Source: http://www.google.com/patents/US5486555?dq=6,073,142
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Patent US5486555 - Process for production of stabilized polycarbonate - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA process for the production of a stabilized polycarbonate which comprises melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polycondensation catalyst and then, after the reaction mixture shows an intrinsic viscosity of at least 0.1, adding at least one...http://www.google.com/patents/US5486555?utm_source=gb-gplus-sharePatent US5486555 - Process for production of stabilized polycarbonateAdvanced Patent SearchPublication numberUS5486555 APublication typeGrantApplication numberUS 08/437,980Publication dateJan 23, 1996Filing dateMay 10, 1995Priority dateAug 26, 1993Fee statusPaidAlso published asDE69431642D1, DE69431642T2, EP0640646A1, EP0640646B1, EP1221459A1, US5494952, US5668202Publication number08437980, 437980, US 5486555 A, US 5486555A, US-A-5486555, US5486555 A, US5486555AInventorsWataru Funakoshi, Masumi Hirata, Katsushi SasakiOriginal AssigneeTeijin LimitedExport CitationBiBTeX, EndNote, RefManPatent Citations (39), Referenced by (13), Classifications (25), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetProcess for production of stabilized polycarbonateUS 5486555 AAbstract A process for the production of a stabilized polycarbonate which comprises melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polycondensation catalyst and then, after the reaction mixture shows an intrinsic viscosity of at least 0.1, adding at least one stabilizer selected from the group consisting of specific compounds having either a sulfonate group, a sulfonic acid anhydride group or a sulfate group in an amount of 0.01 to 500 ppm of a polycarbonate to be formed, to form a polycarbonate having a desired intrinsic viscosity.
We claim: 1. A process for the production of a stabilized polycarbonate which comprises melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polycondensatlon catalyst and then, after the reaction mixture shows an intrinsic viscosity of at least 0.1, adding at least one stabilizer selected from the group consisting of a compound of the formula (IV) A.sup.5 --Ad.sup.1 --A.sup.4 --(Ad.sup.2 --A.sup.5).sub.l  (IV) wherein A.sup.5 is a monovalent or divalent hydrocarbon group, A.sup.4 is a divalent hydrocarbon group, each of Ad.sup.1 and Ad.sup.2 is independently an acid anhydride group selected from the group consisting of --SO.sub.2 --O--SO.sub.2 --, --SO.sub.2 --O--CO-- and --CO--O--SO.sub.2 --, and l is 0 or 1, provided that when l is 0, --(Ad.sup.2 --A.sup.5).sub.l is a hydrogen atom or a bond between A.sup.4 and A.sup.5, in which A.sup.5 is a divalent hydrocarbon group or a single bond,in an amount of 0.01 to 500 ppm of a polycarbonate to be formed, to form a polycarbonate having a desired intrinsic viscosity. 2. The process of claim 1, wherein A.sup.5 in the formula (IV) is an alkyl group, an aryl group or an aralkyl group.
3. The process of claim 1, wherein A.sup.4 in the formula (IV) is an alkylene group, an arylene group or an aralkylene group.
4. The process of claim 1, wherein l in the formula (IV) is 0 and --(Ad.sup.1 --A.sup.5)l is a hydrogen atom.
5. The process of claim 1, wherein the polycondensation catalyst is selected from the group consisting of an alkali metal compound, an alkaline earth metal compound and a nitrogen-containing basic compound.
6. The process of claim 1, wherein the polycondensation catalyst is used in an amount of 0.01 to 100 ppm of the polycarbonate to be formed.
7. The process of claim 1, wherein the stabilizer is used in an amount of 0.5 to 50 mols per mole of the polycondensation catalyst.
8. The process of claim 1, wherein the stabilizer is added after the polycarbonate shows an intrinsic viscosity of at least 0.2.
9. The process of claim 1, wherein the stabilizer is added after the polycarbonate shows an intrinsic viscosity of at least 0.3.
10. The process of claim 1, wherein the desired intrinsic viscosity of the polycarbonate to be formed is in the range of from 0.3 to 1
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) The aromatic dihydroxy compound used in this invention is preferably a compound of the formula (A) ##STR5##
In the above formula, X is ##STR6## --S--, --SO-- or --SO.sub.2 --, in which each of R.sup.22 and R.sup.23 is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted. Examples of the alkyl group are methyl, ethyl and propyl groups, and an example of the aryl group is a phenyl group. R.sup.24 is an alkylene group having 3 to 8 carbon atoms, and examples thereof include pentylene and hexylene groups. Each of R.sup. 20 and R.sup. 21 is independently a halogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom are chlorine and bromine, and examples of the alkyl group are methyl and tert-butyl groups. Each of p and q is independently 0, 1 or 2.
Specific examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Of these, diphenyl carbonate is especially preferable.
In this invention, as a polycondensation catalyst used in this invention, those which give less colored polycarbonate polymer having good qualities from the aforesaid carbonic acid diester and aromatic dihydroxy compound as starting materials with less side reaction is preferably used. For example, at least one compound selected from the group consisting of an alkali metal compound, an alkaline earth metal compound and a nitrogen-containing basic compound is preferably used as the polycondensation catalyst. It is advantageous to use other catalysts concurrently with the above polycondensation catalyst.
Examples of the nitrogen-containing basic compound as the polycondensation catalyst includes hydroxides of ammonium having alkyl, aryl and aralkyl groups, such as tetramethylammonium hydroxide (Me.sub.4 NOH), tetraethylammonium hydroxide (Et.sub.4 NOH), tetrabutylammonium hydroxide (Bu.sub.4 NOH) and trimethylbenzylammonium hydroxide (Φ-CH.sub.2 (Me).sub.3 NOH); tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine and hexadecyldimethylamine; secondary amines of the formula R.sup.0.sub.2 NH (wherein R.sup.0 is alkyl such as methyl or ethyl, or an aryl group such as phenyl or toluyl); primary amines of the formula R.sup.0 NH.sub.2 (wherein R.sup.0 is as defined above); imidazoles such as 2-methylimidazole and 2-phenylimidazole; and basic salts such as tetramethylammonium borohydride (Me.sub.4 NBH.sub.4), tetrabutylammonium borohydride (Bu.sub.4 NBH.sub.4), tetrabutylammonium tetraphenylborate (Bu.sub.4 NBPh.sub.4) and tetramethylammonium tetraphenylborate (Me.sub.4 NBPh.sub.4).
Examples of the metal compounds used as the polycondensation catalyst include zinc compounds, e.g., carboxylates of zinc such as Zn(OAc).sub.2 and Zn(OBz).sub.2, oxides and sulfides of zinc such as ZnO and ZnS, hydroxides of zinc such as Zn(OH).sub.2, organic zinc compounds such as (C.sub.2 H.sub.5).sub.2 Zn, Ph.sub.2 Zn, C.sub.2 H.sub.5 ZnOC.sub.2 H.sub.5, PhZnOAc and C.sub.4 H.sub.9 ZnOAc, alkoxides and aryloxides of zinc such as Zn(OC.sub.2 H.sub.5).sub.2 and Zn(OPh).sub.2, and chelate compounds of zinc such as Zn(acac).sub.2, and Zn(oxin).sub.2 ; aluminum compounds, e.g., carboxylates of aluminum such as Al(OAc).sub.3 and Al(OBz).sub.3, oxides of aluminum such as Al.sub.2 O.sub.3, hydroxides of aluminum such as Al(OH).sub.3, organoaluminum compounds such as Ph.sub.3 Al, alkoxides and aryloxides of aluminum such as Al(OCH.sub.3).sub.3, Al(OC.sub.3 H.sub.7 -i).sub.3 and Al(OPh).sub.3, and chelate compounds of aluminum such as Al(acac).sub.3 and Al(oxin).sub.3 ; gallium compounds, e.g., carboxylates of gallium such as Ga(OAc).sub.3, Ga(OBz).sub.3 and GaO(OAc), oxides of gallium such as Ga.sub.2 O.sub.3, hydroxides of gallium such as Ga(OH).sub.3, organogallium compounds such as (CH.sub.3).sub.3 Ga and Ph.sub.3 Ga, alkoxides and aryloxides of gallium such as Ga(OCH.sub.3).sub.3 and Ga(OPh).sub.3, and chelate compounds of gallium such as Ga(acac).sub.3 ; indium compounds, e.g., carboxylates of indium such as In(OAc).sub.3, oxides of indium such as In.sub.2 O.sub.3, organoindium compounds such as (C.sub.2 H.sub.5).sub.3 In and Ph.sub.3 In, and chelate compounds of indium such as In(acac).sub.3 ; germanium compounds. e.g., carboxylates of germanium such as Ge(OAc).sub.4 and Ge(OBz).sub.4, oxides of germanium such as GeO.sub.2, hydroxides of germanium such as Ge(OH).sub.2 and Ge(OH).sub.4, organogermanium compounds such as (C.sub.2 H.sub.5).sub.4 Ge, Ph.sub.4 Ge, [(C.sub.4 H.sub.9).sub.2 GeO].sub.n and [Ph.sub.2 GeO].sub.n, alkoxides and aryoxides of germanium such as Ge(OCH.sub.3).sub.4 and Ge(OPh).sub.4 ; tin compounds, e.g., carboxylates of tin such as Sn(OAc).sub.2, Sn(OAc).sub.4 and Sn(OBz).sub.4, organotin compounds such as (C.sub.2 H.sub.5).sub.4 Sn and Ph.sub.4 Sn, organotin oxides such as (C.sub.2 H.sub.5).sub.4 Sn and Ph.sub.2 Sn, organotin hydroxides such as (C.sub.4 H.sub.9).sub.2 SnO, [(C.sub.4 H.sub.9).sub.2 SnO].sub.n, [C.sub.8 H.sub.17).sub.2 SnO].sub.n and [(C.sub.4 H.sub.9)PhSnO].sub.n, organotin carboxylates such as (C.sub.4 H.sub.9).sub.2 Sn(OAc).sub.2 and dibutyltin laurate, oxides of tin such as SnO and SnO.sub.2, hydroxides of tin such as Sn(OH).sub.2 and Sn(OH).sub.4, and organotin alkoxides and aryloxides such as Sn(OCH.sub.3).sub.2, Sn(OCH).sub.3, Sn(OC.sub.4 H.sub. 9).sub.4, Sn(OPh).sub.2, Sn(OPh).sub.4 and (C.sub.4 H.sub.9)Sn(OCH.sub.3).sub.2 ; lead compounds, e.g., carboxylates of lead such as Pb(OAc).sub.2, Pb(OAc).sub.4 and Pb(OBz).sub.2, inorganic acid salts of lead such as PbCO.sub.3 and 2PbCO.sub.3.Pb(OH).sub.2, complex compounds of lead such as Na.sub.2 [Pb(OH).sub.6 ], oxides of lead such as PbO, PbO.sub.2 and Pb.sub.3 O.sub.4, hydroxides of lead such as Pb(OH).sub.2, organolead compounds such as (C.sub.4 H.sub.9).sub.4 Pb, Ph.sub.4 Pb and (C.sub.2 H.sub.5).sub.3 Pb(OAc), alkoxides and aryloxides of lead and organolead such as Pb(OCH.sub.3).sub.4 and Pb(OPh).sub.4 and (C.sub.4 H.sub.9).sub.2 Pb(OPh).sub.2 ; and zirconium compounds, e.g., carboxylates of zirconium such as Zr(OAc).sub.4 and Zr(OBz).sub.4, oxides of zirconium such as ZrO.sub.2, alkoxides and aryloxides of zirconium such as Zr(OC.sub.4 H.sub.9).sub.4 and Zr(OPh).sub.4, organozirconium compounds such as Zr(OAc).sub.3 (π-C.sub.2 H.sub.5) and ZrH.sub.2 (π -C.sub.2 H.sub.5).sub.2, and chelate compounds of zirconium such as Zr(acac).sub.4. These catalysts can be used either singly or in combination.
A.sup.1 -(Y.sup.1 -SO.sub.3 X.sup.1).sub.m                 (I)
R.sup.17 is the same as or different from R.sup.15 and has the same definition as R.sup.15,
provided that two of R.sup.15, R.sup.16 and R.sup.17 cannot be hydrogen atoms.
In the formula (I)-a, preferable examples of the monovalent hydrocarbon group indicated by R.sup.1, etc. include an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 10 carbon atoms, and an aralkyl group having 1 to 10 carbon atoms.
The phosphonium cation includes, for example, a cation of the formula (I)-b ##STR9## wherein each of R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently a hydrogen atom or a monovalent hydrocarbon group.
Of these examples of X.sup.1, the secondary or tertiary alkyl group, the alkali metal cation, the cation of The formula (I)-a and the cation of the formula (I)-b are preferable.
For convenience sake, the compounds of the formula (I) are divided into two groups according to the definition of Y.sup.1 : a compound group in which Y.sup.1 is a single bond and a compound group in which Y.sup.1 is an oxygen atom. The compound group in which Y.sup.1 is a single bond and m is 1, for example, is represented by the formula (I)-1
Of the compounds of the formula (I)-1, preferable is a compound wherein A.sup.1 is a monovalent saturated aliphatic hydrocarbon group or a monovalent saturated aliphatic-aromatic hydrocarbon group; especially preferable is a compound wherein A.sup.1 is a group of the formula (I)-c ##STR10## wherein A.sup.11 is an alkyl group having 1 to 18 carbon atoms, and l is an integer of 0 or 1.
The compound group in which Y.sup.1 is an oxygen atom and m is 1, for example, is represented by the formula (I)-2.
Compounds of the formula (I) in which Y.sup.1 is a single bond, X.sup.1 is a phosphonium cation of the formula (I)-b and m is 1:
tetrahexylphosphonium hexylsulfonate,
tetraetylphosphonium dodecylsulfonate,
tetrahexylphosphonium toluenesulfonate.
Sodium octylsulfate, potassium octylsulfate. cesium octylsulfate, lithium decylsulfate, sodium decylsulfate, sodium dodecylsulfate, potassium dodecylsulfate, lithium tetradecylsulfate, sodium tetradecylsulfate, potassium decylsulfate, lithium hexadecylsulfate, sodium oleylsulfate, and potassium hexadecylsulfate.
Ammonium salts such as ammonium octylsulfate, ammonium decylsulfate, ammonium dodecylsulfate and ammonium hexadecylsulfate; primary ammonium salts such as methylammonium hexylsulfate, methylammonium octylsulfate, methylammonium hexadecylsulfate, ethylammonium hexylsulfate, butylammonium nonadecylsulfate, hexylammoniium octadecylsulfate, decylammonium ethylsulfate, decylammonium butylsulfate, decylammonium decylsulfate, dodecylammonium methylsulfate, dodecylammonium ethylsulfate, dodecylammonium octylsulfate, tetradecylammonium butylsulfate, pentadecylammonium methylsulfate, hexadecylammonium butylsulfate, hexadecylammonium octylsulfate, hexadecylammonium decylsulfate and hexadecylammonium dodecylsulfate; secondary ammonium salts such as dimethylammonium hexylsulfate, dimethylammonium octylsulfate, dimethylammonium tetradecylsulfate, diethylammonium octadecylsulfate, butylmethylammonium tetradecylsulfate, hexylmethylammonium tetradecylsulfate, decylmethylammonium methylsulfate, decylethylammonium ethylsulfate, decylmethylammonium octylsulfate, dodecylmethylammonium methylsulfate, tetradecylmethylammonium methylsulfate, tetradecylethylammonium ethylsulfate, pentadecylmethylammonium methylsulfate, pentadecylethylammonium ethylsulfate, hexadecylmethylammonium methylsulfate and hexadecylethylammonium ethylsulfate; tertiary ammonium salts such as trimethylammonium octylsulfate, trimethylammonium decylsulfate, butyldimethylammonium decylsulfate, hexyldimethylammonium dodecylsulfate, decyldimethylammonium methylsulfate, decyldimethylammonium tridecylsulfate, dodecyldiethylammonium ethylsulfate, dodecyldibutylammonium butylsulfate, dodecyldimethylammonium tetradecylsulfate, tetradecyldimethylammonium methylsulfate, tetradecylmethylethylammonium methylsulfate, pentadecyldimethylammonium ethylsulfate, hexadecyldimethylammonium methylsulfate and hexadecylmethylethylammonium ethylsulfate; and quaternary ammonium salts such as tetramethylammonium hexylsulfate, tetraethylammonium tridecylsulfate, butyltrimethylammonium octylsulfate, decyltrimethylammonium methylsulfate, decyltriethylammonium ethylsulfate, decyltrimethylammonium hexadecylsulfate, pentadecyltrimethylammonium methylsulfate and pentadecyldimethylethylammonium ethylsulfate.
.sup.&#8853; X.sup.2 --A.sup.2 --Y.sup.1 --SO.sub.3.sup.&#8854; (II)
.sup.⊕ X.sup.2 is an ammonium cation or a phosphonium cation, and
.sup.⊕ X.sup.2 is an ammonium cation or a phosphonium cation.
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.3 --N.sup.⊕ (CH.sub.3).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.3 --N.sup.⊕ (C.sub.2 H.sub.5).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.3 --P.sup.⊕ (C.sub.4 H.sub.9).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.3 --P.sup.⊕ (C.sub.6 H.sub.5).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.15 --N.sup.⊕ (C.sub.2 H.sub.5).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.15 --P.sup.⊕ (C.sub.6 H.sub.5).sub.3,
.sup.⊖ SO.sub.3 --(--CH.sub.2).sub.15 --P.sup.⊕ (C.sub.4 H.sub.9).sub.3.
Stabilizer of the formula (III) ##EQU1## wherein A.sup.3 is a hydrocarbon group having a valence of n, .sup.⊕ X.sup.3 is an ammonium cation or a phosphonium cation,
The hydrocarbon group having a valence of n, which is indicated by A.sup.3, is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a saturated aliphatic-aromatic hydrocarbon group, each of these groups having a valence of n.
Examples of the ammonium cation and the phosphonium cation of .sup.⊕ X.sup.3 are the same as those shown in the formulas (II)-a and (II)-b.
Compounds of the formula (III) in which Y.sup.1 is a single bond, .sup.⊕ X.sup.3 is an ammonium cation of the formula (II)-a and n is2: ##STR13##
Compounds of the formula (III) in which Y.sup.1 is an oxygen atom, .sup.⊕ X.sup.3 is an ammonium cation of the formula (II)-a and n is 2:
[(CH.sub.3).sub.3 N.sup.⊕ --(CH.sub.2).sub.10 --N.sup.⊕ (CH.sub.3).sub.3 ].(C.sub.15 H.sub.31 --SO.sup.⊖.sub.4).sub.2,
[(CH.sub.3).sub.3 N.sup.⊕ --(CH.sub.2).sub.15 --N.sup.⊕ (CH.sub.3).sub.3 ].(C.sub.15 H.sub.31 --SO.sup.⊖.sub.4).sub.2,
[(C.sub.4 H.sub.9).sub.3 N.sup.⊕ --(CH.sub.2).sub.10 --N.sup.⊕ (C.sub.4 H.sub.9).sub.3 ].(C.sub.15 H.sub.31 --SO.sup.⊖.sub.4).sub.2.
Compounds of the formula (III) in which Y.sup.1 is a single bond, .sup.⊕ X.sup.3 is a phosphonium cation of the formula (II)-b and n is 2: ##STR14##
Compounds of the formula (III) in which Y.sup.1 is an oxygen atom, .sup.⊕ X.sup.3 is a phosphonium cation of the formula (II)-b and n is 2:
[(C.sub.4 H.sub.9).sub.3 P.sup.⊕ --(CH.sub.2).sub.10 --P.sup.⊕ (C.sub.4 H.sub.9).sub.3 ].(C.sub.15 H.sub.31 --SO.sup.⊖.sub.4).sub.2,
[(C.sub.6 H.sub.5).sub.3 P.sup.⊕ --(CH.sub.2).sub.10 --P.sup.⊕ (C.sub.6 H.sub.5).sub.3 ].(C.sub.15 H.sub.31 --SO.sup.⊖.sub.4).sub.2.
Stablizer of the formula (IV) ##EQU2## wherein A.sup.5 is a monovalent or divalent hydrocarbon group, A.sup.4 is a divalent hydrocarbon group,
each of Ad.sup.1 and Ad.sup.2 is independently an acid anhydride group selected from the group consisting of --SO.sub.2 --O--SO.sub.2 --, --SO.sub.2 --O--CO-- and --CO--O--SO.sub.2 --, and l is 0 or 1,
provided that when l is 0, --(Ad.sup.2 -A.sup.5).sub.l is a hydrogen atom or a bond between A.sup.4 and A.sup.5, in which A.sup.5 is a divalent hydrocarbon group or a single bond.
A.sup.5 --Ad.sup.1 --A.sup.4 H                             (IV)-2
In the formulas (IV), (IV)-1 and (IV)-2, preferred examples of the monovalent hydrocarbon group of A.sup.5 include an alkyl group, an aryl group or an aralkyl group. Preferably, the alkyl group is an alkyl group having 1 to 20 carbon atoms, the aryl group is an aryl group having 1 to 20 carbon atoms, and the aralkyl group is an aralkyl group having 1 to 20 carbon atoms.
In the formula (IV) and (IV)-3, preferred examples of the divalent hydrocarbon group of A.sup.5 include an alkylene group, an arylene group and an aralkylene group. Preferably, the alkylene group is an alkylene group having 1 to 20 carbon atoms, the arylene group is an arylene group having 1 to 20 carbon atoms, and the aralkylene group is an aralkylene group having 1 to 20 carbon atoms.
Each of Ad.sup.1 and Ad.sup.2 is independently an acid anhydride group selected from the group consisting of --SO.sub.2 --O--SO.sub.2 --, --SO.sub.2 --O--CO-- and --CO--O--SO.sub.2 --. The acid anhydride group is an acid anhydride group (--SO.sub.2 --O--SO.sub.2 --) between sulfonic acids or an acid anhydride group (--SO.sub.2 --O--CO-- or --CO--O--SO.sub.2 --) between sulfonic acid and carboxylic acid.
Compounds of the formula (IV) -3: ##STR18##
Among the stabilizers of the formulas (I) to (IV), phosphonium salt or ammonium salt type stabilizers (X.sup.1, X.sup.2 and X.sup.3 in the formulas (I) to (III) is a phosphonium cation or an ammonium cation) are especially stable even above 200
In the process for the production of the polycarbonate in this invention, it is also advisable to add an epoxy compound along with the above stabilizer. On this occasion, an epoxy compound having at least one epoxy group in one molecule is used. Specific examples of the epoxy compound include an epoxidized soybean oil, an epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, tert-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexyl carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexyl carboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl-3',4'-epoxycyclohexyl carboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexyl carboxylate, bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl phthalate, diglycidyl hexahydrophthalate, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxyphthalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-tert-butyl-1,2-epoxycycrohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3',4'-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexyl carboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-tert-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, and di-n-butyl-3-tert-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate.
Specific examples of the phosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearylpentaerythrityl diphosphate, tosyl(2-chloroethyl)phosphate, and tris(2,3-dichloropropyl)phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; and triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl)phosphate and 2-ethylphenyldiphenyl phosphate.
Specific examples of the compound of the above formula include trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris(2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, tristearyl phosphite, tris(2-chloroethyl)phosphite and tris(2,3-dichloropropyl) phosphite; tricycloalkyl phosphite such as tricyclohexyl phosphite; arylalkyl phosphites such as triphenyl phosphite, tricresyl phosphite, tris(ethylphenyl)phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl)phosphite and tris(hydroxyphenyl)phosphite; and arylalkyl phosphites such as phenyldidecyl phosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, phenylisooctyl phosphite and 2-ethylhexyldiphenyl phosphite.
Examples of the thioether-type stabilizer include dilauryl.thiodipropionate, distearyl.thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and pentaerythritol-tetrakis-(β-laurylthiopropionate). They may be used either singly or in combination.
Examples of the hindered amine-type stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro[4,5]undecane-2,4-dione, 4-benzyloxy -2,2,6,6-tetramethylpiperidien, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalic acid-bis(1,2,2,6,6-pentamethyl-4-piperidyl), and tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate.
Examples of the benzotriazole-type ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-[2'-hydroxy-3"-(3",4",5",6"-tetrahydrophthalimldomethyl)-5'-methylphenyl]benzotriazole, and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol].
These colorants may be used either singly or in combination. The colorant can be used in an amount of usually 1 weight, preferably 1 preferably 1 of the polycarbonate.
The polycondensation reaction of the aromatic dihydroxy compound and the carbonic acid diester can be conducted under the same conditions as hitherto known polycondensation reaction conditions of an aromatic dihydroxy compound and a carbonic acid diester. Specifically, the reaction is first conducted at a temperature of 80 preferably 100 230 preferably 0.25 to 3 hours under normal pressure. Then, while the pressure of the reaction system is reduced, the reaction temperature is elevated to conduct the reaction of the aromatic dihydroxy compound and the carbonic acid diester. Finally, the polycondensation reaction of the aromatic dihydroxy compound and the carbonic acid diester is conducted at a temperature of 200 mmHg or less.
EXAMPLES This invention will be illustrated by referring to the following Examples. However, this invention is not limited to these Examples.
An intrinsic viscosity [IV] was measured in methylene chloride at 20
A change of viscosity was measured at 270 an RAA-type flow analyzer of Rheometrics to find a change rate per minute. This change rate becomes a parameter of catalyst deactivation.
A polymer was subjected to heat aging at 320 the properties after heat aging was evaluated according to an IV decrease rate (%) and a change of hue.
A polymer was reacted in a water seal autoclave at 125 hours to find a rate of main chain breakage (%).
Examples 1 to 33 2,2'-Bis(4-hydroxyphenyl)propane [bisphenol A] (228 parts by weight), 214 parts by weight of diphenyl carbonate and a predetermined amount of a catalyst shown in Table 1-1 to Table 1-11 were charged into a reactor fitted with a stirrer, a pressure reduction device and a distillation column. They were stirred in an N.sub.2 atmosphere at 180 30 minutes and dissolved.
Then, the mixture was reacted at the same temperature for 1 hour under reduced pressure of 100 mmHg while distilling off phenol. Further, while the temperature was elevated to 200 to 30 mmHg, and the reaction was performed at the same temperature for 1 hour under the same pressure. The reaction system was further heated to 280 performed at the same temperature for 1 hour under the same pressure to obtain a resin.
The intrinsic viscosity (IV) before stabilizer addition of the above resins was measured. The results are shown in Tables 1-1to 1-11.
Subsequently, each stabilizer of the kind and amount shown in Tables 1-1 to 1-11 was added to the resins in the molten state, and they were mixed under reduced pressure for a predetermined period of time. Then, the molten resins were fed into a twin-screw extruder (L/D=20, barrel temperature 290 amounts of a phosphorus compound or a phenolic compound were added to the resins as required.
Example 34 A polycarbonate was produced in the same manner as in Example 1 except that the reaction time at 280 changed from 1 hour to 20 minutes.
Example 35 A polycarbonate was produced in the same manner as Example 8 except 268 parts by weight of 1,1'-bis(4-hydroxyphenol)cyclohexane was used instead of 228 parts by weight of 2,2'-bis(4-hydroxyphenol)propane.
TABLE 1   Example 1 Example 2 Example 3 Example 4 Example 5   Catalyst Kind Bisphenol A Bisphenol A Sodium hydroxide Sodium acetate Sodium stearate  disodium salt disodium salt Amount (part by weight) 0.0014 0.0014 0.0004 0.0008 0.0061 Intrinsic viscosity (IV) 0.51 0.52 0.50 0.48 0.50 before addition Additives Stabilizer  Kind            ##STR19##  ##STR20##  ##STR21##  ##STR22##  ##STR23##   Amount (part by weight) 0.0046 [2.0]* 0.0077 [2.0]* 0.0109 [2.0]* 0.0082 [2.0]* 0.014 [1.5]* Mixing time (min.) 20 20 10 10 10 Phosphorus compound Kind Tris(nonylphenyl)- -- Tris(nonylphenyl)- -- --  phosphite phosphite Amount (part by weight) 0.025 -- 0.025 -- -- Phenolic compound Kind IRGANOX 245 -- IRGANOX 1010 -- -- Amount (part by weight) 0.025 -- 0.025 -- -- Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.52 0.53 0.52 0.50 0.51 Hue Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change rate 0.3 0.3 0.2 0.4 0.3 (%/min.) Properties after heat aging (320.degree . C./15 min.) IV decrease rate (%) 2 2 2 2 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to 3 3 1 5 5 hydrolysis (%)    Example 6 Example 7 Example 8 Example 9 Example 10   Catalyst Kind Sodium salicylate Sodium hydroxide Bisphenol A Tetramethy lammonium Tetramethylammonium    disodium salt hydroxide/sodium hydroxide  hydroxide/sodium hydroxide Amount (part by 0.0032 0.0004 0.0014 0.0091/0.000004 0.0091/0.000004 weight) Intrinsic viscosity (IV) 0.49 0.52 0.53 0.51 0.52 before addition Additives  Stabilizer  Kind            ##STR24##  C.sub.15 H.sub.31SO.sub.3 N(C.sub.4  H.sub.9).sub.4            ##STR25##  ##STR26##  ##STR27##   Amount (part by 0.014 [.2]* 0.0107 [2.0]* 0.012 [2.0].sup.' 0.00012 [2.0]* 0.0003 [5.0]* weight) Mixing time (min.) 10 10 10 10 10 Phosphorus  compound Kind -- -- Tris(nonylphenyl)- Triphenyl phosphite Triphenyl phosphite    phosphite Amount (part by -- -- 0.03 0.03 0.03 weight) Phenolic compound Kind -- -- 2,6-di-tert-butyl-4- 2,6-di-tert-butyl-4- 2,6-di-tert-butyl-4-    methylphenol methylphenol methylphenol Amount (part by -- -- 0.03 0.03 0.03 weight) Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.50 0.52 0.54 0.52 0.53 Hue Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change 2 0.4 0.1 0.1 0.1 rate (%/min.) Properties after heat aging (320 (%) 2 3 1 2 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to 6 5 1 1 2 hydrolysis (%)    Example 11 Example 12 Example 13 Example 14 Example 15 Example 16   Catalyst Sodium thiocyanate Sodium acetate Bisphenol A Bisphenol A Calcium hydroxide Bisphenol A Kind   disodium salt disodium salt disodium salt  Amount (part 0.0008 0.0008 0.0014 0.0014 0.0004 0.0014 by weight) Intrinsic viscosity (IV) 0.52 0.49 0.52 0.50 0.49 0.52 before addition Additives Stabilizer  Kind C.sub.18 H.sub.37SO.sub.3 P(C.sub.4 H.sub.9).sub.4  ##STR28##  ##STR29##  C.sub. 15 H.sub.31SO.sub.3 P(C.sub.10  H.sub.21).sub.4            ##STR30##  ##STR31##   Amount (part by 0.012 [2.0]* 0.036 [5.0]* 0.018 [2.0]* 0.029 [5.0]* 0.0048 [1.5]* weight) Mixing time (min.) 10 15 15 10 15 10 Phosphorus compound Kind Tris(nonylphenyl)- ADK STAB PEP-36 ADK STAB PEP-36 ADK STAB PEP-36 -- ADK STAB PEP-36  phosphite Amount (part by 0.03 0.03 0.03 0.03 -- 0.03 weight) Phenolic compound Kind 2,6-di-tert-butyl- IRGANOX 1076 IRGANOX 1076 IRGANOX 1076 -- IRGANOX 1076  4-methylphenol Amount (part by 0.03 0.03 0.03 0.03 -- 0.03 weight) Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.53 0.50 0.52 0.51 0.50 0.52 Hue Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change 0.1 0.2 0.2 0.3 0.2 0.3 rate (%/min.) Properties after heat aging (320 min.) IV decrease rate (%) 2 2 3 2 2 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to 1 2 3 3 2 4 hydrolysis (%)    Example 17 Example 18 Example 19 Example 20 Example 21 Example 22       Catalyst Kind Bisphenol A Bisphenol A Bisphenol A Sodium acetate Sodium acetate Bisphenol A  disodium salt disodium salt disodium salt   disodium salt Amount (part 0.0014 0.0014 0.0014 0.0008 0.0008 0.0014 by weight) Intrinsic viscosity (IV) 0.52 0.55 0.54 0.54 0.51 0.52 before addition Additives Stabilizer  Kind            ##STR32##  C.sub.12 H.sub.25OSO.sub.3  Na            ##STR33##  ##STR34##  C.sub.12 H.sub.25OSO.sub.3 P(C.sub.4 H.sub.9).sub.4 t-C.sub.4 H.sub.9 O.sub.3 SC.sub.15 H.sub.30SO.sub.3-t-C.sub.4 H.sub.9   Amount (part by 0.0095 [2.0]* 0.0043 [1.5]* 0.0035 [1.0]* 0.0062 [2.0]* 0.010 [2.0]* 0.0045 [2.0]* weight) Mixing time (min.) 10 20 20 15 10 10 Phosphorus compound Kind ADK STAB PEP-36 -- -- Trilauryl Trilauryl ADK STAB PEP-36    thiophosphite thiophosphite Amount (part by 0.03 -- -- 0.025 0.025 0.03 weight) Phenolic compound Kind IRGANOX 1076 -- -- 2,6-di-tert-butyl-  2,6-di-tert-butyl- IRGANOX 1076     4-methylphenol 4-methylphenol Amount (part by 0.03 -- -- 0.025 0.025 0.03 weight) Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.53 0.55 0.54 0.55 0.52 0.52 Hue Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change 0.4 0.3 0.3 0.3 0.3 0.2 rate (%/min.) Properties after heat aging (320.degree . C./15 min.) IV decrease rate (%) 2 2 2 3 2 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to 3 6 7 7 7 4 hydrolysis (%)    Example 23 Example 24 Example 25 Example 26   Catalyst Bisphenol A Bisphenol A Bisphenol A Tetramethylammonium Kind disodium salt disodium salt disodium salt hydroxide/sodium hydroxide Amount (part 0.0014 0.0014 0.0014 0.0091/0.000014 by weight) Intrinsic viscosity (IV) 0.52 0.51 0.51 0.50 before addition Additives Stabilizer Kind  ##STR35##  (CH.sub.3).sub.3 NC.sub.3 H.sub.6SO.sub.3 (C.sub.6 H.sub.5).sub.3 PC.sub.15  H.sub.30SO.sub.3            ##STR36##   Amount (part by 0.0076 [2.0]* 0.0036 [2.0]* 0.011 [2.0]* 0.0003 [1.5]* weight) Mixing time (min.) 10 10 10 10 Phosphorus compound Kind ADK STAB PEP-36 -- -- IRGAFOS 168  Amount (part by weight) 0.03 -- -- 0.03 Phenolic compound Kind IRGANOX 1076 -- -- IRGANOX 245  Amount (part by weight) 0.03 -- -- 0.03 Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.53 0.52 0.50 0.52 Hue Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change 0.2 0.5 0.3 0.2 rate (%/min.) Properties after heat aging (320 min.) IV decrease rate (%) 3 3 3 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to hydrolysis (%) 3 6 4 2 Example 27 Example 28 Example 29 Example 30 Example 31   Catalyst Kind Bisphenol A Bisphenol A Bisphenol A Sodium acetate Sodium acetate  disodium salt disodium salt disodium salt Amount (part by weight) 0.0014 0.0014 0.0028 0.0008 0.0008 Intrinsic viscosity (IV) before 0.50 0.52 0.48 0.51 0.50 addition Additives Stabilizer  Kind [(C.sub.6 H.sub.5).sub.3 P(CH.sub.2).sub.10P(C.sub.6 H.sub.5).sub.3 ].[((C.sub.15 H.sub.31SO.sub.3).sub.2  ]            ##STR37##  (C.sub.7 H.sub.15SO.sub.2).sub.2  O            ##STR38##   Amount (part by weight) 0.012 [2.0]* 0.012 [2.0]* 0.0065 [2.0]* 0.0068 [4.0]* 0.0059 [1.5]* Mixing time (min.) 10 10 10 10 10 Phosphorus compound Kind IRGAFOS 168 IRGAFOS 168 Tris (2,4-di-tert- -- Tris(nonylphe nyl)-    butylphenyl)phosphite  phosphite Amount (part by weight) 0.03 0.03 0.025 -- 0.025 Phenolic compound Kind IRGANOX 245 IRGANOX 245 -- IRGANOX 259 IRGANOX 259 Amount (part by weight) 0.03 0.03 0.025 -- 0.025 Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.51 0.52 0.49 0.52 0.51 Hue Almost colorless Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change rate 0.4 0.4 0.2 0.3 0.2 (%/min.) Properties after heat aging (320 C./15 min.) IV decrease rate (%) 3 3 2 4 2 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to hydrolysis (%) 5 5 2 1 3    Example 32 Example 33 Example 34 Example 35   Catalyst Kind Bisphenol A Bisphenol A Bisphenol A Bisphenol A disodium salt disodium salt disodium salt disodium salt Amount (part by weight) 0.0028 0.0028 0.0014 0.0014 Intrinsic viscosity (IV) before 0.503 0.49 0.31 0.51 addition Additives Stabilizer  Kind            ##STR39##  ##STR40##  ##STR41##  ##STR42##   Amount (part by weight) 0.0071 [1.5]* 0.0089 [2.0]* 0.0046 [2.0]* 0.012 [2.0]* Mixing time (min.) 10 10 10 10 Phosphorus compound Kind Triphenyl phosphite Triphenyl phosphite Tris(nonylphenyl)- Tris(nonylphen yl)-    phosphite phosphite Amount (part by weight) 0.025 0.025 0.025 0.03 Phenolic compound Kind IRGANOX 259 IRGANOX 259 IRGANOX 1010 2,6-di-tert-butyl-4-     methylphenol Amount (part by weight) 0.025 0.025 0.025 0.03 Properties of the obtained polycarbonate Intrinsic viscosity (V) 0.51 0.49 0.31 0.52 Hue Almost colorless Almost colorless Almost colorless Almost colorless Melt viscosity change rate 0.2 0.2 0.2 0.1 (%/min.) Properties after heat aging (320 decrease rate (%) 2 2 3 1 Hue Almost unchanged Almost unchanged Almost unchanged Almost unchanged Resistance to hydrolysis (%) 2 2 2 1 *Amount (mol) of stabilizer per mol of the catalyst
Japanese Patent Publication No. 44,303/1979 discloses a method for stabilizing a polycarbonate resin in which methyl benzenesulfonate or a compound represented by the formula ##STR1## wherein R.sub.1 is a C.sub.1-12 alkyl group, and R.sub.2 is a C.sub.1-6 alkyl group,
Japanese Laid-open Patent Application No. 171,024/1993 (Kokai Sho 64-13267) discloses a polycarbonate resin composition comprising 100 parts by weight of a polycarbonate resin, 0.1 to 20 parts by weight of a sulfonic acid phosphonium salt represented by the formula ##STR2## wherein R.sup.1 is a C.sub.1-40 alkyl group or an aryl group, and each of R.sup.2 to R.sup.5 is independently H, a C.sub.1-10 alkyl group or an aryl group,
Japanese Laid-open Patent Application No. 9,285/1993 (Kokai Hei 5-9285) discloses a process for producing a polycarbonate, which comprises adding 0.05 to 10 ppm of a sulfonic acid compound represented by the formula ##STR3## wherein R.sup.7 is a C.sub.1-6 hydrocarbon group which may be substituted with halogen, R.sup.8 is H or a C.sub.1-8 hydrocarbon group which may be substituted with halogen, and n is an integer of 0 to 3,
to a polycarbonate obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester. This document simply describes a compound having a primary alkyl group as a compound in which the C.sub.1-8 hydrocarbon group is an alkyl group.
Japanese Laid-open Patent Application No. 17,564/1993 (Kokai Hei 5-17564) discloses a process for producing a polycarbonate, which comprises melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a catalyst formed of a nitrogen-containing basic compound (1st step), and then adding a nitrogen-containing basic compound at least once and further a sulfonic acid compound represented by the formula ##STR4## wherein R.sup.31 is a C.sub.1-6 hydrocarbon group which may be substituted with halogen, R.sup.32 is H or a hydrocarbon group which may be substituted with halogen, and n is an integer of 0 to 3,
SUMMARY OF THE INVENTION In accordance with this invention, the above objects and advantages of this invention are achieved by a process for the production of a stabilized polycarbonate which comprises melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polycondensation catalyst and then, after the reaction mixture shows an intrinsic viscosity of at least 0.1, adding at least one stabilizer selected from the group consisting of
provided that when Y*.sup.1 is a single bond, all of X.sup.1 s in an amount of m cannot be metal cations of one equivalent,
A.sup.4 is a divalent hydrocarbon group,
each of Ad.sup.1 and Ad.sup.2 is independently an acid anhydride group selected from the group consisting of --SO.sub.2 --O--SO.sub.2 --, --SO.sub.2 --O--CO-- and CO--O--SO.sub.2 --, and
provided that when l is 0, --(Ad.sup.2 --A.sup.4).sub.l is a hydrogen atom or a bond between A.sup.4 and A.sup.5, in which A.sup.5 is a divalent hydrocarbon group or a single bond,
The process of this invention comprises, as stated above melt-polymerizing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polycondensation catalyst, and then, after the reaction mixture shows an intrinsic viscosity of at least 0.1. adding at least one stabilizer selected from the compounds of the formulas (I) to (IV) in an amount of 0.01 to 500 ppm of a polycarbonate to be formed, to form a polycarbonate having a desired intrinsic viscosity.
This is a divisional application of Ser. No. 08/294,995, filed Aug. 24, 1994.
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