CA1285692C - Branched polycarbonates containing methylene-bis-naphthalene compounds and process for their preparation - Google Patents
Branched polycarbonates containing methylene-bis-naphthalene compounds and process for their preparationInfo
- Publication number
- CA1285692C CA1285692C CA000542769A CA542769A CA1285692C CA 1285692 C CA1285692 C CA 1285692C CA 000542769 A CA000542769 A CA 000542769A CA 542769 A CA542769 A CA 542769A CA 1285692 C CA1285692 C CA 1285692C
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- Prior art keywords
- bis
- methylene
- naphthalene
- hydroxy
- compound
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
Abstract
"BRANCHED POLYCARBONATES CONTAINING METHYLENE-BIS-NAPHTHALENE COMPOUNDS AND PROCESS FOR THEIR PREPARATION"
Abstract Branched, thermoplastic polycarbonates, suitable for being processed by means of the blow-moulding technique, are prepared by means of copolymerization with methylene-bis-naphthalene compounds.
Abstract Branched, thermoplastic polycarbonates, suitable for being processed by means of the blow-moulding technique, are prepared by means of copolymerization with methylene-bis-naphthalene compounds.
Description
ii~2 - 1. C/~SE 2 3 t "BRANCHED POLYCAR~30NATES CONTAINING METl'YL~NE-elS-NAPHTHALEN~ CO~lP~UNDS AND ~ROCESS FQR -I'HEI~ PREPARATION"
The present invent-ion relates to brarlched, thermoplastic, polycarbonates, suitable for being transformed by means oF the blow-moulding technique (blow moulding of hollow bodies)~ i L;near polycarbonates have been long known in the art.
Such polyrners are widely used in different applicative sectors, but, contrarily to most thermoplastic polymers, they are not suitable for t,eing processed by nleans of extrusion or blo~s-moulclir1g techniques, which are the techniques suitable for `~ supplying particular transformation products ~cellular sheets, bottles, hollow containers, and so forth).
This dif,iculty in processability of lir,ear polycarbonate is due to ;ts exclusively N~wtonian behaviour, according to which the apparent viscosity ~rl) - is substantially independent from the shear rate ~
- The transformation of a material acccrding to the techniques of extrusion or of blow-moulding requires, on the contrary, that it has a decreasing apparent viscosity with increasing shear rate, a typical aspect of non-Newtonian behaviour, so that the state of the molten polymer can be differentiated ;nto two successive moments: a first moment, when it is inside the transformation machine ~e.g., an extruder), and a second moment, when the product leaves it ~e.g., from the die oF
the same extruder).
In the first step, the shear rates the fluid is subject to, are high, and its apparent v;scos;ty ;s, -:
-:
. ~
~' ' ~
, , !
' 2.
vice~versa, low, so that the processability thereof resul-ts fac1l-itated; ~Ihen the fluid leaves the extrucler, on the con~rary, low values o'f ~, and high v;scosity values appear, and this prevents the 'product from collapsing, and makes it poss;ble a good dimensional stability of the manufactured articLe to be achieved.
The non-Ne~tonian behaviour of the molten polymer has a considerable influence on two properties, i~e., the melt elasticity, or pseudo-elasticity, and the melt strength, thereof, ~Jhich are equally very important for the transformation techniques of extrusion and blow-moulding.
The melt elasticity consists essentially in the ;~ capability of the non-Newtonian fluid of swelLing to a ~reater extent, when exiting the die, than a Newtonian fluid~ as a consequence of a higher recovery of elastic energy inside its interior, thanks to a greater molecular deflection and orientation under the act;on of a shear stress~
That results in an increase in the proc'essability of the product, due to the effect of a greater flexibility and ductility of the material.
' The s'econd property ;ndicated, viz., the melt tenacity, becomes vice-versa meaningful when the molten polyoer exits the transformation machine. It can be considered as the tenacity of the polymer in the molten state, i~e., the stress-supporting capacity shown by the polymer. If, in fact, the molten mass is not capable of supporting its own weight, the collapse occurs of the extrudate, and, as a consequence, obtaining the desired shape of the marufactured artlcLe is nrt possibLe.
.
It results evident from the above that the polyMers which display a non-Newtonian behaviour are endowed with two basic characteristics, wh1ch enable ~h~rn to be transformed by extrusion and/or blow-moulding techniques:
a very easy processability inside the machine (low apparent viscosity for high val-les of ~ and h;gh melt elasticity), and very good shape retention when exiting said machine (high apparent viscosity For low values of and considerable melt tenacity).
10In the art, branched polycarbonates are known, which have non-Newtonian rheological properties, su;table for being processed according to techniques of extrusion and of blow-moulding.
Such polycarbonates can bc obtained by means of the copolymer;zation w;th polyfunctional comonomers containing three or more -OH and/or -COOH and/or -COCl groups.
- The main technical problems which can be met in the - preparation of the branched polycarbonates consist essentially in the reactivity of the polyfunctional comonomer used, and in the characteristics of the branched polycarbonate obtained with such a comonomer.
In particular, the comonomer should show a so high reactivity, as to make it possible to achieve the desired branching degree ~such to give the polymer a shear-sensitivity > 15)~ when used in small amounts.
The branched polycarbonate, besides showing a shear sensitivity > 15, should maintain unchanged the other characteristics which are typical of the linear polycarbonates.
The polyfunctional comonomers of the prior art have ~2~i5~
not shown to be completely satis-factory from all of these v;ewpoints.
It l1as been found now tha~ it is poss;ble to overcome the drawbac~s deriving from the prior art, and obtain branched, thermoplasticr polycarbonates, suitatle for be;ng transformed by blow-moulding, by copolymer;zat;on with a poly-funGtional, h;ghly react;ve, comonorner, used ;n small amo~ -ts.
Such polycarbonates, thanks to the branch;ngs due to 1~ the presel1ce of the polyFunct;onal comonomer ;n the macromolecule, show a shear~sensit;vity (wh;ch ;s the rat;o bet~leen the flow rates of the molten polymer at two different shear ral:es) > 15, wh;le ma;ntain;ng unchanged the other character;st;cs typ;caL of the l;near polycarbonates.
Therefore, a purpose of the present ;nvention are branched, thermoplast;c polycarbonates, su;table for be;ng transforrned by blow-mould;ng.
Another purpose of the present ;nvention ;s a process for the preparat;on of sa;d polycarbonates.
Thus, the present invention provides such branched polycarbona-tes derived from at leas-t one aromatic dihy-droxy compound, phosgene, and, as branching agen-t, a methy1ene-bib-rlaphthalene compound having -the formula:
t. ~
~ ~ ~ .
~0~, ~
CH2 (I?
C ~
wherein R1, R~, ale equal to, or different from each other, and represent -COOH or COCl;
10The branched polycarbonates disclosed in the present invention can be prepared by means of a process comprising the followil1g process steps, carr;ed ou~
successively:
. a) Preparat;on of a chloroformyl-capped ol;gorner, by 15reaction between phosgene and a dillydroxyarornatic ` cornpound, corresponding to the formula:
HO - ~ - R - ~ - OH tII
tx) ~y) n m wherein:
R - substituted or unsubstituted alkyl radical, contain;ng from O to 5 C, -0-~ -S~ atoms, -S02-and -CO- groups;
25x, y are equal to or different from each other, and represent H, CH3~ halogens;
m, ~ are integers, equal to, or different from, each other, comprised within the range of from 1 to 4.
b~ Condensation of the so-obta;ned oligomer with the 30polyfunction3l comonomer corresponding to the formula tI), wherein R1, R2, have the above seen meaning.
~ ~ .
:
~2~5~
c) Add;tion of a dihydroxyaroma-tic compour)d (II~ to the mixture cleriviny -from (b), anc! polycondensatiol1~
d) Recovery of the brancl1ed polycarborlate from the reaction mixture.
According to the present invention, tl1e chloroformyl~capped oligomers are prepared by means o~
the interfacial reaction between phosgene and a dihydroxyaromatic compound (II) dissolved in aqueous-alkaline solutiol1, in the presence of an otganic solvent 1b imm;sc;ble with water and ot a molecular weight regulator, such as, e~g~r p-tert.butyl-phenol or p-isopropyl-pllellol orf phenol i;tsel:E.
As dihydroxyaromatic compounds, e.g., the ~ollow;ng can be used:
-- 4,4'-dihydroxydiphenyl;
-- 2,2-bis(4-hydroxyphenyl)propane (bisphenol A);
-- 2,2-bis(3,5-dichloro-4-hytlroxypllenyl)propane;
-- bis~4-hydroxyphenyl)methane;
-- 2,2-bis(3~5-dimethyl-4-hydroxyphenyl)propane.
Also bivalent compounds with one aromat;c ring only can be used, such as resorc;nol, hydroqu;none and pyrocatechol.
The process ;s carr;ed out at a temperature compr;sed w;thin the range of from 15 C to 35 C, and, preferably~ at room ternperature ~20-25 C).
The so obta;nèd ol;gotners have a molecular we;ght of from 400 to 2000.
After the separat;on of the -two phases, to the organ;c phase, conta;n;ng the chloroformyl-capped ol;qomers, the polyfunct;onal comonomer ~I), dissolved in an organ;c solvent ;moliscible w;th water, preferably ~B
.
~2 7.
methylerle cllloride~ is added, so ,o ob-tain in the end polycarbonate from 0.01 to 1~5 MOl of comonomer per each 100 mol of arornatic dihydroxy~-compound.
Some examples of polyfunct;onal comonomers used are:
S -- 4,4'-me~hylenebis(3-hydroxy-2-carboxynaphthalene;
-- 3-hydroY~y-4--rnethylerle(3:-hydroxy-4'-clllorocarbonyl~
naphthalene)-2-naphthoic acid;
-- 4,4'-methylene-bis(3-hydroxy-2 chlorocarbonyl-naphthalene) An aqueous-alkaline solution is then added, which contains a reducing agent, preferably sodium dith;onite, for the purpose of preventillg the formaticn of coloured byproducts, and an aqueous solution is added, whicr contains the phase-transfer ca~alyst, e.g, a tertiary amine, preferably triethylamine.
~ The temperature at which tt,e condensation is carried ; out ranges from 15 C to 35 C and is preferably kept around room values (20-25 C).
- After a time per;od ranging from 30 to 60 minutes, - 20 preferably 40 minutes, the biphasic system coming from the condensa-tion with the polyfunctional comonomer is treated with an alkaline solution of the aromatic dihydroxy-derivative.
An aqueolls alkaline solution of sod;um hydroxide at 40% by weight ;s then added.
After a ~ime period of from 2 to 3 hours, the S4 obta;ned branched polycarbonate is ;solated by wash;ng the organ;c phase accord;ng to the methods of the known art, and distillat;on of the solvent, or precipitat;on by means of a non-solvent.
The preparation of such branched polycarbonates can be carr;ed out also by means of other processes~ such as, e.g~, the process which prov;des the condensation betwee~
aromatic dihydroxy derivativesr phosgene an~
polyFunctional comonomer~ by means of an interfacial reaction, or of a reaction in solution, in one single reaction step~
Such polycarbonates can be also obta;ned by tranc;es~eriFication in thc molten state, by reacting the dihydroxyaroolatic compourld witll d;aryl-, dialkyl-- or alkylaryl-carbonates at temperatures of from 100 to 300 C, in the presence of transesterification catalystsu The branched polycarbonates oF the present invention have a molecular weight ranging from 209000 to 30,000, - and are characterized in that tlley are completely soLuble ;~ 15 ;n the usual solvents of the linear polycarbonate, and show a high dependence of the melt viscosity from the shear rate~
- Such polycarbonates are hence well su;table for ; being processed both by the ;njection-mould;ng techn;que, - 20 typ;cal of the linear polycarbonates, and by~ e.g., extrus;on.
Due to the,excellent stab;lity of the molten mass, such polycarbonates are part;cularly well suitable for being transformed by the blow-Moulding method, ~or the product;on o~ hollow boclies.
The reactivity of the polyfunctional comonomer used as the branching agents is such that an amount of from 0.01 to 1.5 mol of such comonomer per each 100 mol of aromatic d;hydroxy~compound are enough for reaching such a crossl;nkin~ degree that the shear-sensit;vity has values always higher than 15.
6~:
~or thc Gharac~eri~a~;on o-f the branched polycarbonates according to the present inven.ion, the following mett,ods ~lere used: .
Intrinsic Viscositx ~ the intrinsic viscosity is 5 deterlnined in methylene chloride at 20 C by means o~ an Ubbelhode viscometer and ;s expressed as dl/g.
Shear Sens;tiv;ty - the evaluation of this quantity is ._~__. _.. ____.
10 carried out on the ~elt indexer~
:~ under loads o-f from 2~1~ to 21~6 ~g, - at ZhO C, according to ASTM D 1238~ :
Ir~act l~esis nce (12(X))~ - The impact resistance is measured on - specimens with notch, at O C, . 15 according to ASTM D 256.
The following examples are illustrative and not lim;tat;ve of the same ;nvent;on.
Examele 1 Preearat;on of 4,4'-Methylene~bis(3-hydroxb_-2_chlQrocaf-bonyl-naehthalene) ___ ____ ____ ____ To a flask of 250 ml of capacity, 20.0 g (51 mmol) of 4,4'-methylene-bis(3-hydroxy-2-carboxy-naphthalena ~pamo;c ac;d), 21.2 g t102 mmol) of phosphorus pentachloride and 145 ml of th;onyl chlor;de are charged:
the mixture is refluxed, with stirring, for 5 hours.
The reaction kinetics can be monitored by I.R.
spectroscopy, by observing the disappearance of the absorption band around 1,660 cm ~ and the contextual appearance of a wider band at 1,760:1,780 cm When the reaction has subsided, the prec;p;tated product is recovered by f;ltrationr and is then 9~`
1 0 .
thoroughly washecl with ethyl ether and ;s dr;ed~
Said product us a solid ofllhite colour. The yield is of ~0%.
Element3l_Anal~sls Cl = 17.2%
(C,l3~ 0~CI2 requ1res: Cl = 16.7%
The equivalent weight and molecular w~ight values (chloride titration) are in good agreement with the proposed formula.
The other hemichlorinated methylene-bis~naphthalene derivatives corresponding to fo~rmula (I) are prepared by modalities analogous to those as above disclosed.
.Xan!2 l -._2 To a glass reactor of S l of capacity, kept at the controlled temperature of 25 Cr 84 g of bisphenol A~ 115 mg of pamo;c ac;d (branching agent, equ;valent to 0.08%
by mol, relat;vely to b;sphenol), 65.2 9 of sodium hydroxide dissolved in 650 ml of water, 20 mg of sodium dithion;te (as a reducing agent) and 6.3 ml of an O.S N
- aqueous solut;on of triethylamine are charged under -- nitrogen~
Then, 2.7 g of p-tert.butyl~phenol dissolved in 1,300 ml of methylene chloride is added, and through ~he m;xture 44 g tf phosgene gas is bubbled, within a 30-m-inute time, with vigorous stirring.
The reaction is continued for 2 hours, with aqueous soclium hy~rox;de ~at 20% by weigh~) being added For the purpose of ma;ntaining a pH value hi~her than 11.
At the end, the reaction mixture is diluted with 500 ml of methylene chloride, antd the organic phase is separated and successively washed with 300 ml of water ~twice), 800 ml of 0.15 N aqueous sodium hydroxide (three times), 600 ml of water ~twice), ~00 ml of 0.1 N hydro-!
!
'~'.
S~:~3~
chloric acid an(l, ~inally, with portions of 600 ml oF
water until n~u-~rality.
At the end, ~he polymer is recoverecl by distilling of the organic solvent, is dried and ground until a powder is obtained~
The branched polycarbor)ate displays the following characteristics:
- Intrinsic Viscosity = 0.571 dl/cJ;
; Shear Sensitivity = 20.0;
- IZOD Impact Resistance -- 821 j~m~
Exam~le~3 : An amount of 243 g of chloroformy!-capped .~ polycarbonate oligomers (number average molecular weight = 826, chloroformyl end groups = 2,30D meq~kg; hydroxy '- 15 end groups - 121 m.eq/k~), prepared ~rom bisphenol A, phosgene and p-tert.butyl-phenol and dissolv~d in 900 ml : of methylene chloride, ;s charged, under nitrogerl, to a ! glass reactor of 2.5 l of capacity, kept at the controlled temperature of 25 C.
With the above solut;on bein kept mechanically stirred, by means of a magnetic-anchor stirrer (300 rpm), to it 50 ml of water containing 490 mg of pamoic acid (branching agent, equivalent to 0.12% by mol relatively to total bisphenol A), 1.0 g of sodium'hydroxide, 31~g of sodium d;thionite and 5 ml of an o.as N'aqueous solution of triethylamine are added in the order shown.
Forty minutes later, 300 ml of water is added, containing 54.0 g of bisphenol A and 20 g of sod-ium hydroxide and, then, 92 ml of an aqueous solution of sodium hydroxide at Zû% (by weight) is charged over a 10 minute time, by using a metering pump.
~ - .
12.
Aft-er 140 minutes, the mixture is poured ;nto 2,20U
ml of nethylene chloride; the organic phase is subse~uently separated and ~lashed, in the order, w;th 450 ml of water (t~l;ce), 1,300 ml of 0.15 N aq~leous sodium hydroxide (3 times), 900 ml of ~later (twice), 1,3QO ml of 0.1 N hydrochloric aciclt and, f;nally, ~I;th ~ortions of 900 ml of ~atel, unt;l neutral;ty.
The branched polycarbol1a~e, isolated by means of the usual methodology, shows the following characterist;cs:
- Intrinsic Viscosity = 0.563 dl~g;
- Shear Sensitiv;ty = 18.6;
- IZOD Impact Res;stance = 806 j/m.
EX ele_4 The process is carried out by the same operat;ve i 15 modal;t;es and amounts of reactants as of Example 3, except that 980 mg of pamoic acid (0.24% by mol relatively to total b;sphenol A) is added.
The branched polycarbonate obta;ned has the following character;stics:
- Intrinsic Viscosity = 0.589 dl/g;
- Shear Sensit;vity --2Z.7;
- IZOD Impact Resistance = 830 j/m.
ExamE!.l_-5 1he process ;s carr;ed out by the same operative modal;t;es as o~ ExampLe 3, except that 540 mg of 4,41_ methylene~bis~3-hydroxy-2-chlorocarbonyl-naphthalene) ~0~12% by mol relatively to total b;sphenol A) is added.
The branched polycarbonate obtained has the following characterist;cs:
- Intrinsic V;scos;ty = 0.542 dl/g;
- Shear Sens;t;v~ty =_~8.8;
5~
13.
IZOD Irllpact Resistance ~ 810 j/m~
Exam~le_6 1he process ;s carried out by the sane operativ2 modaL;ties as of Example 7~f except thac 1~08 y of 4,4'~
S methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalt.~ne) (U.24% by mol relatively to total b;sphenol A) is added.
1he branched polycarbonate obtained tlas the followiny charact:erist;cs:
- Intr;nsic Viscosity = 0.549 cll/g;
- Shear Sensitivity 20.0;
- IZOD Irnpact Resistance = 830 j/m.
:, ' .
, ' ' ' :~
, ,
The present invent-ion relates to brarlched, thermoplastic, polycarbonates, suitable for being transformed by means oF the blow-moulding technique (blow moulding of hollow bodies)~ i L;near polycarbonates have been long known in the art.
Such polyrners are widely used in different applicative sectors, but, contrarily to most thermoplastic polymers, they are not suitable for t,eing processed by nleans of extrusion or blo~s-moulclir1g techniques, which are the techniques suitable for `~ supplying particular transformation products ~cellular sheets, bottles, hollow containers, and so forth).
This dif,iculty in processability of lir,ear polycarbonate is due to ;ts exclusively N~wtonian behaviour, according to which the apparent viscosity ~rl) - is substantially independent from the shear rate ~
- The transformation of a material acccrding to the techniques of extrusion or of blow-moulding requires, on the contrary, that it has a decreasing apparent viscosity with increasing shear rate, a typical aspect of non-Newtonian behaviour, so that the state of the molten polymer can be differentiated ;nto two successive moments: a first moment, when it is inside the transformation machine ~e.g., an extruder), and a second moment, when the product leaves it ~e.g., from the die oF
the same extruder).
In the first step, the shear rates the fluid is subject to, are high, and its apparent v;scos;ty ;s, -:
-:
. ~
~' ' ~
, , !
' 2.
vice~versa, low, so that the processability thereof resul-ts fac1l-itated; ~Ihen the fluid leaves the extrucler, on the con~rary, low values o'f ~, and high v;scosity values appear, and this prevents the 'product from collapsing, and makes it poss;ble a good dimensional stability of the manufactured articLe to be achieved.
The non-Ne~tonian behaviour of the molten polymer has a considerable influence on two properties, i~e., the melt elasticity, or pseudo-elasticity, and the melt strength, thereof, ~Jhich are equally very important for the transformation techniques of extrusion and blow-moulding.
The melt elasticity consists essentially in the ;~ capability of the non-Newtonian fluid of swelLing to a ~reater extent, when exiting the die, than a Newtonian fluid~ as a consequence of a higher recovery of elastic energy inside its interior, thanks to a greater molecular deflection and orientation under the act;on of a shear stress~
That results in an increase in the proc'essability of the product, due to the effect of a greater flexibility and ductility of the material.
' The s'econd property ;ndicated, viz., the melt tenacity, becomes vice-versa meaningful when the molten polyoer exits the transformation machine. It can be considered as the tenacity of the polymer in the molten state, i~e., the stress-supporting capacity shown by the polymer. If, in fact, the molten mass is not capable of supporting its own weight, the collapse occurs of the extrudate, and, as a consequence, obtaining the desired shape of the marufactured artlcLe is nrt possibLe.
.
It results evident from the above that the polyMers which display a non-Newtonian behaviour are endowed with two basic characteristics, wh1ch enable ~h~rn to be transformed by extrusion and/or blow-moulding techniques:
a very easy processability inside the machine (low apparent viscosity for high val-les of ~ and h;gh melt elasticity), and very good shape retention when exiting said machine (high apparent viscosity For low values of and considerable melt tenacity).
10In the art, branched polycarbonates are known, which have non-Newtonian rheological properties, su;table for being processed according to techniques of extrusion and of blow-moulding.
Such polycarbonates can bc obtained by means of the copolymer;zation w;th polyfunctional comonomers containing three or more -OH and/or -COOH and/or -COCl groups.
- The main technical problems which can be met in the - preparation of the branched polycarbonates consist essentially in the reactivity of the polyfunctional comonomer used, and in the characteristics of the branched polycarbonate obtained with such a comonomer.
In particular, the comonomer should show a so high reactivity, as to make it possible to achieve the desired branching degree ~such to give the polymer a shear-sensitivity > 15)~ when used in small amounts.
The branched polycarbonate, besides showing a shear sensitivity > 15, should maintain unchanged the other characteristics which are typical of the linear polycarbonates.
The polyfunctional comonomers of the prior art have ~2~i5~
not shown to be completely satis-factory from all of these v;ewpoints.
It l1as been found now tha~ it is poss;ble to overcome the drawbac~s deriving from the prior art, and obtain branched, thermoplasticr polycarbonates, suitatle for be;ng transformed by blow-moulding, by copolymer;zat;on with a poly-funGtional, h;ghly react;ve, comonorner, used ;n small amo~ -ts.
Such polycarbonates, thanks to the branch;ngs due to 1~ the presel1ce of the polyFunct;onal comonomer ;n the macromolecule, show a shear~sensit;vity (wh;ch ;s the rat;o bet~leen the flow rates of the molten polymer at two different shear ral:es) > 15, wh;le ma;ntain;ng unchanged the other character;st;cs typ;caL of the l;near polycarbonates.
Therefore, a purpose of the present ;nvention are branched, thermoplast;c polycarbonates, su;table for be;ng transforrned by blow-mould;ng.
Another purpose of the present ;nvention ;s a process for the preparat;on of sa;d polycarbonates.
Thus, the present invention provides such branched polycarbona-tes derived from at leas-t one aromatic dihy-droxy compound, phosgene, and, as branching agen-t, a methy1ene-bib-rlaphthalene compound having -the formula:
t. ~
~ ~ ~ .
~0~, ~
CH2 (I?
C ~
wherein R1, R~, ale equal to, or different from each other, and represent -COOH or COCl;
10The branched polycarbonates disclosed in the present invention can be prepared by means of a process comprising the followil1g process steps, carr;ed ou~
successively:
. a) Preparat;on of a chloroformyl-capped ol;gorner, by 15reaction between phosgene and a dillydroxyarornatic ` cornpound, corresponding to the formula:
HO - ~ - R - ~ - OH tII
tx) ~y) n m wherein:
R - substituted or unsubstituted alkyl radical, contain;ng from O to 5 C, -0-~ -S~ atoms, -S02-and -CO- groups;
25x, y are equal to or different from each other, and represent H, CH3~ halogens;
m, ~ are integers, equal to, or different from, each other, comprised within the range of from 1 to 4.
b~ Condensation of the so-obta;ned oligomer with the 30polyfunction3l comonomer corresponding to the formula tI), wherein R1, R2, have the above seen meaning.
~ ~ .
:
~2~5~
c) Add;tion of a dihydroxyaroma-tic compour)d (II~ to the mixture cleriviny -from (b), anc! polycondensatiol1~
d) Recovery of the brancl1ed polycarborlate from the reaction mixture.
According to the present invention, tl1e chloroformyl~capped oligomers are prepared by means o~
the interfacial reaction between phosgene and a dihydroxyaromatic compound (II) dissolved in aqueous-alkaline solutiol1, in the presence of an otganic solvent 1b imm;sc;ble with water and ot a molecular weight regulator, such as, e~g~r p-tert.butyl-phenol or p-isopropyl-pllellol orf phenol i;tsel:E.
As dihydroxyaromatic compounds, e.g., the ~ollow;ng can be used:
-- 4,4'-dihydroxydiphenyl;
-- 2,2-bis(4-hydroxyphenyl)propane (bisphenol A);
-- 2,2-bis(3,5-dichloro-4-hytlroxypllenyl)propane;
-- bis~4-hydroxyphenyl)methane;
-- 2,2-bis(3~5-dimethyl-4-hydroxyphenyl)propane.
Also bivalent compounds with one aromat;c ring only can be used, such as resorc;nol, hydroqu;none and pyrocatechol.
The process ;s carr;ed out at a temperature compr;sed w;thin the range of from 15 C to 35 C, and, preferably~ at room ternperature ~20-25 C).
The so obta;nèd ol;gotners have a molecular we;ght of from 400 to 2000.
After the separat;on of the -two phases, to the organ;c phase, conta;n;ng the chloroformyl-capped ol;qomers, the polyfunct;onal comonomer ~I), dissolved in an organ;c solvent ;moliscible w;th water, preferably ~B
.
~2 7.
methylerle cllloride~ is added, so ,o ob-tain in the end polycarbonate from 0.01 to 1~5 MOl of comonomer per each 100 mol of arornatic dihydroxy~-compound.
Some examples of polyfunct;onal comonomers used are:
S -- 4,4'-me~hylenebis(3-hydroxy-2-carboxynaphthalene;
-- 3-hydroY~y-4--rnethylerle(3:-hydroxy-4'-clllorocarbonyl~
naphthalene)-2-naphthoic acid;
-- 4,4'-methylene-bis(3-hydroxy-2 chlorocarbonyl-naphthalene) An aqueous-alkaline solution is then added, which contains a reducing agent, preferably sodium dith;onite, for the purpose of preventillg the formaticn of coloured byproducts, and an aqueous solution is added, whicr contains the phase-transfer ca~alyst, e.g, a tertiary amine, preferably triethylamine.
~ The temperature at which tt,e condensation is carried ; out ranges from 15 C to 35 C and is preferably kept around room values (20-25 C).
- After a time per;od ranging from 30 to 60 minutes, - 20 preferably 40 minutes, the biphasic system coming from the condensa-tion with the polyfunctional comonomer is treated with an alkaline solution of the aromatic dihydroxy-derivative.
An aqueolls alkaline solution of sod;um hydroxide at 40% by weight ;s then added.
After a ~ime period of from 2 to 3 hours, the S4 obta;ned branched polycarbonate is ;solated by wash;ng the organ;c phase accord;ng to the methods of the known art, and distillat;on of the solvent, or precipitat;on by means of a non-solvent.
The preparation of such branched polycarbonates can be carr;ed out also by means of other processes~ such as, e.g~, the process which prov;des the condensation betwee~
aromatic dihydroxy derivativesr phosgene an~
polyFunctional comonomer~ by means of an interfacial reaction, or of a reaction in solution, in one single reaction step~
Such polycarbonates can be also obta;ned by tranc;es~eriFication in thc molten state, by reacting the dihydroxyaroolatic compourld witll d;aryl-, dialkyl-- or alkylaryl-carbonates at temperatures of from 100 to 300 C, in the presence of transesterification catalystsu The branched polycarbonates oF the present invention have a molecular weight ranging from 209000 to 30,000, - and are characterized in that tlley are completely soLuble ;~ 15 ;n the usual solvents of the linear polycarbonate, and show a high dependence of the melt viscosity from the shear rate~
- Such polycarbonates are hence well su;table for ; being processed both by the ;njection-mould;ng techn;que, - 20 typ;cal of the linear polycarbonates, and by~ e.g., extrus;on.
Due to the,excellent stab;lity of the molten mass, such polycarbonates are part;cularly well suitable for being transformed by the blow-Moulding method, ~or the product;on o~ hollow boclies.
The reactivity of the polyfunctional comonomer used as the branching agents is such that an amount of from 0.01 to 1.5 mol of such comonomer per each 100 mol of aromatic d;hydroxy~compound are enough for reaching such a crossl;nkin~ degree that the shear-sensit;vity has values always higher than 15.
6~:
~or thc Gharac~eri~a~;on o-f the branched polycarbonates according to the present inven.ion, the following mett,ods ~lere used: .
Intrinsic Viscositx ~ the intrinsic viscosity is 5 deterlnined in methylene chloride at 20 C by means o~ an Ubbelhode viscometer and ;s expressed as dl/g.
Shear Sens;tiv;ty - the evaluation of this quantity is ._~__. _.. ____.
10 carried out on the ~elt indexer~
:~ under loads o-f from 2~1~ to 21~6 ~g, - at ZhO C, according to ASTM D 1238~ :
Ir~act l~esis nce (12(X))~ - The impact resistance is measured on - specimens with notch, at O C, . 15 according to ASTM D 256.
The following examples are illustrative and not lim;tat;ve of the same ;nvent;on.
Examele 1 Preearat;on of 4,4'-Methylene~bis(3-hydroxb_-2_chlQrocaf-bonyl-naehthalene) ___ ____ ____ ____ To a flask of 250 ml of capacity, 20.0 g (51 mmol) of 4,4'-methylene-bis(3-hydroxy-2-carboxy-naphthalena ~pamo;c ac;d), 21.2 g t102 mmol) of phosphorus pentachloride and 145 ml of th;onyl chlor;de are charged:
the mixture is refluxed, with stirring, for 5 hours.
The reaction kinetics can be monitored by I.R.
spectroscopy, by observing the disappearance of the absorption band around 1,660 cm ~ and the contextual appearance of a wider band at 1,760:1,780 cm When the reaction has subsided, the prec;p;tated product is recovered by f;ltrationr and is then 9~`
1 0 .
thoroughly washecl with ethyl ether and ;s dr;ed~
Said product us a solid ofllhite colour. The yield is of ~0%.
Element3l_Anal~sls Cl = 17.2%
(C,l3~ 0~CI2 requ1res: Cl = 16.7%
The equivalent weight and molecular w~ight values (chloride titration) are in good agreement with the proposed formula.
The other hemichlorinated methylene-bis~naphthalene derivatives corresponding to fo~rmula (I) are prepared by modalities analogous to those as above disclosed.
.Xan!2 l -._2 To a glass reactor of S l of capacity, kept at the controlled temperature of 25 Cr 84 g of bisphenol A~ 115 mg of pamo;c ac;d (branching agent, equ;valent to 0.08%
by mol, relat;vely to b;sphenol), 65.2 9 of sodium hydroxide dissolved in 650 ml of water, 20 mg of sodium dithion;te (as a reducing agent) and 6.3 ml of an O.S N
- aqueous solut;on of triethylamine are charged under -- nitrogen~
Then, 2.7 g of p-tert.butyl~phenol dissolved in 1,300 ml of methylene chloride is added, and through ~he m;xture 44 g tf phosgene gas is bubbled, within a 30-m-inute time, with vigorous stirring.
The reaction is continued for 2 hours, with aqueous soclium hy~rox;de ~at 20% by weigh~) being added For the purpose of ma;ntaining a pH value hi~her than 11.
At the end, the reaction mixture is diluted with 500 ml of methylene chloride, antd the organic phase is separated and successively washed with 300 ml of water ~twice), 800 ml of 0.15 N aqueous sodium hydroxide (three times), 600 ml of water ~twice), ~00 ml of 0.1 N hydro-!
!
'~'.
S~:~3~
chloric acid an(l, ~inally, with portions of 600 ml oF
water until n~u-~rality.
At the end, ~he polymer is recoverecl by distilling of the organic solvent, is dried and ground until a powder is obtained~
The branched polycarbor)ate displays the following characteristics:
- Intrinsic Viscosity = 0.571 dl/cJ;
; Shear Sensitivity = 20.0;
- IZOD Impact Resistance -- 821 j~m~
Exam~le~3 : An amount of 243 g of chloroformy!-capped .~ polycarbonate oligomers (number average molecular weight = 826, chloroformyl end groups = 2,30D meq~kg; hydroxy '- 15 end groups - 121 m.eq/k~), prepared ~rom bisphenol A, phosgene and p-tert.butyl-phenol and dissolv~d in 900 ml : of methylene chloride, ;s charged, under nitrogerl, to a ! glass reactor of 2.5 l of capacity, kept at the controlled temperature of 25 C.
With the above solut;on bein kept mechanically stirred, by means of a magnetic-anchor stirrer (300 rpm), to it 50 ml of water containing 490 mg of pamoic acid (branching agent, equivalent to 0.12% by mol relatively to total bisphenol A), 1.0 g of sodium'hydroxide, 31~g of sodium d;thionite and 5 ml of an o.as N'aqueous solution of triethylamine are added in the order shown.
Forty minutes later, 300 ml of water is added, containing 54.0 g of bisphenol A and 20 g of sod-ium hydroxide and, then, 92 ml of an aqueous solution of sodium hydroxide at Zû% (by weight) is charged over a 10 minute time, by using a metering pump.
~ - .
12.
Aft-er 140 minutes, the mixture is poured ;nto 2,20U
ml of nethylene chloride; the organic phase is subse~uently separated and ~lashed, in the order, w;th 450 ml of water (t~l;ce), 1,300 ml of 0.15 N aq~leous sodium hydroxide (3 times), 900 ml of ~later (twice), 1,3QO ml of 0.1 N hydrochloric aciclt and, f;nally, ~I;th ~ortions of 900 ml of ~atel, unt;l neutral;ty.
The branched polycarbol1a~e, isolated by means of the usual methodology, shows the following characterist;cs:
- Intrinsic Viscosity = 0.563 dl~g;
- Shear Sensitiv;ty = 18.6;
- IZOD Impact Res;stance = 806 j/m.
EX ele_4 The process is carried out by the same operat;ve i 15 modal;t;es and amounts of reactants as of Example 3, except that 980 mg of pamoic acid (0.24% by mol relatively to total b;sphenol A) is added.
The branched polycarbonate obta;ned has the following character;stics:
- Intrinsic Viscosity = 0.589 dl/g;
- Shear Sensit;vity --2Z.7;
- IZOD Impact Resistance = 830 j/m.
ExamE!.l_-5 1he process ;s carr;ed out by the same operative modal;t;es as o~ ExampLe 3, except that 540 mg of 4,41_ methylene~bis~3-hydroxy-2-chlorocarbonyl-naphthalene) ~0~12% by mol relatively to total b;sphenol A) is added.
The branched polycarbonate obtained has the following characterist;cs:
- Intrinsic V;scos;ty = 0.542 dl/g;
- Shear Sens;t;v~ty =_~8.8;
5~
13.
IZOD Irllpact Resistance ~ 810 j/m~
Exam~le_6 1he process ;s carried out by the sane operativ2 modaL;ties as of Example 7~f except thac 1~08 y of 4,4'~
S methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalt.~ne) (U.24% by mol relatively to total b;sphenol A) is added.
1he branched polycarbonate obtained tlas the followiny charact:erist;cs:
- Intr;nsic Viscosity = 0.549 cll/g;
- Shear Sensitivity 20.0;
- IZOD Irnpact Resistance = 830 j/m.
:, ' .
, ' ' ' :~
, ,
Claims (11)
1. Thermoplastic, blow moldable, branched polycarbonate derived from at least one aromatic dihydroxy compound, phosgene, and a branching agent methylene-bis-naphthalene compound having the formula:
(I) wherein R1 and R2, are the same or different from each other, and represent -COOH or COC1.
(I) wherein R1 and R2, are the same or different from each other, and represent -COOH or COC1.
2. Branched polycarbonate according to claim 1, wherein the methylene-bis-naphthalene compound, (I), is selected from:
4,4'-methylene-bis(3-hydroxy-2carboxy-naphthalene);
4,4'-methylene-bis(3-hydroxy-2carboxy-naphthalene);
3-hydroxy-4-methylene-3'-hydroxy-4'-chlorocarbonyl-naphthalene)-2-naphthoic acid; or
4,4'-methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalene).
3. Branched polycarbonate according to claim 1, wherein there is from 0.01 to 1.5 mol percent of methylene-bis-naphthalene compound (I), per each 100 mol of aromatic dihydroxy-compound.
4. Process for the preparation of thermoplastic, blow moldable, branched polycarbonate derived from at least one aromatic dihydroxy compound, phosgene, and the branching agent methylene-bis-naphthalene compound having the formula (I) (I) wherein R1 and R2, are the same or different from each other, and represent -COOH or COC1, comprising the following steps carried out successively:
(a) preparing a chloroformyl-capped oligomer, by reacting phosgene and a dihydroxyaromatic compound, corresponding to the formula:
(II) wherein:
R is substituted or unsubstituted alkyl radical, containing from 0 to 5 carbon atoms, -O- or -S- atoms, -SO2- or -CO- groups;
x, y are the same or different from each other and represent H and CH3, halogen;
m and n are integers, the same or different from each other, within the range of from 1 to 4;
(b) condensing the so-obtained oligomer with the branching agent methylene-bis-naphthalene compound having the formula (I), wherein R1 and R2 have the above meaning;
(c) adding a dihydroxyaromatic compound (II) to the mixture resulting from (b) and polycondensing said mixture: and (d) recovering the branched polycarbonate from the reaction mixture.
3. Branched polycarbonate according to claim 1, wherein there is from 0.01 to 1.5 mol percent of methylene-bis-naphthalene compound (I), per each 100 mol of aromatic dihydroxy-compound.
4. Process for the preparation of thermoplastic, blow moldable, branched polycarbonate derived from at least one aromatic dihydroxy compound, phosgene, and the branching agent methylene-bis-naphthalene compound having the formula (I) (I) wherein R1 and R2, are the same or different from each other, and represent -COOH or COC1, comprising the following steps carried out successively:
(a) preparing a chloroformyl-capped oligomer, by reacting phosgene and a dihydroxyaromatic compound, corresponding to the formula:
(II) wherein:
R is substituted or unsubstituted alkyl radical, containing from 0 to 5 carbon atoms, -O- or -S- atoms, -SO2- or -CO- groups;
x, y are the same or different from each other and represent H and CH3, halogen;
m and n are integers, the same or different from each other, within the range of from 1 to 4;
(b) condensing the so-obtained oligomer with the branching agent methylene-bis-naphthalene compound having the formula (I), wherein R1 and R2 have the above meaning;
(c) adding a dihydroxyaromatic compound (II) to the mixture resulting from (b) and polycondensing said mixture: and (d) recovering the branched polycarbonate from the reaction mixture.
5. Process according to claim 4 for the preparation of the branched polycarbonate wherein the branching agent methylene-bis-naphthalene compound having the formula (I) is selected from:
4,4'-methylene-bis(3 hydroxy-2-carboxy-naphthalene;
3-hydroxy-4-methylene(3'-hydroxy-4'-chlorocarbonyl-naphthalene)-2-naphthoic acid; or 4,4'-methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalene).
4,4'-methylene-bis(3 hydroxy-2-carboxy-naphthalene;
3-hydroxy-4-methylene(3'-hydroxy-4'-chlorocarbonyl-naphthalene)-2-naphthoic acid; or 4,4'-methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalene).
6. Process according to claim 4 for preparation of the branched polycarbonate wherein there is from 0.01 to 1.5 mol percent of methylene-bis-naphthalene compound (I), per each 100 mol of aromatic dihydroxy compound.
7. Process according to claim 4, 5 or 6, wherein, in the (a) and (c) process steps, the dihydroxyaromatic compound is selected from:
4,4'-dihydroxydiphenyl;
2,2-bis(4-hydroxyphenyl)propane;
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; or bis(4-hydroxyphenyl)methane.
4,4'-dihydroxydiphenyl;
2,2-bis(4-hydroxyphenyl)propane;
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; or bis(4-hydroxyphenyl)methane.
8. A process according to claim 4, 5 or 6, wherein, in the (a) process step, the reaction is carried out in a water/organic solvent two phase system, in the presence of a molecular weight control agent, constituted by a monofunctional phenol, and that the oligomers obtained have a molecular weight of from 400 to 2,000.
9. A process according to claim 8, wherein, in the (a) process step, the organic solvent is methylene chloride and the monofunctional phenol is selected from:
phenol;
p-isopropyl-phenol; or p-tert-butyl-phenol.
phenol;
p-isopropyl-phenol; or p-tert-butyl-phenol.
10. A process according to claim 4, 5 or 6, wherein, in the (b) step the process is carried out in a water/organic solvent two phase system, in the presence of a phase transfer catalyst, and that said branching agent methylene-bis-naphthalene compound having the formula (I), is selected from:
4,4'-methylene-bis(3-hydroxy-2-carboxy-naphthalene);
3-hydroxy-4-methylene(3'-hydroxy-4'-chlorocarbonyl-naphthalene)-2-naphthoic acid; or 4,4'-methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalene).
4,4'-methylene-bis(3-hydroxy-2-carboxy-naphthalene);
3-hydroxy-4-methylene(3'-hydroxy-4'-chlorocarbonyl-naphthalene)-2-naphthoic acid; or 4,4'-methylene-bis(3-hydroxy-2-chlorocarbonyl-naphthalene).
11. A process according to claim 10, wherein, in the (b) process step, the organic solvent is methylene chloride and the catalyst is a tertiary amine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21233/86A IT1196988B (en) | 1986-07-23 | 1986-07-23 | BRANCHED POLYCARBONATES CONTAINING METHYL-BIS-NAPHTHALENIC COMPOUNDS AND PROCEDURE FOR THEIR PREPARATION |
| IT21233A/86 | 1986-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1285692C true CA1285692C (en) | 1991-07-02 |
Family
ID=11178784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000542769A Expired - Fee Related CA1285692C (en) | 1986-07-23 | 1987-07-22 | Branched polycarbonates containing methylene-bis-naphthalene compounds and process for their preparation |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4798882A (en) |
| EP (1) | EP0254371B1 (en) |
| JP (1) | JPS6330524A (en) |
| AT (1) | ATE72255T1 (en) |
| CA (1) | CA1285692C (en) |
| DE (1) | DE3776445D1 (en) |
| DK (1) | DK379987A (en) |
| ES (1) | ES2030709T3 (en) |
| GR (1) | GR3003933T3 (en) |
| IT (1) | IT1196988B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5610317A (en) | 1985-09-05 | 1997-03-11 | The Boeing Company | Multiple chemically functional end cap monomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| JP2517541Y2 (en) * | 1988-09-28 | 1996-11-20 | アイシン精機株式会社 | Bearing mechanism of turbocharger |
| US5166306A (en) * | 1988-12-02 | 1992-11-24 | Enichem Technoresine S.P.A. | Flame-resistant polycarbonate containing units from halogenated pyrimidine compounds in the polymer chain |
| JP2628563B2 (en) * | 1989-08-03 | 1997-07-09 | 出光石油化学株式会社 | Branched polycarbonate and method for producing the same |
| JP2628562B2 (en) * | 1989-08-03 | 1997-07-09 | 出光石油化学株式会社 | Branched polycarbonate and method for producing the same |
| US5447989A (en) * | 1993-09-17 | 1995-09-05 | Enichem S.P.A. | High impact modified polycarbonate compositions |
| JP6097627B2 (en) * | 2013-04-25 | 2017-03-15 | 帝人株式会社 | Polycarbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3525712A (en) * | 1965-09-01 | 1970-08-25 | Gen Electric | Process for preparing thermoplastic polycarbonates |
| US4562242A (en) * | 1984-12-24 | 1985-12-31 | General Electric Company | Branched polycarbonate from carboxy containing diphenol |
| IT1214645B (en) * | 1985-12-19 | 1990-01-18 | Enichem Polimeri | BRANCHED POLYCARBONATES CONTAINING BINUCLEAR AROMATIC COMPOUNDS. |
-
1986
- 1986-07-23 IT IT21233/86A patent/IT1196988B/en active
-
1987
- 1987-07-17 ES ES198787201368T patent/ES2030709T3/en not_active Expired - Lifetime
- 1987-07-17 DE DE8787201368T patent/DE3776445D1/en not_active Expired - Fee Related
- 1987-07-17 AT AT87201368T patent/ATE72255T1/en not_active IP Right Cessation
- 1987-07-17 US US07/075,042 patent/US4798882A/en not_active Expired - Fee Related
- 1987-07-17 EP EP87201368A patent/EP0254371B1/en not_active Expired - Lifetime
- 1987-07-21 DK DK379987A patent/DK379987A/en not_active Application Discontinuation
- 1987-07-22 CA CA000542769A patent/CA1285692C/en not_active Expired - Fee Related
- 1987-07-23 JP JP62182438A patent/JPS6330524A/en active Pending
-
1992
- 1992-02-28 GR GR920400357T patent/GR3003933T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3776445D1 (en) | 1992-03-12 |
| IT8621233A1 (en) | 1988-01-23 |
| EP0254371B1 (en) | 1992-01-29 |
| GR3003933T3 (en) | 1993-03-16 |
| IT8621233A0 (en) | 1986-07-23 |
| EP0254371A3 (en) | 1989-05-10 |
| DK379987D0 (en) | 1987-07-21 |
| EP0254371A2 (en) | 1988-01-27 |
| DK379987A (en) | 1988-01-24 |
| ES2030709T3 (en) | 1992-11-16 |
| JPS6330524A (en) | 1988-02-09 |
| US4798882A (en) | 1989-01-17 |
| ATE72255T1 (en) | 1992-02-15 |
| IT1196988B (en) | 1988-11-25 |
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