WO2017119657A1 - Nouveau polyorganosiloxane et copolycarbonate préparé au moyen de celui-ci - Google Patents

Nouveau polyorganosiloxane et copolycarbonate préparé au moyen de celui-ci Download PDF

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Publication number
WO2017119657A1
WO2017119657A1 PCT/KR2016/015339 KR2016015339W WO2017119657A1 WO 2017119657 A1 WO2017119657 A1 WO 2017119657A1 KR 2016015339 W KR2016015339 W KR 2016015339W WO 2017119657 A1 WO2017119657 A1 WO 2017119657A1
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WO
WIPO (PCT)
Prior art keywords
polyorganosiloxane
formula
independently
copolycarbonate
alkylene
Prior art date
Application number
PCT/KR2016/015339
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English (en)
Korean (ko)
Inventor
박정준
황영영
반형민
이기재
홍무호
Original Assignee
주식회사 엘지화학
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
Priority claimed from KR1020160179495A external-priority patent/KR101831886B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16884040.3A priority Critical patent/EP3401352B1/fr
Priority to PL16884040T priority patent/PL3401352T3/pl
Priority to CN201680010960.3A priority patent/CN107250218B/zh
Priority to US15/546,217 priority patent/US10465045B2/en
Publication of WO2017119657A1 publication Critical patent/WO2017119657A1/fr

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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
    • C08G64/18—Block or graft polymers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

Definitions

  • the present invention relates to a novel polyorganosiloxane capable of producing copolycarbonates with improved hardness and chemical resistance and to copolycarbonates prepared using the same.
  • Polyorganosiloxane is a kind of silicon (si li cone) means a polymer mainly composed of siloxane bonds substituted by organic groups (organi c groups), for example, aromatic diols such as bisphenol A and carbonate precursors such as phosgene Manufactured by condensation polymerization, colorless odorless, slow oxidation and stable at room temperature, hypoallergenic insulator, used in electrical, electronics, automotive, machinery, medical, cosmetics, lubricants, adhesives, gaskets, molded artificial aids, Patent Publication No. 10-2002-0016922 (published Mar. 06, 2002) discloses polyorganosiloxanes that are endblocked with trimethylsilyl useful as hydrogel contact lens materials.
  • copolycarbonate resins have recently been copolymerized with aromatic diols of two or more different structures in order to be applied to a wider variety of fields, thereby introducing different structural units into the main chain of polycarbonate.
  • Many studies have been attempted to obtain desired physical properties. In particular, research into introducing a polysiloxane structure into the main chain of polycarbonate has been conducted, but most of the technologies have high production costs, and if the chemical resistance, the laminar strength, especially the low temperature laminar strength increases, the transparency decreases, and the transparency is improved.
  • the present inventors have diligently studied the copolycarbonate with improved hardness and chemical resistance, and thus, include alkylene or isosorbide in the polyorganosiloxane structure used as a monomer of the copolycarbonate, as described below.
  • the present invention was completed by confirming that the inherent physical properties of H can improve hardness and chemical resistance at the same time.
  • the present invention is to provide a novel polyorganosiloxane and a method for producing the same, which can produce copolycarbonate with improved hardness and chemical resistance.
  • the present invention is to provide a copolycarbonate prepared using the polyorganosiloxane and a method for producing the same.
  • the present invention is to manufacture a molded article and a method for producing the same produced with the codley carbonate.
  • the present invention provides a polyorganosiloxane represented by the following formula (1).
  • Ri to R4 are each independently hydrogen; Unsubstituted or oxiranyl group, a d- 10 alkoxy substituted by oxiranyl group, or a C 6 - 15 alkyl substituted with a d- 20 aryl; halogen; Cwo alkoxy; Allyl; (10 halo-alkyl, C 6 - 20 aryl, and,
  • 3 ⁇ 4 is each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d-6
  • Each X is independently selected from -C0-, -C0- or - a (C 6 arylene 10) -CO-,
  • Y is independently alkylene
  • Z are each independently a bond, or -C00-,
  • L is d- 10 alkylene, or * ego,
  • n is each independently an integer of 1 to 99.
  • the polyorganosiloxane represented by the formula (1) is used as a monomer of the copolycarbonate, as will be described later, by the structure (L) derived from alkylene or isosorbide contained in the structure of the copolycarbonate It is characterized by improving hardness and chemical resistance while maintaining duct ili ty.
  • R4 are each independently hydrogen, methyl, ethyl, Propyl 3—phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ecoxy, propoxy, allyl, 2, 2,2-tri Fluoroethyl, 3, 3, 3—trifluoropropyl, phenyl, or naphthyl.
  • R 5 is hydrogen or C 1 alkoxy, more preferably hydrogen or methoxy.
  • X is -co- or -CO- (phenylene) -CO-.
  • Y is alkylene, more preferably propylene, butylene, isobutylene, pentylene, isopentylene or neopentylene.
  • Z is • If the C00-, carbonyl group of Z is preferred to combine a benzene ring 0.
  • L is a C 5 - 9 straight chain alkylene, or *
  • L is C 8 straight chain alkylene.
  • the polyorganosiloxane represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2:
  • n is as defined above.
  • n is as defined above. Also, preferably the weight average molecular weight of the polyorganosiloxane is
  • n is 1 to 99, more preferably 20 to 50.
  • the present invention provides a method for producing a polyorganosiloxane represented by the formula (1) as shown in Scheme 1 below.
  • Ri to R 5 , X, Y, Z, L and n are represented by the formula As defined in 1, Rio is hydroxy or halogen, preferably hydroxy or chloro.
  • the reaction is a step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula A with the compound represented by Chemical Formula B.
  • the molar ratio of the compound represented by Formula A and the compound represented by Formula B is preferably 2: 1 to 3: 1.
  • the present invention provides a weight average molecular weight of 1,000 to 100, 000 g / mol copolycarbonate comprising a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3).
  • To 3 ⁇ 4 are each independently hydrogen, dK) alkyl, d- 10 alkoxy, or halogen,
  • 3 ⁇ 4 is unsubstituted or substituted with d- 10 alkylene, unsubstituted or Cwo alkyl, substituted phenyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO.
  • R 6 to 3 ⁇ 4 are each independently hydrogen, methyl, chloro, or bromo.
  • 3 ⁇ 4 is straight or branched chain alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2, 2-diyl butane-2, 2 -Diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene.
  • 3 ⁇ 4 nucleic acid is a cycloalkyl-1, 1-diyl, 0, S, SO, S0 2 or CO l.
  • the copolycarbonate is prepared by polymerizing a polyorganosiloxane, an aromatic diol compound, and a carbonate precursor represented by Formula 1, and as described above, alkylene or isosorb in the polyorganosiloxane represented by Formula 1
  • the bead-derived structure allows the duct ili ty to be maintained while improving hardness and chemical resistance.
  • the aromatic diol compound corresponds to the compound represented by Formula 4 below.
  • aromatic diol compound examples include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide bis (4- Hydroxyphenyl) sulfide bis (4-hydroxyphenyl) ketone, 1, 1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2, 2 Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid (bisphenol Z), 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, 2, 2-bis (4-hydroxy-3-methylphenyl)
  • the aromatic diol compound is 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A).
  • the carbonate precursor serves to connect the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 4, and specific examples thereof include phosgene, triphosgene, diphosgene, ⁇ lomophosgene, dimethyl carbonate, diethyl carbonate, di Butyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate or bishaloformate.
  • the carbonate precursor is phosgene.
  • the present invention provides a method for producing the copolycarbonate comprising the step of polymerizing a polyorganosiloxane, an aromatic diol compound and a carbonate precursor represented by the formula (1).
  • the aromatic diol compound and the carbonate precursor may be used in an amount of 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight, respectively, relative to 100 parts by weight of the polyorganosiloxane represented by Formula 1.
  • the polymerization is preferably carried out by interfacial polymerization and interfacial polymerization and pressure during the 'possible polymerization at low temperature, and it is easy to control molecular weight.
  • the polymerization temperature is 0 ° C to 40 ° C, the reaction time is preferably 10 minutes to 5 hours. In addition, pH of reaction should be kept at 9 or more or 11 or more. desirable.
  • polymerization if it is a solvent used for superposition
  • the polymerization is preferably carried out in the presence of an acid binder, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.
  • Alkylphenol may be used as the molecular weight regulator, and specific examples thereof include p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, doco Silphenol or triacontylphenol.
  • the molecular weight regulator may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization.
  • the molecular weight modifier may be, for example, 0.01 part by weight, 0, 1 part by weight, or 1 part by weight, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound.
  • the desired molecular weight can be obtained within this range.
  • reaction agents such as triethylamine, tetra-n-butylammonium bromide, tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds Can be used additionally.
  • the present invention provides a molded article made of the copolycarbonate.
  • the duct ili ty of the copolycarbonate is maintained by the structure derived from alkylene or isosorbide in the polyorganosiloxane represented by Chemical Formula 1, As the chemical resistance is increased, the field is wider than the molded articles made of copolycarbonate.
  • the molded article is selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments and dyes, if necessary, in addition to copolycarbonates according to the present invention.
  • the copolycarbonate and other additives according to the present invention are well mixed by using a mixer, and then extruded into an extruder to produce pellets, and the pellets are dried and then injected into an injection molding machine. It can include steps.
  • novel pylorganosiloxane according to the present invention can be used as a monomer of the copolycarbonate, and by the alkylene or isosorbide-derived structure included in the structure thereof, the hardness and The chemical resistance can be improved.
  • FIG. 1 shows NMR data of a polyorganosiloxane according to an embodiment of the present invention.
  • Isosorbide hereinafter referred to as ISB
  • methylene chloride 50 g was added to a 1000 mL equilibrium flask reactor capable of reflux
  • 80 g of triethylamine was added thereto.
  • 65 g of triphenylphosgene was added and reacted at room temperature for 10 minutes to 3 hours.
  • Fi lter The triethylamine salt was removed, and then 100 g of AP-PDMS prepared in Preparation Example 1 was added thereto. Workup with sodium bicarbonate, washing with distilled water, and adjusting the pH to neutral and overnight under reduced pressure to prepare a compound represented by the formula (1-1).
  • Copolycarbonate was prepared by the same method as Example 1, except that Compound 14 (14 g) represented by Chemical Formula 1-2 prepared in Preparation Example 3 was used.
  • Example 3
  • Copolycarbonate was prepared by the same method as Example 1, but using 3.94 g of a compound represented by Formula 1-2 prepared in Preparation Example 3.
  • Example 4
  • Copolycarbonate was prepared by the same method as Example 1, but using 1.31 g of the compound represented by Formula 1-2 prepared in Preparation Example 3.
  • Example 5
  • Copolycarbonate was prepared by the same method as Example 1, except that 6.57 g of the compound represented by Chemical Formula 1-1 prepared in Preparation Example 2 was used. Comparative example
  • the weight average molecular weight was measured by GPC using PC standard (Standard) using Agi lent 1200 ser ies. Further, 0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3, 5), relative to 1 part by weight of each copolycarbonate prepared in Examples and Comparative Examples.
  • a specimen was prepared by injection molding at a cylinder temperature of 300 ° C. and a mold temperature of 90 ° C. using a JSW Co., Ltd. N—20C injection molding machine. Using this, physical properties were measured as follows.
  • Pencil Hardness The extruded pellets were made of 10X 10 specimens using a heat ing press, and then the specimens were drawn with a pencil hardness tester (500 g) and visually checked.
  • Tg Glass transition temperature

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un nouveau polyorganosiloxane capable de produire des copolycarbonates ayant une dureté améliorée et un copolycarbonate préparé au moyen de celui-ci. Le nouveau polyorganosiloxane selon la présente invention peut être utilisé en tant que monomère de copolycarbonate et peut améliorer la dureté tout en maintenant les propriétés physiques inhérentes du copolycarbonate au moyen d'une structure dérivée d'une structure d'alkylène ou d'isosorbide compris dans la structure de celui-ci.
PCT/KR2016/015339 2016-01-07 2016-12-27 Nouveau polyorganosiloxane et copolycarbonate préparé au moyen de celui-ci WO2017119657A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16884040.3A EP3401352B1 (fr) 2016-01-07 2016-12-27 Nouveau polyorganosiloxane et copolycarbonate préparé au moyen de celui-ci
PL16884040T PL3401352T3 (pl) 2016-01-07 2016-12-27 Nowy poliorganosiloksan i kopoliwęglan wytwarzany z jego wykorzystaniem
CN201680010960.3A CN107250218B (zh) 2016-01-07 2016-12-27 聚有机硅氧烷以及使用其制备的共聚碳酸酯
US15/546,217 US10465045B2 (en) 2016-01-07 2016-12-27 Polyorganosiloxane and copolycarbonate prepared by using the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160002245 2016-01-07
KR10-2016-0002245 2016-01-07
KR1020160179495A KR101831886B1 (ko) 2016-01-07 2016-12-26 신규한 폴리오르가노실록산, 및 이를 사용하여 제조되는 코폴리카보네이트
KR10-2016-0179495 2016-12-26

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932677A (en) 1993-05-27 1999-08-03 General Electric Company Terpolymer having aromatic polyester, polysiloxane and polycarbonate segments
JP3195848B2 (ja) 1993-03-16 2001-08-06 出光興産株式会社 ポリカーボネート共重合体の製造方法
KR20020016922A (ko) 1999-07-27 2002-03-06 로버트 비. 스틸레스 콘택트 렌즈 재료
KR20070012499A (ko) * 2004-05-20 2007-01-25 이데미쓰 고산 가부시키가이샤 폴리카보네이트 수지 및 이를 이용한 전자사진 감광체
WO2011122767A2 (fr) * 2010-03-29 2011-10-06 주식회사 삼양사 Siloxane à terminaison hydroxy, copolymère polysiloxane-polycarbonate, et leurs méthodes de synthèse
WO2013066002A1 (fr) * 2011-10-31 2013-05-10 Samyang Corporation Copolymère de polysiloxane et de polycarbonate, et procédé de fabrication correspondant
KR20140145161A (ko) * 2012-03-23 2014-12-22 다케오 구루시마 배기 가스의 처리 방법
KR20150119823A (ko) * 2014-04-16 2015-10-26 주식회사 엘지화학 신규한 폴리오르가노실록산, 이를 포함하는 코폴리카보네이트 수지 및 이의 성형품

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3195848B2 (ja) 1993-03-16 2001-08-06 出光興産株式会社 ポリカーボネート共重合体の製造方法
US5932677A (en) 1993-05-27 1999-08-03 General Electric Company Terpolymer having aromatic polyester, polysiloxane and polycarbonate segments
KR20020016922A (ko) 1999-07-27 2002-03-06 로버트 비. 스틸레스 콘택트 렌즈 재료
KR20070012499A (ko) * 2004-05-20 2007-01-25 이데미쓰 고산 가부시키가이샤 폴리카보네이트 수지 및 이를 이용한 전자사진 감광체
WO2011122767A2 (fr) * 2010-03-29 2011-10-06 주식회사 삼양사 Siloxane à terminaison hydroxy, copolymère polysiloxane-polycarbonate, et leurs méthodes de synthèse
WO2013066002A1 (fr) * 2011-10-31 2013-05-10 Samyang Corporation Copolymère de polysiloxane et de polycarbonate, et procédé de fabrication correspondant
KR20140145161A (ko) * 2012-03-23 2014-12-22 다케오 구루시마 배기 가스의 처리 방법
KR20150119823A (ko) * 2014-04-16 2015-10-26 주식회사 엘지화학 신규한 폴리오르가노실록산, 이를 포함하는 코폴리카보네이트 수지 및 이의 성형품

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