WO2020060148A1 - Copolymère de polysiloxane-polycarbonate ayant une résistance aux chocs, une résistance à la flamme et une transparence élevées, et son procédé de préparation - Google Patents

Copolymère de polysiloxane-polycarbonate ayant une résistance aux chocs, une résistance à la flamme et une transparence élevées, et son procédé de préparation Download PDF

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Publication number
WO2020060148A1
WO2020060148A1 PCT/KR2019/011986 KR2019011986W WO2020060148A1 WO 2020060148 A1 WO2020060148 A1 WO 2020060148A1 KR 2019011986 W KR2019011986 W KR 2019011986W WO 2020060148 A1 WO2020060148 A1 WO 2020060148A1
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polysiloxane
formula
group
carbon atoms
polycarbonate
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PCT/KR2019/011986
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English (en)
Korean (ko)
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김지은
신경무
이재훈
허성현
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주식회사 삼양사
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Publication of WO2020060148A1 publication Critical patent/WO2020060148A1/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
    • C08G64/18—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
    • 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
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to a polysiloxane-polycarbonate copolymer having improved impact resistance, flame retardancy, and transparency, and more particularly, a branched polysiloxane having a specific structure, a linear polysiloxane having a specific structure, and a polycarbonate block as repeat units It relates to a polysiloxane-polycarbonate copolymer having excellent flame retardancy and transparency while improving mechanical strength such as impact resistance, and a method for manufacturing the same.
  • Polycarbonate resins are widely used as electrical parts, mechanical parts and industrial resins because of their excellent heat resistance, mechanical properties (especially impact strength) and transparency. Particularly, when polycarbonate resin is used as a TV housing, computer monitor housing, copier, printer, notebook battery, lithium battery case material, etc., in which heat is dissipated in the electric and electronic field, excellent flame retardancy as well as heat resistance and mechanical properties are required. .
  • the most common method used to impart flame retardancy to a polycarbonate resin is to mix a halogen flame retardant bromine or chlorine compound with the polycarbonate resin.
  • a halogen flame retardant when used, the function of flame retardant is sufficiently exhibited in the event of a fire, but hydrogen halide gas is generated during resin processing, which causes mold corrosion and environmental pollution, and also produces dioxin, a toxic gas harmful to the human body during combustion.
  • the use regulation movement is expanding.
  • a flame retardant polycarbonate resin composition using a fluorinated polyolefin-based resin simultaneously as an alkali metal salt and an anti-dripping agent as a non-halogen flame retardant has been developed.
  • the present invention is to solve the problems of the prior art as described above, as well as excellent flame retardancy, and provides a polysiloxane-polycarbonate copolymer excellent in impact resistance and transparency as well as a technical problem.
  • the present invention to solve the above technical problem, the polysiloxane of formula 1; Polysiloxanes other than the polysiloxane of Formula 1; And it provides a polysiloxane-polycarbonate copolymer comprising a polycarbonate block as a repeating unit:
  • R 1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group
  • R 2 independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms
  • R 3 independently represents an alkylene group having 2 to 8 carbon atoms
  • R 4 independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
  • k independently represents an integer from 1 to 4,
  • l, m and n each independently represent an integer of 0 to 4, provided that at least one of l, m and n is not 0,
  • x and y each independently represent an integer from 0 to 100.
  • the present invention also comprises the steps of forming a polysiloxane-polycarbonate intermediate by reacting polysiloxane of Formula 1, polysiloxane other than polysiloxane of Formula 1, and oligomeric polycarbonate under interface reaction conditions; And it provides a method for producing a polysiloxane-polycarbonate copolymer comprising the step of polymerizing the intermediate using a first polymerization catalyst:
  • R 1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group
  • R 2 independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms
  • R 3 independently represents an alkylene group having 2 to 8 carbon atoms
  • R 4 independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
  • k independently represents an integer from 1 to 4,
  • l, m and n each independently represent an integer of 0 to 4, provided that at least one of l, m and n is not 0,
  • x and y each independently represent an integer from 0 to 100.
  • the present invention also provides a molded article manufactured using the polysiloxane-polycarbonate copolymer according to the present invention to solve the above technical problem.
  • the polysiloxane-polycarbonate copolymer according to the present invention can dramatically improve flame retardancy without the addition of a flame retardant, and at the same time, it is possible to maintain excellent properties of polycarbonate, such as impact resistance and transparency, an area in need of flame retardancy, for example For example, it can be variously applied to construction materials, automobile parts, office equipment, and housings for electric / electronic products.
  • reaction product refers to a substance formed by the reaction of two or more reactants.
  • first, second, and the like are used to describe a polymerization catalyst, but the polymerization catalyst is not limited by these terms. These terms are only used to distinguish the polymerization catalysts from each other.
  • the first polymerization catalyst and the second polymerization catalyst may be the same type of catalyst or different types of catalyst.
  • the English letter "R” used to represent hydrogen, halogen atoms, and / or hydrocarbon groups, etc. in the formulas described herein has a subscript represented by a number, but the “R” is a subscript. It is not limited by.
  • the “R” s independently of each other represent hydrogen, halogen atoms and / or hydrocarbon groups. For example, regardless of whether two or more "R” s have the same or different numbers of subscripts, these "Rs" may represent the same hydrocarbon group or different hydrocarbon groups.
  • the present invention is a polysiloxane of the formula (1); Polysiloxane of the following formula (2); And a polysiloxane-polycarbonate copolymer comprising a polycarbonate block as a repeating unit.
  • the polysiloxane-polycarbonate copolymer according to the present invention includes a polysiloxane of formula 1 as a repeating unit.
  • the polysiloxane represented by the following Chemical Formula 1 is a compound in which siloxanes including a siloxane having a hydroxyphenyl group are linked to a side chain.
  • R 1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group
  • R 2 independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms
  • R 3 independently represents an alkylene group having 2 to 8 carbon atoms
  • R 4 independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
  • k independently represents an integer from 1 to 4,
  • l, m and n each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, provided that at least one of l, m and n is not 0,
  • x and y each independently represent an integer from 0 to 100, preferably an integer from 0 to 50, more preferably an integer from 0 to 10, Or it may represent an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 2 to 10.
  • the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group or an alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, and 6 to 10 carbon atoms. It may be an aryloxy group, an aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.
  • the alkyl group can be methyl, ethyl or propyl;
  • the alkylene group may be ethylene or propylene;
  • the halogen atom may be Cl or Br;
  • the alkoxy group can be methoxy, ethoxy or propoxy;
  • the aryl group may be phenyl, chlorophenyl or tolyl (preferably phenyl).
  • the polysiloxane of Formula 1 may be a reaction product of a polysiloxane of Formula 4 and a compound of Formula 5 below.
  • R 1 , R 2 , l, m, n, x and y are as defined in Formula 1 above.
  • R 4 and k are the same as defined in Chemical Formula 1, and h represents an integer of 1 to 7.
  • the molar ratio of the compound of Formula 4 to the compound of Formula 5 used for preparing the polysiloxane of Formula 1 is preferably maintained in the range of 1: 4 to 1: 1, and maintained in the range of 1: 3 to 1: 2. It is more preferable. If the molar ratio of the compound of Formula 4 to the compound of Formula 5 is outside the above range, it may affect the degree of polymerization of polysiloxane and polycarbonate, which may be a factor of deterioration in flame retardancy and transparency.
  • the polysiloxane-polycarbonate copolymer according to the present invention includes a polysiloxane other than the polysiloxane of Formula 1 as a repeating unit, and specifically includes the polysiloxane of Formula 2 below.
  • the polysiloxane represented by the following Chemical Formula 2 is a hydroxy terminal siloxane compound having a hydroxyl group at the terminal.
  • R 5 independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
  • R 6 independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms
  • R 7 independently represents an alkylene group having 2 to 8 carbon atoms
  • A is X or NH-X-NH, where X is a linear or branched aliphatic group having 1 to 20 carbon atoms; A cycloalkylene group having 3 to 20 carbon atoms; Or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,
  • n independently represents an integer from 0 to 10, preferably an integer from 0 to 4,
  • n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100.
  • the halogen atom may be Cl or Br;
  • the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl;
  • the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy or propoxy;
  • the aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl;
  • the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, 3 to 3 carbon atoms.
  • X is, for example, an aliphatic group having 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, an aliphatic group having 1 to 20 carbon atoms containing oxygen, nitrogen or sulfur atoms in the main chain, and 3 to 3 carbon atoms. It may be a cycloalkylene group of 6, or an arylene group that may be derived from bisphenol A, lesocinol, hydroquinone or diphenylphenol, and may be represented by the following formulas Aa to Ah.
  • the hydroxy-terminated siloxane of Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Formula 2a and an acyl compound (ie, a hydroxy-terminated siloxane having an ester bond).
  • R 5 , R 6 , R 7 , m and n are as defined in Formula 2 above.
  • the hydroxy-terminated siloxane of Formula 2a is synthesized by, for example, a molar ratio of 2: 1 using a platinum catalyst and a compound of Formula 2b containing a hydroxy group and a double bond and a compound of Formula 2c containing silicon. Can be manufactured.
  • R 5 and m are the same as defined in Formula 2 above, and k represents an integer of 1 to 7.
  • R 6 and n are as defined in Formula 2 above.
  • the acyl compound used in the preparation of the hydroxy-terminated siloxane of Chemical Formula 2 may have, for example, an aromatic, aliphatic or mixed structure containing both aromatic and aliphatic.
  • the acyl compound may have 6 to 30 carbon atoms, and aliphatic may have 1 to 20 carbon atoms.
  • the acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.
  • the hydroxy-terminated siloxane of Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Formula 2a and a diisocyanate compound (ie, a hydroxy-terminated siloxane having a urethane bond).
  • the diisocyanate compound is, for example, 1,4-phenylenediisocyanate (1,4-phenylenediisocyanate), 1,3-phenylenediisocyanate (1,3-phenylenediisocyanate) or 4,4'- methylenediphenyl di It may be an isocyanate (4,4'-methylenediphenyl diisocyanate).
  • the polysiloxane-polycarbonate copolymer according to the present invention is a polysiloxane of Formula 1 (ie, a polysiloxane block having a hydroxyphenyl group on the side chain) and a polysiloxane other than the polysiloxane of Formula 1 (ie, a polysiloxane of Formula 2, with a hydroxyl group at the terminal)
  • Polysiloxane block having a) comprises a polycarbonate block of the formula (3) to be described later as a repeating unit.
  • R 8 is an alkyl group (eg, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 6 carbon atoms), an alkenyl group (eg, Alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 13 carbon atoms, alkoxy groups (eg, alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms), halogen atoms (eg Cl or Br) or nitro It represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • the aromatic hydrocarbon group may be derived from, for example, a compound of Formula 6 below.
  • X is a straight, branched or cyclic alkylene group having no functional group; Or a linear, branched or cyclic alkylene group including at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl (for example, a linear alkylene group having 1 to 10 carbon atoms, A branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms),
  • R 9 and R 10 are each independently a halogen atom (eg, Cl or Br), or a straight, branched or cyclic alkyl group (eg, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a carbon number) 3 to 10 cyclic alkyl group),
  • a halogen atom eg, Cl or Br
  • a straight, branched or cyclic alkyl group eg, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a carbon number
  • p and q each independently represent the integer of 0-4.
  • the compound of Formula 6 is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4- Hydroxyphenyl)-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl- 1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10 -Bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pen
  • dihydric phenol examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
  • Other functional dihydric phenols may refer to U.S. Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the divalent phenols alone or in combination of two or more. Can be used.
  • a carbonate precursor for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate may be used.
  • the content of the polysiloxane of Formula 1 in the polysiloxane-polycarbonate copolymer of the present invention is 0.5 to 20% by weight relative to the total weight of the copolymer, preferably 1 to 20% by weight, more preferably 3 It may be from 15 to 15% by weight.
  • the content of the polysiloxane of Formula 1 is less than 0.5% by weight, flame retardancy may be poor, and when the content of the polysiloxane of Formula 1 exceeds 20% by weight, transparency and processability may be deteriorated.
  • the content of the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) in the polysiloxane-polycarbonate copolymer of the present invention is preferably 0.5 to 20% by weight based on the total weight of the copolymer, preferably May be 1 to 20% by weight, more preferably 2 to 15% by weight.
  • polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 0.5% by weight, impact resistance may be poor, and polysiloxanes other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) When the content of) exceeds 20% by weight, transparency may be deteriorated.
  • the total content of the polysiloxane of Formula 1 and polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) in the polysiloxane-polycarbonate copolymer of the present invention is 1 based on the total weight of the copolymer. To 25% by weight, preferably 3 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 5 to 15% by weight.
  • the weight ratio of the polysiloxane of Formula 1 and the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) included in the polysiloxane-polycarbonate copolymer of the present invention as a repeating unit is 1: 9. To 9: 1, preferably 1: 8 to 8: 1, more preferably 2: 7 to 7: 2, even more preferably 2: 7 to 6: 3, most preferably 4: 5 to 5 : 4.
  • the content of the polycarbonate block in the polysiloxane-polycarbonate copolymer of the present invention is 75 to 99% by weight, preferably 80 to 97% by weight, more preferably 80 to 95% based on the total weight of the copolymer. Weight percent, even more preferably 85 to 95 weight percent.
  • the content of the polycarbonate block is less than 75% by weight, transparency and processability may be deteriorated, and when the content of the polycarbonate block exceeds 99% by weight, flame retardancy and impact resistance may be deteriorated.
  • the viscosity average molecular weight (M V ) of the polysiloxane-polycarbonate copolymer according to the present invention may be 15,000 to 200,000, more preferably 15,000 to 100,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is less than 15,000, mechanical properties may be remarkably deteriorated, and if it exceeds 200,000, a problem in processing of the resin may occur due to an increase in melt viscosity.
  • the present invention also relates to a method for preparing the aforementioned polysiloxane-polycarbonate copolymer.
  • the method for producing a polysiloxane-polycarbonate copolymer according to the present invention includes polysiloxane of Formula 1, polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) and oligomeric polycarbonate in an aqueous alkali solution. And forming a polysiloxane-polycarbonate intermediate by reacting under an interface reaction condition consisting of an organic phase. And polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst.
  • the step of forming the polysiloxane-polycarbonate intermediate comprises the polysiloxane mixture content and the oligomeric polycarbonate content of the polysiloxane of Formula 1 and polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2).
  • the polysiloxane mixture content of the polysiloxane of Formula 1 and the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 1% by weight, flame retardancy and / or impact resistance may be poor, and the polysiloxane of Formula 1 and Formula
  • the content of the polysiloxane (specifically, the polysiloxane of Formula 2) other than the polysiloxane of 1 is more than 25% by weight, processability and transparency may be deteriorated.
  • the oligomeric polycarbonate used in the preparation of the polysiloxane-polycarbonate copolymer according to the present invention may be an oligomeric polycarbonate having a viscosity average molecular weight of 800 to 20,000, preferably 1,000 to 15,000. If the viscosity average molecular weight of the polycarbonate is less than 800, the molecular weight distribution may be broadened and the physical properties may be deteriorated, and if it exceeds 20,000, the reactivity may be reduced.
  • the oligomeric polycarbonate may be prepared by adding the above-described divalent phenol compounds to an aqueous alkali solution to make a phenol salt state, and then reacting the salt phenols with dichloromethane injected with phosgene gas.
  • phosgene divalent phenolic compounds
  • the molar ratio of phosgene to the divalent phenolic compound is less than 1, reactivity may be lowered, and if the molar ratio of phosgene to the divalent phenolic compound exceeds 1.5, processability may be caused by excessive molecular weight increase.
  • the polycarbonate oligomer forming reaction may be generally performed at a temperature in the range of about 15 to 60 ° C, and alkali metal hydroxide (eg, sodium hydroxide) may be used to adjust the pH of the reaction mixture.
  • alkali metal hydroxide eg, sodium hydroxide
  • the step of forming the polysiloxane-polycarbonate intermediate includes polysiloxane of Formula 1, polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2), and oligomeric polycarbonate. It includes the step of forming a mixture, the mixture may be one comprising a phase change catalyst, a molecular weight modifier and a second polymerization catalyst.
  • the step of forming the polysiloxane-polycarbonate intermediate includes polysiloxane of Formula 1, polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2), and oligomeric polycarbonate. Forming a mixture to be made; And extracting the organic phase from the resulting mixture after the reaction of the polysiloxane of Formula 1, the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) and the oligomeric polycarbonate is completed, and the polysiloxane -Polymerizing the polycarbonate intermediate may include providing a first polymerization catalyst to the extracted organic phase.
  • the polysiloxane-polycarbonate copolymer according to the present invention is a polysiloxane (polysiloxane of formula 2) other than the polysiloxane of formula 1 and polysiloxane of formula 1 described above to the organic phase-aqueous mixture containing polycarbonate It can be prepared by adding and adding the molecular weight modifier and catalyst step by step.
  • a monofunctional compound similar to a monomer used in polycarbonate production may be used.
  • Monofunctional materials include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, and p-isononyl Phenol-based derivatives such as phenol; Or it may be an aliphatic alcohol.
  • PTBP p-tert-butylphenol
  • PTBP p-tert-butylphenol
  • a polymerization catalyst and / or a phase transfer catalyst may be used.
  • the polymerization catalyst for example, triethylamine (TEA) may be used
  • the phase transfer catalyst for example, a compound represented by Chemical Formula 7 may be used.
  • R 11 represents an alkyl group having 1 to 10 carbon atoms
  • Q represents nitrogen or phosphorus
  • X represents a halogen atom or -OR 12
  • R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
  • the phase transfer catalyst is, for example, [CH 3 (CH 2 ) 3 ] 4 NX, [CH 3 (CH 2 ) 3 ] 4 PX, [CH 3 (CH 2 ) 5 ] 4 NX, [CH 3 ( CH 2 ) 6 ] 4 NX, [CH 3 (CH 2 ) 4 ] 4 NX, CH 3 [CH 3 (CH 2 ) 3 ] 3 NX or CH 3 [CH 3 (CH 2 ) 2 ] 3 NX .
  • X represents Cl, Br or -OR 12 , where R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • the content of the phase transfer catalyst is preferably about 0.01 to 10% by weight based on the total weight of the mixture of the polysiloxane of Formula 1, polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) and the oligomeric polycarbonate. Do. If the content is less than 0.01% by weight, reactivity may be deteriorated, and when the content exceeds 10% by weight, precipitation as a precipitate or transparency may be deteriorated.
  • a polysiloxane-polycarbonate copolymer can be prepared and then the organic phase dispersed in methylene chloride is alkali washed and separated. Subsequently, the organic phase may be washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2-3 times. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride may be constantly adjusted to granulate using a certain amount of pure water in the range of 70 to 80 ° C. If the temperature of the pure water is less than 70 ° C, the assembly speed becomes slow and the assembly time can be very long.
  • the temperature of the pure water exceeds 80 ° C, it may be difficult to obtain a polycarbonate shape with a certain size.
  • the present invention also relates to a molded article produced using the polysiloxane-polycarbonate copolymer of the present invention.
  • the method for manufacturing a molded article using the polysiloxane-polycarbonate copolymer of the present invention is not particularly limited, and a method (for example, an extrusion process or an injection process, etc.) generally used for manufacturing a resin molded article is modified as it is or appropriately Can be used.
  • the molded article according to the present invention can be variously applied to fields that require flame retardancy, for example, variously applied to construction materials, automotive parts, office equipment, and parts (housing) of electrical / electronic products, etc. It does not work.
  • a 500 mL 3-neck flask was equipped with a condenser, and under nitrogen atmosphere, 50.44 g (0.1 mole) of polysiloxane (F5032, Damipoly Chem, colorless transparent liquid, viscosity: 5 cP) corresponding to Formula 4 was dissolved in 50 ml of toluene, and then platinum ( Pt) 0.008 g (100 ppm) of a catalyst (CP101 from Damipolychem) was added. While heating the solution, 2-allylphenol (2-allylphenol) 26.8g (0.2mole) was slowly added for 1 hour and refluxed for 5 hours. After removing the solvent toluene of the solution after reaction, the polysiloxane of Formula 8 was prepared by drying in a vacuum oven for 24 hours.
  • polysiloxane F5032, Damipoly Chem, colorless transparent liquid, viscosity: 5 cP
  • a 500 mL three-neck flask was equipped with a condenser, and under nitrogen atmosphere, 49.04 g (0.1 mole) of polysiloxane corresponding to Formula 4 (F5032 manufactured by Dami Polychem, colorless transparent liquid, viscosity: 5 cP) was dissolved in 50 ml of toluene, and then platinum ( Pt) 0.008 g (100 ppm) of a catalyst (CP101 from Damipolychem) was added. While the solution was heated, 40.2 g (0.3 mole) of 2-allylphenol was slowly added for 1 hour and refluxed for 5 hours. After removing the solvent toluene of the solution after the reaction, a polysiloxane of Formula 9 was prepared by drying in a vacuum oven for 24 hours.
  • a condenser was attached to a 500 mL 3-neck flask, and 0.4 mol of Dow Corning's monomer BY16-799 was dissolved in 300 mL of chloroform under a nitrogen atmosphere, and then 67 mL of a triethylamine (TEA) catalyst was added. After refluxing the solution, 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform, and then slowly added for 1 hour and refluxed for 12 hours. After the reaction solution was removed, the solvent was dissolved in acetone and washed with hot distilled water. By drying in a vacuum oven for 24 hours, a hydroxy-terminated siloxane having an ester bond of Formula 10 was prepared.
  • TCA triethylamine
  • An oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000 was prepared by interfacial reaction of bisphenol A and phosgene gas in an aqueous solution in the presence of methylene chloride.
  • the organic phase is collected from the obtained oligomeric polycarbonate mixture, and a sodium hydroxide aqueous solution, branched polysiloxane of formula 8 prepared in Preparation Example 1 (8% by weight based on the total weight of the copolymer), the preparation example Linear polysiloxane of formula 10 prepared in 3 (amount of 1% by weight relative to the total weight of the copolymer), tetrabutylammonium chloride (tetrabutyl ammonium chloride, TBACl, 0.1% by weight based on the total weight of the copolymer), methylene chloride and p-tert-butylphenol (PTBP, an amount of 0.4% by weight based on the total weight of the copolymer) was mixed and
  • the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2-3 times. After the washing was completed, the organic phase was assembled using 76% of pure water. After the assembly was completed, it was first dried at 110 ° C for 8 hours, and secondly dried at 120 ° C for 10 hours.
  • the physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 7% by weight, and the content of the linear polysiloxane of Formula 10 was changed from 1% to 2% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 6% by weight, and the content of the linear polysiloxane of Formula 10 was changed from 1% to 3% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 5% by weight, and the content of linear polysiloxane of Formula 10 was changed from 1% to 4% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 4% by weight, and the content of the linear polysiloxane of Formula 10 was changed from 1% to 5% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 3% by weight, and the content of linear polysiloxane of Formula 10 was changed from 1% to 6% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 2% by weight, and the content of the linear polysiloxane of Formula 10 was changed from 1% to 7% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • Example 2 The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8% to 1% by weight, and the content of the linear polysiloxane of Formula 10 was changed from 1% to 8% by weight.
  • a polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • the branched polysiloxane of Formula 8 prepared in Preparation Example 1 (8% by weight based on the total weight of the copolymer)
  • the branched polysiloxane of Formula 9 prepared in Preparation Example 2 (5% by weight based on the total weight of the copolymer) Used, and the polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the content of the linear polysiloxane of Formula 10 was changed from 1% by weight to 4% by weight.
  • the physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • the branched polysiloxane of Formula 9 prepared in Preparation Example 2 (4% by weight based on the total weight of the copolymer) was used. Used, and the polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the content of the linear polysiloxane of Formula 10 was changed from 1% by weight to 5% by weight.
  • the physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 1 below.
  • a linear polycarbonate having a viscosity average molecular weight of 70,000 was prepared in the same manner as in Example 1, except that polysiloxane was not used.
  • the physical properties of the prepared polycarbonate resin were measured and are shown in Table 2 below.
  • -A polycarbonate copolymer was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.
  • -A polycarbonate copolymer was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.
  • the polysiloxane-polycarbonate copolymers prepared in Examples 1 to 10 according to the present invention had excellent impact strength at a low impact strength of 30 (kg cm / cm) or higher, and a transmittance of at least 85%. As a result, the transparency was excellent, and the flame retardancy was also excellent.
  • Viscosity average molecular weight (M V ) The viscosity of the methylene chloride solution was measured at 20 ° C using a Ubbelohde Viscometer, from which the intrinsic viscosity [ ⁇ ] was calculated by the following equation.
  • (d) Flame retardancy It was measured by the UL-94 flame retardant test method, which is a method prescribed by Underwriter's Laboratories (UL) in the United States. This method is to evaluate the flame retardancy from the burning time or dripping property after attaching the burner's flame for 10 seconds to a specimen of fixed size vertically fixed. Combustion time is the length of time that the specimen continues to be flame-fired after the flame is distant away, and the flamming of the cotton by the drip is that the labeled cotton, about 300 mm below the bottom of the specimen, is flammed by the loading from the specimen. Determined by, the class of flame retardancy is divided according to Table 3 below.

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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

La présente invention concerne un copolymère de polysiloxane-polycarbonate ayant une résistance au choc, une résistance à la flamme et une transparence améliorées et son procédé de préparation et, plus spécifiquement, un copolymère de polysiloxane-polycarbonate qui comprend, en tant qu'unités de répétition, un polysiloxane ramifié, un polysiloxane linéaire, et un bloc de polycarbonate, et présente une haute résistance aux chocs ainsi qu'une excellente résistance à la flamme et une excellente transparence, et son procédé de préparation.
PCT/KR2019/011986 2018-09-19 2019-09-17 Copolymère de polysiloxane-polycarbonate ayant une résistance aux chocs, une résistance à la flamme et une transparence élevées, et son procédé de préparation WO2020060148A1 (fr)

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CN115850944B (zh) * 2022-12-21 2024-01-30 福建华塑新材料有限公司 一种高透光薄壁阻燃聚碳酸酯组合物及制备方法

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