WO2001098402A1 - Composition de polycarbonate laissant moins de depots de moule - Google Patents

Composition de polycarbonate laissant moins de depots de moule Download PDF

Info

Publication number
WO2001098402A1
WO2001098402A1 PCT/US2001/013400 US0113400W WO0198402A1 WO 2001098402 A1 WO2001098402 A1 WO 2001098402A1 US 0113400 W US0113400 W US 0113400W WO 0198402 A1 WO0198402 A1 WO 0198402A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
pentaerythritol diphosphite
polycarbonate
aralkylphenyl
product produced
Prior art date
Application number
PCT/US2001/013400
Other languages
English (en)
Inventor
Hongkyu Kim
John Michael Fischer
Original Assignee
General Electric Company
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.)
Filing date
Publication date
Application filed by General Electric Company filed Critical General Electric Company
Publication of WO2001098402A1 publication Critical patent/WO2001098402A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • This invention relates to improved polycarbonate compositions in general, and bisphenol-A-polycarbonate compositions in particular, for molding operations.
  • Bisphenol-A-polycarbonate (BPA-PC) is one of the most versatile engineering plastics, having an attractive combination of toughness, transparency, and heat stability. This combination makes bisphenol-A-polycarbonate an ideal material for demanding applications where resistance to impact and good transparency are important. Processing of BPA-PC is typically carried out at elevated temperatures in order to reduce its high melt viscosity. Like most polyesters and other polycarbonates, BPA-PC is susceptible to hydrolysis and thermal degradation, especially at elevated temperatures. Thus, phosphorous-containing thermal stabilizers, in an amount that is effective to increase the melt stability of the polymer, are commonly added into the polycarbonate.
  • Such stabilizers include triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonyl- phenyl)phosphites, triauryl phosphite, trioctadecyl phosphite, tris(2,4-di-t-butyl- phenyl) phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, and tetrakis(2,4-di- t-butylphenyl) 4,4'-biphenylene diphosphite.
  • thermal stabilizers or antioxidants improves thermal stability of the polycarbonate, it often leads to mold deposits, or "plateout", that causes imperfection of a molded part surface and/or plugging of the vent lines of a mold.
  • a preform of molten plastic is extruded from an extruder, hanging downward into the cavity of a mold.
  • high pressure air is injected into the parison to cause the molten preform to inflate within the closed mold.
  • the air is released, via an exhausting pin, through the same tube that was used to inflate.
  • This invention describes an aromatic polycarbonate composition which results in reduced plateout (mold deposits), and maintains the advantageous processing and thermal properties of polycarbonates.
  • This composition is formed by combining an aromatic polycarbonate with a bis(aralkylphenyl)pentaerythritol diphosphite.
  • a preferred additive is bis(2,4-dicumyl-phenyl)pentaerythritol diphosphite.
  • the resulting composition is proven surprisingly useful in blow- molding large objects with reduced plateout compared to other commonly used additives. Also this formulation can be used in injection molding objects which require detail replication with reduced plateout.
  • This invention describes an aromatic polycarbonate composition giving reduced plateout (mold deposits) while maintaining good processing and thermal properties.
  • This composition comprises the combination of an aromatic polycarbonate and thermal-stabilizing additives, namely at least one bis(aralkylphenyl)pentaerythritol diphosphite of the general formula:
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , and R 11 are selected independently from the group consisting of hydrogen and alkyl radicals of the formula C m H im+1 where m ranges from 1 to 4, including substituted derivatives thereof.
  • R n ⁇ R ⁇ 6 , R ⁇ 9 , and R n are selected independently from the group consisting of hydrogen, aryl radicals, and alkyl radicals of the formula C m K 2 m + i where m ranges from 1 to 4 and n ranges from 0 to 3 with the proviso that the substituent be located at the ortho, meta, or para position with respect to the bridging methylene radical.
  • a preferred additive is bis(2,4-dicumyl-phenyl)pentaerythritol diphosphite, having the formula:
  • bis(2,4-dicumyl- phenyl)pentaerythritol diphosphite will be the only bis(aralkylphenyl)pentaerythritol diphosphite utilized, but this is not required.
  • the polycarbonate composition comprising a diphosphite according to general formula (I) can be used in blow-molding large objects with reduced plateout and vent line plugging. Also this formulation can be used in injection molding objects which require detail replication together with reduced plateout.
  • These additives are known to be useful as antioxidants when combined with polypropylene, as is described in Stevenson, et al., US 5,364,895 for "Hydrolytically Stable Pentaerythritol Diphosphites" issued November 15, 1994, and US 5,438,086, issued August 1, 1995, under the same title, the disclosures of both of which are incorporated by reference herein in their entirety. The references describe useful methods of making the additives with higher yield.
  • the present invention is directed to a thermoplastic resin composition, comprising an aromatic polycarbonate and a bis(aralkylphenyl)pentaerythritol diphosphite of Formula I.
  • This resin composition comprising exhibits significantly reduced plateout and mold deposits under polycarbonate processing conditions.
  • the composition of the present invention exhibits improved resistance to thermal degradation and reduced plateout during blow molding and injection molding of polycarbonates.
  • the pentaerythitol diphosphite effective in providing heat-stabilization while reducing plateout in comparison to prior art stabilizers.
  • an amount of the pentaerythitol diphosphite effective in providing heat-stabilization while reducing plateout in comparison to prior art stabilizers.
  • anywhere from about 0.01 to about 0.1 parts pentaerythitol diphosphite per hundred parts polycarbonate will be combined to create the composition of the invention.
  • Preferably about 0.02 pph to about 0.09 pph will be combined, more preferable about 0.03 pph to about 0.05 pph.
  • the exact quantities will vary with circumstances, because one must make a tradeoff between how much heat stabilization is desired versus how much one wishes to reduce plateout.
  • One can determine the optimum amount by experimenting with different concentrations used in different molding applications as described below.
  • plateout is common during molding polycarbonate and other thermoplastic parts, it has been difficult to quantify and predict the degree of this occurrence prior to actual molding.
  • a twin screw extruder equipped with a vacuum vent and a set of screws with a venting design, was employed with a small leaking in the vent port. This leaking provides air-sweeping action in the vent area and helps to efficiently remove gaseous products generated during melt extrusion to a cold tap.
  • the cold glass trap was to condense and accumulate the released gaseous (plateout) products at ice/water mixture temperature.
  • a small length of fluorinated polymeric tubing was connected between the vent port and the trap.
  • the twin screw set was designed and assembled to give an adequate melting, mixing, and melt surface area at the vent section for evaluation. After extrusion, the trap and tubing were weighed to quantify the plateout of the resin formulation.
  • a linear grade of polycarbonate (Lexan® 100) was formulated with 3 different levels of two heat stabilizers.
  • the formulations (in pph, parts-per-hundred) were preblended prior to compounding the 40-mm twin screw Werner & Pfleiderer extruder without venting. After compounding, the resins were pelletized, and then dried for 3 hours at 250°F. The dried resins were extruded in the same extruder with vacuum using only 80% of available total vacuum (20-in Hg).
  • the vent port that was devised with an air leakage was connected to a glass trap with a short Teflon® tubing. The trap was cooled with ice/water mixture to capture evaporating products.
  • approximately 100 pounds of resin was extruded with an extruder temperature profile of (480-570-610-630-580F) at 500 rpm and a feed rate, which yields 80% of maximum torque.
  • Table I lists polycarbonate formulations and plateout collected in the trap.
  • the additive of the invention was bis(2,4-dicumyl-phenyl)pentaerythritol diphosphite as shown in Formula II.
  • the prior art additive was tris(2,4-di-t-butylphenyl)phosphite.
  • the resin compositions containing bis(2,4-dicumyl-phenyl)pentaerythritol diphosphite generate less plateout during extrusion.
  • increase of a stabilizer content in the resin increase the amount of plateout during extrusion. Note the surprising and unexpected result in formulation #2, where the amount of plateout is reduced in comparison to formulation #1, where no additive is used at all.
  • the plateout was extracted with 25 ml of methylene chloride.
  • the extracted solution was then diluted with methylene chloride and analyzed by high temperature GC-MS.
  • the major compounds detected are listed in the following tables:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une composition formée à partir de la combinaison d'un polycarbonate aromatique et d'un additif se composant d'au moins un diphosphite de bis(aralkylphényl)pentaérythritol, un tel additif préféré étant le diphosphite de bis (2,4-dicumylphényl)pentaérythritol. Cet additif ajouté au polycarbonate permet d'obtenir une composition résultante étonnamment utile dans le moulage par soufflage de grands objets, avec un dépôt réduit par rapport aux autres additifs généralement utilisés. Cette composition est également utile pour le moulage par injection.
PCT/US2001/013400 2000-06-22 2001-04-25 Composition de polycarbonate laissant moins de depots de moule WO2001098402A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59976900A 2000-06-22 2000-06-22
US09/599,769 2000-06-22

Publications (1)

Publication Number Publication Date
WO2001098402A1 true WO2001098402A1 (fr) 2001-12-27

Family

ID=24401006

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/013400 WO2001098402A1 (fr) 2000-06-22 2001-04-25 Composition de polycarbonate laissant moins de depots de moule

Country Status (1)

Country Link
WO (1) WO2001098402A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110071241A1 (en) * 2009-09-23 2011-03-24 Bayer Materialscience Llc Flame retardant, optically clear thermoplastic molding composition
WO2012106425A1 (fr) * 2011-02-03 2012-08-09 Sabic Innovative Plastics Ip B.V. Compositions de polycarbonate à couleur stable et thermostables et leurs procédés de fabrication
US20140005311A1 (en) * 2012-07-02 2014-01-02 Bayer Materialscience Llc Polycarbonate composition with low static performance
US20150299428A1 (en) * 2012-03-30 2015-10-22 Bayer Intellectual Property Gmbh Polycarbonate composition with improved optical properties

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112891A (en) * 1989-09-06 1992-05-12 Asahi Denka Kogyo Kabushiki Kaisha Polycarbonate resin composition
US5438086A (en) * 1993-08-30 1995-08-01 Stevenson; Donald R. Hydrolytically stable pentaerythritol diphosphites
US5679284A (en) * 1993-12-28 1997-10-21 Polyplastics Co., Ltd. Liquid crystal polyester resin composition
EP0827981A2 (fr) * 1996-09-06 1998-03-11 General Electric Company Stabilisation de couleur de résines polycarbonates
EP0885929A1 (fr) * 1997-06-16 1998-12-23 General Electric Company Compositions de polycarbonate pour le moulage dégazé.
WO2000078869A1 (fr) * 1999-06-18 2000-12-28 Solvay Advanced Polymers, Llc Procede et composition pour reduire la formation de depots de moulage pendant le moulage de polyamides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112891A (en) * 1989-09-06 1992-05-12 Asahi Denka Kogyo Kabushiki Kaisha Polycarbonate resin composition
US5438086A (en) * 1993-08-30 1995-08-01 Stevenson; Donald R. Hydrolytically stable pentaerythritol diphosphites
US5679284A (en) * 1993-12-28 1997-10-21 Polyplastics Co., Ltd. Liquid crystal polyester resin composition
EP0827981A2 (fr) * 1996-09-06 1998-03-11 General Electric Company Stabilisation de couleur de résines polycarbonates
EP0885929A1 (fr) * 1997-06-16 1998-12-23 General Electric Company Compositions de polycarbonate pour le moulage dégazé.
WO2000078869A1 (fr) * 1999-06-18 2000-12-28 Solvay Advanced Polymers, Llc Procede et composition pour reduire la formation de depots de moulage pendant le moulage de polyamides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110071241A1 (en) * 2009-09-23 2011-03-24 Bayer Materialscience Llc Flame retardant, optically clear thermoplastic molding composition
WO2012106425A1 (fr) * 2011-02-03 2012-08-09 Sabic Innovative Plastics Ip B.V. Compositions de polycarbonate à couleur stable et thermostables et leurs procédés de fabrication
US9234096B2 (en) 2011-02-03 2016-01-12 Sabic Global Technologies B.V. Color and heat stable polycarbonate compositions and methods of making
US20150299428A1 (en) * 2012-03-30 2015-10-22 Bayer Intellectual Property Gmbh Polycarbonate composition with improved optical properties
US20140005311A1 (en) * 2012-07-02 2014-01-02 Bayer Materialscience Llc Polycarbonate composition with low static performance

Similar Documents

Publication Publication Date Title
US5102591A (en) Method for removing volatile substances from polyphenylene ether resin blends
EP2913360B1 (fr) Composition de résine polyester aliphatique et corps moulé contenant la composition de résine polyester aliphatique
EP2907850B1 (fr) Composition de résine de polyester et article moulé à base de ladite composition de résine
KR101841538B1 (ko) 난연성 수지 조성물 및 난연성 수지 성형체
KR101875999B1 (ko) 열안정성이 우수한 난연 열가소성 수지 조성물, 이의 제조방법 및 이로부터 제조된 성형품
CN115058108B (zh) 可海洋降解的聚羟基烷酸酯组合物、成型体及其制备方法
JPS6234934A (ja) ポリオレフイン樹脂組成物
JPH1171512A (ja) ベント式成形物品用のポリカーボネート組成物
CN111117188A (zh) 一种医疗级免喷涂阻燃耐候pc材料及其制备方法
AU750817B2 (en) Reducing ionic impurities content in aromatic polycarbonate resins
WO2001098402A1 (fr) Composition de polycarbonate laissant moins de depots de moule
JP5389468B2 (ja) ポリアセタール樹脂組成物の製造方法
CN108530789B (zh) 环保阻燃注塑级acs改性材料及其制备方法
CN114031918B (zh) 一种低黄度指数的聚碳酸酯组合物及其制备方法与用途
CN113429788B (zh) 一种ppsu再生料及其制备工艺
JPWO2014189139A1 (ja) オキシメチレン共重合体の製造方法
JPH0732454A (ja) ブロー成形用樹脂組成物及びブロー成形方法
US5498656A (en) Polyvinyl alcohol molding resin composition
JP4602490B2 (ja) 熱可塑性樹脂混練物の製造方法
WO2015008537A1 (fr) Procédé de préparation d'un copolymère d'oxyméthylène
JP2008024889A (ja) イグニッションコイル部品用樹脂組成物及びそれからなるイグニッションコイル部品
CN111100355A (zh) 一种抗冲增强防霉高密度聚乙烯材料及其制备方法
KR102108242B1 (ko) 폴리(페닐렌 에테르) 조성물 및 물품
JP3374870B2 (ja) オキシメチレン共重合体樹脂組成物の製造方法
CN114350132B (zh) 一种低气味低散发pc/abs及其制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP