CA2083878A1 - Block copolymers of aromatic polycarbonates - Google Patents
Block copolymers of aromatic polycarbonatesInfo
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- CA2083878A1 CA2083878A1 CA 2083878 CA2083878A CA2083878A1 CA 2083878 A1 CA2083878 A1 CA 2083878A1 CA 2083878 CA2083878 CA 2083878 CA 2083878 A CA2083878 A CA 2083878A CA 2083878 A1 CA2083878 A1 CA 2083878A1
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- aliphatic
- polycarbonate
- bis
- carbonate
- polyol
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Abstract
Mo-3679CIP
BLOCK COPOLYMERS OF AROMATIC POLYCARBONATES
ABSTRACT OF THE DISCLOSURE
A copolycarbonate resin having improved properties and a method for its preparation is disclosed. Accordingly, a block oligocarbonate is first produced and in a second step a polycarbonate resin is reactively blended with said oligo-carbonate to produce a copolycarbonate.
Mo3679CIP
BLOCK COPOLYMERS OF AROMATIC POLYCARBONATES
ABSTRACT OF THE DISCLOSURE
A copolycarbonate resin having improved properties and a method for its preparation is disclosed. Accordingly, a block oligocarbonate is first produced and in a second step a polycarbonate resin is reactively blended with said oligo-carbonate to produce a copolycarbonate.
Mo3679CIP
Description
Mo-3679CIP
BLOCK COPOLYMERS OF AROMATIC POLYCARBONATES
Field of the Invention The invention relates to thermoplastic molding compositions, in particular to molding resins which contain copolycarbonates and to a process for their manufacture.
SUMMARY OF THE INYENTION
A copolycarbonate resin having improved properties and a method for its preparation is disclosed. Accordingly, a block ol;gocarbonate is first produced and in a second step a lo polycarbonate resin is reactively blended with said o1igo-carbonate to produce a copolycarbonate.
BACKGROUND OF THE INVENTION
Polycarbonate molding composit;ons conta;n;ng an aromat;c carbonate polymer and an ester have been disclosed ;n GB 1,567,517. Accordingly, esters of certa;n organic ac;ds and certa;n alcohols can be incorporated ;n a thermoplastic aromatic polycarbonate resulting ;n a res;n having release propert;es. In addit;on, the composit;on ;s sa;d to be compat;ble with polycarbonate melt. The incorporation o~ the esters in the polycarbonate composition ;n accordance with the '517 document can be effected by admixing the ester with granules of polycarbonate composition and subsequently extruding these through an extruder under standard conditions.
The esters may also be incorporated by d;~ssolving them in a solvent in which the polycarbonate is d;ssolved and sub-sequently recovering the po~ymer composition from the solvent by known methods.
The preparation of relevant copolycarbonates was disclosed by Schreckenberg in U.S. Patent 4,281,101. ~he process ~nvolYed solut70n reaction of oliyomers w;th diphenols. In accordance with tne process disclosed in the ~101 document, an aliphatic aromatic polycarbonate with d;phenol carbonate end -2~
~roups is prepared by react~ng in the melt an aliphatic diol,oarbonic acid b~s aryl ester - for example d~phenyl carbonate - and diphenols. The resulting polycarbonate ~s characterized ~n that each of its end groups constitute a residue of one diphenol. The polycarbonate disclosed in the 'lOI document are unsuitable in the practice of the present invQntion for the preparation of block copolycarbonates.
DETAILED DESCRTPTION OF THE INYENTION
The present invention concerns oligomerie block copolymers of the type o R-A-B-A-R and R-A-B-A-C-A-B-A-R
where R
R denotes hydrogen or -C-O-Ar, and where A denotes an aromatic carbonate structure conforming to ~O-Ar-O-C~n and where Ar denotes an aromatic radical, n is 2-6 and where B is the residue of an aliphatic polyol, with the proviso that sald B is bonded to said A through the terminal 25. carboxyl in sa~d A. The term resldue in the context of the present disclosurs refers to that part of the motecule of the polyol without the hydroxyl groups.
~he oll~omerlc block copolymer of the invent~on is useful as a reactant ln a transester~ficat~on process ln the melt wlth 30. any of aromat1c polycarbonate resins, aromat~c polyester carbonate resins, aromatlc polyesters and aromatic allphat~c polyesters~ preferably aromatic polycarbonate resins, to ~or~
useful copolymers, preferably copolycarbonate resins having desirable propert~es.
Mo3679CIP
BLOCK COPOLYMERS OF AROMATIC POLYCARBONATES
Field of the Invention The invention relates to thermoplastic molding compositions, in particular to molding resins which contain copolycarbonates and to a process for their manufacture.
SUMMARY OF THE INYENTION
A copolycarbonate resin having improved properties and a method for its preparation is disclosed. Accordingly, a block ol;gocarbonate is first produced and in a second step a lo polycarbonate resin is reactively blended with said o1igo-carbonate to produce a copolycarbonate.
BACKGROUND OF THE INVENTION
Polycarbonate molding composit;ons conta;n;ng an aromat;c carbonate polymer and an ester have been disclosed ;n GB 1,567,517. Accordingly, esters of certa;n organic ac;ds and certa;n alcohols can be incorporated ;n a thermoplastic aromatic polycarbonate resulting ;n a res;n having release propert;es. In addit;on, the composit;on ;s sa;d to be compat;ble with polycarbonate melt. The incorporation o~ the esters in the polycarbonate composition ;n accordance with the '517 document can be effected by admixing the ester with granules of polycarbonate composition and subsequently extruding these through an extruder under standard conditions.
The esters may also be incorporated by d;~ssolving them in a solvent in which the polycarbonate is d;ssolved and sub-sequently recovering the po~ymer composition from the solvent by known methods.
The preparation of relevant copolycarbonates was disclosed by Schreckenberg in U.S. Patent 4,281,101. ~he process ~nvolYed solut70n reaction of oliyomers w;th diphenols. In accordance with tne process disclosed in the ~101 document, an aliphatic aromatic polycarbonate with d;phenol carbonate end -2~
~roups is prepared by react~ng in the melt an aliphatic diol,oarbonic acid b~s aryl ester - for example d~phenyl carbonate - and diphenols. The resulting polycarbonate ~s characterized ~n that each of its end groups constitute a residue of one diphenol. The polycarbonate disclosed in the 'lOI document are unsuitable in the practice of the present invQntion for the preparation of block copolycarbonates.
DETAILED DESCRTPTION OF THE INYENTION
The present invention concerns oligomerie block copolymers of the type o R-A-B-A-R and R-A-B-A-C-A-B-A-R
where R
R denotes hydrogen or -C-O-Ar, and where A denotes an aromatic carbonate structure conforming to ~O-Ar-O-C~n and where Ar denotes an aromatic radical, n is 2-6 and where B is the residue of an aliphatic polyol, with the proviso that sald B is bonded to said A through the terminal 25. carboxyl in sa~d A. The term resldue in the context of the present disclosurs refers to that part of the motecule of the polyol without the hydroxyl groups.
~he oll~omerlc block copolymer of the invent~on is useful as a reactant ln a transester~ficat~on process ln the melt wlth 30. any of aromat1c polycarbonate resins, aromat~c polyester carbonate resins, aromatlc polyesters and aromatic allphat~c polyesters~ preferably aromatic polycarbonate resins, to ~or~
useful copolymers, preferably copolycarbonate resins having desirable propert~es.
Mo3679CIP
-3- 2~3~
In the practice of the invention there is first produced an ollgomeric block copolymer, herein block oligomer. The block ol~gomer ~ay, in one eMbodiment of the inven~ion, be end-capped upon a reaction with d1phenyl carbonate. The ~lock ollgomer thus produced is in the second s~ep then blended - by react~ve blending with a polycarbonate resin to produc~
oopolycarbonate reslns havlng des;rable properties. In the first step 3f the process of the invention, there ~s reacted ~n the melt, in the presence of a transesterif~cat~on catalyst, an aromat~c polycarbonate with an aliphat~c polyol to produce to oligomer.
Aromatic polycarbonates within the scope of the present invent~on are homopolycarbonates and copolycarbonates and ~ixtures thereo~.
The polycarbonates generally have a weight aYerage molecular we;ght of 109000-200,000, preferably 20,000-809000 and their melt flow rate, per ASTM D-1238 at 300'C, is about 1 to about 65 gm/10 min., preferably about 2-15 gm/10 min. They may be prepared, for exa~ple, by the kno~n diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by polycondensation (see German Offen-legunysschriften 2,063,050; 2,063,052; 1,570,703; 2,21~,956;
2,211,957 and 2,248,817; French Patent 1,561,518; and the monograph H. Schnell, "Chem;stry and Phy~sics of Poly-carbonatesn, lnterscience Publ~shers, New York, New York, 19649 all ~ncorporated herein by refQrence).
In the present sontext, dihydroxy compounds suitabl~ for $he preparation of the polycarbonates of the invent~on lnclude the cGmpounds of structural formulae (1) or (2~.
3~
(A ~ ~ ~ HO
(Z)d ~)f ~Z)~
(Z)d ~ 2) Mo3679CIP
In the practice of the invention there is first produced an ollgomeric block copolymer, herein block oligomer. The block ol~gomer ~ay, in one eMbodiment of the inven~ion, be end-capped upon a reaction with d1phenyl carbonate. The ~lock ollgomer thus produced is in the second s~ep then blended - by react~ve blending with a polycarbonate resin to produc~
oopolycarbonate reslns havlng des;rable properties. In the first step 3f the process of the invention, there ~s reacted ~n the melt, in the presence of a transesterif~cat~on catalyst, an aromat~c polycarbonate with an aliphat~c polyol to produce to oligomer.
Aromatic polycarbonates within the scope of the present invent~on are homopolycarbonates and copolycarbonates and ~ixtures thereo~.
The polycarbonates generally have a weight aYerage molecular we;ght of 109000-200,000, preferably 20,000-809000 and their melt flow rate, per ASTM D-1238 at 300'C, is about 1 to about 65 gm/10 min., preferably about 2-15 gm/10 min. They may be prepared, for exa~ple, by the kno~n diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by polycondensation (see German Offen-legunysschriften 2,063,050; 2,063,052; 1,570,703; 2,21~,956;
2,211,957 and 2,248,817; French Patent 1,561,518; and the monograph H. Schnell, "Chem;stry and Phy~sics of Poly-carbonatesn, lnterscience Publ~shers, New York, New York, 19649 all ~ncorporated herein by refQrence).
In the present sontext, dihydroxy compounds suitabl~ for $he preparation of the polycarbonates of the invent~on lnclude the cGmpounds of structural formulae (1) or (2~.
3~
(A ~ ~ ~ HO
(Z)d ~)f ~Z)~
(Z)d ~ 2) Mo3679CIP
wherein A denotes an alkylene group with 1 to 8 carbon atoms, an alkylidene group wi~h 2 to 8 carbon atoms, a cycloalkylenQ
group with 5 to 15 carbon atoms, a cycloalkylidene group w~th 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom9 S0- or -S02- or a rad~cal conforming to ~H3 lo ~H3 ~ CH3 e and g both denote the number 0 to 1;
Z denotes F, Cl, Br or Cl-C4-alkyl and if several Z radicals are substituents ~n one aryl radioal, they may be identical or d~fferent from one another;
d denotes an integer of from 0 to 4; and f denotes an integer of from 0 to 3.
Amon~ the dihydroxy compounds useful in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxy-phenylJ-alkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxy-phenyl)-ketones, bis-(hydroxyphenyl)-sulloxides, bis-(hydrcxy-phenyl)-sulfides, bis-(hydroxyphenyl~-sulfones, and ~,~-bis-(hydroxyphenyl)-diisopropyl-benzenes, as well as their 25. nuclear-alkylated compounds, Also suitable are blsphenols wh~ch are derived fro~
~luorenone 30..
(A)g Mo3679CIP
group with 5 to 15 carbon atoms, a cycloalkylidene group w~th 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom9 S0- or -S02- or a rad~cal conforming to ~H3 lo ~H3 ~ CH3 e and g both denote the number 0 to 1;
Z denotes F, Cl, Br or Cl-C4-alkyl and if several Z radicals are substituents ~n one aryl radioal, they may be identical or d~fferent from one another;
d denotes an integer of from 0 to 4; and f denotes an integer of from 0 to 3.
Amon~ the dihydroxy compounds useful in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxy-phenylJ-alkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxy-phenyl)-ketones, bis-(hydroxyphenyl)-sulloxides, bis-(hydrcxy-phenyl)-sulfides, bis-(hydroxyphenyl~-sulfones, and ~,~-bis-(hydroxyphenyl)-diisopropyl-benzenes, as well as their 25. nuclear-alkylated compounds, Also suitable are blsphenols wh~ch are derived fro~
~luorenone 30..
(A)g Mo3679CIP
-5- ~3~
where A and g are as described above.
These and further suitable aromatic dihydroxy compounds are described, for example, in U.S. Patents 3,028j356;
2,999,835; 3,148,172; 2~991,273; 3,271,367; 4,982,014 and 2,999,846, all incorporated herein by reference.
Further examples of suitable b~sphenols are 2,2-b~s-(4-hydroxy-phenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxy-phenyl)-2-methyl-butane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, ~,~'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-b~s-o (3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxy phenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfide, bis-(3,5-dimethyl-4-hydroxy-phenyl)-sulfoxide, bis-(3,5-dimethyl-4-hydroxyphenyl~-sulfone, d;hydroxy-benzophenone, 2,4-bis-~3,S-dime~hyl-4-hydroxy-phenyl~-cyclohexane, ~,~'-bis-(315-dimethyl-4 hydroxyphenyl)-p-di~sopropylbenzene and 4,4'-sulfonyl diphenol.
Examples of particularly preferred aromatic bisphenols are ~,2,-bis-(4-hydroxyphenyl)-propane, 2,2-b~s-(3,5-dimethyl-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
The most preferred bisphenol is 2,2-bis-(4-hydroxy-phenyl)-propane (bisphenol A).
The polycarbonates of the invent~on may entail in their 25 ~ structure units derived from one or more of the suitable b~sphenols.
~mong the reslns suitable ln the practice of the invention are included phenolphthalein-based polycarbonate, copoly-carbonat~s and terpolycarbonates suoh as are descr~bed ~n U.S. Patents 3,036,036 and 4,210,741, both incorporated by r~ference herein.
The polycarbonates of the invention ~ay also be branched by condensing therein up to 5 mol p~rcent, preferably 0.05-2.0 mol % ~relative to the b~sphenols) of polyhydroxyl co~pounds.
Mo367gClP
where A and g are as described above.
These and further suitable aromatic dihydroxy compounds are described, for example, in U.S. Patents 3,028j356;
2,999,835; 3,148,172; 2~991,273; 3,271,367; 4,982,014 and 2,999,846, all incorporated herein by reference.
Further examples of suitable b~sphenols are 2,2-b~s-(4-hydroxy-phenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxy-phenyl)-2-methyl-butane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, ~,~'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-b~s-o (3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxy phenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfide, bis-(3,5-dimethyl-4-hydroxy-phenyl)-sulfoxide, bis-(3,5-dimethyl-4-hydroxyphenyl~-sulfone, d;hydroxy-benzophenone, 2,4-bis-~3,S-dime~hyl-4-hydroxy-phenyl~-cyclohexane, ~,~'-bis-(315-dimethyl-4 hydroxyphenyl)-p-di~sopropylbenzene and 4,4'-sulfonyl diphenol.
Examples of particularly preferred aromatic bisphenols are ~,2,-bis-(4-hydroxyphenyl)-propane, 2,2-b~s-(3,5-dimethyl-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
The most preferred bisphenol is 2,2-bis-(4-hydroxy-phenyl)-propane (bisphenol A).
The polycarbonates of the invent~on may entail in their 25 ~ structure units derived from one or more of the suitable b~sphenols.
~mong the reslns suitable ln the practice of the invention are included phenolphthalein-based polycarbonate, copoly-carbonat~s and terpolycarbonates suoh as are descr~bed ~n U.S. Patents 3,036,036 and 4,210,741, both incorporated by r~ference herein.
The polycarbonates of the invention ~ay also be branched by condensing therein up to 5 mol p~rcent, preferably 0.05-2.0 mol % ~relative to the b~sphenols) of polyhydroxyl co~pounds.
Mo367gClP
-6- 2~3`$~
Polycarbonates of this type have been described~ for example, in German Offenlegungsschriften 1,570,533; ?,116,974 and 2,113,314; British Patents 885,442 an~ 1,079,821 and U.S.
Patent 3,544,514. The follo~ing are some examples of polyhydroxyl compounds which may be used for thls purpose:
phloroglucinol; 4,6-dimethyl-2,4,6-tri-~4-hydroxyphenyl)-heptane; 1,3,5-tri-(4-hydroxphenyl)-benzene; 1,1,1-tri-(4-hydrQxyphenyl)-ethan2; tri-(4-hydroxyphenyl~-phenylmethane;
2,2-bis-~4,4-(4,4'-dihydroxydiphenyl)~-cyclohexyl-propane;
lo 2,4-bis-(4-hydroxy~l-isopropylidine)-phenol; 2,6-bis-(2'-dihydroxy-5'-methylben~yl)-4-methylphenol; 2,4-dihydroxy-benzoic acid) 2-t4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane and 194-bis-(4,4'-dihydroxytriphenylmethyl)-benzene.
Some of the other polyfunctional compounds are 2,q-dihydroxy-l~ benzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyl~2-oxo-2,3-dihydroindole.
In addition to the polycondensation process mentioned above; other processes for the preparation of the poly-carbonates of the invention are polycondensat~on in a 2~ homogeneous phase and transesterification. The suitable processes are disclosed in the incorporated herein by references, U.S Patents 3,028,365; 2,999~846; 3,153,008; and 2,991,273.
The preferred process for the preparatlon of poly-carbonates is the interfacial po1ycondensation process.
Other methods of synthes~s in form~ng the polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688, incorporated herein by re~erence, may be used.
Suitable polycarbonate reslns are available in commerce, for instance, Makrolon FCR, Makrolon 2600, Makrolon 2800 and Makrolon CD2000, all of which are bisphenol based homopoly-carbonate resins differin~ in terms of thelr respective molecular weights and characteri~ed ~n that their melt flow indices (MFR) per ASTM D-1238 are about 16.5~24, 13-16, 7.5-13.0 and 50 - 60 gm/10 min., respectively. Also suitable Mo3679CIP
-7- 2~
are aromatic polyester carbonate and aromatic polyester resins available as APEC and APEC HT from Mobay and the widely known PBT and PET aromatic aliphatic polyester resins.
Suitable polycarbonate resins are known and methods of S their pneparation have been disclosed, for example ;n U.S.
Patents 3,~30~331; 3,169,121; 3,395,119; 3,729,447; 4,255,5$6;
4,260~731; 4,369,303 and 4,714,746 all of which are incorporated by reference here~n.
The aliphatic polycl in accordance with the present invention is an aliphatic compound having 1 or more hydroxyl funct;onal groups and a molecular welght of up to 30,000.
Preferably the polyol has 2 to 5 hydroxyl groups, most pre~erably, the polyol is a diol.
ExamplPs of the aliphatic polyols are aliphatic polyester polyols, aliphatic polyether polyols, aliphatic polyhydroxy polycarbonates, aliphatic polyhydroxy polyacetals, aliphatic silicone based polyols, aliphatic polyhydroxy polyacrylates, al;phat;c polyhydroxy polyester amides and aliphat;c polyhydroxy polythioethers. The aliphatic polyester polyols, ~o aliphatic polyether polyols and aliphatic polyhydroxy polycarbonates are preferred.
Suitable aliphatic polyester polyols include reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added and poly~as;c, preferably d;basic carboxyl;c acids. Instead of these polycarboxyl;c ac1ds, the corresponding carboxyl~c acid anhydrides or polycarboxylic acid esters of lower alcohols or m;xtures thereof may be used for preparing the polyesters. The polycarboxyl;c acids may be aliphatic, cycloaliphat1c or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following a~e ment~oned as examples: succinic ac;d; ad;p~c acid; suber~c acidi azela k acid; sebacic acid; glutar;c acid anhydride; male;c acid;
maleic ac;d anhydride; fumar;c acid; dimeric and tr;meric fatty ac;ds such as oleic ac;d, which may be mixed w;th monomer;c Mo3679CIP
fatty ac~ds. Suitable polyhydric alcohols ~nclude, e.g.
ethylene glycol; propylene glycol-~1,2) and -(1,3~; butylene glycol-~l,4J and -(1,3); hexanediol-(1,5); octanediol~ 8~;
neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethyl-cyclohexane~; 2-methyl-1,3-propanediol; 2,2,4-trimethyl-1,3-pentanediol; triethylene glycol; tetraethylene glycol;
polyethylene gl~col; dipropylene glycol; polypropylene glycol;
dibutylene glycol and polybutylene glycol, glycerine, sorbitol and trimethlyolpropane.
lo Also suitable are copolymers and cooligomers of ethylene and propylene glycols, pentaerythritol, mannitol, glucose, fructose, sucrose, affinoses, thioglycerol, thiodiglycol, th10monoglycol and the like.
Al~phat~c polycarbonates containing hydroxyl groups include those known per se such as the products obtained from the reaction of diols such as propanediol-~1,3~, butane-diol-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol w~th phosgene, or with cyclic carbonates such as ethylene or propylene carbonate.
Also suitable are polyester carbonates obtained ~rom the above-mentioned polyesters with phosgene, or cyclic carbonates.
Suitable aliphatic polyether polyols are obtained in kno~n manner by the reaction of starting compounds which contain reactive hydrogen atoms with alkylene oxldes such as ethylene cxide, propylene oxide, butylene oxide, tetrahydrofuran9 epichlorohydrin or mixtures of these alkylene oxides. Suitable starting compsunds conta~ning reactive hydrogen atoms include the polyhydric alcohols set forth for preparing the polyester polyols and, ~n addition, water, ~ethanol, ethanol, 1~2,B-hexane triol.
Polyethers modified by v~nyl polymers are also suitable for the process according to the ~nvention.
Suitable aliphatic polyhydroxy polyester amides and polyamines include the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxyl~c Mo3679CIP
9 2 ~
acids or their anhydrides and polyvalent saturated or unsaturated aminoalcohols, diamlnes, polyamlnes and mlxtures thereof.
Su;table monomers for producing hydroxy-functional polyacrylates include acrylic acld, ~ethacrylic acld, croton~c ac~d, malelc anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl me$hacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glyc~dyl acrylate, glycidyl methacrylate~
2--socyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
The most preferred embodiment entails polyols having a molecular weight of up to 10,000 g/mole. The most preferred polyols in the present context are polyethylene glycol, po1ypropy1ene glycol and polyester polyol derived from a ls dimeric fatty acid and neopPntyl glycol, having a molecular weight of about 2000 to 10,000 g/mole.
The catalysts suitable in the reaction are transesteri-fication catalysts which are well known in the art. These include transition metal compounds, such as titanic and tetraalkyl esters, dialkyl-tin dicarboxylates, tin dicarboxylates, chelates of Fe, Zn, Co, Ni or Pb and carboxylates of Pb, Co, Ni or Fe, and bases such as tertiary amines or oxides, hydroxides9 carbonates, alcoholates, phenolates or carboxylates of alkali metals or alkaline earth 25 . m~tals9 lmldizoles and pyridine der~vatives, espec~ally dimethyl amino pyrid~ne. The catalyst ~s used in amounts of beSween 0.0001 and 1%, preferably 0.001 to 0.1% relatlYe to the weight of the reaction m;xture.
In the presence of a catalyst, the aliphat~c hydroxyl performs a displacement of a phenol from a carbonate bond followlng the schemat~c O O
R~-CH2-011 + Rn~O-C-ORn~DR'-CH2-û-C-ORn' + R"~OH
Mo3679ClP
-lo- 2~8~7~
The reaction is known and is kinetically driven to favor dlsplacement of phenolic groups. The result is ~capping~ of all the aliphatic hydroxyls with aromatic carbonate residues.
The statistical chain length of the aromatic carbonate residues is determined by the ratio oF the carbonate repeat units to aliphatic hydroxyls in the melt reaction. In the process of the lnvention it is critical that the chain length be at least 2, preferably at least 3, most preferably 3 to 4.
In the process for the preparat~on of the blo~k ol~gomer l~ Of the invention the reaction proceeds at 180-23~C, preferably 210-225C while stirring until a homogeneous melt is obtained. Typically this may take about 1 to 3 hours~ The resulting product conforms structurally to H-40-Ar-0-~ - ~ 0-~residue}-0-~-~-0-Ar- ~ ~ (I) wherein ~residueU denotes the residue of an aliphatic polyol as described above, Ar is an aromatic radical and n denotes the ratio of the carbonate repeat units to the aliphatic hydroxyls in the melt reaction. In an additional embodiment of the invention, ln instances where it is des~rable to have multiblock structures having higher molecular weight or if end-capping is desired, the resulting product (1~ is reacted with diphenyl carbonate, phenol b~ing distilled off.
Typically, the a~ount of diphenyl carbonlate used is 0.5 to I
molar equivalents based on the hydrsxy functional~ty. Use of less than a 1:1 ratio results in the build up of A-B-A-A-~-A
type of structures.
In the first instance, where a stoichiometric amount of diphenyl carbonate is reacted with the compound termed (I) abo~e, the resultlng product conforms to O O
Ar-0~-~0-Ar-0-~ ~ 0-~residue~-0~ -0-Ar-0 ~ ~0-Ar (Il) Mo3679CIP
2~:3~
where the terms are as noted above.
In instances where the added phenyl carbonate ls added in substoich;ometric amounts~ the resulting product conforms to Ar-0-~-A-B-A-C-A-B-A-C-0-Ar ~III) where A denotes (o-Ar-~ n-~ and where B denotes -0-~residuet-0-The reactive blending procedure for the preparation of the blends in accordance with the present invention entails ~ntroducing the oligomer blocks in liquid or tacky form, at a temperature of about 100-150 C, by a heated liquid metering pump to an extruder where it is blended with a concurrently fed polycarbonate resin.
Alternat~vely or in addition to extruders, mixing and kneading machines suitable for high viscos;ty materials and producing sufficient internal shear can be employed, such as e~g. kneaders, double-arm mixers, sigma-arm or z-blade mixer, planetary mixers or roller mills. In selecting the proper equipment the artisan wlll usually select the ~qu~pment best su~ted for the viscosity/shear requirements, the volume to b~
2~ produced, the need for continuous or batch operat~on, open, closed or vented systems9 and pressures, lf any~
At the extrusion temperature, approximately 230 to 3~0'C, the transesterificat~on react~on takes place to produce a copolycarbonate. It is also possible to first form granules of the ol~gomer blocks, by conventlonal means and then tumble btend these with the polycarbonate resin at room temperature~
The combined granules are then fed into a 1 or 2 screw extruder at 230-320C
Mo3679CI~
-12- 2~3~
The end groups of the block oligomers in accordance with the invention compr~se aromatic carbonate repeat units.
At the high temperature and/or shear prevailing in the extruder, these repeat units transestPrify with the polycarbona~e. As a result, the original block oligomer dlsappears leaving tne block "B" dispersed and diluted in the polycarbonate chains.
It ~s lmportant that the molecular welght of the thus fed polycarbonate is sufficiently hlgh to compensat~ for any lo reduction in the molecular weight which might result upon the transesterification. The reduction in the molecular weight can be determined by a skilled artisan by using standard mathematical formulas for thP number average molecular weight (Mn~ calculations provided the Mn and the concentration of each of the reaction partners are known. Preferably the weight a~erage molecular weight of the polycarbonate is about 32,000 g/mole.
~ he copolycarbonates of the invention are useful as thermoplastic ~olding compositions. Additives which are customarily used in the polycarbonate art, including fillers, reinforcements, stabilizers, flame retardants, mold release aqents and the like may be 1ncorporated in the composltions following methods which are well known in the polycarbonate art.
Expe~lmental I: Droduction of block ol~qomers Block oopolymers in accordance with the invention were prepared as follows-Ser~es 1. The A units were bisphenol-A ol;gocarbonate wherein 3~ n -1.5-3, and where the B units corresponded to Me O O Me HO ~ CH2 + CH2 0 ~ -~C34 ~ O ~ CH ~ CH~ OH
Me Me n~ 1-10 Mo3679CI P
~3~
having a molecular weight of approx;mately 1000, 2000, 3000 an~
4000 g/mol, n bein~ about 1,3,5 and 6.
Series ~. Where A was a bisphenol-A oligocarbonate, n=3 and corresponded to structure II
Ho~cH2 c~2 cH2 cH2 o~H
n - 5-250 having a moleoul3r weight of a~out 2000 g/mol Series 3. A-BPA oligocarbonate, n=3; B corresponding to structure III
H0 t CH2-CH2-0 ~ H
n 8 5 500 having a molecular weight of about 2000, 3400 and 8000 g~mol.
Series 4. A=BPA oligocarbonate, n-3; B corresponding to structure IY
' H~CH2-CH-O~H
5.
n ~ 5-500 having a molecular weight o~ approximately 2000 and 4000 g/mol.
In the preparation of the blocks described aboYe, the polymeric d~ol was heated under n;trogen atmosphene to about 180-230'C with stirring in a sturdy reactor. A polycarbonate resin (Makrolon homopolycarbonate) was added while stirring and while the temperature was maintained. Before completing the add;t~on of the BPA polycarbonate there was added to the reactor a BPA^d;sod~um salt catalyst. The react;cn continued Mo3679CIP
-14- 2~387~
for about 1 to 3 hours while stirring. The resulting oligomers con~ormed structurally to O O
H-(O-Ar-O-~ ~ 0 O-~residue)-O-(-e-O-Ar-O ~ H
where the residue is derived from the polyether polyol or the polyester polyol as the case may be. The resulting products are suitable for reactive blending with polycarbonates.
In some applications, as was described above the capping with diphenyl carbonate is required where heat might cause unwanted degrada~ion of polycarbonate caused by phenolic OH
term~nat;on.
If and when the phenolic end groups are detrimental, they may ln accordance with the present invention be further reacted with diphenyl carbonate. Accordingly, a stoieh;ometric equivalence of diphenyl carbonate based on the the starting aliphatic hyclroxyl was added while stirring, at a temperature of about 20 60~C under nitrogen atmosphere. Vacuum was then slowly applied (1 Torr) to start remov~ng phenol. Stirring continued until the evolution of phenol stopped.
imental II: PreParation of the copolvmers.
ReactiYe blends of Makrolon 3200 (a bisphenol A based homopolycarbonate having a relative viscosity of about 1.32 wlth the block oli~omer described above were prepared as follows:
For Series I: Blends with a final polyestQr concentration of between 2 and 6 weight percent. The polyester was reacted with Makrolon 3200 polycarbonate ln a 30 mm twin screw extruder.
The polyester was added via a ~iquid addit~on pump heated to 150-C. ~crew rotation was 300 rpm, with 26~ vacuum. Melt temperature was about 320~C~
For Series II: Blends with a final concentration of polytetramethylene glyeol oF about 10 X were prepared as fcllows: A 25% masterbatch of the modified poly(tetrahydro-Mo3~79CIP
2~3~7~
furan) was prepared in Makrolon 3200 with a 1.5" single screw extruder. A 2.75/1 L/D screw was used. The Makrolon was pre~ried in a forced air oven. Melt temperature wa~ about 280CC, screw speed 50-60 rpm. The pelletized masterbatch was let down at various levels in a 3Q mm twin screw extruder.
Makrolon 3200 and the pelletized masterbatch were tumble blended together and processed at a melt temperature of about 320C. Screw speed was 300 rpm, vacuum 26n.
For Series III: A 25% blend of the modified polyethylene 0 glycol and Makrolon 3200 polycarbonate were tumble blended. The melt reaction has been accomplished in a 1.5" single screw extruder under the following cond;t;ons:
Temperature 239 Screw 2.75/1 (Length/Diameter~
Screw speed 60 rpm.
The copolymer may also be produced on a ZSK twin screw extruder; with the following conditions:
Temperature 220 Screw Speed 150 rpm, Yacuum 26n.
Pellets must be dried before production on a non vented machine.
For series IV blends with final polypropylene glycol concentration of between 1.0 and 10 weight percent.
Masterbatches of between 10% to 25% have been prepared on the 1 1~?n single screw extruder as described in Series 2. Thes~
wer~ let down to ~arious levels as on the twln screw extruder also as described in Serles 2.
Experimental III.
3~ The present inYention has been compared with the prior art as represented by Schreckenberg's U.S.Patent 4, 281,101.
According to the co~parisons, a combination of poly~erlc diol with 8PA carbonate endcaps, directly with a polycarbonate in an extruder does not yield block copoly~er.
Mo3679CIP
~18~
Although the invention has been described in detail in the foregolng for the purpose of illustration, lt is to be understood that such detail is solely for that purpose and that var~atlons can be made therein by those skllled in the art without departing from the sp;rit and scope of the ~nvention except as it may be l;m~ted by the claims.
25~ `
30 .
Mo3679CIP
Polycarbonates of this type have been described~ for example, in German Offenlegungsschriften 1,570,533; ?,116,974 and 2,113,314; British Patents 885,442 an~ 1,079,821 and U.S.
Patent 3,544,514. The follo~ing are some examples of polyhydroxyl compounds which may be used for thls purpose:
phloroglucinol; 4,6-dimethyl-2,4,6-tri-~4-hydroxyphenyl)-heptane; 1,3,5-tri-(4-hydroxphenyl)-benzene; 1,1,1-tri-(4-hydrQxyphenyl)-ethan2; tri-(4-hydroxyphenyl~-phenylmethane;
2,2-bis-~4,4-(4,4'-dihydroxydiphenyl)~-cyclohexyl-propane;
lo 2,4-bis-(4-hydroxy~l-isopropylidine)-phenol; 2,6-bis-(2'-dihydroxy-5'-methylben~yl)-4-methylphenol; 2,4-dihydroxy-benzoic acid) 2-t4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane and 194-bis-(4,4'-dihydroxytriphenylmethyl)-benzene.
Some of the other polyfunctional compounds are 2,q-dihydroxy-l~ benzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyl~2-oxo-2,3-dihydroindole.
In addition to the polycondensation process mentioned above; other processes for the preparation of the poly-carbonates of the invention are polycondensat~on in a 2~ homogeneous phase and transesterification. The suitable processes are disclosed in the incorporated herein by references, U.S Patents 3,028,365; 2,999~846; 3,153,008; and 2,991,273.
The preferred process for the preparatlon of poly-carbonates is the interfacial po1ycondensation process.
Other methods of synthes~s in form~ng the polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688, incorporated herein by re~erence, may be used.
Suitable polycarbonate reslns are available in commerce, for instance, Makrolon FCR, Makrolon 2600, Makrolon 2800 and Makrolon CD2000, all of which are bisphenol based homopoly-carbonate resins differin~ in terms of thelr respective molecular weights and characteri~ed ~n that their melt flow indices (MFR) per ASTM D-1238 are about 16.5~24, 13-16, 7.5-13.0 and 50 - 60 gm/10 min., respectively. Also suitable Mo3679CIP
-7- 2~
are aromatic polyester carbonate and aromatic polyester resins available as APEC and APEC HT from Mobay and the widely known PBT and PET aromatic aliphatic polyester resins.
Suitable polycarbonate resins are known and methods of S their pneparation have been disclosed, for example ;n U.S.
Patents 3,~30~331; 3,169,121; 3,395,119; 3,729,447; 4,255,5$6;
4,260~731; 4,369,303 and 4,714,746 all of which are incorporated by reference here~n.
The aliphatic polycl in accordance with the present invention is an aliphatic compound having 1 or more hydroxyl funct;onal groups and a molecular welght of up to 30,000.
Preferably the polyol has 2 to 5 hydroxyl groups, most pre~erably, the polyol is a diol.
ExamplPs of the aliphatic polyols are aliphatic polyester polyols, aliphatic polyether polyols, aliphatic polyhydroxy polycarbonates, aliphatic polyhydroxy polyacetals, aliphatic silicone based polyols, aliphatic polyhydroxy polyacrylates, al;phat;c polyhydroxy polyester amides and aliphat;c polyhydroxy polythioethers. The aliphatic polyester polyols, ~o aliphatic polyether polyols and aliphatic polyhydroxy polycarbonates are preferred.
Suitable aliphatic polyester polyols include reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added and poly~as;c, preferably d;basic carboxyl;c acids. Instead of these polycarboxyl;c ac1ds, the corresponding carboxyl~c acid anhydrides or polycarboxylic acid esters of lower alcohols or m;xtures thereof may be used for preparing the polyesters. The polycarboxyl;c acids may be aliphatic, cycloaliphat1c or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following a~e ment~oned as examples: succinic ac;d; ad;p~c acid; suber~c acidi azela k acid; sebacic acid; glutar;c acid anhydride; male;c acid;
maleic ac;d anhydride; fumar;c acid; dimeric and tr;meric fatty ac;ds such as oleic ac;d, which may be mixed w;th monomer;c Mo3679CIP
fatty ac~ds. Suitable polyhydric alcohols ~nclude, e.g.
ethylene glycol; propylene glycol-~1,2) and -(1,3~; butylene glycol-~l,4J and -(1,3); hexanediol-(1,5); octanediol~ 8~;
neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethyl-cyclohexane~; 2-methyl-1,3-propanediol; 2,2,4-trimethyl-1,3-pentanediol; triethylene glycol; tetraethylene glycol;
polyethylene gl~col; dipropylene glycol; polypropylene glycol;
dibutylene glycol and polybutylene glycol, glycerine, sorbitol and trimethlyolpropane.
lo Also suitable are copolymers and cooligomers of ethylene and propylene glycols, pentaerythritol, mannitol, glucose, fructose, sucrose, affinoses, thioglycerol, thiodiglycol, th10monoglycol and the like.
Al~phat~c polycarbonates containing hydroxyl groups include those known per se such as the products obtained from the reaction of diols such as propanediol-~1,3~, butane-diol-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol w~th phosgene, or with cyclic carbonates such as ethylene or propylene carbonate.
Also suitable are polyester carbonates obtained ~rom the above-mentioned polyesters with phosgene, or cyclic carbonates.
Suitable aliphatic polyether polyols are obtained in kno~n manner by the reaction of starting compounds which contain reactive hydrogen atoms with alkylene oxldes such as ethylene cxide, propylene oxide, butylene oxide, tetrahydrofuran9 epichlorohydrin or mixtures of these alkylene oxides. Suitable starting compsunds conta~ning reactive hydrogen atoms include the polyhydric alcohols set forth for preparing the polyester polyols and, ~n addition, water, ~ethanol, ethanol, 1~2,B-hexane triol.
Polyethers modified by v~nyl polymers are also suitable for the process according to the ~nvention.
Suitable aliphatic polyhydroxy polyester amides and polyamines include the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxyl~c Mo3679CIP
9 2 ~
acids or their anhydrides and polyvalent saturated or unsaturated aminoalcohols, diamlnes, polyamlnes and mlxtures thereof.
Su;table monomers for producing hydroxy-functional polyacrylates include acrylic acld, ~ethacrylic acld, croton~c ac~d, malelc anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl me$hacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glyc~dyl acrylate, glycidyl methacrylate~
2--socyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
The most preferred embodiment entails polyols having a molecular weight of up to 10,000 g/mole. The most preferred polyols in the present context are polyethylene glycol, po1ypropy1ene glycol and polyester polyol derived from a ls dimeric fatty acid and neopPntyl glycol, having a molecular weight of about 2000 to 10,000 g/mole.
The catalysts suitable in the reaction are transesteri-fication catalysts which are well known in the art. These include transition metal compounds, such as titanic and tetraalkyl esters, dialkyl-tin dicarboxylates, tin dicarboxylates, chelates of Fe, Zn, Co, Ni or Pb and carboxylates of Pb, Co, Ni or Fe, and bases such as tertiary amines or oxides, hydroxides9 carbonates, alcoholates, phenolates or carboxylates of alkali metals or alkaline earth 25 . m~tals9 lmldizoles and pyridine der~vatives, espec~ally dimethyl amino pyrid~ne. The catalyst ~s used in amounts of beSween 0.0001 and 1%, preferably 0.001 to 0.1% relatlYe to the weight of the reaction m;xture.
In the presence of a catalyst, the aliphat~c hydroxyl performs a displacement of a phenol from a carbonate bond followlng the schemat~c O O
R~-CH2-011 + Rn~O-C-ORn~DR'-CH2-û-C-ORn' + R"~OH
Mo3679ClP
-lo- 2~8~7~
The reaction is known and is kinetically driven to favor dlsplacement of phenolic groups. The result is ~capping~ of all the aliphatic hydroxyls with aromatic carbonate residues.
The statistical chain length of the aromatic carbonate residues is determined by the ratio oF the carbonate repeat units to aliphatic hydroxyls in the melt reaction. In the process of the lnvention it is critical that the chain length be at least 2, preferably at least 3, most preferably 3 to 4.
In the process for the preparat~on of the blo~k ol~gomer l~ Of the invention the reaction proceeds at 180-23~C, preferably 210-225C while stirring until a homogeneous melt is obtained. Typically this may take about 1 to 3 hours~ The resulting product conforms structurally to H-40-Ar-0-~ - ~ 0-~residue}-0-~-~-0-Ar- ~ ~ (I) wherein ~residueU denotes the residue of an aliphatic polyol as described above, Ar is an aromatic radical and n denotes the ratio of the carbonate repeat units to the aliphatic hydroxyls in the melt reaction. In an additional embodiment of the invention, ln instances where it is des~rable to have multiblock structures having higher molecular weight or if end-capping is desired, the resulting product (1~ is reacted with diphenyl carbonate, phenol b~ing distilled off.
Typically, the a~ount of diphenyl carbonlate used is 0.5 to I
molar equivalents based on the hydrsxy functional~ty. Use of less than a 1:1 ratio results in the build up of A-B-A-A-~-A
type of structures.
In the first instance, where a stoichiometric amount of diphenyl carbonate is reacted with the compound termed (I) abo~e, the resultlng product conforms to O O
Ar-0~-~0-Ar-0-~ ~ 0-~residue~-0~ -0-Ar-0 ~ ~0-Ar (Il) Mo3679CIP
2~:3~
where the terms are as noted above.
In instances where the added phenyl carbonate ls added in substoich;ometric amounts~ the resulting product conforms to Ar-0-~-A-B-A-C-A-B-A-C-0-Ar ~III) where A denotes (o-Ar-~ n-~ and where B denotes -0-~residuet-0-The reactive blending procedure for the preparation of the blends in accordance with the present invention entails ~ntroducing the oligomer blocks in liquid or tacky form, at a temperature of about 100-150 C, by a heated liquid metering pump to an extruder where it is blended with a concurrently fed polycarbonate resin.
Alternat~vely or in addition to extruders, mixing and kneading machines suitable for high viscos;ty materials and producing sufficient internal shear can be employed, such as e~g. kneaders, double-arm mixers, sigma-arm or z-blade mixer, planetary mixers or roller mills. In selecting the proper equipment the artisan wlll usually select the ~qu~pment best su~ted for the viscosity/shear requirements, the volume to b~
2~ produced, the need for continuous or batch operat~on, open, closed or vented systems9 and pressures, lf any~
At the extrusion temperature, approximately 230 to 3~0'C, the transesterificat~on react~on takes place to produce a copolycarbonate. It is also possible to first form granules of the ol~gomer blocks, by conventlonal means and then tumble btend these with the polycarbonate resin at room temperature~
The combined granules are then fed into a 1 or 2 screw extruder at 230-320C
Mo3679CI~
-12- 2~3~
The end groups of the block oligomers in accordance with the invention compr~se aromatic carbonate repeat units.
At the high temperature and/or shear prevailing in the extruder, these repeat units transestPrify with the polycarbona~e. As a result, the original block oligomer dlsappears leaving tne block "B" dispersed and diluted in the polycarbonate chains.
It ~s lmportant that the molecular welght of the thus fed polycarbonate is sufficiently hlgh to compensat~ for any lo reduction in the molecular weight which might result upon the transesterification. The reduction in the molecular weight can be determined by a skilled artisan by using standard mathematical formulas for thP number average molecular weight (Mn~ calculations provided the Mn and the concentration of each of the reaction partners are known. Preferably the weight a~erage molecular weight of the polycarbonate is about 32,000 g/mole.
~ he copolycarbonates of the invention are useful as thermoplastic ~olding compositions. Additives which are customarily used in the polycarbonate art, including fillers, reinforcements, stabilizers, flame retardants, mold release aqents and the like may be 1ncorporated in the composltions following methods which are well known in the polycarbonate art.
Expe~lmental I: Droduction of block ol~qomers Block oopolymers in accordance with the invention were prepared as follows-Ser~es 1. The A units were bisphenol-A ol;gocarbonate wherein 3~ n -1.5-3, and where the B units corresponded to Me O O Me HO ~ CH2 + CH2 0 ~ -~C34 ~ O ~ CH ~ CH~ OH
Me Me n~ 1-10 Mo3679CI P
~3~
having a molecular weight of approx;mately 1000, 2000, 3000 an~
4000 g/mol, n bein~ about 1,3,5 and 6.
Series ~. Where A was a bisphenol-A oligocarbonate, n=3 and corresponded to structure II
Ho~cH2 c~2 cH2 cH2 o~H
n - 5-250 having a moleoul3r weight of a~out 2000 g/mol Series 3. A-BPA oligocarbonate, n=3; B corresponding to structure III
H0 t CH2-CH2-0 ~ H
n 8 5 500 having a molecular weight of about 2000, 3400 and 8000 g~mol.
Series 4. A=BPA oligocarbonate, n-3; B corresponding to structure IY
' H~CH2-CH-O~H
5.
n ~ 5-500 having a molecular weight o~ approximately 2000 and 4000 g/mol.
In the preparation of the blocks described aboYe, the polymeric d~ol was heated under n;trogen atmosphene to about 180-230'C with stirring in a sturdy reactor. A polycarbonate resin (Makrolon homopolycarbonate) was added while stirring and while the temperature was maintained. Before completing the add;t~on of the BPA polycarbonate there was added to the reactor a BPA^d;sod~um salt catalyst. The react;cn continued Mo3679CIP
-14- 2~387~
for about 1 to 3 hours while stirring. The resulting oligomers con~ormed structurally to O O
H-(O-Ar-O-~ ~ 0 O-~residue)-O-(-e-O-Ar-O ~ H
where the residue is derived from the polyether polyol or the polyester polyol as the case may be. The resulting products are suitable for reactive blending with polycarbonates.
In some applications, as was described above the capping with diphenyl carbonate is required where heat might cause unwanted degrada~ion of polycarbonate caused by phenolic OH
term~nat;on.
If and when the phenolic end groups are detrimental, they may ln accordance with the present invention be further reacted with diphenyl carbonate. Accordingly, a stoieh;ometric equivalence of diphenyl carbonate based on the the starting aliphatic hyclroxyl was added while stirring, at a temperature of about 20 60~C under nitrogen atmosphere. Vacuum was then slowly applied (1 Torr) to start remov~ng phenol. Stirring continued until the evolution of phenol stopped.
imental II: PreParation of the copolvmers.
ReactiYe blends of Makrolon 3200 (a bisphenol A based homopolycarbonate having a relative viscosity of about 1.32 wlth the block oli~omer described above were prepared as follows:
For Series I: Blends with a final polyestQr concentration of between 2 and 6 weight percent. The polyester was reacted with Makrolon 3200 polycarbonate ln a 30 mm twin screw extruder.
The polyester was added via a ~iquid addit~on pump heated to 150-C. ~crew rotation was 300 rpm, with 26~ vacuum. Melt temperature was about 320~C~
For Series II: Blends with a final concentration of polytetramethylene glyeol oF about 10 X were prepared as fcllows: A 25% masterbatch of the modified poly(tetrahydro-Mo3~79CIP
2~3~7~
furan) was prepared in Makrolon 3200 with a 1.5" single screw extruder. A 2.75/1 L/D screw was used. The Makrolon was pre~ried in a forced air oven. Melt temperature wa~ about 280CC, screw speed 50-60 rpm. The pelletized masterbatch was let down at various levels in a 3Q mm twin screw extruder.
Makrolon 3200 and the pelletized masterbatch were tumble blended together and processed at a melt temperature of about 320C. Screw speed was 300 rpm, vacuum 26n.
For Series III: A 25% blend of the modified polyethylene 0 glycol and Makrolon 3200 polycarbonate were tumble blended. The melt reaction has been accomplished in a 1.5" single screw extruder under the following cond;t;ons:
Temperature 239 Screw 2.75/1 (Length/Diameter~
Screw speed 60 rpm.
The copolymer may also be produced on a ZSK twin screw extruder; with the following conditions:
Temperature 220 Screw Speed 150 rpm, Yacuum 26n.
Pellets must be dried before production on a non vented machine.
For series IV blends with final polypropylene glycol concentration of between 1.0 and 10 weight percent.
Masterbatches of between 10% to 25% have been prepared on the 1 1~?n single screw extruder as described in Series 2. Thes~
wer~ let down to ~arious levels as on the twln screw extruder also as described in Serles 2.
Experimental III.
3~ The present inYention has been compared with the prior art as represented by Schreckenberg's U.S.Patent 4, 281,101.
According to the co~parisons, a combination of poly~erlc diol with 8PA carbonate endcaps, directly with a polycarbonate in an extruder does not yield block copoly~er.
Mo3679CIP
~18~
Although the invention has been described in detail in the foregolng for the purpose of illustration, lt is to be understood that such detail is solely for that purpose and that var~atlons can be made therein by those skllled in the art without departing from the sp;rit and scope of the ~nvention except as it may be l;m~ted by the claims.
25~ `
30 .
Mo3679CIP
Claims (10)
1. A process for preparing a copolycarbonate comprising melt blending a polycarbonate resin and a block oligocarbonate, said oligocarbonate being of the type selected from the group consisting of R-A-B-A-R and where R denotes hydrogen or , and where Ar denotes an aromatic carbonate structure conforming to and where Ar denotes an aromatic radical, n is 2-6 and where B is the residue of an aliphatic polyol, with the proviso that said B is bonded to said A through the terminal carboxyl in said A, and wherein resin has a weight average molecular weight of 10,000 to 200,000.
2. The process of Claim 1 wherein molecular weight is 20,000 to 80,000.
3. The process of Claim 1 wherein said type is R-A-B-A-R.
4. The process of Claim 1 wherein said type is
5. The process of Claim 3 wherein said aliphatic polyol is a polyether polyol.
6. The process of Claim 4 wherein said aliphatic polyol is a polyether polyol.
7. The process of Claim 1 wherein aliphatic polyol is polyether polyol.
Mo3679CIP
Mo3679CIP
8. The process of Claim 1 wherein said aliphatic polyol is polypropylene glycol having a molecular weight of about 1500 to 4000.
9. The process of Claim 1 wherein said aliphatic polyol is polyethylene glycol having a molecular weight of about 6000 to
10,000.
Mo3679CIP
Mo3679CIP
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80330991A | 1991-12-04 | 1991-12-04 | |
| US07/803,309 | 1991-12-04 | ||
| US96699492A | 1992-10-27 | 1992-10-27 | |
| US07/966,994 | 1992-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2083878A1 true CA2083878A1 (en) | 1993-06-05 |
Family
ID=27122571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2083878 Abandoned CA2083878A1 (en) | 1991-12-04 | 1992-11-26 | Block copolymers of aromatic polycarbonates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2083878A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9994760B2 (en) | 2008-11-01 | 2018-06-12 | Saudi Aramco Technologies Company | Polycarbonate block copolymers |
| US11180609B2 (en) | 2018-08-02 | 2021-11-23 | Saudi Aramco Technologies Company | Sustainable polymer compositions and methods |
| US11427679B2 (en) * | 2018-03-27 | 2022-08-30 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
-
1992
- 1992-11-26 CA CA 2083878 patent/CA2083878A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9994760B2 (en) | 2008-11-01 | 2018-06-12 | Saudi Aramco Technologies Company | Polycarbonate block copolymers |
| US10392556B2 (en) | 2008-11-01 | 2019-08-27 | Saudi Aramco Technologies Company | Polycarbonate block copolymers |
| US11155747B2 (en) | 2008-11-01 | 2021-10-26 | Saudi Aramco Technologies Company | Polycarbonate block copolymers |
| US11427679B2 (en) * | 2018-03-27 | 2022-08-30 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
| US11180609B2 (en) | 2018-08-02 | 2021-11-23 | Saudi Aramco Technologies Company | Sustainable polymer compositions and methods |
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