measured in the same manner as in Example 1 as lauryl alcohol. Table 1 shows the results.

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  • 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)

Abstract

L'invention concerne un polycarbonate linéaire produit avec un terminateur de chaîne comprenant des monoalkylphénols à longue chaîne dans lesquels les groupes alkyle ont un nombre de carbone moyen allant de 19 à 35, et ayant une teneur de monalkylphénols à longue chaîne n'ayant pas réagi de 300 ppm au maximum et un poids moléculaire moyen en terme de viscosité de 13 500 à 30 000. Le polycarbonate linéaire présente une meilleure aptitude à l'écoulement, ne laisse pas de dépôt de moulage en moulage par injection et permet de produire un article moulé d'aspect satisfaisant.
PCT/JP2001/009392 2000-11-13 2001-10-25 Polycarbonate lineaire WO2002038647A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000344862A JP2002146006A (ja) 2000-11-13 2000-11-13 直鎖状ポリカーボネート
JP2000-344862 2000-11-13

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WO2002038647A1 true WO2002038647A1 (fr) 2002-05-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007004332A1 (de) 2007-01-29 2008-07-31 Bayer Materialscience Ag Mehrschichtverbundwerkstoff mit einer Schicht aus Polycarbonat

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003096180A (ja) * 2001-09-27 2003-04-03 Idemitsu Petrochem Co Ltd 直鎖状ポリカーボネート
WO2003029324A1 (fr) * 2001-09-27 2003-04-10 Idemitsu Petrochemical Co., Ltd. Resine de polycarbonate et procede permettant de produire cette resine
JP2004083776A (ja) * 2002-08-28 2004-03-18 Idemitsu Petrochem Co Ltd 直鎖状ポリカーボネート樹脂
DE10354546A1 (de) * 2003-11-21 2005-06-23 Bayer Materialscience Ag Polycarbonat-Massivformkörper mit verbesserten optischen und verarbeitungstechnischen Eigenschaften

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60203632A (ja) * 1984-03-28 1985-10-15 Mitsubishi Gas Chem Co Inc ポリカ−ボネ−ト樹脂光学成形品
EP0969031A1 (fr) * 1998-01-19 2000-01-05 Mitsubishi Chemical Corporation Resine de polycarbonate, substrat de support de donnees optiques fabrique dans cette resine et support de donnees optiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60203632A (ja) * 1984-03-28 1985-10-15 Mitsubishi Gas Chem Co Inc ポリカ−ボネ−ト樹脂光学成形品
EP0969031A1 (fr) * 1998-01-19 2000-01-05 Mitsubishi Chemical Corporation Resine de polycarbonate, substrat de support de donnees optiques fabrique dans cette resine et support de donnees optiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007004332A1 (de) 2007-01-29 2008-07-31 Bayer Materialscience Ag Mehrschichtverbundwerkstoff mit einer Schicht aus Polycarbonat

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