JP2009528428A - Poly (arylene ether) block copolymer compositions, methods and articles - Google Patents

Abstract

  Poly (arylene ether) block copolymers and methods for their preparation are provided. The block copolymer includes poly (arylene ether), activated aromatic carbonate, and structural units derived from the polymer, the polymer comprising poly (alkylene ether), hydroxy-terminated polyester, hydroxyaryl-terminated polysiloxane Or a polycarbonate containing repeating units derived from hydroquinone.

Description

  The present invention generally relates to block copolymers comprising at least one poly (arylene ether) block and at least one other polymer block. Furthermore, the present invention relates to a method for producing these poly (arylene ether) block copolymers.

  This application is filed on March 2, 2006, US Provisional Application No. 60 / 778,540, filed June 15, 2006, US Patent Application No. 11 / 424,337, filed June 15, 2006. US Patent Application No. 11 / 424,347, US Patent Application No. 11 / 424,358, filed June 15, 2006, and US Patent Application No. 11 / 424,374, filed June 15, 2006. Claim priority.

  Copolymers have been used in a myriad of modern technology applications ranging from aviation and automotive applications to the manufacture of medical devices. Many of the applications in which copolymers are employed include mechanical, thermal and environmental stresses, and the copolymers are required to exhibit a high degree of mechanical, thermal and chemical stability. The development of applications where known copolymers are insufficient due to one or more weaknesses leading to mechanical, thermal or chemical instabilities continues.

  While the number of known copolymer materials is enormous, there remains a need for new copolymer compositions with improved mechanical, thermal and chemical stability properties. There also remains a need for an economical block copolymer that can compatibilize polymer blends with limited or little miscibility.

  One embodiment is a general preparation route to block copolymers comprising at least one poly (arylene ether) block. One embodiment comprises (A) hydroquinone, (B) a poly (arylene ether) containing a hydroxyl group, (C) optionally a dihydroxy aromatic compound other than the hydroquinone, and (D) an activated aromatic carbonate, A poly (arylene ether) -polycarbonate block copolymer containing structural units derived from In some embodiments, the copolymer is a molten crystal.

  Another embodiment is (A) hydroquinone selected from the group consisting of 1,4-hydroquinone, 2-methyl-1,4-hydroquinone and mixtures thereof, (B) poly (2,6-dimethyl) containing hydroxyl groups (1,4-phenylene ether), (C) bisphenol A, and (D) poly (arylene ether) -polycarbonate block copolymer containing structural units derived from bis (methylsalicyl carbonate). This block copolymer is a molten crystal.

  Another embodiment is a process for making a poly (arylene ether) -polycarbonate block copolymer at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst. Heating a mixture comprising (A) polycarbonate, (B) poly (arylene ether) containing hydroxyl groups, and (C) an activated aromatic carbonate.

  Another embodiment is a process for making a poly (arylene ether) -polycarbonate block copolymer at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst. Heating a mixture comprising (A) polycarbonate, (B) poly (arylene ether) containing hydroxyl groups, and (C) an activated aromatic carbonate.

  Another embodiment is a process for making a poly (arylene ether) -polycarbonate block copolymer at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst. A method comprising heating a mixture containing (A) hydroquinone, (B) a poly (arylene ether) containing a hydroxyl group, (C) a dihydroxy aromatic compound other than the hydroquinone, and (D) an activated aromatic carbonate. It is.

  Another embodiment is a method for producing a poly (arylene ether) -polycarbonate block copolymer comprising hydroquinone, a poly (arylene ether) containing a hydroxyl group, optionally in the presence of a transesterification catalyst, A mixture comprising one or more dihydroxy aromatic compounds other than the hydroquinone and an active aromatic carbonate is heated at a temperature in the range of about 100 to about 300 ° C. to produce polycarbonate, poly (arylene ether), and active aroma. Providing a solution comprising a solvent derived from a group carbonate and at one or more temperatures in the range of about 100 to about 400 ° C. and one or more screw speeds in the range of about 50 to about 1200 rpm Extruding a vent suitable for solvent removal It runs with no extruder, poly (arylene ether) - to provide a polycarbonate block copolymer, the method comprising.

  Another embodiment is a method of preparing a poly (arylene ether) -polycarbonate block copolymer comprising melting a poly (arylene ether), a polycarbonate comprising structural units derived from hydroquinone, and an active aromatic carbonate. Including reacting.

  Another embodiment is a poly (arylene ether) block, a polycarbonate block containing units derived from hydroquinone, and a carbonate block connecting the poly (arylene ether) block and the polycarbonate block.

  Other embodiments including block copolymers prepared by the above methods and articles comprising the block copolymers are described in detail below.

  In another embodiment, a general preparation route to block copolymers comprising at least one poly (arylene ether) block is provided. One embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer, wherein the poly (arylene ether), the poly (alkylene ether), and the active aromatic carbonate are melt reacted. Including that.

  Another embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a poly (alkylene ether) containing a hydroxyl group, and The poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., and 2,6-dimethyl- Including 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, and the poly (alkylene ether) is from about 1,000 to about 10,000 atomic mass units (AMU) ) And the poly (alkylene ether) is polyethylene glycol And the weight ratio of poly (arylene ether) to poly (alkylene ether) is from about 1: 5 to about 2: 1 and the active aromatic carbonate is selected from the group consisting of Used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by poly (arylene ether) and poly (alkylene ether).

  Another embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) block, a poly (alkylene ether) block, and a poly (arylene ether) block and a poly (alkylene). It contains a carbonate group connecting the ether) block.

  Another embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer comprising at least one poly (arylene ether) block, at least one poly (alkylene ether) block, and poly (arylene ether) ) And at least one carbonate group connecting the block and the poly (alkylene ether) block.

  Another embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. , 6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or poly (arylene ether) blocks containing combinations thereof, from about 1,000 to about 10, A poly (alkylene ether) block having a number average molecular weight of 000 atomic mass units, the poly (alkylene ether) selected from the group consisting of polyethylene glycol, polytetramethylene glycol, and mixtures thereof, and poly (arylene ether) Block and poly (alkylene ether) block Including department carbonate group.

  Another embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. At least one poly (arylene ether) block comprising 1,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof; At least one poly (alkylene ether) block having a number average molecular weight of about 10,000 atomic mass units, wherein the poly (alkylene ether) is selected from the group consisting of polyethylene glycol, polytetramethylene glycol, and mixtures thereof. Poly (alkylene ether) block; poly (ary N'eteru) blocks and poly (at least one carbonate group linking the alkylene ether) block; and optionally, comprising at least one terminal protecting groups derived from endcapping agent.

  Other embodiments comprising a poly (arylene ether) -poly (alkylene ether) block copolymer prepared by the above method and an article comprising the poly (arylene ether) -poly (alkylene ether) block copolymer Is described in detail below.

  In another embodiment, a general preparation route to block copolymers comprising at least one poly (arylene ether) block is provided. One embodiment is a method of preparing a poly (arylene ether) -polysiloxane block copolymer, wherein a poly (arylene ether) containing hydroxyl groups, a hydroxyaryl-terminated polysiloxane, and an active aromatic carbonate are reacted. Including that.

Another embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a hydroxyaryl-terminated polysiloxane, and bis (methyl carbonate) The poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl-1,4- Comprising a phenylene ether unit, a 2,3,6-trimethyl-1,4-phenylene ether unit, or a combination thereof, the hydroxyaryl-terminated polysiloxane has a structure

Have Where n is from about 10 to about 100. The weight ratio of poly (arylene ether) to hydroxyaryl-terminated polysiloxane is from about 1: 3 to about 6: 1. The activated aromatic carbonate is used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the hydroxyaryl-terminated polysiloxane.

  Another embodiment is a poly (arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) block; a hydroxyaryl-terminated polysiloxane block; and a poly (arylene ether) block and a polysiloxane block. Contains carbonate groups.

  Another embodiment is a poly (arylene ether) -polysiloxane block copolymer comprising at least one poly (arylene ether) block; at least one hydroxyaryl-terminated polysiloxane block; and a poly (arylene ether) block; It consists of at least one carbonate group connecting the polysiloxane block.

Another embodiment is a poly (arylene ether) -polysiloxane block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram at 25 ° C. in chloroform, A poly (arylene ether) block comprising dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof; from about 1,000 to about 5,000 atomic mass A hydroxy-terminated polysiloxane block having a number average molecular weight of a unit having a structure

Wherein the n is from about 5 to about 200; and a carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block.

Another embodiment is a poly (arylene ether) -polysiloxane block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram at 25 ° C. in chloroform, At least one poly (arylene ether) block comprising dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof; from about 1,000 to about 8, At least one hydroxy-terminated polysiloxane block having a number average molecular weight of 000 atomic mass units,

Wherein n is from about 5 to about 200; at least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block; and, optionally, It consists of at least one terminal protecting group derived from a terminal protecting agent.

  Other embodiments including poly (arylene ether) -polysiloxane block copolymers prepared by the above method and articles comprising poly (arylene ether) -polysiloxane block copolymers are described in detail below. To do.

  In another embodiment, a general preparation route to block copolymers comprising at least one poly (arylene ether) block is provided. One embodiment is a method of preparing a poly (arylene ether) -polyester block copolymer comprising reacting a hydroxyl-containing poly (arylene ether), a hydroxy-terminated polyester, and an activated aromatic carbonate. Including.

  Another embodiment is a method of preparing a poly (arylene ether) -polyester block copolymer comprising melt reacting a poly (arylene ether) containing a hydroxyl group, a polyester diol, and bis (methylsalicyl carbonate). And the poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., 2,6-dimethyl-1,4-phenylene ether units, 2,3 , 6-trimethyl-1,4-phenylene ether units, or combinations thereof, the polyester diol is a polycaprolactone diol having a number average molecular weight of about 500 to about 10,000 atomic mass units, (Arylene ether) weight ratio is about 1: 3 Et about 6: 1, activated aromatic carbonate is used in an amount of about 2 mol of total hydroxyl groups 2 per mole to about 0.5 which is provided with the polyester diol poly (arylene ether).

  Another embodiment is a poly (arylene ether) -polyester block copolymer comprising a poly (arylene ether) block; a hydroxy-terminated polyester block; and a carbonate ester linking the poly (arylene ether) block and the hydroxy-terminated polyester block Contains groups.

  Another embodiment is a poly (arylene ether) -polyester block copolymer comprising at least one poly (arylene ether) block; at least one hydroxy-terminated polyester block; and a poly (arylene ether) block and a hydroxy-terminated polyester. It consists of at least one carbonate group connecting the blocks.

  Another embodiment is a poly (arylene ether) -polyester block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl A poly (arylene ether) block comprising 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof; a number of about 500 to about 10,000 atomic mass units A polycaprolactone diol block having an average molecular weight; and a carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block.

  Another embodiment is a poly (arylene ether) -polyester block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl At least one poly (arylene ether) block comprising 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or poly (arylene ether) combinations thereof; At least one polycaprolactone diol block having a number average molecular weight of 10,000 atomic mass units; at least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block; and, optionally, terminal At least one derived from a protective agent Consisting terminal protecting groups.

  Other embodiments are described in detail below, including poly (arylene ether) -polyester block copolymers prepared by the above method, as well as articles comprising poly (arylene ether) -polyester block copolymers.

  The present invention can be understood more readily by reference to the following detailed description of preferred embodiments and the examples contained therein. In the following specification and the claims that follow, reference will be made to a plurality of terms that are defined to have the following meanings.

  The singular forms “a”, “an”, and “the” include plural referents unless the context clearly varies.

  “Optional” or “as optional” means that the event or situation described below may or may not occur, and the description includes cases where the event occurs and cases where the event does not occur .

  The terms “first”, “second”, and similar terms herein are used to distinguish one element from another without specifying any order, quantity or significance.

  The modifier “about” used in connection with a quantity includes the stated value and has a meaning determined by the situation (eg, including the degree of error associated with the measurement of a particular quantity).

  As used herein, the term “molten crystal” refers to a block copolymer that exhibits a melt transition when heated by differential scanning calorimetry.

  As used herein, the term “hydroxyl group” is understood to include “aliphatic hydroxyl group” and “aromatic hydroxyl group” (or “phenolic hydroxyl group”) when applied to poly (arylene ether). . As used herein, the term “aliphatic hydroxyl group” refers to a hydroxyl group attached to a non-aromatic carbon atom. Methanol, ethanol, ethylene glycol, cyclohexanol, sucrose, dextrose, benzyl alcohol and cholesterol are illustrative examples of compounds containing aliphatic hydroxyl groups. The term “aromatic hydroxyl group” refers to a hydroxyl group attached to an aromatic carbon atom. Examples include compounds in which phenol, hydroquinone, β-naphthol, 1,3,5-trihydroxybenzene, and 3-hydroxypyridine contain one or more aromatic hydroxyl groups. A “terminal hydroxyl group” is a hydroxyl group at the end of a polymer or oligomer chain.

As used herein, the term “aliphatic radical” refers to an organic radical having at least one valence comprising a linear or branched atomic arrangement that is not a ring. An aliphatic radical is defined as containing at least one carbon atom. The atomic arrangement containing the aliphatic radical may contain heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen, or may consist solely of carbon and hydrogen. For convenience, the term “aliphatic radical” is used herein as part of “a linear or branched atomic arrangement that is not a ring”, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a conjugated dienyl group, an alcohol group, an ether group. Defined as encompassing a wide range of functional groups such as groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (eg carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and similar groups. For example, a 4-methylpent-1-yl radical is a C ₆ aliphatic radical containing a methyl group, and the methyl group is a functional group that is an alkyl group. Similarly, the 4-nitrobut-1-yl radical is a C ₄ aliphatic radical comprising a nitro group, the nitro group being a functional group. The aliphatic radical may be a haloalkyl group containing one or more halogen atoms, which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine. Aliphatic radicals containing one or more halogen atoms are alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl; difluorovinylidene; trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (—CH ₂ CHBrCH ₂ —), and the like. Yet another example of an aliphatic radical is allyl, aminocarbonyl (—CONH ₂ ), carbonyl, dicyanoisopropylidene (—CH ₂ C (CN) ₂ CH ₂ —), methyl (—CH ₃ ), methylene (—CH _2- ), ethyl, ethylene, formyl (—CHO), hexyl, hexamethylene, hydroxymethyl (—CH ₂ OH), mercaptomethyl (—CH ₂ SH), methylthio (—SCH ₃ ), methylthiomethyl (—CH ₂₎ SCH ₃ ), methoxy, methoxycarbonyl (CH ₃ CO—), nitromethyl (—CH ₂ NO ₂ ), thiocarbonyl, trimethylsilyl ((CH ₃ ) ₃ Si—), t-butyldimethylsilyl, trimethoxysilylpropyl (( _{CH 3 O) 3 SiCH 2 CH} 2 CH 2 -), vinyl, vinylidene Oyo Including the like. As yet another example, a C ₁ -C ₁₀ aliphatic radical contains at least one but no more than 10 carbon atoms. A methyl group (CH ₃ —) is an example of a C ₁ aliphatic radical. The decyl group (CH ₃ (CH ₂ ) ₉ —) is an example of a C ₁₀ aliphatic radical.

As used herein, the term “aromatic radical” refers to an atomic arrangement having at least one valence comprising at least one aromatic group. The atomic arrangement having at least one valence containing at least one aromatic group may contain heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may consist solely of carbon and hydrogen. The term “aromatic radical” as used herein includes, but is not limited to, phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene and biphenyl radicals. As mentioned above, the aromatic radical contains at least one aromatic group. An aromatic group is necessarily a cyclic structure with 4n + 2 “delocalized” electrons, where “n” is an integer greater than or equal to one. Examples are phenyl group (n = 1), thienyl group (n = 1), furanyl group (n = 1), naphthyl group (n = 2), azulenyl group (n = 2), anthracenyl group (n = 3) And similar groups. The aromatic radical may also contain non-aromatic components. For example, a benzyl group is an aromatic radical containing a phenyl ring (aromatic group) and a methylene group (non-aromatic component). Similarly, a tetrahydronaphthyl radical is an aromatic radical containing an aromatic group (C ₆ H ₃ ) condensed with a non-aromatic component — (CH ₂ ) ₄ —. For convenience, the term “aromatic radical” is used herein to refer to an alkyl group, alkenyl group, alkynyl group, haloalkyl group, haloaromatic group, conjugated dienyl group, alcohol group, ether group, aldehyde group, ketone group, carboxylic acid group. , Defined as encompassing a wide range of functional groups such as acyl groups (eg carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and similar groups. For example, the 4-methylphenyl radical is a C ₇ aromatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 2-nitrophenyl group is a C ₆ aromatic radical comprising a nitro group, the nitro group being a functional group. Aromatic radicals include trifluoromethylphenyl, hexafluoroisopropylidenebis (4-phen-1-yloxy) (—OPhC (CF ₃ ) ₂ PhO—), chloromethylphenyl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl _{(3-CCl 3 Ph -)} , halogen such as 4- (3-bromoprop-1-yl) phen-1-yl _{(BrCH 2 CH 2 CH 2 Ph-} ) , and the like groups Containing aromatic aromatic radicals. Yet another example of an aromatic radical is 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (H ₂ NPh-), 3-aminocarbonylphen-1-yl (NH ₂ COPh-) 4-benzoylphen-1-yl, dicyanoisopropylidenebis (4-phen-1-yloxy) (—OPhC (CN) ₂ PhO—), 3-methylphen-1-yl, methylenebis (phen-4-yloxy) _{) (- OPhCH 2 PhO -)} , 2- Echirufen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl; hexamethylene-1,6-bis (phen-4 _{yloxy) (- OPh (CH 2)} 6 PhO -); 4- hydroxymethyl-1-yl _{(4-HOCH 2 Ph -)} , 4- Merukaputome Rufen 1-yl _{(4-HSCH 2 Ph -)} , 4- methyl-thiophen-1-yl _{(4-CH 3 SPh -)} , 3- methoxy-1-yl, 2-methoxycarbonyl phen-1-yloxy ( Methyl salicyl), 2-nitromethylphen-1-yl (-PhCH ₂ NO ₂ ), 3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphen-1-yl, 4-vinylphen-1- Yl, vinylidenebis (phenyl) and similar groups. The term “C ₃ -C ₁₀ aromatic radical” includes aromatic radicals containing at least three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C ₃ H ₂ N ₂ —) represents a C ₃ aromatic radical. Benzyl radical _(C 7 _{H 8} -) is represents a _{C 7} aromatic radical.

The term “alicyclic radical” as used herein refers to a radical having an atomic arrangement that has at least one valence and is cyclic but not aromatic. An “alicyclic radical” as defined herein does not contain an aromatic group. An “alicyclic radical” may include one or more acyclic components. For example, a cyclohexylmethyl group (C ₆ H ₁₁ CH ₂ —) is an alicyclic radical containing a cyclohexyl ring (a cyclic but non-aromatic atomic arrangement) and a methylene group (acyclic component). An alicyclic radical may contain heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may consist solely of carbon and hydrogen. For convenience, the term “alicyclic radical” refers herein to an alkyl group, alkenyl group, alkynyl group, haloalkyl group, conjugated dienyl group, alcohol group, ether group, aldehyde group, ketone group, carboxylic acid group, acyl group ( For example, carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and similar groups. For example, a 4-methylcyclopent-1-yl radical is a C ₆ alicyclic radical containing a methyl group, and the methyl group is a functional group that is an alkyl group. Similarly, a 2-nitrocyclobut-1-yl radical is a C ₄ alicyclic radical containing a nitro group, and the nitro group is a functional group. The alicyclic radical may contain one or more halogen atoms which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine. Cycloaliphatic radicals containing one or more halogen atoms are 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoro-2,2-bis _{(cyclohex-4-yl) (- C 6 H 10 C} (CF 3) 2 C 6 H 10 -), 2- chloromethyl-cyclohex-1-yl; 3- Difluoromethylenecyclohex-1-yl; 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex 1-yloxy _{(CH 3 CHBrCH 2 C 6 H} 10 -) and a similar group. Still other examples of alicyclic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (H ₂ NC ₆ H _10- ), 4-aminocarbonylcyclopent-1- yl _{(NH 2 COC 5 H 8 -} ), 4- acetyloxy cyclohex-1-yl, 2,2-dicyano isopropylidene bis _{(cyclohex-4-yloxy) (- OC 6 H 10 C} (CN) 2 C ₆ H ₁₀ O -), 3- methyl-cyclohex-1-yl, methylenebis _{(cyclohex-4-yloxy) (- OC 6 H 10 CH} 2 C 6 H 10 O -), 1- ethyl cyclo but-1 Yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamethylene-1,6-bis (cyclohexyl) _{4-yloxy) (- OC 6 H 10 (} CH 2) 6 C 6 H 10 O -); 4- hydroxymethyl-cyclohex-1-yl _{(4-HOCH 2 C 6 H} 10 -), 4- mercaptomethyl cyclohex-1-yl _{(4-HSCH 2 C 6 H} 10 -), 4- methylthiophenyl cyclohex-1-yl _{(4-CH 3 SC 6 H} 10 -), 4- methoxy-cyclohex-1-yl, 2 - methoxycarbonyl cyclohex-1-yloxy _{(2-CH 3 OCOC 6 H} 10 O -), 4- nitro-methyl cyclohex-1-yl _{(NO 2 CH 2 C 6 H} 10 -), 3- trimethylsilyl cyclohex - 1-yl, 2-t-butyldimethylsilylcyclopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl ((CH ₃ O) ₃ Si _{CH 2 CH 2 C 6 H 10} -), containing 4-vinylcyclohexene-1-yl, vinylidene bis (cyclohexyl) and similar groups. The term “C ₃ -C ₁₀ alicyclic radical” includes alicyclic radicals containing at least three but no more than 10 carbon atoms. The alicyclic radical 2-tetrahydrofuranyl (C ₄ H ₇ O—) represents the C ₄ alicyclic radical. The cyclohexylmethyl radical (C ₆ H ₁₁ CH ₂ —) represents a C ₇ alicyclic radical.

  The term “hydrocarbyl” as used herein, whether used alone or as a prefix, suffix or stem of another term, refers to a residue containing only carbon and hydrogen. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated. Combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon moieties may also be included. However, hydrocarbyl residues may contain heteroatoms on the carbon and hydrogen constituent atoms of substituent residues, even when so described. Thus, when specifically designated to contain such heteroatoms, the hydrocarbyl residue or hydrocarbylene residue may also contain a carbonyl group, an amino group, a hydroxyl group or a similar group, or the backbone of the hydrocarbyl residue. May contain heteroatoms.

  The phrase “polycarbonate repeat unit derived from a dihydroxy aromatic compound” as used herein when describing an oligomeric polycarbonate refers to the reaction of a dihydroxy aromatic compound with a source of carbonyl units, such as bisphenol A and bis (methylsalicyl carbonate). Means a repeating unit incorporated into the oligomeric polycarbonate by reaction with

  As used herein, the term “solvent” may refer to a single solvent or a mixture of solvents.

  As used herein, the term “molten polycarbonate” refers to a polycarbonate comprising structural units made by transesterification of a diaryl carbonate and a dihydroxy aromatic compound.

  “BPA” is defined herein as bisphenol A or 2,2-bis (4-hydroxyphenyl) propane.

  As used herein, the terms “diaryl carbonate” and “ester-substituted diaryl carbonate” are used interchangeably with the terms “aromatic carbonate” and “ester-substituted aromatic carbonate”, respectively.

  The terms “twin screw extruder” and “twin screw extruder” are used interchangeably herein.

  The terms “formula” and “structure” are used interchangeably herein.

  The term “monofunctional phenol” as used herein means a phenol that contains a single aromatic hydroxyl group.

  The terms “vent port” and “vent” are used interchangeably herein.

  The term “atmospheric vent” as used herein means a vent that operates at or near atmospheric pressure. Thus, an atmospheric vent that operates under a slight vacuum, such as what is commonly referred to as a “household vacuum”, shall fall within the scope of the term “atmospheric vent”.

  As mentioned above, the present invention generally relates to block copolymers comprising poly (arylene ether) blocks, methods for making such block copolymers, and articles comprising such copolymers. In general, the block copolymer is a poly (arylene ether), another (non-poly (arylene ether)) polymer having at least one reactive hydroxyl group, and another polymer than poly (arylene ether). Prepared by reaction of a carbonate ester precursor capable of forming a linkage between Considering the low reactivity of ortho-disubstituted phenols with diaryl carbonate, and considering the suspicion regarding the solubility of diaryl carbonate in low concentrations of poly (arylene ether) and the corresponding aromatic alcohol, It was surprising that the poly (arylene ether) -containing block copolymer could be efficiently formed, particularly by a melt reaction.

  In one embodiment, the other polymer is a polycarbonate and the resulting block copolymer is a poly (arylene ether) -polycarbonate block copolymer. In another embodiment, the other polymer is a poly (alkylene ether) and the resulting block copolymer is a poly (arylene ether) -poly (alkylene ether) block copolymer. In another embodiment, the other polymer is a hydroxyaryl-terminated polysiloxane and the resulting block copolymer is a poly (arylene ether) -polysiloxane block copolymer. In another embodiment, the other polymer is a hydroxy-terminated polyester and the resulting block copolymer is a poly (arylene ether) -polyester block copolymer.

Poly (arylene ether) -polycarbonate block copolymer:
One embodiment comprises (A) hydroquinone, (B) poly (arylene ether) containing a hydroxyl group, (C) optionally a dihydroxy aromatic compound other than hydroquinone, and (D) an activated aromatic carbonate. A poly (arylene ether) -polycarbonate block copolymer containing derived structural units.

  In one embodiment, the poly (arylene ether) -polycarbonate block copolymer is a molten crystal. Generally, a poly (arylene ether) -polycarbonate block copolymer is a molten crystal if differential scanning calorimetry of the copolymer reveals a melting transition on heating. In one embodiment, melt crystallinity becomes apparent during the melt polymerization process used to form the crystalline block copolymer. In another embodiment, the molten crystal behavior results from the presence of a morphological hierarchy that may exist in the molten state, for example, spherulites, block copolymer microdomains, lamellar crystals, and crystal block unit cells. it is conceivable that. Thus, for example, one or more of these morphological states may function as microphase separated domains and act as a crystallization template, thereby inducing rapid crystallization of the block copolymer. Thus, in one embodiment, the melt crystal behavior becomes apparent when the poly (arylene ether) -polycarbonate block copolymer melt is at a temperature just above the glass transition point and just below the melting point.

The reactant (A) is hydroquinone. Suitable hydroquinone has the structure

Including those having In the formula, R ¹ represents a monovalent C _{1 to} C ₁₂ aliphatic radical, a C _{3 to} C ₁₀ alicyclic radical, or a C _{3 to} C ₁₀ aromatic radical. In one embodiment, the hydroquinone monomer comprises at least one of 1,4-hydroquinone and 2-methyl-1,4-hydroquinone.

Reactant (B) is a poly (arylene ether) containing hydroxyl groups. It is understood that the poly (arylene ether) may contain more than one hydroxyl group. The term “poly (arylene ether)” includes any oligomer or polymer described as “polyphenylene ether” in US Provisional Application No. 60 / 778,540 filed Mar. 2, 2006. Suitable poly (arylene ether) is the structure

Including a repeating unit having In which each Z ¹ is independently a halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl and not a tertiary hydrocarbyl group, a C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or at least two carbon atoms is a C ₂ -C ₁₂ halohydrocarbyloxy separate the halogen and oxygen atoms, each Z ² is independently hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl is a by tertiary hydrocarbyl group is not a _hydrocarbyl, C to C 1 _{-C 12 hydrocarbylthio,} it is C 1 _{-C 12} hydrocarbyloxy or at least two carbon atoms, separate the halogen and oxygen atoms it is ₂ -C ₁₂ halohydrocarbyloxy. In one embodiment, each Z ¹ is methyl and each Z ² is independently hydrogen or methyl. In one embodiment, the poly (arylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof.

  In one embodiment, the poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.6 deciliters per gram at 25 ° C. in chloroform. Within this range, the poly (arylene ether) may have an intrinsic viscosity of at least about 0.06 deciliter per gram, or at least about 0.09 deciliter per gram, or at least about 0.12 deciliter per gram. Within this range, the poly (arylene ether) may have an intrinsic viscosity of up to about 0.4 deciliter per gram, or up to about 0.3 deciliter per gram, or up to about 0.2 deciliter per gram. One skilled in the art understands that the intrinsic viscosity of the poly (arylene ether) may increase up to 30% under melt reaction and / or melt kneading conditions. The above intrinsic viscosity range of 0.04 to about 0.6 deciliter per gram is intended to encompass both intrinsic viscosity both before and after the melt reaction and / or melt kneading. A blend of two or more poly (arylene ethers) having different intrinsic viscosities may be used.

  In one embodiment, about 50 to about 95 mole percent of the total molar amount of poly (arylene ether) contains hydroxyl groups.

  In one embodiment, the poly (arylene ether) has an average of about 0.5 to 1 aromatic hydroxyl groups per molecular chain. The aromatic hydroxyl group may be at the end or inside of the poly (arylene ether) chain. Poly (arylene ethers) prepared by oxidative polymerization of monohydric phenols or mixtures of monohydric phenols often have a hydroxyl group content within this range. A blend of two or more poly (arylene ethers) having an average number of different hydroxyl groups per molecular chain may be used.

  In one embodiment, the poly (arylene ether) has on average more than one aromatic hydroxyl group per molecular chain. Various methods are known for producing such poly (arylene ethers), some called bifunctional poly (arylene ethers). For example, poly (arylene ether) produced by oxidative polymerization of monohydric phenols may be “redistributed” by reaction with an oxidant and a di- or polyhydric phenol. As another example, a bifunctional poly ((2) by oxidative polymerization of a mixture of a monohydric phenol such as 2,6-xylenol and a dihydric or polyhydric phenol such as 4,4'-isopropylidenebis (2,6-xylenol). Arylene ether) may be produced directly. US Patent Application Publication No. 2006/0041086 to Birsak et al. Describes another method for producing poly (arylene ethers) having more than one phenolic hydroxyl group per molecule. Methods for determining the number of aromatic hydroxyl groups per molecular chain are known in the art. For example, the number of aromatic hydroxyl groups per molecular chain may be calculated from the weight parts per million of the hydroxyl groups of poly (arylene ether) and the number average molecular weight, where the weight parts per million of hydroxyl groups are aromatic The number average molecular weight of the poly (arylene ether) may be measured by gel permeation chromatography using a poly (arylene ether) standard.

  In some embodiments, the poly (arylene ether) on average has more than 2 hydroxyl groups per molecular chain, such hydroxyl groups may be in the middle of the molecular chain and at the end of the molecular chain. Also good.

  Any suitable poly (arylene ether) disclosed in the art may also be used. Both homopolymer poly (arylene ether) and copolymer poly (arylene ether) are included. Suitable homopolymers are those containing, for example, 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-1,4-phenylene ether units. The patent literature discloses a number of suitable random copolymers as well as homopolymers.

  Also included are poly (arylene ethers) that contain moieties that change properties such as molecular weight, melt viscosity and / or impact strength. Such polymers are described in the patent literature, and vinyl monomers such as acrylonitrile and vinyl aromatic compounds (eg styrene) or polymers and elastomers such as polystyrene on poly (arylene ether) in a known manner. It may be prepared by grafting onto Usually, the product contains both grafted and ungrafted parts.

  Another suitable polymer is a coupled poly (arylene ether). In this case, the coupling agent is reacted with the hydroxyl groups of the two poly (arylene ether) chains in a known manner, and if a significant proportion of hydroxyl groups still exists, the reaction product of the hydroxyl group and the coupling agent is reduced. A higher molecular weight polymer containing is produced. Illustrative coupling agents are low molecular weight polycarbonates, quinones, heterocyclic compounds and formals. In some embodiments, the poly (arylene ether) is functionalized only with reactive groups that are the result of the oxidative polymerization formed. For example, in one embodiment, the poly (arylene ether) is an epoxy group, a carboxylic acid group, an acid anhydride group, a polymerizable carbon-carbon double bond (as present in an acrylate group), a carbodiimide group, or the like Not functionalized to contain groups.

  In some embodiments, the poly (arylene ether) may include aliphatic hydroxyl groups, or a combination of aliphatic and aromatic hydroxyl groups. These poly (arylene ethers) can be prepared, for example, by reaction of hydroxy-terminated poly (arylene ethers) with ω-haloalkylhydroxy compounds, where the hydroxyl groups can be aliphatic hydroxyl groups. The resulting product ω-hydroxyalkyl group terminated poly (arylene ether) may be used as a macromonomer to prepare a poly (arylene ether) -polycarbonate block copolymer. In one embodiment, the poly (arylene ether) is a poly (arylene ether) comprising 2,6-dimethyl-1,4-phenylene ether groups. Such poly (arylene ethers) contain aromatic hydroxyl groups and are readily prepared by oxidative polymerization of 2,6-xylenol or a mixture of phenols containing 2,6-xylenol.

Component (C) used in forming the PPE-PC block copolymer is optional and is a dihydroxy aromatic compound other than the hydroquinone. The dihydroxy aromatic compound of component (C) has the structure

Containing bisphenol. Wherein each G ¹ is independently a C ₆ -C ₂₀ aromatic radical at each position, and E is a bond, C ₃ -C ₂₀ alicyclic radical, C ₃ independently at each position. -C ₂₀ aromatic _radical, C 1 _{-C 20} aliphatic radical, a nitrogen-containing coupling portion, a silicon-containing coupling portion, a sulfur-containing linkage unit, a selenium-containing bond portion, a phosphorus-containing bond unit, or an oxygen atom, [t] Is a number of 1 or more, “s” is 0 or 1, and “u” is an integer including 0. In various embodiments, “t” may have a value from 1 to 10, 1 to 5, 1 to 3, preferably 1. Similarly, in various embodiments, “u” may have a value from 1 to 10, from 1 to 5, from 1 to 3, preferably 1.

A “nitrogen-containing bond” as defined herein includes a tertiary nitrogen-containing bond. As defined herein, a “silicon-containing bond” includes a silane bond and a siloxane bond. The “sulfur-containing linking group” as defined herein includes a sulfide group, a sulfoxide group and a sulfone group. A “selenium-containing bond” as defined herein includes a selenide group, a selenoxide group, and a selenone group. “Phosphorus-containing linkages” as defined herein are defined to include trivalent, tetravalent or pentavalent phosphorus, and some non-limiting examples include phosphonyl-type and phosphonyl-type linkages. . The phosphorus atom may be bonded through a carbon-containing group, oxygen-containing group, sulfur-containing group or selenium-containing group. In some embodiments, the phosphorus atom may be attached to other inorganic groups such as hydroxyl groups, or their metal salt derivatives such as ONa, OK, OLi and the like. Phosphorus atom, oxygen, through the sulfur or _selenium, C 3 _{-C 20} cycloaliphatic _radical, may be bound to an organic group such as C 3 _{-C 20} aromatic radical or _C 1 _{-C 20} aliphatic radical .

Suitable examples of the structural unit “E” are cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, methylcyclohexylidene, [2.2.1] -bicycloheptylidene, neopentylidene. , Cyclopentadecylidene, cyclododecylidene and adamantylidene. Suitable bisphenols are 1,1-bis (4-hydroxyphenyl) cyclopentane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (2-tert-butyl-4- Hydroxy-5-methylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxy-6-methylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxy-6-) Methylphenyl) butane, 1,3-bis [4-hydroxyphenyl-1- (1-methylethylidyne)] benzene, 1,4-bis [4-hydroxyphenyl-1- (1-methylethylidyne)] benzene 1,3-bis [3-tert-butyl-4-hydroxy-6-methylphenyl-1- (1-methylethylidyne)] benzene, 1,4-bis [3-tert-butyl-4-hydro Ci-6-methylphenyl-1- (1-methylethylidine)] benzene, 4,4'-biphenol, 3,3 ', 5,5'-tetrabromo-2,2', 6,6'-tetramethyl -4,4'-biphenol, 2,2 ', 6,6'-tetramethyl-3,3', 5-tribromo-4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) -2 , 2,2-trichloroethane, 2,2-bis (4-hydroxyphenyl-1,1,1,3,3,3-hexafluoropropane), 1,1-bis (4-hydroxyphenyl) -1-cyanoethane 1,1-bis (4-hydroxyphenyl) dicyanomethane, 1,1-bis (4-hydroxyphenyl) -1-cyano-1-phenylmethane, 2,2-bis (3-methyl-4-hydroxyphenyl) )propane 1,1-bis (4-hydroxyphenyl) norbornane, 9,9-bis (4-hydroxyphenyl) fluorene, 3,3-bis (4-hydroxyphenyl) phthalide, 1,2-bis (4-hydroxyphenyl) Ethane, 1,3-bis (4-hydroxyphenyl) propenone, bis (4-hydroxyphenyl) sulfide, 4,4'-oxydiphenol, 4,4-bis (4-hydroxyphenyl) pentanoic acid, 4,4 -Bis (3,5-dimethyl-4-hydroxyphenyl) pentanoic acid, 2,2-bis (4-hydroxyphenyl) acetic acid, 2,4'-dihydroxydiphenylmethane, 2,2-bis (2-hydroxyphenyl) methane Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-nitrophenyl) methane, bis (4- Droxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-2-chlorophenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane (bisphenol-A), 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3- Bromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3 -T-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis ( , 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3- Chloro-4-hydroxy-5-isopropylphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-5-chloro-) 4-hydroxyphenyl) propane, 2,2-bis (3-bromo-5-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-5- Enyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-5-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-diisopropyl-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-diphenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy) -2,3,5,6-tetrachlorophenyl) propane, 2,2-bis (4-hydroxy-2,3,5,6-tetrabromophenyl) propane, 2,2-bis (4-hydroxy-2, 3,5,6-tetramethylphenyl) propane, 2,2-bis (2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (2,6 -Dibromo-3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) Propane, 2,2-bis (3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexylmethane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3- Bromo-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis 4-hydroxy-3-isopropylphenyl) cyclohexane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1 -Bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 4,4 '-[1-methyl-4- (1-methyl-ethyl) -1,3-cyclohexanediyl] bisphenol (1,3-BHPM), 4- [1- [3- (4 -Hydroxyphenyl) -4-methylcyclohexyl] -1-methyl-ethyl] -phenol (2,8-BHPM), 3,8- Hydroxy-5a, 10b-diphenylcomarano-2 ', 3', 2,3-coumaran (DCBP), 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 1,1-bis (3- Chloro-4-hydroxy-5-methylphenyl) cyclohexane, 1,1-bis (3-bromo-4-hydroxy-5-methylphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxy-5- Isopropylphenyl) cyclohexane, 1,1-bis (3-bromo-4-hydroxy-5-isopropylphenyl) cyclohexane, 1,1-bis (3-tert-butyl-5-chloro-4-hydroxyphenyl) cyclohexane, , 1-bis (3-bromo-5-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro Ro-5-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-bromo-5-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-diisopropyl-4-hydroxyphenyl) ) Cyclohexane, 1,1-bis (3,5-di-t-butyl-4-hydroxyphenyl) cyclohexane.
1,1-bis (3,5-diphenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-2,3,5,6-tetrachlorophenyl) cyclohexane, 1,1-bis (4 -Hydroxy-2,3,5,6-tetrabromophenyl) cyclohexane, 1,1-bis (4-hydroxy-2,3,5,6-tetramethylphenyl) cyclohexane, 1,1-bis (2,6 -Dichloro-3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Phenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) -3,3,5-trimethyl Hexane, 1,1-bis (3-bromo-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethyl Cyclohexane, 1,1-bis (4-hydroxy-3-isopropylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, , 1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-chloro-4-hydroxy-5-methylphenyl) -3,3 5-trimethylcyclohexane, 1,1-bis (3-bromo-4-hydroxy-5-methylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-chloro-4-hydroxy-5- Isopropylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-bromo-4-hydroxy-5-isopropylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3- t-butyl-5-chloro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-bromo-5-t-butyl-4- Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-chloro-5-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3- Bromo-5-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-diisopropyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3,5-di-t-butyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane, 1,1-bis (4-hydroxy-2,3,5,6-tetrachlorophenyl) -3,3,5-trimethylcycle Hexane, 1,1-bis (4-hydroxy-2,3,5,6-tetrabromophenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-2,3,5, 6-tetramethylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, , 1-bis (2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclo Decane, 4,4'-dihydroxy-1,1-biphenyl, 4,4'-dihydroxy-3,3'-dimethyl-1,1-biphenyl, 4,4'-dihydroxy-3,3'-dioctyl-1 , 1-biphenyl, 4,4 '-(3,3,5-trimethylcyclohexylidene) diphenol, 4,4'-bis (3,5-dimethyl) diphenol, 4,4'-dihydroxydiphenyl ether, 4 , 4'-dihydroxydiphenylthioether, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxy-3-methylphenyl) -2- Propyl) benzene, 1,4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,4-bis (2- (4-hydroxy-3-methylphenyl)- 2-propyl) benzene, 2,4′-dihydroxyphenylsulfone, 4,4′-dihydroxydiphenylsulfone (BPS), bis (4-hydroxyphenyl) methane, 2,6-dihydroxynaphthalene, resorcinol, C _1-3 alkyl Substituted resorcinol, 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 4,4 -Dihydroxydiphenyl ether, 4,4-dihydroxy-3,3-dichlorodiphenyl ether, 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4-thiodiphenol, 2,2,2 ', 2'-tetrahydro- 3,3,3 ', 3'-tetramethyl-1,1'-spirobi [1 H-indene] -6,6'-diol, and mixtures thereof. In a preferred embodiment, bisphenol A is used as the dihydroxy aromatic compound forming the polycarbonate block.

As described above, the poly (arylene ether) -polycarbonate block copolymer composition includes structural units derived from an activated aromatic carbonate (component (D)). The term “activated aromatic carbonate” as used herein is defined as a diaryl carbonate that is more reactive than diphenyl carbonate in a model transesterification reaction with a monofunctional phenol. Such activated aromatic carbonates have the structure

Wherein A ¹ and A ² are each independently an aromatic ring having multiple positions that can each be utilized for substitution; R ² and R ³ are independently halogen, cyano at each position group, nitro _group, C 1 _{-C 20} alkyl _group, C 4 _{-C 20} cycloalkyl _group, C 4 _{-C 20} aromatic _radical, C 1 _{-C 20} alkoxy group, C4～C ₂₀ cycloalkoxy _{group, C} 4 ~ C ₂₀ aryloxy _group, C 1 _{-C 20} alkylthio _group, C 4 _{-C 20} cycloalkylthio _group, C 4 _{-C 20} arylthio _group, C 1 _{-C 20} alkylsulfinyl _group, C 4 _{-C 20} cycloalkylsulfinyl group, C ₄ -C ₂₀ arylsulfinyl _group, C 1 _{-C 20} alkylsulfonyl _group, C 4 _{-C 20} cycloalkylsulfonyl _group, C 4 -C ₂ Arylsulfonyl _group, C 1 _{-C 20} alkoxycarbonyl _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxycarbonyl _group, C 2 _{-C 60} alkylamino _group, C 6 _{-C 60} cycloalkylamino _group, C 5 _{-C 60} arylamino _group, C 1 _{-C 40} alkylaminocarbonyl _group, C 4 _{-C 40} cycloalkylaminocarbonyl _group, C 4 _{-C 40} arylaminocarbonyl group, and _C 1 _{-C 20} acylamino group “D” and “e” are each independently an integer from 0 to 0 up to the number of positions available for substitution on A ¹ and A ² respectively; Q ³ and Q ⁴ Each independently represents an alkoxycarbonyl group, a formyl group, a halogen atom, a nitro group, an amide group, a sulfone group, Sulfoxide groups and imine groups, amidine groups, and structure

Wherein M ¹ and M ² are independently N-alkyl, N, N-dialkyl, N-aryl, N, N-diaryl or N-alkylaryl, N, N-dialkylaryl, and R ⁴ is An activating group selected from the group consisting of an aminocarbonyl and amidine moiety having an alkyl group or an aryl group; “b” and “c” independently include 0, where b + c is 1 or greater , 0 to integers up to the number of positions available for substitution on A ¹ and A ² respectively. One or more such activated aromatic carbonates may be used to form the PC block of the PPE-PC block copolymer.

In one embodiment, the activated aromatic carbonate has the structure

Ester substituted diaryl carbonates having In the formula, R ⁵ is independently a C _{1 to} C ₂₀ aliphatic radical, a C _{4 to} C ₂₀ alicyclic radical, or a C _{4 to} C ₂₀ aromatic radical, and R ⁶ is independently at each position. independently at the position of, halogen, cyano group, nitro _group, C 1 _{-C 20} alkyl _group, C 4 _{-C 20} cycloalkyl _group, C 4 _{-C 20} aromatic _radical, C 1 _{-C 20} alkoxy, _{C 4} -C ₂₀ cycloalkoxy _group, C 4 _{-C 20} aryloxy _group, C 1 _{-C 20} alkylthio _group, C 4 _{-C 20} cycloalkylthio _group, C 4 _{-C 20} arylthio _group, C 1 _{-C 20} alkylsulfinyl group, C ₄ -C ₂₀ cycloalkylsulfinyl _group, C 4 _{-C 20} arylsulfinyl _group, C 1 _{-C 20} alkylsulfonyl _group, C 4 _{-C 20} cycloalkylsulfinyl Alkylsulfonyl _group, C 4 _{-C 20} arylsulfonyl _group, C 1 _{-C 20} alkoxycarbonyl _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxycarbonyl _group, C 2 _{-C 60} alkylamino group, C ₆ -C ₆₀ cycloalkylamino _group, C 5 _{-C 60} arylamino _group, C 1 _{-C 40} alkylaminocarbonyl _group, C 4 _{-C 40} cycloalkylaminocarbonyl _group, C 4 _{-C 40} arylaminocarbonyl group, and it is a _C 1 _{-C 20} acylamino radical; "e" is independently at each position, an integer from 0 to 4.

  Specific non-limiting examples of activated aromatic carbonates include bis (o-chlorophenyl) carbonate, bis (o-nitrophenyl) carbonate, bis (o-acetylphenyl) carbonate, bis (o-phenylketone phenyl) carbonate, Including bis (o-formylphenyl) carbonate and bis (methylsalicyl) carbonate. In a particular embodiment, the activated aromatic carbonate is bis (methylsalicyl) carbonate (CAS Registry Number 82091-12-1), hereinafter abbreviated as “BMSC”. BMSC can be readily prepared by reaction of methyl salicylate with phosgene in the presence of an acid scavenger such as a trialkylamine (eg, triethylamine) in an inert solvent such as dichloromethane. BMSC is preferred even under melt polymerization conditions used to produce polycarbonate chains because of its low molecular weight and high vapor pressure.

  The activated aromatic carbonate contains at least one active group that makes the activated aromatic carbonate more reactive than diphenyl carbonate in the transesterification reaction. Such active groups are discussed herein. For further clarity, it is useful to provide examples of groups that do not activate aromatic carbonates. Some non-limiting examples of such “deactivating groups” are alkyl and cycloalkyl groups. Diphenyl carbonate and aromatic carbonates that do not have an active group and contain a non-activated group are referred to as “deactivated carbonate esters”. Some specific non-limiting examples of non-activated carbonates include bis (o-methylphenyl) carbonate, bis (p-cumylphenyl) carbonate, bis (p- (1,1,3,3-tetramethyl) carbonate Butylphenyl) and bis (o-isopropylphenyl) carbonate. Asymmetric combinations of these structures are also expected to result in non-activated carbonate esters.

  As should be apparent from this discussion, asymmetric aromatic carbonates containing two aryl groups, including one aryl group containing an activating group and one aryl group containing a non-activating group, are also activated. You may use as carbonate ester.

As mentioned above, one method for determining whether an aromatic carbonate is an activated aromatic carbonate is the specific aromatic carbonate and para- (1,1,3,3-tetramethyl). ) Performing a model melt transesterification reaction with a phenol such as butylphenol and comparing the observed reaction rate with that observed for the same reaction using diphenyl carbonate as the aromatic carbonate. In performing these model reactions, para- (1,1,3,3-tetramethyl) butylphenol often has a single hydroxyl group, low volatility, and similar reactivity to bisphenol A. Is preferable. The model melt transesterification reaction is usually carried out at a temperature above the melting point of the particular aromatic carbonate and phenol in the presence of a transesterification catalyst that is an aqueous solution of sodium hydroxide or sodium phenoxide. A preferred transesterification catalyst concentration is about 0.001 mole percent based on the moles of phenol or aromatic carbonate. The preferred reaction temperature is 200 ° C., but depending on the reactivity and melting point of the reactants, the choice of reaction conditions and catalyst concentration may be adjusted to provide a convenient reaction rate. The reaction temperature is preferably kept below the degradation temperature of the reactants. A sealed tube may be used if the reaction temperature causes the reactants to volatilize and affect the reactant molar balance. Measurement of the equilibrium concentration of the reactants is accomplished by taking a reaction sample during the reaction and subsequent analysis of the reaction mixture. The reaction mixture is conveniently analyzed by HPLC (high pressure liquid chromatography). Special care must be taken so that the reaction does not continue after the sample is removed from the reactor. This may be accomplished by cooling the sample in an ice bath and using a quenching acid such as acetic acid in the aqueous phase of the HPLC solvent system. In addition to cooling the reaction mixture, it may be desirable to introduce a quenching acid directly into the reaction sample. A preferred concentration of quenching acid, such as acetic acid, in the aqueous phase of the HPLC solvent system is about 0.05 mole percent. Next, the equilibrium constant is determined from the concentration of the reactant and product after reaching equilibrium. As a result of sampling the reaction mixture, it is assumed that an equilibrium has been reached when the concentration of the components in the reaction mixture reaches a point where there is little or no change. The equilibrium constant can be determined from the reactant and product concentrations by methods known to those skilled in the art. Aromatic carbonates having a relative equilibrium constant greater than 1 (K _{diaryl carbonate} / K _{diphenyl carbonate} ) are considered activated aromatic carbonates, whereas aromatic carbonates having a relative equilibrium constant of 1 or less are non-activated fragrances. Is considered a family carbonate. In general, when carrying out the transesterification reaction to produce a polycarbonate, it is preferred to use an activated aromatic carbonate that has a very high reactivity compared to diphenyl carbonate in the model reaction. Activated aromatic carbonates having an equilibrium constant greater than at least 1,000 times that of diphenyl carbonate are preferred.

As mentioned above, poly (arylene ether) -polycarbonate (PPE-PC) block copolymers contain structural units derived from activated aromatic carbonates. Usually, these structural units include a carbonyl group of the carbonate ester bond group of the PC block, and a carbonyl group of the carbonate ester group that combines the PC block and the PPE block. In addition, the product PPE-PC block copolymer may contain other structural units derived from activated aromatic carbonates. These structural units may be end groups incorporated into the polycarbonate block (PC block) or may be incorporated into the backbone of the polycarbonate block. PC blocks comprising carbonate units derived from activated carbonates preferably comprise at least one end group derived from activated carbonates. In one embodiment, the end group derived from the activated aromatic carbonate has the structure

Have In the formula, A ¹ , Q ³ , R ² , “b” and “e” are defined as above.

In particular, when a polycarbonate block is prepared by melt polymerization of an ester-substituted aromatic carbonate such as BMSC and a dihydroxy aromatic compound (eg BPA), the product PPE-PC block copolymer is used during the melt polymerization reaction. It may further include very low levels of structural features arising from side reactions occurring in One such structural feature is structural

Have Wherein R ² and “e” are defined the same as in structure (IV). Note that “e” is an integer greater than or equal to 0 and up to 4, where 4 is the maximum number of positions available for substitution. This structure is called “inner ester-carbonate ester bond” or “bend”. Without wishing to be bound by any theory, it is believed that this structure results from reaction with an ester-substituted phenol by-product, such as a dihydroxy aromatic compound in the ester carbonyl group of methyl salicylate or the hydroxyl group of the growing polymer chain. . Further reaction of the ester substituted phenolic hydroxyl group leads to the formation of a carbonate ester bond. Thus, the ester-substituted phenol by-product of the reaction of an ester-substituted diaryl carbonate and a dihydroxy aromatic compound may be incorporated into the main chain of a linear polycarbonate, for example.

Another structural feature that may be present in polycarbonate prepared by a melt transesterification polymerization reaction between an ester-substituted aromatic carbonate and a dihydroxy aromatic compound is the structure

Is an ester bond end group. Wherein R ² and “e” are defined the same as in the previous structure. Although not wishing to be bound by any theory, it is believed that this structure occurs in the same way as structure (VII). However, this structure is thought to occur if the hydroxyl group of the ester-substituted phenol does not react any further. In the structures provided herein, the wavy line represents a polycarbonate polymer chain structure.

The end protection of polymer chains formed during melt transesterification reactions such as those described herein may be only partial. In general, the hydroxyl group content in polycarbonate systems related to PPE-PC block copolymer polycarbonates prepared by the methods described herein should be 7 to 50 percent of the total number of end groups present. In some embodiments, the percent end protection may be at least about 90 percent. While not wishing to be bound by any theory, the polycarbonate formed during the reaction that ultimately results in the formation of the PPE-PC block copolymer is not fully end-capped, and the hydroxy end groups and It is believed to have both an aryloxy end group. When the activated aromatic carbonate used is an ester-substituted activated aromatic carbonate, the polycarbonate formed during the reaction that ultimately results in the formation of the PPE-PC block copolymer is hydroxy-terminated. It is believed to have both groups and ester-substituted aryloxy end groups. In preparing the polycarbonate, the amount of hydroxy end groups relative to the total number of end groups may be adjusted. The type and concentration of end groups may be changed by changing the reaction conditions or by adding additional end-protecting agents. In one embodiment of preparing polycarbonate using activated carbonate ester BMSC, a structure having hydroxyl groups

An ester bond end group having The hydroxyl groups present in this structure may in principle participate in polycarbonate chain formation and copolymer formation. The chemistry observed in the polycarbonate system is believed to be substantially similar to that occurring in the reaction mixture that ultimately provides the PPE-PC block copolymer.

In one embodiment, the polycarbonate block of the product PPE-PC block copolymer has the structure

It may contain end groups having

  The end group having this structure is usually bonded to the remaining part of the polycarbonate via a carbonate ester bond. Thus, the terminal group containing this structure represents an activated carbonate moiety that is readily reactive with the hydroxyl group of the poly (arylene ether) component. When the polycarbonate containing the activated carbonate moiety reacts with the hydroxyl groups of the poly (arylene ether) component, the result is a polymer containing poly (arylene ether) (PPE) blocks and polycarbonate (PC) blocks. Such a process is believed to account for the formation of the PPE-PC block copolymers described herein. Useful end groups include other salicyl groups such as ethyl salicyl, isopropyl salicyl and butyl salicyl groups.

  The poly (arylene ether) -polycarbonate block copolymer may further comprise structural units derived from a terminal protecting agent that is not derived from an activated aromatic carbonate. A terminal protecting agent is generally used to adjust the molecular weight of the polycarbonate. Suitable end capping agents include phenol and monoalkyl and monoaryl substituted phenols such as para-cumylphenol, para-cresol and the like. The term “end-protecting agent” is understood not to include polymeric species such as poly (arylene ether) having a single hydroxyl group, or polycarbonate having a single reactive end group.

  In some embodiments, certain poly (arylene ether) -polycarbonate block copolymers (referred to hereinafter as composition “A” for convenience) include (A) 1,4-hydroquinone and 2-methyl-1,4-hydroquinone. Derived from hydroquinone selected from the group consisting of: (B) poly (2,6-dimethyl-1,4-phenylene ether) containing hydroxyl groups, (C) bisphenol A, and (D) activated aromatic carbonates. Including structural units. In one embodiment, the block copolymer comprises structural units derived from 1,4-hydroquinone and bisphenol A, and more than 60 mole percent of those units are derived from 1,4-hydroquinone. In one embodiment, composition A comprises structural units derived from 2-methyl-1,4-hydroquinone, bisphenol A, and optionally 1,4-hydroquinone, and comprises about 94 moles of structural units. More than a percent is derived from methyl-1,4-hydroquinone. In another embodiment, Composition A comprises structural units derived from 1,4-hydroquinone, 2-methyl-1,4-hydroquinone, and bisphenol A, wherein about 97 mole percent or more of the structural units are 1 , 4-hydroquinone and 2-methyl-1,4-hydroquinone. In yet another embodiment, the block copolymer is about 6 to 60 weight percent or about 30 to about 50 weight percent poly (2,6-dimethyl-1,4, based on the total weight of the block copolymer. A structural unit derived from (-phenylene ether) may be included. In another specific embodiment, the PPE-PC block copolymer comprises the structural units described for “Composition A” wherein the activated aromatic carbonate is BMSC.

  In still another embodiment, (A) hydroquinone selected from the group consisting of 1,4-hydroquinone and 2-methyl-1,4-hydroquinone, (B) poly (2,6-dimethyl-1, which contains a hydroxyl group Specific PPE-PC block copolymers comprising structural units derived from (4-phenylene ether), (C) bisphenol A, and (D) bis (methylsalicyl) carbonate are provided. In some embodiments, the PPE-PC block copolymer is a molten crystal.

  The structure of the poly (arylene ether) -polycarbonate block copolymer may take various forms. For example, a poly (arylene ether) -polycarbonate block copolymer may be a diblock copolymer, a triblock copolymer, a linear multiblock copolymer having 4 or more blocks, or a star-shaped teleblock copolymer. It may be. In one embodiment, the poly (arylene ether) -polycarbonate block copolymer is a poly (arylene ether) -polycarbonate-poly (arylene ether) triblock copolymer. The block building form of the copolymer is activated carbonic acid for the number of hydroxyl groups on poly (arylene ether), the number of hydroxyl groups on polycarbonate, and the total number of moles of hydroxyl groups on poly (arylene ether) and polycarbonate. It may be adjusted by the molar ratio of esters, the use of end-protecting agents, and other reaction conditions.

  One embodiment is a general methodology for the preparation of PPE-PC block copolymers. Thus, one embodiment is a general and efficient method for the preparation of PPE-PC block copolymers that can be amorphous or crystalline. In this embodiment, the PPE-PC block copolymer is obtained by transesterifying a mixture comprising polycarbonate, poly (2,6-dimethyl-1,4-phenylene ether) containing hydroxyl groups, and an activated aromatic carbonate. It may be prepared by heating at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of the catalyst. There is no particular limitation on the composition of the polycarbonate, and any polycarbonate containing at least one reactive hydroxyl group (eg, a BPA polycarbonate containing aromatic hydroxy end groups) may be used. Further, the PPE-PC block copolymer is obtained by transesterifying a mixture containing a dihydroxy aromatic compound, a poly (2,6-dimethyl-1,4-phenylene ether) containing a hydroxyl group, and an activated aromatic carbonate. It may be prepared by heating at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of the catalyst.

  Another embodiment is a general and efficient method for the preparation of molten crystalline PPE-PC block copolymers. In this embodiment, the molten crystalline PPE-PC block copolymer is a poly (2,6-dimethyl-1,4-phenylene ether) containing hydroxyl groups, an activated aromatic carbonate, and a polycarbonate comprising hydroquinone. The mixture containing the derived structural unit may be prepared by heating in the presence of a transesterification catalyst at one or more temperatures in the temperature range of about 100 to about 400 ° C. Further, the melt crystalline PPE-PC block copolymer comprises poly (2,6-dimethyl-1,4-phenylene ether) containing hydroxyl groups, activated aromatic carbonates, and 1,4-hydroquinone and methyl-1 Preparing a mixture comprising 1,4-hydroquinone selected from the group consisting of 1,4-hydroquinone at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst. Good. In some embodiments, the mixture is melt mixed in an extruder with a vent that facilitates removal of volatile components. Alternatively, the block copolymer may be prepared using any polymerization reactor commonly used to produce polycarbonate by a melt polymerization process. The polymerization may be carried out in the presence of a suitable solvent. For example, a mixture comprising a solution of polycarbonate in a solvent, poly (arylene ether) containing hydroxyl groups, and an activated aromatic carbonate is extruded through an extruder adapted to remove the solvent to form a block copolymer. provide.

  In one embodiment, the mixture fed to the extruder may comprise from about 10 weight percent to about 99 weight percent solvent, in another embodiment from about 30 weight percent to about 70 weight percent solvent. Non-limiting examples of suitable solvents include ester-substituted phenols, halogenated aromatic solvents, halogenated aliphatic solvents, non-halogenated aromatic solvents, non-halogenated aliphatic solvents, and mixtures thereof. Examples of halogenated aromatic solvents are ortho-dichlorobenzene (ODCB), chlorobenzene and similar compounds. Non-halogenated aromatic solvents are examples of toluene, xylene, anisole, phenol, 2,6-xylenol and the like. Examples of halogenated aliphatic solvents are methylene chloride, chloroform, 1,2-dichloroethane and the like. Examples of non-halogenated aliphatic solvents are ethanol, acetone, ethyl acetate, cyclohexanone and the like. In one embodiment, the solvent used comprises a mixture of a halogenated aromatic solvent and an ester-substituted phenol, such as, for example, a mixture of ortho-dichlorobenzene (ODCB) and methyl salicylate.

  The solvent may also include a monohydroxy aromatic compound by-product obtained as a result of the reaction of the activated aromatic carbonate with the aromatic hydroxyl group of the dihydroxy aromatic compound. For example, in the reaction of bisphenol A or a mixture of bisphenol A, hydroquinone, and poly (arylene ether) having a hydroxyl group with bis (methyl salicyl) carbonate (BMSC), 2-methoxycarbonylphenol (methyl salicylate) Obtained as a living organism, it acts as a solvent component. In another embodiment, a monohydroxy aromatic compound produced as a by-product upon formation of the oligomeric polycarbonate from the dihydroxy aromatic compound and the activated aromatic carbonate is present during the formation of the molten crystalline PPE-PC block copolymer. It is the only solvent.

  Solution polymerization (eg, by reaction of a dihydroxy aromatic compound with bis (chloroformate) of a dihydroxy aromatic compound), or melt polymerization (eg, bisphenol A and carbonic acid to provide a hydroxy-terminated bisphenol A polycarbonate in the presence of a transesterification catalyst. Hydroxy-substituted polycarbonates such as bisphenol A polycarbonates containing hydroxy end groups may be obtained by any of a number of known methods such as melt polymerization with diphenyl). Polycarbonates contain terminal hydroxyl groups that can participate in the formation of block copolymers by reaction with poly (arylene ethers) containing hydroxyl groups in the presence of activated aromatic carbonates. In addition to PPE-PC block copolymer formation, the method results in (i) conversion of polycarbonate to higher molecular weight polycarbonate (by coupling of polycarbonate chains), and (ii) product PPE-PC block. Separation of the solvent from the copolymer may be performed. In some embodiments, the method may be present in the initial feed solution or other product that may be formed as a by-product when the reaction components are converted to the product PPE-PC block copolymer. Provides removal of volatiles.

  The exact sequence of reactions leading to the formation of the PPE-PC block copolymer is not known, but the entire process is divided into (1) polycarbonate, hydroxyl groups containing activated terminal aryloxyl groups where the reactants are heated together. A first step of forming an “equilibrated” mixture comprising poly (arylene ether) containing and by-product phenolic compounds generated from the transesterification of the activated aromatic carbonate; and (2) removing the by-product phenolic compounds It is convenient to describe a two-part reaction model that includes a second stage in which polymer chain growth and copolymer formation occur to yield the product PPE-PC block copolymer. Those skilled in the art will appreciate that the reactions described herein leading to PPE-PC block copolymers are more complex than this simple model. Thus, the first stage “equilibrated” mixture may comprise an oligomeric PPE-PC block copolymer, which is converted to a high molecular weight PPE-PC block copolymer in the second stage of the reaction. Further, the polycarbonate present in the equilibration reaction mixture may contain hydroxyl groups, and the poly (arylene ether) oligomers contain activated terminal aryloxyl groups that are linked to the poly (arylene ether) oligomer structure via the carbonyl group. Good (poly (arylene ether) has an activated carbonate moiety at the end). In the second reaction step, the hydroxyl groups of the polycarbonate may replace the activated terminal aryloxy groups of the poly (arylene ether) to give a PPE-PC block copolymer. Thus, when reference is made herein to a polycarbonate formed in an equilibration reaction in which a poly (arylene ether) containing a hydroxyl group is present as a reactant, the polycarbonate has either a terminal hydroxyl group or a terminal activated aryloxy group. It is understood that the polycarbonate may actually comprise an oligomeric PPE-PC block copolymer.

Typically, the equilibration step involves heating the hydroquinone, poly (arylene ether) component, and optional aromatic dihydroxy compound with an ester-substituted diaryl carbonate in the presence of a transesterification catalyst. Accordingly, the reactants are combined in the tank at a ratio of about 0.5 to about 2 moles of activated aromatic carbonate per mole of dihydroxy compound present. Within this range, the ratio may be at least about 0.75, at least about 0.95, or at least about 1, and within this range the ratio may be up to about 1.5, up to about 1.3, up to about 1 .2, up to about 1.1 or up to about 1.05. The amount of the transesterification catalyst used is, dihydroxy compounds per mole to about 1.0 × ^{10 -8} to about 1 × ^{10 -3} or present from about 1.0 × ^{10 -6} to about 2.5 × 10, ^{- 4} moles of transesterification catalyst. When the mixture is heated at one or more temperatures in the range of about 100 to about 400 ° C., about 100 to about 300 ° C., or about 100 to about 250 ° C., the reaction takes place and the product polycarbonate, byproduct ester-substituted phenol ( Solvent), a transesterification catalyst and low levels of starting materials, an equilibrium mixture of dihydroxy aromatic compound and activated aromatic carbonate is obtained. This is called “equilibrating” the reactants. Equilibrium is usually very advantageous for the formation of product polycarbonate and by-product substituted phenols (derived from activated aromatic carbonates) and only trace amounts of starting material are observed. The product polycarbonate contains terminal ester-substituted phenoxycarbonyl groups that serve as sites for PPE-PC block copolymer formation by reaction with the hydroxyl group (s) of poly (arylene ether). In one embodiment, the polycarbonate produced has a number average molecular weight of about 500 atomic mass units or greater. In one embodiment, the polycarbonate produced has a number average molecular weight of about 5000 atomic mass units or greater.

  Usually, the amount of catalyst present during the second reaction stage is approximately the same as the amount of catalyst used in the equilibration stage. It should be noted that in one embodiment, the polycarbonate is prepared using methods such as interfacial polymerization. In this embodiment, the polycarbonate, the poly (arylene ether) containing hydroxyl groups, and the activated aromatic carbonate are heated together in the melt to provide a PPE-PC block copolymer. Under such circumstances, the equilibration step is not included, and the addition of an exogenous catalyst may be necessary to achieve PPE-PC block copolymer formation. In one embodiment, polycarbonate, poly (arylene ether) containing hydroxyl groups, catalyst and activated diaryl carbonate are combined in an extruder and extruded to provide a PPE-PC block copolymer. In some embodiments, the catalyst may be added before the extrusion process, during the extrusion process, or both.

In some instances, it may be desirable to remove some of the ester-substituted phenol byproduct that is formed during the equilibration of the reactants. This may be conveniently performed by heating the reactants and transesterification catalyst under vacuum, usually at a pressure of about 0.01 to about 0.9 atmospheres, and distilling off a portion of the ester-substituted phenol. As the ester-substituted phenol is distilled from the mixture undergoing the equilibration reaction, the molecular weight of the polycarbonate tends to increase. When sufficient ester-substituted phenol by-product is removed, the number average molecular weight (M _n ) of the oligomeric polycarbonate can exceed 5,000 AMU and in some cases can exceed 7,000 AMU. Thus, in one embodiment, the mixture containing the reactants is heated at a temperature of about 100 to about 300 ° C. in the presence of a transesterification catalyst, and a portion of the byproduct ester-substituted phenol is removed by distillation to produce a substituted phenol, transesterification. An equilibrated product mixture is obtained comprising a catalyst and a polycarbonate comprising a terminally substituted phenoxycarbonyl group. In one embodiment, the equilibrated product mixture is fed to a devolatilized extruder and extruded to provide a PPE-PC block copolymer.

  In one embodiment, the mixture fed to the extruder to prepare the PPE-PC block copolymer comprises a transesterification catalyst, hydroquinone, a poly (arylene ether) containing hydroxyl groups, an activated aromatic carbonate, and Optionally, one or more dihydroxy aromatic compounds other than the hydroquinone are included. The activated aromatic carbonate may be used in an amount of about 0.95 to about 1.05 moles per mole of hydroquinone, poly (arylene ether), and dihydroxy aromatic compound combined. The mixture is heated to a suitable temperature in the range of about 100 to about 400 ° C. to achieve the formation of a block copolymer. By-product phenolic compounds formed during the course of the reaction may be removed by conventional techniques such as distillation at normal pressure or pressure below normal pressure.

  As described above, in one embodiment, the PPE-PC box copolymer is prepared using an extruder. The extruder may be a devolatilizer type extruder. That is, an extruder that is adapted to separate a significant amount of volatile components from the polymer-containing mixture. Thus, the extruder must have at least one, and preferably two or more vents adapted to remove volatile materials.

  The devolatilizing extruder may be a single screw or multi-screw extruder. Typically, the devolatilizing extruder has one or more temperatures within the range of about 100 to about 400 ° C., one or more screw speeds within the screw speed range of about 50 to about 1200 rpm, or about 50 to about 500 rpm. Operate with.

  Suitable devolatilizing extruders include co-rotating meshing twin screw extruders, counter-rotating non-meshing twin screw extruders, single screw reciprocating extruders and single screw non-reciprocating extruders.

  Extruder screw speed and feed rate are usually interdependent. It is useful to characterize this relationship between feed rate and screw speed as a ratio. Typically, the extruder has a ratio of starting material introduced into the extruder in pounds per hour to screw speed expressed in rpm from about 0.0045 to about 45 kilograms per hour per rpm (about about per hour per rpm). 0.01 to about 100 pounds), or about 0.0023 to about 2.3 kilograms per hour per rpm (about 0.05 to about 5 pounds per hour per rpm). For example, when the solution is introduced at 454 kilograms per hour (1000 pounds per hour) into an extruder operating at 400 rpm, the ratio of feed rate to screw speed is 1.13 kilograms per hour per rpm ( 2.5 pounds per hour). Maximum and minimum feed rates and extruder screw speed are determined by the size of the extruder, among other factors, and the general rule is that the larger the extruder, the higher the maximum and minimum feed rates.

  In one embodiment, a feed mixture comprising a transesterification catalyst, hydroquinone, a poly (arylene ether) containing a hydroxyl group, an activated aromatic carbonate, and optionally one or more dihydroxy aromatic compounds other than the hydroquinone. Of the equilibrated product prepared in a reactor and heated at a temperature of about 100 to about 300 ° C., or about 150 to about 250 ° C., a pressure of about 1 to about 10 atmospheres, or about 1 to about 2 atmospheres. Prepare the solution. The phenol by-product formed in the transesterification reaction of the activated aromatic carbonate serves as the solvent. In some embodiments, the phenol by-product is an ester-substituted phenol, such as methyl salicylate. The resulting solution may be transferred by a gear pump into an extruder, for example a twin screw extruder with a 14 barrel vent. The extruder can be any suitable screw design that is suitable to achieve material transfer and solvent (ester substituted phenol) removal and allow sufficient residence time to complete the formation of the PPE-PC block copolymer. It may be. The extruder screw design consists of a conveying screw element and a mixing section that includes an initial mixing section and one or more mixing sections that provide intense mixing of the contents of the extruder. The extruder is operated at a screw speed of about 100 to about 400 ° C., or about 200 to about 350 ° C., about 50 to about 1200 rpm. The solution is introduced into the upstream portion of the extruder barrel. The extruder is equipped with a vent (operating at or below atmospheric pressure) that removes the ester-substituted phenolic solvent and other volatile byproducts formed during the formation of the PPE-PC block copolymer. Connected to the manifold system for The resulting PPE-PC block copolymer is isolated as an extrudate.

  In some embodiments, the reactant mixture used includes a chain terminator such as a monofunctional monohydroxy aromatic compound, such as phenol, para-cumylphenol or the like.

  As mentioned above, the equilibration mixture supplied to the extruder may optionally include one or more solvents. In one embodiment, the equilibrated mixture containing the solvent is heated under pressure to create a “superheated” solution, which means that the temperature of the heated solution is higher than the boiling point of the solvent at atmospheric pressure. Typically, the temperature of the superheated solution is about 2 to about 200 ° C. above the boiling point of the solvent at atmospheric pressure. When multiple solvents are present, the solution is “superheated” for at least one solvent component. If the solution contains significant amounts of both high and low boiling solvents, it may be advantageous to superheat the solution for all solvents present (ie above the boiling point of the highest boiling solvent at atmospheric pressure). Superheating is usually achieved by heating the solution mixture at a pressure of up to about 10 atmospheres under pressure, but higher than 1 atmosphere. Such superheated solutions are conveniently prepared in pressurized heated feed tanks, pressurized heat exchangers, extruders, pressurized reactors and similar equipment. The superheated solution is then introduced into the devolatilizing extruder through a pressure control valve. In one embodiment, the devolatilizer extruder comprises at least one side feeder. In another embodiment, the extruder in combination with the side feeder comprises one or more atmospheric vents in the vicinity of the main feed inlet that includes a pressure control valve.

  In some cases, the product PPE-PC block copolymer may be found to have an insufficient molecular weight or retain excess solvent or other volatile by-products generated during the formation of the block copolymer. is there. In such cases, the resulting product is subjected to a second extrusion on the same or different devolatilized extruder to increase the molecular weight and reduce the level of residual solvent and / or volatile reaction by-products. PPE-PC block copolymers may be obtained.

  One embodiment is a method for making a poly (arylene ether) -polycarbonate block copolymer comprising hydroquinone, a poly (arylene ether) containing a hydroxyl group, and optionally one or more other than the hydroquinone. A mixture comprising a dihydroxy aromatic compound and an activated aromatic carbonate is heated in the presence of a transesterification catalyst at a temperature in the range of about 100 to about 300 ° C. to produce polycarbonate, poly (arylene ether), and activated aromatic Providing a solution comprising a solvent derived from a carbonate and at one or more temperatures in the range of about 100 to about 400 ° C. and at one or more screw speeds in the range of about 50 to about 1200 rpm. Extruded to provide a poly (arylene ether) -polycarbonate block copolymer And a fact, extruding is a method performed by the extruder comprising a vent adapted to suit the solvent removed.

  The method may be performed in a batch mode or a continuous mode. In one embodiment, the method is performed as a batch process in which the reactants are equilibrated in a batch reactor to form a solution containing the equilibrated product of the feed components. The solution is then fed to a devolatilizing extruder and the product PPE-PC block copolymer is separated at the exit end of the extruder. Alternatively, the process may be carried out in a continuous process, in which case the reactants are fed continuously into a continuous reactor and the resulting solution containing the equilibrated product of the feed components is devolatilized. The product PPE-PC block copolymer appears from the extruder as it is continuously fed into the product extruder.

  Especially in the case of melt reactions, the purity of the reactants, ie the monomers used (hydroquinone, activated aromatic carbonates and dihydroxyaromatic compounds) and polymers (polycarbonates and poly (arylene ethers having hydroxyl groups)). Can be strongly influenced by the properties of the product PPE-PC block copolymer polycarbonate. Thus, it is often desirable that the raw material components used be free of or very limited in amounts of contaminants such as metal ions, halide ions, acidic contaminants and other organic species. Typically, the concentration of metal ions, such as iron, nickel, cobalt, sodium, and potassium present in the monomer is less than about 10 parts per million (ppm), less than about 1 ppm, or about 100 parts per part by weight. Must be less than (ppb). The amount of halide ions, such as fluoride, chloride and bromide ions, should be minimized to avoid the corrosive effects of halide ions on the equipment used to prepare the PPE-PC block copolymer . Preferably, the level of halide ions present in each raw material component used should be less than about 1 ppm. The presence of organic sulfonic acids that may be present in bisphenols such as BPA, such as BPA, should be minimized because only trace amounts of basic catalyst are used in the oligomerization and subsequent polymerization steps. . Even small amounts of acidic impurities can neutralize a significant portion of the basic catalyst used, and can have a significant effect on the rate of oligomerization and polymerization. Finally, the tendency of polycarbonate to decompose with high molecular weight, for example molding, with molecular weight reduction and fading during molding is strongly correlated with the presence of contaminating species in the polycarbonate block of the block copolymer. In general, the level of purity of the product PPE-PC block copolymer prepared using the melt reaction method closely reflects the level of purity of the starting ingredients.

  Usually, the transesterification catalyst is not consumed in the equilibration step and is not removed prior to extrusion, so it is usually not necessary to add additional catalyst during extrusion. The transesterification catalyst may be any catalyst that is effective in promoting a common melt reaction to form a polycarbonate of a bisphenol such as BPA and a diaryl carbonate such as diphenyl carbonate. The transesterification catalyst may comprise an onium catalyst such as a quaternary ammonium compound, a quaternary phosphonium compound, or a mixture thereof. Quaternary onium hydroxides, halides, carboxylates, phenoxides, sulfonates, sulfates, carbonates and bicarbonates may be used as catalysts. Non-limiting examples showing examples of quaternary ammonium compounds include tetramethylammonium hydroxide, tetrabutylammonium acetate, tetrabutylammonium hydroxide and similar compounds and mixtures thereof. Non-limiting examples of quaternary phosphonium compounds include tetramethylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydroxide and similar compounds and mixtures thereof.

  In one embodiment, the transesterification catalyst used is a combination of a quaternary ammonium compound, a quaternary phosphonium compound, or a mixture thereof and an alkali metal hydroxide, alkaline earth metal hydroxide, or mixture thereof. is there. For example, a mixture of tetrabutylphosphonium acetate and sodium hydroxide may be used.

Other transesterification catalysts that may be used include one or more alkali metal carboxylates, one or more alkaline earth metal carboxylates, and mixtures thereof. Such transesterification catalysts are examples of simple salts of carboxylic acids such as sodium acetate, calcium stearate and the like. Furthermore, alkali metal salts and alkaline earth metal salts of organic polybasic acids can be used as efficient transesterification catalysts. Alkali metal and alkaline earth metal salts of organic polybasic acids such as ethylenediaminetetracarboxylate may be used. An example of the organic polybasic acid salt is disodium magnesium ethylenediaminetetraacetate (Na ₂ MgEDTA).

  In one embodiment, the transesterification catalyst comprises a salt of a non-volatile acid. “Non-volatile” means that the acid from which the catalyst is made has no measurable vapor pressure under melt polymerization conditions. Examples of non-volatile acids include phosphorous acid, phosphoric acid and sulfuric acid, and metal “oxo acids” such as germanium, antimony, niobium and similar element oxo acids.

Non-volatile acid salts useful as melt polymerization catalysts are alkali metal salts of phosphites, alkaline earth metal salts of phosphites, alkaline metal salts of phosphate esters, alkaline earth metal salts of phosphate esters , Alkali metal salts of sulfate esters, alkaline earth metal salts of sulfate esters, alkali metal salts of metal oxo acids and alkaline earth metal salts of metal oxo acids. Specific examples of non-volatile acid salts are NaH ₂ PO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₄ , KH ₂ PO ₄ , CsH ₂ PO ₄ , Cs ₂ HPO ₄ , NaKHPO ₄ , NaCsHPO ₄ , KCsHPO ₄ , Na ₂ SO ₄ , NaHSO ₄ , NaSbO ₃ , LiSbO ₃ , KSbO ₃ , Mg (SbO ₃ ) ₂ , Na ₂ GeO ₃ , K ₂ GeO ₃ , Li ₂ GeO ₃ , MgGeO ₃ , Mg ₂ GeO ₄ and mixtures thereof including.

In one embodiment, the transesterification catalyst, from about 1.0 × ^{10 -8} to about 1 × ^{10 -3} mole per transesterification catalyst activated aromatic carbonate for use, or about 1.0 × 10, ^- Used in an amount of ⁶ to about 2.5 × 10 ⁻⁴ moles.

  One embodiment comprises a poly (arylene ether) -polycarbonate block copolymer comprising melt reacting a poly (arylene ether), a polycarbonate containing structural units derived from hydroquinone, and an activated aromatic carbonate. It is a method of preparation.

  In embodiments where the PPE-PC block copolymers are melt crystalline, they comprise an advantageous combination of processability and high melting point. In one embodiment, the PPE-PC block copolymer has a glass transition point of about 95 to about 140 ° C and a melting point of about 260 to about 330 ° C. In one embodiment, the PPE-PC block copolymer has a glass transition point of about 110 to about 140 ° C and a melting point of about 260 to about 300 ° C. Melt process processability allows these block copolymers to be processed using conventional molding equipment to prepare various shaped articles. The high melting point provides other valuable properties such as chemical resistance and / or solvent resistance that make them useful in aviation and automotive engine applications and in the manufacture of articles useful as storage media for chemicals. . In addition, the molten crystalline block copolymer is valuable for producing articles useful in the healthcare industry, such as packaging pharmaceutical and healthcare products and manufacturing medical devices. In some embodiments, the PPE-PC block copolymer is essentially opaque. Those skilled in the art will recognize that the block copolymer can be modified by changing the structure of the hydroquinone monomer, the structure and / or molecular weight of the poly (arylene ether), the structure and / or molecular weight of the polycarbonate, and the type of activated aromatic carbonate. It will be appreciated that properties can be changed. Similarly, the structure of hydroquinone monomer, the structure and / or molecular weight of poly (arylene ether), the structure and / or molecular weight of the dihydroxy aromatic compound (s) used to produce the polycarbonate, and the activated fragrance The properties of the block copolymer can also be changed by changing the type of the aromatic carbonate. In other embodiments, PPE-PC block copolymers have excellent impact strength, low water absorption, making them suitable materials for creating robust articles that can withstand high temperature and / or wet environments, And a combination of properties including one or more of good processability.

  The PPE-PC block copolymer may be used as a base substrate for optical data storage media. That is, it may function as a substrate on which a data storage medium can be applied.

  One embodiment is a process for making a poly (arylene ether) -polycarbonate block copolymer at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst ( A method comprising heating a mixture comprising A) polycarbonate, (B) a poly (arylene ether) containing hydroxyl groups, and (C) an activated aromatic carbonate. This method may optionally be performed on an extruder equipped with a vent adapted to remove volatile compounds.

  One embodiment is a process for making a poly (arylene ether) -polycarbonate block copolymer at one or more temperatures in the temperature range of about 100 to about 400 ° C. in the presence of a transesterification catalyst ( A) a method comprising heating a mixture containing hydroquinone, (B) a poly (arylene ether) containing a hydroxyl group, (C) a dihydroxy aromatic compound other than the hydroquinone, and (D) an activated aromatic carbonate. is there. The mixture optionally includes from about 10 to about 99 weight percent solvent selected from the group consisting of ester-substituted phenols, halogenated aromatic solvents, halogenated aliphatic solvents, non-halogenated aliphatic solvents, and mixtures thereof. Further may be included.

  One embodiment is a method of preparing a poly (arylene ether) -polycarbonate block copolymer comprising melting a poly (arylene ether), a polycarbonate comprising structural units derived from hydroquinone, and an activated aromatic carbonate. Including reacting. Note that it is not necessary to synthesize polycarbonate as part of the procedure for preparing the block copolymer. In other words, a separately prepared or purchased polycarbonate may be used in this method of forming a block copolymer.

  One embodiment comprises a poly (arylene ether) block, a polycarbonate block comprising units derived from hydroquinone, and a poly (arylene ether) -polycarbonate block comprising a carbonate group connecting the poly (arylene ether) block and the polycarbonate block. It is a polymer.

Poly (arylene ether) -poly (alkylene ether) block copolymer:
One embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a poly (alkylene ether) containing a hydroxyl group, and an activity Reacting a fluorinated aromatic carbonate. The reaction may be allowed to proceed in the polymer melt (i.e. in the absence of deliberately added solvent) or in solution (i.e. in the presence of deliberately added solvent). Suitable solvents for the solution reaction are aromatic hydrocarbon solvents (eg benzene, toluene, ethylbenzene, xylenes), halogenated aromatic hydrocarbon solvents (eg chlorobenzene, dichlorobenzenes and trichlorobenzenes) and halogenated aliphatic carbonization. Hydrogen solvent (eg methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, dichloroethylenes, trichloroethanes and trichloroethylene).

  The term “melt reacting” refers to a reaction that takes place in the absence of added solvent. (It will be understood that the melt reaction includes a reaction that generates a product that may act as a solvent. For example, a melt reaction of bis (methyl salicyl carbonate) may generate methyl salicylate.) Melt reaction conditions Generally includes temperatures above the melting and / or glass transition temperature of the poly (arylene ether) and poly (alkylene ether) reactants, but below the temperature at which the reactants are substantially unstable. The melt reaction may be performed by mixing poly (arylene ether), poly (alkylene ether), and activated aromatic carbonate and then heating to a temperature suitable for the melt reaction. Alternatively, the activated aromatic carbonate may be melt reacted with either poly (arylene ether) or poly (alkylene ether) and then the other polymer added. In some embodiments, the melt reaction conditions include the following process conditions: one or more temperatures in the range of about 90 to about 400 ° C., removal of volatile components using a vacuum of about 1 to 100 kilopascals, and stirring ( For example, stirring at about 1 to 100 rpm). In the following examples, typical melt reaction conditions are described in detail.

  The poly (arylene ether) and the activated aromatic carbonate are the same as described above for the poly (arylene ether) -polycarbonate block copolymer.

Poly (alkylene ether) has the structure

Repeating units having Where R ⁷ is a C _{2 to} C ₁₂ alkylene group, and the asterisk means the point of attachment to the rest of the poly (alkylene ether) molecule. The poly (alkylene ether) may be linear or branched. It may have one, or more than one hydroxyl group.

In some embodiments, the poly (alkylene ether) has the structure

Have Wherein R ⁷ is a C _{2 to} C ₁₂ alkylene group and r is from 2 to about 1,000. Within the range of 2 to about 1,000, r may be at least about 10, at least about 20, or at least about 40. Within a range of 2 to about 1,000, r may be up to about 500, or up to about 200. In some embodiments, the poly (alkylene ether) has a number average molecular weight of about 100 to about 40,000 atomic mass units. Within this range, the number average molecular weight may be at least about 500, at least about 1,000, or at least about 2,000 atomic mass units, and within this range, the number average molecular weight may be up to about 20,000 or up to about 10 000 atomic mass units. In some embodiments, R ⁷ is an unsubstituted alkylene group. For example, it does not include a hydroxyl group or any other heteroatom-containing group. Suitable poly (alkylene ethers) are, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, at least of ethyleneoxy units, propyleneoxy units, tetramethyleneoxy units, hexamethyleneoxy units and the like. Copolymer glycols containing two, and mixtures thereof. In one embodiment, the poly (alkylene ether) is polyethylene glycol, polytetramethylene glycol, or a mixture thereof.

  In some embodiments, an activated aromatic carbonate in an amount of about 0.5 to about 2 moles per mole of total hydroxyl groups provided by poly (arylene ether) and poly (alkylene ether) may be used. Within this range, the amount of activated aromatic carbonate may be at least about 0.75 mole, at least about 0.95 mole, or at least about 1 mole per 2 moles of hydroxyl groups. Within this range, the amount of activated aromatic carbonate can be up to about 1.5 moles, up to about 1.3 moles, up to about 1.2 moles, up to about 1.1 moles, or up to about 1 mole per 2 moles of hydroxyl groups. .05 mole is also good.

  There are no particular restrictions on the weight ratio of poly (arylene ether) to poly (alkylene ether) used in the reaction mixture or incorporated into the resulting copolymer. In one embodiment, the weight ratio of poly (arylene ether) to poly (alkylene ether) is from about 1:10 to about 10: 1. Within this range, the weight ratio may be at least about 1: 5, or at least about 1: 4. Within this range, the weight ratio may be up to about 2: 1, or up to about 1: 1.

  The structure of the poly (arylene ether) -poly (alkylene ether) block copolymer may take various forms. For example, a poly (arylene ether) -poly (alkylene ether) block copolymer is a diblock copolymer, a triblock copolymer, a linear multiblock copolymer having 4 or more blocks, or a star teleblock. It may be a copolymer. In one embodiment, the poly (arylene ether) -poly (alkylene ether) block copolymer is a poly (arylene ether) -poly (alkylene ether) -poly (arylene ether) triblock copolymer. The block structure of the copolymer consists of the number of hydroxyl groups on the poly (arylene ether), the number of hydroxyl groups on the poly (alkylene ether), the total moles of hydroxyl groups of the poly (arylene ether) and poly (alkylene ether). It can be adjusted by the ratio of the number of moles of activated carbonate to number, the use of end-protecting agents and other reaction conditions. For example, when the poly (arylene ether) is mostly monofunctional (ie, on average has close to 1 hydroxyl group per molecule) and the poly (alkylene ether) averages to have close to 2 hydroxyl groups per molecule, The reaction product may comprise a poly (arylene ether) -poly (alkylene ether) -poly (arylene ether) triblock copolymer.

  One embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a poly (alkylene ether) containing a hydroxyl group, and a carbonic acid The poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram at 25 ° C. in chloroform and comprises 2,6-dimethyl-1 , 4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units or combinations thereof, the poly (alkylene ether) being a number average of about 1,000 to about 10,000 atomic mass units Poly (alkylene ether) with molecular weight is polyethylene glycol, polyteto The weight ratio of poly (arylene ether) to poly (alkylene ether) is selected from the group consisting of methylene glycol and mixtures thereof, and the activated aromatic carbonate is poly (arylene). Used in an amount of about 0.5 to about 2 moles per mole of total hydroxyl groups provided by the ether) and poly (alkylene ether).

  One embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer prepared by any of the above-described methods.

  One embodiment comprises a poly (arylene ether) block, a poly (alkylene ether) block, and a poly (arylene ether) -poly (alkylene) comprising a carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block. Ether) block copolymer.

  One embodiment is a poly (arylene ether) -poly (alkylene ether) block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram at 25 ° C. in chloroform, A poly (arylene ether) block comprising 6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, and about 1,000 to about 10, A poly (alkylene ether) block having a number average molecular weight of 000 atomic mass units, wherein the poly (alkylene ether) is selected from the group consisting of polyethylene glycol, polytetramethylene glycol and mixtures thereof, and poly (arylene ether) Blocks and poly (alkylene ether) blocks Connecting and a carbonate group.

  Another embodiment is an article comprising any of the above-described poly (arylene ether) -poly (alkylene ether) block copolymers. Such articles may be prepared by the article forming methods described for poly (arylene ether) -polycarbonate block copolymers. Specific articles that may use poly (arylene ether) -poly (alkylene ether) block copolymers include, for example, sheets and films for coating and packaging.

Poly (arylene ether) -polysiloxane block copolymer:
One embodiment is a method of preparing a poly (arylene ether) -polysiloxane block copolymer comprising reacting a poly (arylene ether), a hydroxyaryl-terminated polysiloxane, and an activated aromatic carbonate. . The reaction may be allowed to proceed in the polymer melt (i.e. in the absence of deliberately added solvent) or in solution (i.e. in the presence of deliberately added solvent). Suitable solvents for the solution reaction are aromatic hydrocarbon solvents (eg benzene, toluene, ethylbenzene, xylenes), halogenated aromatic hydrocarbon solvents (eg chlorobenzene, dichlorobenzenes and trichlorobenzenes), and halogenated Aliphatic hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, dichloroethylenes, trichloroethanes and trichloroethylene.

  The term “melt reacting” refers to a reaction that takes place in the absence of added solvent. (It will be appreciated that a melt reaction includes a reaction that generates a product that may act as a solvent. For example, a melt reaction of bis (methyl salicyl carbonate) may generate methyl salicylate.) In general, it includes temperatures above the melting temperature and / or glass transition temperature of the poly (arylene ether) and hydroxyaryl-terminated polysiloxane reactants, but below the temperature at which the reactants are substantially unstable. The melt reaction may be carried out by mixing poly (arylene ether), polysiloxane, and activated aromatic carbonate and then heating to a temperature suitable for the melt reaction. Alternatively, the activated aromatic carbonate may be melt reacted with one of poly (arylene ether) or polysiloxane and the other polymer added. In some embodiments, the melt reaction conditions include the following process conditions: one or more temperatures in the range of about 90 to about 400 ° C., removal of volatile compounds using a vacuum of about 1 to 100 kilopascals, and stirring. (Eg, stirring at about 1 to 100 rpm). In the following examples, typical melt reaction conditions are described in detail.

  The poly (arylene ether) and the activated aromatic carbonate are the same as described above for the poly (arylene ether) -polycarbonate block copolymer.

Hydroxyaryl-terminated polysiloxane has a structure

Repeating units having Wherein R ⁸ and R ⁹ are independently at each position hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halohydrocarbyl, and at least one terminal (end group) is a structure

Have Where Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyloxy or halogen, and R ¹⁰ and R ¹¹ are independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ at each position. _{1 to} C ₁₂ halohydrocarbyl. In one embodiment, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently at each position methyl or phenyl and Y is methoxy. In addition to the terminal hydroxyaryl group, the polysiloxane may include one or more hydroxyaryl groups in the molecular chain. The polysiloxane is, for example, the use of one or more monomers such as CH ₃ SiCl ₃ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , SiCl ₄ and Si (OCH ₂ CH ₃ ) _{4 in} the synthesis of the polysiloxane One or more branch units as a result of Thus, polysiloxanes are optionally branched units

May further include one or more of the following: Where R ¹⁶ is hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halohydrocarbyl each time independently used.

In one embodiment, the hydroxyaryl-terminated polysiloxane has the structure

Have Where n is from 5 to about 200. Within this range, n may be at least 10, at least 20, or at least 30. Within this range, n may be up to about 100, up to about 60, or up to about 40.

  In some embodiments, an activated aromatic carbonate in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the hydroxyaryl-terminated polysiloxane may be used. . Within this range, the amount of activated aromatic carbonate may be at least about 0.75 mole, at least about 0.95 mole, or at least about 1 mole per 2 moles of hydroxyl groups. Within this range, the amount of activated aromatic carbonate can be up to about 1.5 moles, up to about 1.3 moles, up to about 1.2 moles, up to about 1.1 moles, or up to about 1 mole per 2 moles of hydroxyl groups. .05 moles are preferred.

  There are no particular restrictions on the weight ratio of poly (arylene ether) to hydroxyaryl-terminated polysiloxane used in the reaction mixture or incorporated into the resulting copolymer. In one embodiment, the weight ratio of poly (arylene ether) to hydroxyaryl-terminated polysiloxane is from about 1:10 to about 10: 1. Within this range, the weight ratio may be at least about 1: 3, or at least about 1: 1. Within this range, the weight ratio may be up to about 6: 1, or up to about 3: 1.

  The structure of the poly (arylene ether) -polysiloxane block copolymer may take various forms. For example, a poly (arylene ether) -polysiloxane block copolymer is a diblock copolymer, a triblock copolymer, a linear multiblock copolymer having 4 or more blocks, or a star-shaped teleblock copolymer. It may be. In one embodiment, the poly (arylene ether) -polysiloxane block copolymer is a poly (arylene ether) -polysiloxane-poly (arylene ether) triblock copolymer. The block structure of the copolymer is activated for the number of hydroxyl groups on poly (arylene ether), the number of hydroxyl groups on polysiloxane, and the total number of moles of hydroxyl groups on poly (arylene ether) and polysiloxane. It may be adjusted by the molar ratio of carbonate esters, the use of end-protecting agents as well as other reaction conditions. For example, when poly (arylene ether) is mostly monofunctional (ie, having on average close to 1 hydroxyl group per molecule) and polysiloxane on average having close to 2 hydroxyl groups per molecule, the reaction The product may comprise a poly (arylene ether) -polysiloxane-poly (arylene ether) triblock copolymer.

One embodiment is a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a hydroxyaryl-terminated polysiloxane, and bis (methylsalicyl carbonate) The poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl-1,4-phenylene Comprising ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, the hydroxyaryl-terminated polysiloxane has a structure

Have Where n is from about 10 to about 100, the weight ratio of poly (arylene ether) to hydroxyaryl-terminated polysiloxane is from about 1: 3 to about 6: 1, and the activated aromatic carbonate is a poly ( An arylene ether) and a hydroxy-terminated polysiloxane are used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups.

  Other embodiments include poly (arylene ether) -polysiloxane block copolymers prepared by any of the above-described methods.

  One embodiment is a poly (arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) block, a hydroxy-terminated polysiloxane block, and a carbonate group connecting the poly (arylene ether) block and the polysiloxane block. is there. In the context of describing product block copolymers, a “hydroxy-terminated polysiloxane block” is understood to refer to a block that does not contain the hydroxyl group hydrogen atom (s) of the reactant hydroxyaryl-terminated polysiloxane. In other words, in the context of product block copolymers, a “hydroxy-terminated polysiloxane block” may also be referred to as an “oxyaryl-terminated polysiloxane block”.

  One embodiment is a poly (arylene ether) -polysiloxane block copolymer comprising at least one poly (arylene ether) block, at least one hydroxy-terminated polysiloxane block, and a poly (arylene ether) block and a polysiloxane It consists of at least one carbonate group connecting the blocks.

One embodiment is a poly (arylene ether) -polysiloxane block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., and 2,6-dimethyl A poly (arylene ether) block comprising 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, and from about 1,000 to about 5,000 atomic mass A hydroxyaryl-terminated polysiloxane block having a number average molecular weight of the unit and having a structure

Wherein n is from about 5 to about 200, and a hydroxyaryl-terminated polysiloxane block having a carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block.

One embodiment is a poly (arylene ether) -polysiloxane block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl At least one poly (arylene ether) block comprising 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, and from about 1,000 to about 8, At least one hydroxyaryl-terminated polysiloxane block having a number average molecular weight of 000 atomic mass units

Wherein n is from about 5 to about 200, and optionally at least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block, and optionally And at least one terminal protecting group derived from a terminal protecting agent.

  Another embodiment is an article comprising any of the above-described poly (arylene ether) -polysiloxane block copolymers. Such articles may be prepared by the article molding methods described in connection with poly (arylene ether) -polycarbonate block copolymers. Specific articles that may use poly (arylene ether) -polysiloxane block copolymers include, for example, low smoke building materials, high heat application coatings.

Poly (arylene ether) -polyester block copolymer:
One embodiment is a method of preparing a poly (arylene ether) -polyester block copolymer comprising reacting a hydroxyl-containing poly (arylene ether), a hydroxy-terminated polyester, and an activated aromatic carbonate. Including. The reaction may be allowed to proceed in the polymer melt (i.e. in the absence of deliberately added solvent) or in solution (i.e. in the presence of deliberately added solvent). Suitable solvents for the solution reaction are aromatic hydrocarbon solvents (eg benzene, toluene, ethylbenzene, xylenes), halogenated aromatic hydrocarbon solvents (eg chlorobenzene, dichlorobenzenes and trichlorobenzenes), and halogens Hydrous aliphatic hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, dichloroethylenes, trichloroethanes and trichloroethylene.

  The term “melt reacting” refers to a reaction that takes place in the absence of added solvent. (It will be understood that a melt reaction includes a reaction that generates a product that may act as a solvent. For example, a melt reaction of bis (methyl salicyl carbonate) may generate methyl salicylate.) Generally, it includes temperatures above the melting temperature and / or glass transition temperature of the poly (arylene ether) and hydroxy-terminated polyester reactants, but below the temperature at which the reactants are substantially unstable. The melt reaction may be performed by mixing poly (arylene ether), polyester, and activated aromatic carbonate and then heating to a temperature suitable for the melt reaction. Alternatively, the activated aromatic carbonate may be melt reacted with one of poly (arylene ether) or polyester and then the other polymer added. In some embodiments, the melt reaction conditions include the following process conditions: removal of volatile components using one or more temperatures in the range of about 90 to about 400 ° C., a vacuum of about 1 to 100 kilopascals, and Including one or more of stirring (eg, stirring at about 1 to 100 rpm). In the following examples, typical melt reaction conditions are described in detail.

  The poly (arylene ether) and the activated aromatic carbonate are the same as described above for the poly (arylene ether) -polycarbonate block copolymer.

A hydroxy-terminated polyester is a polyester having at least one terminal aliphatic hydroxyl group. The hydroxy-terminated polyester may contain 2, 3 or 4 or more terminal aliphatic hydroxyl groups. In some embodiments, the hydroxy-terminated polyester has the structure

Wherein R ¹² is independently C ₂ -C ₁₂ alkylene at each position, R ¹³ is independently C ₂ -C ₁₂ hydrocarbylene at each position, and R ¹⁴ is independently at each position. a C ₂ -C ₆ alkylene, including ester repeat units and terminal hydroxyl groups with.

In one embodiment, the hydroxy-terminated polyester has the structure

It is a polyester diol having Wherein R ¹² is independently C ₂ -C ₁₂ alkylene at each position, R ¹³ is independently C ₂ -C ₁₂ hydrocarbylene at each position, and R ¹⁴ is independently at each position. C ₂ -C ₆ alkylene, R ¹⁵ is independently C ₂ -C ₁₂ alkylene at each position, m is 2 to about 100, and p is independently 1 to about 50 at each position. , Q is from 0 to about 10. Methods for making hydroxy-terminated polyesters are known. For example, the polyester diol having the above first structure may be prepared by copolymerizing a dibasic acid and a diol, and in this case, the diol is present in an excess mole relative to the dibasic acid. As another example, a polyester diol having the above second structure may be prepared by using lactone (water), diol (HO—R ¹⁵ —OH) or oligomeric polyether (H— (O—R ¹⁵ ) _q —OH). It may be prepared by initiating polymerization. Hydroxy-terminated polyesters having 3 or more hydroxyl groups polymerize a multifunctional compound having at least 3 hydroxyl groups, at least 3 carboxylic acid groups, or a monomer mixture containing at least 3 total hydroxy and carboxylic acid groups May be prepared.

  Suitable hydroxy-terminated polyesters include, for example, polyethylene terephthalate diol, polybutylene terephthalate diol, polycyclohexylene terephthalate diol, polyethylene adipate diol, polybutylene adipate diol, polycyclohexylene adipate diol, polycaprolactone diol and mixtures thereof. In one embodiment, the hydroxy-terminated polyester is a polycaprolactone diol. Suitable hydroxy-terminated polyesters further include the corresponding polyols obtained by including a branching agent in the polyester backbone.

  The hydroxy-terminated polyester may have a number average molecular weight of about 500 to about 10,000 atomic mass units. Within this range, the number average molecular weight may be at least about 1,000 atomic mass units. Within this range, the number average molecular weight may be up to about 8,000, or up to about 5,000 atomic mass units.

  In some embodiments, the activated aromatic carbonate may be used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the hydroxy-terminated polyester. Within this range, the amount of activated aromatic carbonate may be at least about 0.75 mol, at least about 0.95 mol, or at least about 1 mol per 2 mol of hydroxyl groups. Within this range the amount of activated aromatic carbonate is up to about 1.5 moles, up to about 1.3 moles, up to about 1.2 moles, up to 1.1 moles, or up to 1.05 per 2 moles of hydroxyl groups. It should be a mole.

  There are no particular restrictions on the weight ratio of poly (arylene ether) to hydroxy-terminated polyester used in the reaction mixture or incorporated into the resulting copolymer. In one embodiment, the weight ratio of poly (arylene ether) to hydroxy-terminated polyester is from about 1:10 to about 10: 1. Within this range, the weight ratio may be at least about 1: 1, or at least about 2: 1. Within this range, the weight ratio may be up to about 5: 1.

  The structure of the poly (arylene ether) -polyester block copolymer may take various forms. For example, the poly (arylene ether) -polyester block copolymer is a diblock copolymer, a triblock copolymer, a linear multiblock copolymer having 4 or more blocks, or a star-shaped teleblock copolymer. It may be. In one embodiment, the poly (arylene ether) -polyester block copolymer is a poly (arylene ether) -polyester-poly (arylene ether) triblock copolymer. The block configuration of the copolymer is based on the number of hydroxyl groups on the poly (arylene ether), the number of hydroxyl groups on the hydroxy-terminated polyester, and the total number of hydroxyl groups on the poly (arylene ether) and hydroxy-terminated polyester. It may be adjusted by the mole ratio of activated carbonate, the use of end-protecting agents, and other reaction conditions. For example, when the poly (arylene ether) is mostly monofunctional (ie, on average has nearly one hydroxyl group per molecule) and the polyester on average has nearly two hydroxyl groups per molecule, the reaction product May comprise a poly (arylene ether) -polyester-poly (arylene ether) triblock copolymer.

  One embodiment is a method of preparing a poly (arylene ether) -polyester block copolymer comprising melt reacting a poly (arylene ether) containing a hydroxyl group, a polyester diol, and bis (methylsalicyl carbonate). And the poly (arylene ether) has an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and is 2,6-dimethyl-1,4-phenylene ether unit, The polyester diol comprising 6-trimethyl-1,4-phenylene ether units, or combinations thereof, is a polycaprolactone diol having a number average molecular weight of about 500 to about 10,000 atomic mass units, The weight ratio of arylene ether) is about 1: From about 6: 1, activated aromatic carbonate is used in an amount of about 2 mol of total hydroxyl groups 2 per mole to about 0.5 which is provided with the polyester diol poly (arylene ether).

  Other embodiments include poly (arylene ether) -polyester block copolymers prepared by any of the above-described methods.

  One embodiment is a poly (arylene ether) -polyester block copolymer comprising a poly (arylene ether) block, a hydroxy-terminated polyester block, and a carbonate group connecting the poly (arylene ether) block and the hydroxy-terminated polyester block. . In the context of a product block copolymer, it will be understood that a “hydroxy-terminated polyester block” does not contain a hydroxyl group hydrogen at the position where it is bound to a carbonate group connecting different blocks of the copolymer.

  One embodiment is a poly (arylene ether) -polyester block copolymer comprising at least one poly (arylene ether) block, at least one hydroxy-terminated polyester block, and poly (arylene ether) block and a hydroxy-terminated polyester block And at least one carbonate group.

  One embodiment is a poly (arylene ether) -polyester block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl- A poly (arylene ether) block containing 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, number average of about 500 to about 10,000 atomic mass units It includes a polycaprolactone diol block having a molecular weight, and a carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block.

  One embodiment is a poly (arylene ether) -polyester block copolymer having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and 2,6-dimethyl- At least one poly (arylene ether) block comprising 1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof, from about 500 to about 10,000 atomic mass units At least one polycaprolactone diol block having a number average molecular weight of at least one carbonate ester group connecting the poly (arylene ether) block and the poly (alkylene ether) block, and optionally derived from a terminal protecting agent At least one terminal protecting group.

  Another embodiment is an article comprising any of the above-described poly (arylene ether) -polyester block copolymers. Such articles may be prepared by the article forming methods described for poly (arylene ether) -polycarbonate block copolymers. Articles that may use certain poly (arylene ether) -polysiloxane block copolymers include, for example, sheets and films for coating and packaging.

Additives and articles:
Any of the above described block copolymers may optionally be formulated with any conventional additive used in thermoplastic resin applications such as preparing molded articles. These additives are UV stabilizers, antioxidants, heat stabilizers, mold release agents, colorants, antistatic agents, slip agents, anti-sticking agents, lubricants, antifogging agents, natural oils, synthetic oils, Including waxes, organic fillers, inorganic fillers and mixtures thereof. Generally, forming a blend of a block copolymer and a non-filler additive is preferred as it helps to process the blend to form the desired molded article. The blend may optionally include from about 0.0001 to about 10 weight percent of a desired non-filler additive, or from about 0.0001 to about 1 weight percent of a desired non-filler additive. The filler is typically used in an amount of about 1 to about 75 weight percent, based on the total weight of the composition.

  Examples of UV absorbers include, for example, salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers, and mixtures thereof. Examples of heat stabilizers include, for example, phenol stabilizers, organic thioether stabilizers, organic phosphite stabilizers, sterically hindered amine stabilizers, epoxy stabilizers, and mixtures thereof. The heat stabilizer may be added in solid or liquid form. Examples of release agents include, for example, natural and synthetic paraffins, polyethylene waxes, fluorocarbons, and other hydrocarbon release agents; stearic acid, hydroxystearic acid, and other higher fatty acids, hydroxy fatty acids, and other fatty acid release agents. Agents: stearic acid amide, ethylene bis stearamide, and other fatty acid amides, alkylene bis fatty acid amides, and other fatty acid amide release agents; stearyl alcohol, cetyl alcohol, and other aliphatic alcohols, polyhydric alcohols, poly Glycols, polyglycerols and other alcohol release agents; butyl stearate, pentaerythritol tetrastearate, and other fatty acid lower alcohol esters, fatty acid polyalcohol esters, fatty acid polyglycol esters, and other Fatty acid ester mold release agents; silicone oil and other silicone mold release agents, and mixtures of any of the foregoing. Colorants include pigments, dyes and mixtures of both. Inorganic and organic colorants may be used separately or in combination.

  Another embodiment is an article comprising any of the block copolymers described above. For example, the article may comprise a film, sheet, molding or composite, wherein the film, sheet, molding or composite comprises at least one layer comprising a block copolymer. Articles include, for example, single layer and multilayer foam extrusion, single layer and multilayer sheet extrusion, injection molding, blow molding, extrusion, film extrusion, profile extrusion, pultrusion molding, compression molding, thermoforming, pressure molding, isostatic pressing It may be prepared from a composition comprising a block copolymer using fabrication methods known in the art, including vacuum molding, foam molding, and similar methods. A combination of the above-described article manufacturing methods may be used. Specific articles that may use block copolymers include, for example, packaging for medical devices, pharmaceutical and health products, substrates for data storage media, coated wires, ribbon cables, connectors, buffer tubes and battery cases.

  Examples of the invention are further illustrated by the following non-limiting examples.

Example 1 to Example 17:
All molecular weight values referenced in the examples are relative to polystyrene standards and are measured using gel permeation chromatography (GPC).

General procedure for batch preparation of PPE-PC block copolymers:
In the following procedures, various amounts of poly (2,6-dimethyl-1,4-phenylene ether) (abbreviated as PPE), bisphenol A (BPA), BMSC, and 1,4-hydroquinone (abbreviated as HQ). ), 2-methyl-1,4-hydroquinone (abbreviated as MeHQ), or a mixture of 1,4-hydroquinone and 2-methyl-1,4-hydroquinone. An ether) -polycarbonate block copolymer is produced. The poly (2,6-dimethyl-1,4-phenylene ether) had an average of about 0.5 hydroxyl groups per molecule and a number average molecular weight of 1,326 atomic mass units.

To facilitate inspection and achieve sufficient polymer purity levels, the melt transesterification polymerization process was performed in a 500 milliliter glass reactor equipped with a solid nickel helical stirrer. In order to completely remove the sodium from the glass, the reactor was immersed in 3N hydrochloric acid for at least 12 hours followed by immersion in deionized (18 megohm) water for at least 12 hours. The reactor was then dried in the oven overnight and stored with the lid on until use. The reactor temperature was maintained using a fluidized sand bath equipped with a proportional-integral-derivative (PID) controller. The temperature was measured near the reactor / sand bath interface. The pressure in the reactor was adjusted with a nitrogen supply to a vacuum pump downstream of the distillate collection flask and measured with an MKS Pirani gauge. The amount of catalyst required, ie tetramethylammonium hydroxide (TMAH) (Sachem, 2.19 × 10 ⁻⁵ mol) or tetrabutylphosphonium acetate (TBPA) (Sechem, 2.19 × 10 ⁻⁵ mol) ), And sodium hydroxide (JT Baker, 8.76 × 10 ⁻⁶ mol) is 0.22 molar TMAH or TBPA, and 1.00 × 10 ⁻³ molar sodium hydroxide. Were prepared by diluting each with a suitable amount of 18 megohm deionized water. When increased levels of catalyst were required, the concentration of the catalyst solution was increased so that the volume of material injected into the reactor was constant.

  Solid bisphenol A, powdered poly (2,6-dimethylphenylene ether), 1,4-hydroquinone, 2-methyl-1,4-hydroquinone, or 1,4-hydroquinone and 2-methyl-1,4- Appropriate amount of mixture with hydroquinone, solid bis (methyl salicyl) carbonate (1.0 to 1.05 mol per total mole of dihydroxy aromatic compound used), and para-cumylphenol chain terminator (Aldrich ), 1-3 mole percent) was charged to the reactor. Next, the catalyst solution was added. The reactor was assembled and sealed, and the atmosphere was changed three times with nitrogen. During the last nitrogen exchange, the reactor was brought close to atmospheric pressure and submerged in a fluidized bath maintained at a temperature of 180-200 ° C. The reactor contents were stirred at 250 rpm for 5 minutes. After an additional 10 minutes, the temperature was increased to 210 ° C. over 5 minutes, assuming that all reactants were fully melted. Next, the pressure was reduced to 180 mmHg. Byproduct distillation began immediately. After 20 minutes, the pressure was reduced again to 100 mmHg and held for 20 minutes. Next, the temperature was raised to 240 ° C. over 5 minutes and the pressure was reduced to 15 mmHg. After maintaining for 20 minutes under these conditions, the temperature was raised to 270 ° C. over 5 minutes, and the pressure was reduced to 2 mmHg. These conditions were held for 10 minutes. Next, the temperature was raised to 310 ° C. (final temperature) over 10 minutes and the pressure was reduced to 1.1 mmHg. After 30 minutes, the reactor was removed from the sand bath and the resulting molten block copolymer product was withdrawn from the reactor and dropped into liquid nitrogen to stop the reaction.

  The procedure described above was repeated with various mixtures of raw mixture components. The results are shown as Examples 1 to 17 in Table 1.

In Table 1, the amount of PPE is expressed as a percentage by weight relative to the total weight of the raw material mixture. The amounts of BPA, HQ and MeHQ are represented by relative mole percent values relative to the total moles of bisphenol. The glass transition point, melting point, and crystallization temperature were measured using differential scanning calorimetry (DSC). Samples were analyzed on a Perkin Elmer DSC7 differential scanning calorimeter using a circulating nitrogen environment. A heating and cooling cycle was performed, holding from 30 ° C. to 380 ° C. at 20 ° C./min, then holding for 3 minutes and cooling to 30 ° C. at the same rate. Two heating cycles were performed for each sample. T _g and T _m indicate the glass transition point and melting point of the product PPE-PC block copolymer (ie, the temperature indicating the onset of melting). T _c represents the crystallization temperature. The notation “NA” in Table 1 means “not seen” or “not observed”.

Example 18:
The raw mixture components (PPE, MeHQ, HQ, BPA and catalyst) were combined in a melt reactor and allowed to equilibrate at 180 ° C. for about 2 hours to obtain a solution containing the product of the methyl salicylate equilibration reaction. The solution was then fed at 180 ° C. into a 14-cylinder 25 mm Werner & Pfleiderer twin screw extruder with six vacuum vents. The feed rate was 6.8-9,1 kilograms per hour (15-20 pounds per hour). The extruder barrel set temperature was maintained at 280 ° C. and the screw speed was set at 300 rpm. The desired block copolymer was extruded as a clear continuum that crystallized and became opaque on the way to the pelletizer through a cooling water bath. The product melt crystallized PPE-PC block copolymer had a melting point of 281 ° C and a crystallization temperature of 231 ° C. No glass transition point was observed in this sample.

These results indicate that the molten crystal block prepared from poly (2,6-dimethylphenylene) ether having at least one hydroxyl group, various combinations of hydroquinone and / or 2-methyl-1,4-hydroquinone, and BPA The copolymer has a glass transition point of about 100 to about 135 ° C. and in some cases a melting point of about 260 to 330 ° C., and therefore can be easily processed to produce a variety of molded articles. It shows that a material that can be provided can be provided. Furthermore, these block copolymers are economically attractive because these poly (arylene ethers) can be easily prepared at low cost. The results from Examples 8 and 12 show that increasing the amount of 1,4-hydroquinone instead of 2-methyl-1,4-hydroquinone can increase the melting point (T _m ) by about 12 ° C.

Example 19 to Example 21, Comparative Example 6 and Comparative Example 7:
These examples illustrate the preparation of block copolymers of poly (arylene ether) and poly (alkylene ether).

“Monofunctional” poly (2, having a hydroxyl group (OH) content of 5,924 weight parts per million, a weight average molecular weight of about 6,300 atomic mass units and a number average molecular weight of about 3,700 atomic mass units 6-dimethyl-1,4-phenylene ether) was obtained from GE Plastics as PPO ^* SA120 ("PPE, 0.12IV" in Table 4). A “bifunctional” poly (2,6-dimethyl-1,4-phenylene ether) having a hydroxyl group (OH) content of 17,470 parts by weight per million and a weight average molecular weight of about 2,477 atomic mass units is It was prepared by oxidative copolymerization of 2,6-xylenol and tetramethylbisphenol A. Polyethylene glycol having a weight average molecular weight of about 8,548 atomic mass units and a hydroxyl group content of 2,914 parts per million is from Dow Chemical to Carbowax® (CARBOWAX®) 8000. Obtained as.

  The following general process was used for the preparation of the block copolymer. The melt polymerization process was carried out in a glass reactor equipped with a twist anchor type stirrer. To completely remove sodium from the glass, the reactor was immersed in 1N hydrochloric acid for at least 24 hours, followed by rinsing in excess Milli-Q water. The reactor was then flushed with acetone, flushed with air, capped and stored until used. The reactor temperature was adjusted using a mantle heater equipped with an Omega-Newport controller. The temperature was measured near the reactor / mantle heater gap. The pressure in the reactor was adjusted using an Omega controller with nitrogen supply. The required amount of catalyst was prepared by diluting a stock solution of 0.5M sodium hydroxide with an appropriate amount of reverse osmosis water. When increased catalyst levels were required, the concentration of the catalyst solution was increased so that the volume of material injected into the reactor remained constant.

  The amounts of polymer and BMSC detailed in Table 4 were charged to the reactor. In Table 4, poly (arylene ether) and polyethylene glycol component amounts are expressed in parts by weight. The amount of BMSC is expressed as the number of moles of BMSC for every 2 moles of hydroxyl groups provided by poly (arylene ether) and polyethylene glycol. The reactor was sealed and vacuumed to about 2 millibar, followed by a nitrogen purge to return to atmospheric pressure. This purge process was repeated two more times. The reactor was heated to 90 ° C. under full vacuum for 30 minutes to completely remove residual moisture from the catalyst. The pressure was returned to atmospheric pressure using a nitrogen purge and the reactor was heated to various levels depending on the program used (see Program Summary Table 1 for details on the program). Regardless of the reaction program used, there is a melting period that allows all reagents to mix uniformly. Once a uniform melt blend is obtained, a second stage, moderate vacuum oligomerization, is performed to cause low level binding and finally block by removal of volatile methyl salicylate under high temperature and high vacuum. Promote copolymer formation.

  Two different temperature, vacuum and stirring time profiles were used. Examples 19 and 20 and Comparative Example 6 used time profiles detailed in Table 2. Example 21 and Comparative Example 7 used time profiles detailed in Table 3. In Tables 2 and 3, the time is expressed in minutes (min), the temperature is expressed in degrees Celsius (° C.), the vacuum is expressed in millibar (mbar), and the number of stirring is expressed in rpm.

  The product consisted of the entire contents of the reactor and was analyzed without further purification or isolation.

The relative amounts of various molecular fragments were measured using ¹³ C NMR. Specifically, using a pulse sequence that allows quantitative integration of ¹³ C NMR resonances, (1) carbon atoms of carbonate esters linking poly (arylene ether) and polycarbonate fragments (“% PPE in Table 4). -PEG carbonate ester)), (2) carbon atom of carbonate ester connecting two poly (arylene ether) fragments ("% PPE-PPE carbonate ester" in Table 4), (3) two polyethylene glycol fragments Carbon atoms of the linking carbonate ("% PEG-PEG carbonate" in Table 4), (4) all carbon atoms associated with the poly (arylene ether) fragment ("% PPE" in Table 4), And (5) all carbon atoms associated with the polyethylene glycol fragment ("% PEG" in Table 4). The relative molar amounts were measured. Number average molecular weight (M _n ) and weight average molecular weight (M _w ) were determined by gel permeation chromatography (GPC) using a monodisperse polystyrene standard, styrene divinylbenzene gel and a sample having a concentration of 1 milligram per milliliter of chloroform. Measured at ° C. The polydispersity index M _n / M _w is the ratio of the weight average molecular weight to the number average molecular weight. Table 4 shows the characteristic values.

  The results of Examples 19 and 20 show the reproducibility of this process for preparing block copolymers. Specifically, in Example 19, 0.30% of the total carbon resonance can be attributed to the carbonate ester bond in the PPE-PEG block copolymer, and in Example 20, 0.31% of the total carbon resonance. Can be attributed to the carbonate ester bond in the PPE-PEG block copolymer. The results of Example 21 show that this block copolymer process can utilize polyfunctional poly (arylene ethers) (ie, poly (arylene ethers) containing on average more than one hydroxyl group per molecule). . The results of Examples 19-21 show that a significant percentage of the carbonate ester linkage can be attributed to the coupling of PPE units to PEG units. Specifically, in Example 19, 41% (100 × 0.30 / (0.30 + 0.09 + 0.35)) of the total carbonic ester carbon resonance belongs to the carbonic ester bond in the PPE-PEG block copolymer. In Example 20, 44% of the carbonate ester carbon resonance can be attributed to the carbonate ester bond in the PPE-PEG block copolymer, and in Example 21, 42% of the carbonate ester carbon resonance can be attributed to PPE- It could be attributed to the carbonate ester bond in the PEG block copolymer. In all cases, the molecular weight of the resulting copolymer is greater than the molecular weight of the respective polymer used in the synthesis. Comparative Examples 6 and 7 are control examples where formation of a mixed block copolymer was not possible because either poly (arylene ether) (Comparative Example 6) or polyethylene glycol (Comparative Example 7) was omitted. .

Example 22 to Example 28:
These examples show examples of the preparation of block copolymers of poly (arylene ether) and polyester.

Some of the starting materials are the same as those used above. Further, poly (2,6-) having a hydroxyl group (OH) content of 3,240 parts by weight per million, a weight average molecular weight of about 27,700 atomic mass units, and a number average molecular weight of about 10,000 atomic mass units. (Dimethyl-1,4-phenylene ether) (referred to as “PPE, 0.25IV” in Table 8 for this resin blend), both 0.31 deciliters per gram obtained as PPO ^* 808 from GE Plastics Prepared by blending 75 weight percent of PPE resin with viscosity and 25 weight percent of PPE resin with an intrinsic viscosity of 0.12 deciliter per gram obtained as PPO ^* SA120. About 1,000, 2,000, 4,000 and 8,000 atomic mass units of weight average molecular weight, about 33,939, 16,970, 8,489 and 4,242 parts per million hydroxyl group content Polycaprolactone diol (PCL) was obtained from Solvay Chemical as Capa (R) 2100, 2200, 2403 and 2803, respectively.

  The general reaction procedure of Examples 19-21 was used, except that the polyethylene glycol was replaced with polycaprolactone diol. In these experiments, three different temperatures, vacuum and stirring time profiles were used. The conditions detailed in Table 5 were used in Examples 22, 23 and 27, the conditions detailed in Table 6 were used in Examples 24 to 26, and the conditions detailed in Table 7 were used in Example 28. .

  The molecular weight of the product was measured as described for Examples 19-21. The product hydroxy content was measured by Fourier Transform Infrared Spectroscopy (FTIR) using a 2,6-xylenol standard to produce a strength versus concentration curve. The glass transition point of the product was measured by differential scanning calorimetry (DSC). Table 8 summarizes the reaction composition and product characteristics.

  The results of Examples 22, 23, 26 and 27 show that the use of low molecular weight PCL diols is associated with the absolute yield of larger PPE-PCL block copolymers. Specifically, as the PCL diol weight average molecular weight increases from 1,000 to 2,000, 4,000, 8,000, the percent of total carbon atoms associated with the carbonate moiety linking the PPE chain and the PCL chain is 1. It decreased from 09% to 0.53%, 0.16%, and 0%. These same examples also show that the relative yield of the desired block copolymer decreases with increasing PCL diol molecular weight. Specifically, as the PCL diol weight average molecular weight is increased from 1,000 to 2,000, 4,000, 8,000, the percent of total carbonate carbon atoms associated with the carbonate ester moiety connecting the PPE and PCL chains is 72% (100 × 1.09 / (1.09 + 0.26 + 0.16)) to 41%, 31% and 0%. However, surprisingly, when the poly (arylene ether) is a blend of poly (arylene ether) resins having intrinsic viscosities of 0.30 and 0.12 deciliters per gram, the PPE-PCL block copolymer containing high molecular weight PCL fragments It has been found that coalescence can be formed. See Example 28. Examples 23 to 25 show that the absolute yield of the desired PPE-PCL block copolymer is not affected even if the molar amount of the activated carbonate relative to the total number of moles of hydroxyl groups is significantly changed. Show.

Example 29 to Example 33:
These examples illustrate the preparation of block copolymers of poly (arylene ether) and polysiloxane.

  The following eugenol-protected polydimethylsiloxane: D10 fluid having a weight average molecular weight of about 1,202 atomic mass units and a hydroxyl group content of 25,740 parts per million, a weight average molecular weight of about 1,752 atomic mass units And a D15 fluid having a hydroxyl group content of 19,750 parts by weight per million, and a D24 fluid having a weight average molecular weight of about 2,238 atomic mass units and a hydroxyl group content of 15,360 parts by weight per million, Prepared by platinum catalyzed hydrosilylation reaction between eugenol and hydride di-terminated polydimethylsiloxane.

  All these examples used the temperature, vacuum and stirring time profiles detailed in Table 6 above. Table 9 summarizes the reaction composition and properties. It was theoretically possible to observe more than one glass transition point, but only one was observed. Example 29 shows the importance of activated carbonate concentrate for this coupling reaction. In this example, the molar ratio of activated carbonate to total hydroxyl groups was 0.54, and only a low yield of the desired block copolymer was obtained. The lack of activated carbonate is also reflected in the large amount of unreacted hydroxyl groups and the low weight average molecular weight of the product of Example 29.

Example 34 to Example 39:
These examples further illustrate examples of the preparation of block copolymers of poly (arylene ether) and poly (alkylene ether).

  By oxidative copolymerization of 2,6-xylenol and tetramethylbisphenol A, an intrinsic viscosity of 0.12 deciliter per gram, a number average molecular weight of 2,340 atomic mass units, a weight average molecular weight of 4,322 atomic mass units and 9 Poly (2,6-dimethyl-1,4-phenylene ether) having a hydroxyl group content of 618 parts by weight per million. Polytetramethylene glycols having number average molecular weights of about 650, 1,400 and 2,900 were obtained from Invista as TERAzan® PTMEG 650, 1400 and 2900, respectively, p- Cumylphenol was obtained from Schenectady Chemicals.

For ease of observation and purity, the melt transesterification reaction was carried out in a 500 ml glass batch reactor equipped with a solid nickel helical stirrer. To completely remove sodium from the glass, the reactor was immersed in 3N hydrochloric acid for at least 12 hours, followed by immersion in 18 megaohm water for at least 12 hours. The reactor was then dried in the oven overnight and stored with the lid on until use. The reactor temperature was maintained using a fluidized sand bath with a PID controller and was measured near the interface between the reactor and the sand bath. The pressure on the reactor was adjusted by nitrogen supply into a vacuum pump downstream of the distillate collection flask and measured with an MKS Pirani gauge. Tetramethylammonium hydroxide (Sechem, 2.19 × 10 ⁻⁵ mol) or tetrabutylphosphonium acetate (Sechem, 2.19 × 10 ⁻⁵ mol) and sodium hydroxide (JTE Baker, 8.76 × 10 ⁻⁶⁾ Mol) was prepared by dilution to the appropriate concentration (0.220 M tetramethylammonium hydroxide and tetrabutylphosphonium acetate, and 1.00 × 10 ⁻³ M sodium hydroxide) with 18 megaohm water. When increased catalyst levels were required, the catalyst solution concentration was increased to maintain consistent injection volume.

  The procedures of Examples 34-36 were general methods. Powdered poly (arylene ether) (40.0 grams, 0.009 mole), polytetramethylene glycol (60.0 grams, 0.0923 mole) and bis (methylsalicyl carbonate) (35.1 grams, 0 106 moles) was charged to the reactor. In these experiments, the monofunctional phenol was p-cumylphenol added at about 0.02 mol / mol BMSC. The catalyst was added to the solid charge, but could be added after the reactant polymer mixture had melted. The reactor was then assembled, sealed, and the atmosphere was changed 3 times with nitrogen. During the final nitrogen exchange, the reactor was brought to near atmospheric pressure and submerged in a fluidized bath at 180-200 ° C. After 5 minutes, stirring was started at 250 rpm. After an additional 10 minutes, the reactants were completely melted and a uniform mixture was obtained. At this point, timing was started and the temperature was raised to 210 ° C. over 5 minutes. When this temperature was reached, the pressure was reduced to 180 millimeters mercury and a methyl salicylate distillate formed immediately. After 20 minutes, the pressure was again reduced to 100 millimeters mercury and held for 20 minutes. The temperature was then raised to 240 ° C. over 5 minutes and the pressure was reduced to 15 millimeters mercury. These conditions were held for a maximum of 20 minutes. The temperature was then raised to 260 ° C. over 5 minutes and the pressure was reduced to 2.0 millimeters mercury. These conditions were held for 10 minutes. Then the temperature was finally raised over 10 minutes to a final temperature of 260-290 ° C. and the pressure was reduced to 1.1 millimeter mercury. After 30 minutes, the reactor was removed from the sand bath and the melt was withdrawn from the reactor and dropped into liquid nitrogen to stop the reaction.

  Table 10 summarizes the properties of the block copolymers prepared using this procedure. The intrinsic viscosity of the product was measured at 25 ° C. in chloroform for a block copolymer sample dried at 125 ° C. for 1 hour under vacuum. The viscosity measurement sample concentration was 0.40 grams per 50 milliliters of chloroform. Shore A hardness was measured at 25 ° C. using a Rex model DD-3-A digital durometer with OS-2H operating stand according to ASTM D2240.

  This written description uses examples to disclose the invention, including the best mode, and to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are within the scope of the claims if they have structural elements that do not differ from the written language of the claims, or if they contain equivalent structural elements that do not differ substantially from the written language of the claims. Shall.

  All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

  All ranges disclosed herein include endpoints, which can be combined independently of each other.

Claims (96)

  A polymer block selected from the group consisting of a poly (arylene ether) containing a hydroxyl group, an activated aromatic carbonate, a poly (alkylene ether) containing a hydroxyl group, a hydroxyaryl-terminated polysiloxane, and a hydroxy-terminated polyester; A process for preparing a poly (arylene ether) block copolymer comprising reacting   The method of claim 1, wherein the reacting comprises melt reacting.   The method according to any one of claims 1 to 2, wherein the reacting includes reacting in a solvent. 4. The method according to any one of claims 1 to 3, wherein the poly (arylene ether) is of the formula

Wherein each Z ¹ is independently halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl and the hydrocarbyl group is not a tertiary hydrocarbyl, C _1- Each of C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy, wherein at least two carbon atoms separate said halogen and oxygen atoms, Z ² is independently hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl and the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or _C 2 _{~C 12} Harohi The method is a halohydrocarbyloxy least a Rokarubiruokishi two carbon atoms separate the said halogen and oxygen atoms.   5. The method according to any one of claims 1 to 4, wherein the poly (arylene ether) is a 2,6-dimethyl-1,4-phenylene ether unit, 2,3,6-trimethyl- A method comprising 1,4-phenylene ether units, or combinations thereof.   6. The method according to any one of claims 1 to 5, wherein the poly (arylene ether) has an intrinsic viscosity of about 0.04 to 0.6 deciliters per gram at 25 ° C. in chloroform. .   7. A method according to any one of claims 1 to 6, wherein the poly (arylene ether) has on average about 0.5 to 1 aromatic hydroxyl groups per molecular chain.   8. The method according to any one of claims 1 to 7, wherein the poly (arylene ether) has on average more than one aromatic hydroxyl group per molecular chain.   9. The method according to claim 1, wherein the activated aromatic carbonate is bis (o-chlorophenyl) carbonate, bis (o-nitrophenyl) carbonate, bis (o -Acetylphenyl), bis (o-phenylketone phenyl) carbonate, bis (o-formylphenyl) carbonate, bis (methylsalicyl) carbonate, and mixtures thereof.   The method according to any one of claims 1 to 9, wherein the activated aromatic carbonate is bis (methylsalicyl) carbonate.   11. The method according to any one of claims 1 to 10, wherein the activated aromatic carbonate comprises 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the polymer block. Used in an amount of about 0.5 to about 2 moles per unit.   12. The method according to any one of claims 1 to 11, wherein the weight ratio of the poly (arylene ether) to the polymer block is from about 1:10 to about 10: 1.   The method according to any one of claims 1 to 12, wherein the poly (arylene ether) block copolymer comprises a diblock copolymer, a triblock copolymer, and four or more blocks. A method comprising a linear multi-block copolymer or a star-shaped teleblock copolymer.   14. The method according to any one of claims 1 to 13, wherein a terminal protecting agent is melt-reacted with the poly (arylene ether), the polymer block, and the activated aromatic carbonate. Further comprising a method.   15. The method according to any one of claims 1 to 14, wherein the polymer block is a poly (alkylene ether) containing hydroxyl groups. 16. The method of claim 15, wherein the poly (alkylene ether) has the structure

Wherein R ⁷ is a C _{2 to} C ₁₂ alkylene group. 17. A method according to any one of claims 15 to 16, wherein the poly (alkylene ether) is a structure.

Wherein R ⁷ is a C _{2 to} C ₁₂ alkylene group and r is from 2 to about 1,000.   18. The method according to any one of claims 15 to 17, wherein the poly (alkylene ether) comprises polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, ethyleneoxy units and propyleneoxy. A method selected from the group consisting of a unit, a copolymer glycol containing at least two of tetramethyleneoxy units and hexamethyleneoxy units, and mixtures thereof.   19. A method according to any one of claims 15 to 18, wherein the poly (alkylene ether) is polyethylene glycol.   20. A method according to any one of claims 15 to 19, wherein the poly (alkylene ether) is polytetramethylene glycol.   21. A method according to any one of claims 15 to 20, wherein the poly (alkylene ether) has a number average molecular weight of about 100 to about 40,000 atomic mass units.   The method according to any one of claims 15 to 21, wherein the poly (arylene ether) block copolymer is poly (arylene ether) -poly (alkylene ether) -poly (arylene ether) tri. A method which is a block copolymer.   23. A poly (arylene ether) block copolymer prepared by the method of any one of claims 1 to 22. A poly (arylene ether) -poly (alkylene ether) block copolymer comprising a poly (arylene ether) containing a hydroxyl group, a poly (alkylene ether) containing a hydroxyl group, and a melt reaction of bis (methylsalicyl carbonate). A method of preparing comprising:
The poly (arylene ether) has an intrinsic viscosity of from about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., 2,6-dimethyl-1,4-phenylene ether units, 2,3, Containing 6-trimethyl-1,4-phenylene ether units, or combinations thereof,
The poly (alkylene ether) has a number average molecular weight of about 1,000 to about 10,000 atomic mass units, and the poly (alkylene ether) comprises polyethylene glycol, polytetramethylene glycol, and mixtures thereof. Selected from the group,
The weight ratio of the poly (arylene ether) to the poly (alkylene ether) is from about 1: 5 to about 2: 1;
The process wherein the activated aromatic carbonate is used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the poly (alkylene ether).   25. A poly (arylene ether) -poly (alkylene ether) block copolymer prepared by the method of claim 24. A poly (arylene ether) block;
A poly (alkylene ether) block;
A carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
A poly (arylene ether) -poly (alkylene ether) block copolymer. At least one poly (arylene ether) block;
At least one poly (alkylene ether) block;
A poly (arylene ether) -poly (alkylene ether) block copolymer comprising at least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block. Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- A poly (arylene ether) block containing phenylene ether units, or combinations thereof;
A poly (alkylene ether) block having a number average molecular weight of about 1,000 to about 10,000 atomic mass units, wherein the poly (alkylene ether) is a group consisting of polyethylene glycol, polytetramethylene glycol, and mixtures thereof A block selected from
A carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
A poly (arylene ether) -poly (alkylene ether) block copolymer. Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- At least one poly (arylene ether) block comprising phenylene ether units, or combinations thereof;
At least one poly (alkylene ether) block having a number average molecular weight of about 1,000 to about 10,000 atomic mass units, wherein the poly (alkylene ether) is polyethylene glycol, polytetramethylene glycol, and mixtures thereof A poly (alkylene ether) block selected from the group consisting of:
At least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block, and optionally, at least one terminal protecting group derived from a terminal protecting agent;
A poly (arylene ether) -poly (alkylene ether) block copolymer comprising:   The method of claim 1, wherein the polymer block is a hydroxyaryl-terminated polysiloxane. 32. The method of claim 30, wherein the hydroxyaryl-terminated polysiloxane has a structure.

Wherein R ⁸ and R ⁹ are independently at each position hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halohydrocarbyl, and a structure

Where Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyloxy, or halogen, and R ¹⁰ and R ¹¹ are independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ at each position. _{1 to} C ₁₂ halohydrocarbyl. A method according to claims 30 to any one of claims ^{31, R 8, P 9,} R 10 and ^{R 11} are independently at each position, methyl or phenyl, Y is a methoxy Method. 33. The method according to any one of claims 30 to 32, wherein the hydroxyaryl-terminated polysiloxane has a structure.

Wherein n is from 5 to about 200.   34. The method according to any one of claims 30 to 33, wherein the poly (arylene ether) -polysiloxane block copolymer is a poly (arylene ether) -polysiloxane-poly (arylene ether) tri. A method which is a block copolymer.   35. A poly (arylene ether) -polysiloxane block copolymer prepared by the method of any one of claims 30 to 34. In a method of preparing a poly (arylene ether) -poly (alkylene ether) block copolymer comprising melt reacting a poly (arylene ether) containing a hydroxyl group, a hydroxyaryl-terminated polysiloxane, and bis (methylsalicyl carbonate). There,
The poly (arylene ether) has an intrinsic viscosity of from about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., 2,6-dimethyl-1,4-phenylene ether units, 2,3, Containing 6-trimethyl-1,4-phenylene ether units, or combinations thereof,
The hydroxyaryl-terminated polysiloxane has a structure

Wherein n is from about 10 to about 100;
The weight ratio of the poly (arylene ether) to the hydroxyaryl-terminated polysiloxane is about 1: 3 to about 6: 1;
The process wherein the activated aromatic carbonate is used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the hydroxy-terminated polysiloxane.   37. A poly (arylene ether) -polysiloxane block copolymer prepared by the method of any one of claims 30 to 36. A poly (arylene ether) block;
A hydroxyaryl-terminated polysiloxane block;
A carbonate group connecting the poly (arylene ether) block and the polysiloxane block;
A poly (arylene ether) -polysiloxane block copolymer. At least one poly (arylene ether) block;
At least one hydroxyaryl-terminated polysiloxane block;
At least one carbonate group connecting the poly (arylene ether) block and the polysiloxane block;
A poly (arylene ether) -polysiloxane block copolymer comprising: Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- A poly (arylene ether) block containing phenylene ether units, or combinations thereof;
A hydroxyaryl-terminated polysiloxane block having a number average molecular weight of about 1,000 to about 5,000 atomic mass units, wherein the hydroxyaryl-terminated polysiloxane block has the structure

A hydroxyaryl-terminated polysiloxane block having n from about 5 to about 200;
A carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
A poly (arylene ether) -polysiloxane block copolymer. Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- At least one poly (arylene ether) block comprising phenylene ether units, or combinations thereof;
At least one hydroxyaryl-terminated polysiloxane block having a number average molecular weight of about 1,000 to about 8,000 atomic mass units, wherein the hydroxyaryl-terminated polysiloxane block has the structure

A hydroxyaryl-terminated polysiloxane block having n from about 5 to about 200;
At least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
Optionally, at least one terminal protecting group derived from a terminal protecting agent;
A poly (arylene ether) -polysiloxane block copolymer comprising:   The method of claim 1, wherein the polymer block is a hydroxy-terminated polyester. 43. The method of claim 42, wherein the hydroxy-terminated polyester is
Construction

Wherein R ¹² is independently C ₂ -C ₁₂ alkylene at each position, R ¹³ is independently C ₂ -C ₁₂ hydrocarbylene at each position, and R ¹⁴ is independently at each position. ester repeat units having a C ₂ -C ₆ alkylene, and terminal hydroxyl groups,
Including methods. 44. The method of any one of claims 42 to 43, wherein the hydroxy-terminated polyester has a structure.

Wherein R ¹² is independently C ₂ -C ₁₂ alkylene at each position, R ¹³ is independently C ₂ -C ₁₂ hydrocarbylene at each position, and R ¹⁴ is independently at each position. C ₂ -C ₆ alkylene, R ¹⁵ is independently C ₂ -C ₁₂ alkylene at each position, m is 2 to about 100, and p is independently 1 to about 50 at each position. Wherein q is from 0 to about 10.   45. The method according to any one of claims 42 to 44, wherein the hydroxy-terminated polyester is polyethylene terephthalate diol, polybutylene terephthalate diol, polycyclohexylene terephthalate diol, polyethylene asiadipate diol, polybutylene adipate diol. A polyester diol selected from the group consisting of polycyclohexylene adipate diol, polycaprolactone diol, and mixtures thereof.   46. The method according to any one of claims 42 to 45, wherein the hydroxy-terminated polyester is a polycaprolactone diol.   47. The method of any one of claims 42 to 46, wherein the hydroxy-terminated polyester has a number average molecular weight of about 500 to about 10,000 atomic mass units.   48. The method according to any one of claims 42 to 47, wherein the poly (arylene ether) block copolymer is a poly (arylene ether) -polyester-poly (arylene ether) triblock copolymer. The way that is.   49. The method according to any one of claims 42 to 48, wherein a terminal protecting agent is melt reacted with the poly (arylene ether), the hydroxy-terminated polyester, and the activated aromatic carbonate. Further comprising a method.   50. A poly (arylene ether) -polyester block copolymer prepared by the method of any one of claims 42 to 49. A process for preparing a poly (arylene ether) -polyester block copolymer comprising melt reacting a poly (arylene ether) containing a hydroxyl group, a polyester diol, and bis (methylsalicyl carbonate) comprising:
The poly (arylene ether) has an intrinsic viscosity of from about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C., 2,6-dimethyl-1,4-phenylene ether units, 2,3, Containing 6-trimethyl-1,4-phenylene ether units, or combinations thereof,
The polyester diol is a polycaprolactone diol having a number average molecular weight of about 500 to about 10,000 atomic mass units;
The weight ratio of the poly (arylene ether) to the polyester diol is from about 1: 3 to about 6: 1;
The method wherein the activated aromatic carbonate is used in an amount of about 0.5 to about 2 moles per 2 moles of total hydroxyl groups provided by the poly (arylene ether) and the polyester diol.   52. A poly (arylene ether) -polyester block copolymer prepared by the method of claim 51. A poly (arylene ether) block;
A hydroxy-terminated polyester block;
A carbonate group connecting the poly (arylene ether) block and the hydroxy-terminated polyester block;
A poly (arylene ether) -polyester block copolymer. At least one poly (arylene ether) block;
At least one hydroxy-terminated polyester block;
At least one carbonate group connecting the poly (arylene ether) block and the hydroxy-terminated polyester block;
A poly (arylene ether) -polyester block copolymer comprising: Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- A poly (arylene ether) block containing phenylene ether units, or combinations thereof;
A polycaprolactone diol block having a number average molecular weight of about 500 to about 10,000 atomic mass units;
A carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
A poly (arylene ether) -polyester block copolymer. Having an intrinsic viscosity of about 0.04 to about 0.2 deciliters per gram in chloroform at 25 ° C. and having 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4- At least one poly (arylene ether) block comprising phenylene ether units, or combinations thereof;
At least one polycaprolactone diol block having a number average molecular weight of about 500 to about 10,000 atomic mass units;
At least one carbonate group connecting the poly (arylene ether) block and the poly (alkylene ether) block;
Optionally, at least one terminal protecting group derived from a terminal protecting agent;
A poly (arylene ether) -polyester block copolymer comprising:   57. An article comprising the poly (arylene ether) block copolymer according to any one of claims 1 to 56. A first block comprising poly (arylene ether);
A second block selected from the group consisting of a poly (alkylene ether), a hydroxy-terminated polyester, a hydroxyaryl-terminated polysiloxane, and a polycarbonate comprising repeating units derived from hydroquinone;
A divalent carbonate group connecting the first block and the second block;
A poly (arylene ether) block copolymer comprising   59. A poly (arylene ether) block copolymer according to claim 58, wherein the poly (arylene ether) block copolymer is from 1 to 22, 30 to 36, and claim 36. 50. A block copolymer made by the method of any one of claims 42 to 49. (A) hydroquinone,
(B) a poly (arylene ether) containing a hydroxyl group;
(C) Optionally, a dihydroxy aromatic compound other than the hydroquinone,
(D) an activated aromatic carbonate,
A poly (arylene ether) -polycarbonate block copolymer comprising structural units derived from (A) hydroquinone selected from the group consisting of 1,4-hydroquinone, 2-methyl-1,4-hydroquinone, and mixtures thereof;
(B) poly (2,6-dimethyl-1,4-phenylene ether) containing a hydroxyl group;
(C) bisphenol A,
(D) bis (methyl salicyl) carbonate,
A poly (arylene ether) -polycarbonate block copolymer comprising structural units derived from A poly (arylene ether) block;
A polycarbonate block containing units derived from hydroquinone;
A carbonate group connecting the poly (arylene ether) block and the polycarbonate block;
A poly (arylene ether) -polycarbonate block copolymer. At least one poly (arylene ether) block;
At least one polycarbonate block comprising units derived from hydroquinone;
At least one carbonate group connecting the poly (arylene ether) block and the polycarbonate block;
A poly (arylene ether) -polycarbonate block copolymer comprising: A process for producing a poly (arylene ether) -polycarbonate block copolymer, in the presence of a transesterification catalyst, at one or more temperatures in the temperature range of about 100 to about 400 ° C.
(A) polycarbonate,
(B) a poly (arylene ether) containing a hydroxyl group;
(C) an activated aromatic carbonate,
Heating the mixture comprising. A process for producing a poly (arylene ether) -polycarbonate block copolymer, in the presence of a transesterification catalyst, at one or more temperatures in the temperature range of about 100 to about 400 ° C.
(A) hydroquinone,
(B) a poly (arylene ether) containing a hydroxyl group;
(C) a dihydroxy aromatic compound other than the hydroquinone,
(D) a mixture comprising an activated aromatic carbonate,
Heating. A process for producing a poly (arylene ether) -polycarbonate block copolymer comprising the steps of:
About 100 mixtures of hydroquinone, poly (arylene ether) containing hydroxyl groups, and optionally one or more dihydroxy aromatic compounds other than hydroquinone, and activated aromatic carbonates in the presence of a transesterification catalyst. Providing a solution comprising a solvent derived from polycarbonate, poly (arylene ether), and said activated aromatic carbonate by heating at a temperature in the range of from about 300 ° C .;
Extruding the solution at one or more temperatures in the range of about 100 to about 400 ° C. and one or more screw speeds in the range of about 50 to about 1200 rpm, wherein the extrusion is suitable for solvent removal. A poly (arylene ether) -polycarbonate block copolymer is run on an extruder comprising the vent
Including methods.   A method of preparing a poly (arylene ether) -polycarbonate block copolymer comprising melt reacting poly (arylene ether), a polycarbonate comprising structural units derived from hydroquinone, and an activated aromatic carbonate.   68. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 67, wherein the copolymer is a molten crystal. 69. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60, 63, 66, 67 and 68, wherein the hydroquinone has a structure.

In the formula, R ¹ represents a monovalent C _{1 to} C ₁₂ aliphatic radical, a C _{3 to} C ₁₀ alicyclic radical, or a C _{3 to} C ₁₀ aromatic radical.   69. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60, 63, 66, 67 and 68, wherein the hydroquinone is 1,4- A block copolymer selected from the group consisting of hydroquinone, 2-methyl-1,4-hydroquinone, and mixtures thereof. 71. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 70, wherein the activated aromatic carbonate is a structure.

In the formula, A ¹ and A ² are each independently an aromatic ring having a plurality of positions available for substitution, and R ² and R ³ are independently halogen, cyano group, nitro at each position. _group, C 1 _{-C 20} alkyl _group, C 4 _{-C 20} cycloalkyl _group, C 4 _{-C 20} aromatic _radical, C 1 _{-C 20} alkoxy _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxy _group, C 1 _{-C 20} alkylthio _group, C 4 _{-C 20} cycloalkylthio _group, C 4 _{-C 20} arylthio _group, C 1 _{-C 20} alkylsulfinyl _group, C 4 _{-C 20} cycloalkylsulfinyl group, _{C 4} -C ₂₀ arylsulfinyl _group, C 1 _{-C 20} alkylsulfonyl _group, C 4 _{-C 20} cycloalkylsulfonyl _group, C 4 _{-C 20} Arirusuru Honiru _group, C 1 _{-C 20} alkoxycarbonyl _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxycarbonyl _group, C 2 _{-C 60} alkylamino _group, C 6 _{-C 60} cycloalkylamino group , be a _C 5 _{-C 60} arylamino _group, C 1 _{-C 40} alkylaminocarbonyl _group, C 4 _{-C 40} cycloalkylaminocarbonyl _group, C 4 _{-C 40} arylaminocarbonyl group, and _C 1 _{-C 20} acylamino group , “D” and “e” are each independently an integer from 0 to 0 to the number of positions available for substitution on A ² and A ¹ respectively, and Q ³ and Q ⁴ are the respective positions Independently, alkoxycarbonyl group, formyl group, halogen atom, nitro group, amide group, sulfone group, sulfoxide group, and And imine group, amidine group, structure

Wherein M ¹ and M ² are independently N-alkyl, N, N-dialkyl, N-aryl, N, N-diaryl or N-alkylaryl, N, N-dialkylaryl, and R ⁴ is An activating group selected from the group consisting of an aminocarbonyl moiety and an amidine moiety each having an alkyl group or an aryl group, wherein “b” and “c” are independently 0, assuming that b + c is 1 or more. And a block copolymer having an integer from 0 to the number of positions available for substitution on A ¹ and A ² respectively.   72. The poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60, 64 to 71, wherein the activated aromatic carbonate is bis (methyl salicyl) carbonate. A block copolymer. 73. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 72 having a structure

A block copolymer further comprising terminal groups having: 74. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 73 having the structure

Wherein, ^{R 2} is halogen, cyano group, nitro _group, C 1 _{-C 20} alkyl _group, C 4 _{-C 20} cycloalkyl _group, C 4 _{-C 20} aromatic _radical, C 1 _{-C 20} alkoxy, _{C 4} -C ₂₀ cycloalkoxy _group, C 4 _{-C 20} aryloxy _group, C 1 _{-C 20} alkylthio _group, C 4 _{-C 20} cycloalkylthio _group, C 4 _{-C 20} arylthio _group, C 1 _{-C 20} alkylsulfinyl group, C ₄ -C ₂₀ cycloalkylsulfinyl _group, C 4 _{-C 20} arylsulfinyl _group, C 1 _{-C 20} alkylsulfonyl _group, C 4 _{-C 20} cycloalkylsulfonyl _group, C 4 _{-C 20} arylsulfonyl _{group, C} 1 ~ C ₂₀ alkoxycarbonyl _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxy-carbonitrile Alkenyl _group, C 2 _{-C 60} alkylamino _group, C 6 _{-C 60} cycloalkylamino _group, C 5 _{-C 60} arylamino _group, C 1 _{-C 40} alkylaminocarbonyl _group, C 4 _{-C 40} cycloalkylaminocarbonyl _group, selected from the group consisting of C 4 _{-C 40} arylaminocarbonyl group, and _C 1 _{-C 20} acylamino group, "e" is independently at each position, with a 1, 2, 3 or 4 A block copolymer further comprising a structural unit. 75. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 74, wherein the poly (arylene ether) has the formula

Wherein for each structural unit, each ^{Z 1} is independently a halogen, a hydrocarbyl group be unsubstituted or substituted C1～C ₁₂ hydrocarbyl is not tertiary hydrocarbyl _hydrocarbyl, C 1 _{-C 12} hydrocarbylthio, _{C 1} -C was ₁₂ hydrocarbyloxy or C ₂ -C ₁₂ halohydrocarbyloxy wherein at least two carbon atoms a halohydrocarbyloxy is separating the halogen and oxygen atoms, and each Z ² is independently hydrogen, halogen, unsubstituted or the hydrocarbyl group a substituted _C 1 _{-C 12} hydrocarbyl is not tertiary hydrocarbyl _hydrocarbyl, C 1 _{-C 12 hydrocarbylthio,} C 1 _{-C 12} hydrocarbyloxy or _C 2 _{-C 12} halohydrocarbyloxy, And at least Block copolymer comprising a repeating structural unit One of the carbon atoms has a a halohydrocarbyloxy separating the halogen and oxygen atoms.   76. The poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 75, wherein the poly (arylene ether) is poly (2,6-dimethyl-1,4- Block copolymer containing phenylene ether).   68. The method of any one of claims 64 to 67, wherein the poly (arylene ether) has an intrinsic viscosity of about 0.04 to 0.6 deciliters per gram at 25 ° C. in chloroform. .   78. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 77, wherein 50 to about 95 mole percent of the total molar amount of the poly (arylene ether) is a hydroxyl group. A block copolymer.   79. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 78, wherein the poly (arylene ether) averages about 0.5 to 1 hydroxyl per mole. A block copolymer containing groups.   80. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 79, wherein the poly (arylene ether) averages a block comprising more than one hydroxyl group per mole. Copolymer.   81. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 80 having a glass transition point of about 95 to about 140 ° C and a melting point of about 260 to 330 ° C. Block copolymer.   68. The method of any one of claims 64 to 67, wherein the poly (arylene ether) -polycarbonate block copolymer comprises a diblock copolymer, a triblock copolymer, four or more A process which is a linear multiblock copolymer having a block or a star-shaped teleblock copolymer.   The method according to any one of claims 60 to 79 and 81 to 82, wherein the poly (arylene ether) -polycarbonate block copolymer is poly (arylene ether) -polycarbonate-. A method which is a poly (arylene ether) triblock copolymer. 84. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 83 having the structure

In the formula, R ² is halogen, cyano group, nitro group, C _{1 to} C ₂₀ alkyl group, C _{4 to} C ₂₀ cycloalkyl group, C _{4 to} C ₂₀ aromatic group, C _{1 to} C ₂₀ alkoxy group, C ₄ -C ₂₀ cycloalkoxy _group, C 4 _{-C 20} aryloxy _group, C 1 _{-C 20} alkylthio _group, C 4 _{-C 20} cycloalkylthio _group, C 4 _{-C 20} arylthio _group, C 1 _{-C 20} alkylsulfinyl group , _C 4 _{-C 20} cycloalkylsulfinyl _group, C 4 _{-C 20} arylsulfinyl _group, C 1 _{-C 20} alkylsulfonyl _group, C 4 _{-C 20} cycloalkylsulfonyl _group, C 4 _{-C 20} arylsulfonyl group, _{C 1} -C ₂₀ alkoxycarbonyl _group, C 4 _{-C 20} cycloalkoxy _group, C 4 _{-C 20} aryloxy Cal Boniru _group, C 2 _{-C 60} alkylamino _group, C 6 _{-C 60} cycloalkylamino _group, C 5 _{-C 60} arylamino _group, C 1 _{-C 40} alkylaminocarbonyl _group, C 4 _{-C 40} cycloalkylaminocarbonyl group _is selected from C 4 _{-C 40} arylaminocarbonyl group, and _C 1 _-C group consisting ₂₀ acylamino group, "e" is independently at each position, with a 1, 2, 3 or 4 A block copolymer further comprising a structural unit. 85. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 84, comprising:
The hydroquinone is 1,4-hydroquinone and is present in an amount corresponding to 60 mole percent or more of 1,4-hydroquinone based on the total number of moles of the hydroquinone and bisphenol A, or the hydroquinone is 2-methyl- A block copolymer which is 1,4-hydroquinone and is present in an amount corresponding to 94 mole percent or more of 2-methyl-1,4-hydroquinone based on the total number of moles of hydroquinone and bisphenol A.   86. The poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 85, wherein the hydroquinone is 1,4-hydroquinone and 2-methyl-1,4-hydroquinone. A block copolymer in which 1,4-hydroquinone and 2-methyl-1,4-hydroquinone are present in an amount corresponding to 97 mole percent of the total number of moles of hydroquinone and bisphenol A.   87. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 86, derived from said poly (2,6-dimethyl-1,4-phenylene ether). The block copolymer is present in which the structural units are present in an amount of about 6 to about 60 weight percent, based on the total weight of the block copolymer.   88. A poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 87, derived from the poly (2,6-dimethyl-1,4-phenylene ether). The structural unit is a block copolymer present in an amount corresponding to about 30 to about 50% by weight based on the total weight of the block copolymer.   90. The poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 88, further comprising a structural unit derived from a terminal protecting agent.   90. The poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 89, wherein the block copolymer has a terminal protection percentage of at least about 90 percent.   93. A molded article comprising the poly (arylene ether) -polycarbonate block copolymer according to any one of claims 60 to 90.   84. A method as claimed in any one of claims 64 to 67 and 82 to 83, wherein the heating comprises a vent adapted to remove volatile components. A method comprising melt mixing performed above.   93. The method according to any one of claims 64 to 67, 82 to 83, and 92, wherein the mixture comprises an ester-substituted phenol, a halogenated aromatic solvent, a halogenated aliphatic. A method further comprising from about 10 to about 99 weight percent of a solvent selected from the group consisting of a solvent, a non-halogenated aromatic solvent, a non-halogenated aliphatic solvent, and mixtures thereof.   94. The method of any one of claims 64 to 67, 82 to 83, and 92 to 93, wherein the poly (arylene ether) is poly (2,6- Dimethyl-1,4-phenylene ether). A process for producing a poly (arylene ether) -polycarbonate block copolymer comprising the steps of:
Hydroquinone, poly (arylene ether) containing a hydroxyl group, optionally, a mixture comprising one or more dihydroxy aromatic compounds other than the hydroquinone, and an activated aromatic carbonate in the presence of a transesterification catalyst from about 100 to about Heating at a temperature in the range of 300 ° C. to provide a solution comprising polycarbonate, poly (arylene ether), and a solvent derived from the activated aromatic carbonate;
Extruding the solution at one or more temperatures in the range of about 100 ° C. to about 400 ° C. and at one or more screw speeds in the range of about 50 to about 1200 rpm, wherein the extrusion is suitable for solvent removal. A poly (arylene ether) -polycarbonate block copolymer, wherein the poly (arylene ether) -polycarbonate block copolymer is provided,
Including methods.   A process for preparing a poly (arylene ether) -polycarbonate block copolymer comprising melt reacting poly (arylene ether), a polycarbonate comprising structural units derived from hydroquinone, and an activated aromatic carbonate.