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
  • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
• • 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
  • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polycarbonate sequences
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • 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
• • 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
• • 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 hydroxy groups

Definitions

• the present invention relates to branched polycarbonate-polysiloxane copolymers and methods for their preparation. More specifically, the present invention relates to a branched polycarbonate-polysiloxane copolymer excellent in workability according to low temperature impact resistance, chemical resistance, and high temperature fluidity, and a method of manufacturing the same.
• Polycarbonate is a polymer having excellent impact strength, resin stability, and optical properties, and is used as an exterior material for automobiles, automotive materials, building materials, optical lenses, and safety products that require transparency.
• Korean Patent Laid-Open Publication No. 2009-0035031 discloses that one wants to improve chemical resistance and flame retardant properties by copolymerizing a specific structure with polycarbonate.
• US Pat. No. 4,188,314 discloses moldings having improved chemical resistance, including polycarbonates and copolyesters. However, the molding could not obtain sufficient impact strength.
• U.S. Pat. No. 4,634,737 discloses resin compositions consisting of copolycarbonates having 25 to 90 mole percent ester bonds and copolyesters and olefin acrylate copolymers, while these compositions have improved chemical resistance, but have very high transparency. Lowers.
• Another technical attempt is to increase chemical resistance by introducing other polymers into the polycarbonate backbone.
• studies on polycarbonates including polysiloxane structures have been conducted, but most of them have increased chemical resistance and impact resistance, while decreasing transparency.
• All of the polycarbonates in which the other polymer is introduced into the main chain have a linear structure.
• Such linear polycarbonate resins have high impact resistance at room temperature, but have a characteristic of rapidly decreasing impact strength after coating or below -30 ° C. .
• the linear polycarbonate resin does not change in viscosity even when high shear stress is applied during extrusion. That is, in the case of blow molding, it is difficult to mold a product having a uniform thickness due to the low viscosity coefficient.
• One aspect of the invention relates to branched polycarbonate-polysiloxane copolymers.
• the branched polycarbonate-polysiloxane copolymer is obtained from an aromatic dihydroxy compound, a carbonate precursor, a siloxane compound, and a branching agent, and the siloxane compound is represented by Formula 2 below, It is characterized in that the compound, or a combination thereof:
• R 1 to R 8 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently substituted Or an unsubstituted C 1 -C 10 alkylene group, a substituted or unsubstituted C 6 -C 18 arylene group, a C 1 -C 10 alkylene group comprising oxygen or sulfur or a C 6 -C 18 comprising oxygen or sulfur
• Z is a substituted or unsubstituted C 1 -C 18 alkylene group, a substituted or unsubstituted C 6 -C 18 cycloalkylene group, or a substituted or unsubstituted C 6 -C 18 arylene group
• X and Y Are each independently a hydrogen atom, a halogen atom, a C 1 -C 18 alkoxy group, a C 1
• R 1 and R 2 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently substituted or unsubstituted A C 1 -C 10 alkylene group, a substituted or unsubstituted C 6 -C 18 arylene group, a C 1 -C 10 alkylene group containing oxygen or sulfur or a C 6 -C 18 arylene group containing oxygen or sulfur
• n is an integer from 4 to 100.
• the branching agent is characterized in that represented by the following formula (1):
• Y 1 is each independently a hydrogen atom, a halogen atom, a C 1 -C 18 alkoxy group, a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group
• m 1 is an integer of 3 to 4
• n 1 is an integer of 0 to 4
• R is a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group.
• the branched polycarbonate-polysiloxane copolymer may include from about 0.1 to about 5% by weight of units derived from the branching agent represented by the formula (1).
• the branched polycarbonate-polysiloxane copolymer may comprise from about 0.1 to about 20 weight percent of units derived from the siloxane compound.
• the branched polycarbonate-polysiloxane copolymer may have a Si content of about 0.3 to about 10% by weight relative to the total polycarbonate-polysiloxane copolymer.
• the branched polycarbonate-polysiloxane copolymer may have a branching degree of about 0.3 or more and less than about 1.0.
• the mark-hew constant of the branched polycarbonate-polysiloxane copolymer may be at least about 0.50 and less than about 0.65.
• Polycarbonate-polysiloxane copolymers according to another aspect of the present invention comprises a unit represented by the formula (2-1), a unit represented by the formula (3-1), or a combination thereof, the mark-Hink constant is about 0.50 And less than about 0.65:
• R 1 to R 8 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently Substituted or unsubstituted C 1 -C 10 alkylene group, substituted or unsubstituted C 6 -C 18 arylene group, C 1 -C 10 alkylene group including oxygen or sulfur or C 6 -containing oxygen or sulfur
• Z is a substituted or unsubstituted C 1 -C 18 alkylene group, a substituted or unsubstituted C 6 -C 18 cycloalkylene group, or a substituted or unsubstituted C 6 -C 18 arylene group
• X And Y are each independently a hydrogen atom, a halogen atom, a C 1 -C 18 alkoxy group, a C 1 -C 10 alky
• R 1 and R 2 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently substituted or Unsubstituted C 1 -C 10 alkylene group, substituted or unsubstituted C 6 -C 18 arylene group, C 1 -C 10 alkylene group comprising oxygen or sulfur or C 6 -C 18 aryl comprising oxygen or sulfur It is a rene group
• n is an integer of 4-100
• * is a polycarbonate unit coupling group.
• Another aspect of the invention relates to a process for the preparation of branched polycarbonate-polysiloxane copolymers.
• the preparation method comprises the steps of mixing an aromatic dihydroxy compound and the branching agent represented by the formula (1); And reacting the siloxane compound with a carbonate precursor solution by adding the mixture to the mixture, wherein the siloxane compound is a compound represented by Formula 2, a compound represented by Formula 3, or a combination thereof. .
• the present invention provides a branched polycarbonate-polysiloxane copolymer having excellent low temperature impact strength, high temperature fluidity, mechanical strength, chemical resistance, and the like, and a method of manufacturing the same.
• Branched polycarbonate-polysiloxane copolymers according to the present invention can be prepared by reacting aromatic dihydroxy compounds, carbonate precursors, siloxane compounds and branching agents.
• the branched polycarbonate-polysiloxane copolymer is a step of mixing an aromatic dihydroxy compound and a branching agent represented by the formula (1), and the reaction by adding a siloxane compound and a carbonate precursor solution to the mixture It may be prepared to include.
• the aromatic dihydroxy compound used in the present invention may be represented by the following formula (7).
• a 1 is a single bond, a substituted or unsubstituted C 1 -C 30 linear or branched alkylene group, a substituted or unsubstituted C 2 -C 5 alkenyl A cycloene group, a substituted or unsubstituted C 2 -C 5 alkylidene group, a substituted or unsubstituted C 1 -C 30 linear or branched haloalkylene group, a substituted or unsubstituted C 5 -C 6 cyclo Alkylene group, substituted or unsubstituted C 5 -C 6 cycloalkenylene group, substituted or unsubstituted C 5 -C 10 cycloalkylidene group, substituted or unsubstituted C 6 -C 30 arylene group, substituted Or an unsubstituted C 1 -C 20 linear or branched alkoxylene group, halogen acid ester group, carbonate ester group,
• substituted means that the hydrogen atom is a halogen group, C 1 -C 30 alkyl group, C 1 -C 30 haloalkyl group, C 6 -C 30 aryl group, C 1 -C 20 alkoxy group And a substituent selected from the group consisting of a combination thereof.
• the branching agent used in the present invention may be represented by the following formula (1).
• Y 1 is each independently a hydrogen atom, a halogen atom, a C 1 -C 18 alkoxy group, a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group
• m 1 is an integer of 3 to 4
• n 1 is an integer of 0 to 4
• R is a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group.
• the branched polycarbonate-polysiloxane copolymer may include about 0.1 to about 5 wt%, preferably about 0.5 to about 3 wt%, of units derived from the branching agent represented by Formula 1 above. It is possible to prevent the heterogeneous polymerization state due to the gelation and network structure in the above range, to optimize the branching of the branched polycarbonate-polysiloxane copolymer and to maintain a high impact.
• the siloxane compound used in the present invention may be a compound represented by Formula 2, a compound represented by Formula 3, or a combination thereof.
• R 1 to R 8 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently substituted Or an unsubstituted C 1 -C 10 alkylene group, a substituted or unsubstituted C 6 -C 18 arylene group, a C 1 -C 10 alkylene group comprising oxygen or sulfur or a C 6 -C 18 comprising oxygen or sulfur
• Z is a substituted or unsubstituted C 1 -C 18 alkylene group, a substituted or unsubstituted C 6 -C 18 cycloalkylene group, or a substituted or unsubstituted C 6 -C 18 arylene group
• X and Y Are each independently a hydrogen atom, a halogen atom, a C 1 -C 18 alkoxy group, a C 1
• R 1 and R 2 are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 18 aryl group
• a and B are each independently substituted or unsubstituted A C 1 -C 10 alkylene group, a substituted or unsubstituted C 6 -C 18 arylene group, a C 1 -C 10 alkylene group containing oxygen or sulfur or a C 6 -C 18 arylene group containing oxygen or sulfur and n is an integer of 4-100.
• the siloxane compound represented by Chemical Formula 2 may be prepared by reacting a siloxane terminated with a hydride represented by Chemical Formula 4 with a phenol derivative represented by Chemical Formula 5 to synthesize a monohydroxysiloxane represented by Chemical Formula 6. It may be prepared by reacting the monohydroxysiloxane with a diene.
• R 1 to R 4 , A, X, and m are as defined in Formula 2, D is a substituted or unsubstituted C 1 -C 10 alkylene group or substituted having a double bond at the terminal Or an unsubstituted C 6 -C 18 arylene group, or a C 1 -C 10 alkylene group or a C 6 -C 18 arylene group having -O- or -S- having a double bond at the terminal.
• D of the phenol derivative may react with siloxane terminated with hydride to form A of monohydroxysiloxane.
• siloxane compound represented by Formula 2 may include, but are not limited to, the following compounds.
• the branched polycarbonate-polysiloxane copolymer may comprise from about 0.1 to about 20 weight percent, preferably from about 0.5 to about 15 weight percent of units derived from the siloxane compound. In this range, the branched polycarbonate-polysiloxane copolymer can maintain transparency in particular.
• Examples of the carbonate precursor used in the present invention include phosgene, triphosgene, diaryl carbonate, mixtures thereof, and the like.
• the branched polycarbonate-polysiloxane copolymer according to the present invention includes a unit represented by the following Chemical Formula 2-1, a unit represented by the following Chemical Formula 3-1, or a combination thereof.
• R 1 to R 8 , A, B, Z, X, Y, n and m are the same as defined in Formula 2, and * is a polycarbonate unit linking group.
• R 1 , R 2 , A, B, and n are as defined in Formula 3, and * is a polycarbonate unit linking group.
• the branched polycarbonate-polysiloxane copolymer of the present invention may have a Si content of about 0.3 to about 10% by weight, preferably about 0.8 to about 8% by weight relative to the total polycarbonate-polysiloxane copolymer. It is possible to maintain excellent transparency and high impact in the above range.
• the branched polycarbonate-polysiloxane copolymer may have a branching degree of about 0.3 or more and less than about 1.0, preferably about 0.5 to about 0.8.
• the mark-huke constant of the branched polycarbonate-polysiloxane copolymer may be from 0.50 to less than 0.65, preferably from about 0.55 to about 0.60.
• TSA triethylamine
• a branched polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 1 except that the amount of the branching agent represented by Chemical Formula 1-1 was increased from 10.06g to 20.13g.
• a branched polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 1 except that the siloxane compound represented by the following Formula 2-3 was applied instead of the siloxane compound represented by the above Formula 2-2.
• n 40.
• a branched polycarbonate was obtained in the same manner as in Example 1 except that the siloxane compound was not used.
• a polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 1 except that no branching agent was used.
• Weight average molecular weight and number average molecular weight It was measured based on PS standard using GPC (manufactured by ViscoTek) (unit: g / mol).
• Si content (% by weight): measured using a 300MHz Topspin NMR manufactured by Bruker.
• M-H Mark-Hink
• Melt Index ratio It is expressed as a ratio of Melt Index measured at 1.2 kg and 10 kg at 250 ° C. based on ASTM D 1238.
• Example 1 Example 2
• Example 3 Comparative Example 1 Comparative Example 2
• Weight average molecular weight (Mw) 27,200 39,000 26,800 29,100 20,200 PDI 3.24 4.02 3.01 2.94 2.32 Si (% by weight) 2.67 2.65 2.61 - 2.75
• Branching agent content (% by weight) 0.5 1.0 0.5 0.5 - MH constant 0.584 0.515 0.590 0.616 0.668 1/8 "IZOD Impact Strength (-30 °C) 60 62 65 14 63 MIR 15 18 14 13 10
• Comparative Example 1 was compared with Example 1 by adding only a branching agent without a siloxane, it can be seen that shows a similar level of M-H constant.
• Comparative Example 2 is a polycarbonate-polysiloxane copolymer without adding a branching agent, from which it can be seen that the M-H constant increases when no branching agent is added. It can be seen that the impact resistance was improved compared to Comparative Example 1, which is a branched polycarbonate without siloxane.
• Examples 1 to 3 showed overall high MIR, in particular, Example 2, which had a high degree of branching, compared to Comparative Example 2, an unbranched polycarbonate-polysiloxane. It can be seen. From this, it can be seen that when the degree of branching of the branched polycarbonate-polysiloxane copolymer increases, the high temperature fluidity also increases.

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