IE72214B1 - New alpha-mono-olefin based graft copolymer - Google Patents
New alpha-mono-olefin based graft copolymerInfo
- Publication number
- IE72214B1 IE72214B1 IE94589A IE94589A IE72214B1 IE 72214 B1 IE72214 B1 IE 72214B1 IE 94589 A IE94589 A IE 94589A IE 94589 A IE94589 A IE 94589A IE 72214 B1 IE72214 B1 IE 72214B1
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- Prior art keywords
- graft copolymer
- ethylene
- copolymer
- polyamide
- propylene
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyamides (AREA)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
The application relates to a graft copolymer consisting of at least one monoamine polyamide oligomer and of a polymer or copolymer of alpha -monoolefin grafted with a monomer capable of reacting with the amine functional group of the oligomer. It is prepared by radical grafting of the monomer onto the copolymer followed by addition of the oligomer. The application also relates to the use of this graft copolymer especially as an agent producing compatibility of at least two thermoplastic polymers which are incompatible with each other for the manufacture of alloys.
Description
NEW e-NONO-OLEFIN BASED GRAFT COPOLYMER
The present invention relates to an ei-mono-olefin based graft copolymer, a process for its production and its use as an agent enabling at least two incompatible thermoplastic polymers to be made compatible.
It is known how to make two incompatible polymers compatible, in certain specific mixtures, by combining them with a third polymer, which is partially compatible with both of the polymers.
Thus, for example, various third polymers have been proposed for a polypropylene/polyamide mixture:
In Japanese Patent No. 70-030943, a composition comprising polypropylene, polyamide and polypropylene grafted with maleic anhydride is disclosed.
In Japanese Patent No. 59-149940 a composition containing polypropylene, polyamide and an ethylenepropylene copolymer grafted with maleic anhydride is disclosed.
In French Patent No. FR 2,107,538, a composition made from polypropylene and glass fibre-reinforced polyamide, which was rendered compatible by adding a copolymer of
7221 4
- 2 propylene and «-olefin grafted by polyamide chains is disclosed. This graft copolymer is obtained by polycondensation of an amino-acid in the presence of a propylene copolymer previously grafted with maleic anhydride.
Xn Japanese Patent No. 60-233131, the production of a graft copolymer, making a mixture of polypropylene and polyvinyl chloride compatible is disclosed. This graft copolymer is obtained by reacting a polypropylene modified with 2 to 20% by weight of maleic anhydride with a polymethyl methacrylate having a terminal hydroxyl group.
The present invention relates to novel graft copolymers comprising at least one monoamino-substituted polyamide oligomer and an ©-mono-olefin polymer (or copolymer) grafted with a monomer which can react with an amine functional group of the monoamino-substituted polyamide oligomer.
The invention also relates to the process for the production of this graft polymer. It can be produced by freeradical grafting onto a polymer chain containing units derived from «-mono-olefin, of a monomer which can react with an amine functional group, and then by additional of the monoamino-substituted polyamide oligomer onto the graft copolymer.
The invention additionally relates to the use of this graft copolymer with at least two mutually incompatible thermoplastic polymers of which at least one is compatible with the polyamide oligomer and at least one is compatible with the α-monc-olefin polymer or copolymer.
The copolymer according to the invention comprises a graft copolymer represented by the expression AaMbXcPd in which:
AaMb corresponds to the (co)polymer backbone,
XcPd corresponds to the polymers grafted onto the (co)polymer backbone,
A is a unit derived from an e-mono-olefin containing from 2 to 8 carbon atoms, and is preferably a unit derived from propylene,
M is selected from the group comprising:
- units derived from an α-mono-olefin containing from 2 to 8 carbon atoms, and preferably derived from ethylene, units derived from several α-mono-olefins as previously defined, which may be merely mixed together or may be randomly copolymerized or block-copolymerized, and one of these ce-mono-olef ins is preferably ethylene,
- units derived from a monomer which can be polymerized with one of the α-mono-olefins as previously defined, for example an alkyl acrylate, provided that M does not represent a unit derived from a diene, the units A and M which form the said (co)polymer backbone are randomly copolymerized or block-copolyiasrised or are simply mixtures,
X is a unit derived from a monomer which can be grafted by a free-radical mechanism onto an e-mono-olefin homo- or copolymer and containing a functional group which can react with an amino-substituted unit#
P Is derived from a polyamide oligomer of the formula s fl
H2N (CH2)j—c
in which f is a number from 3 to 11 , g is a number from 5 to 80 and preferably from 15 to 55,
Rj is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms,
Re is a linear or branched alkyl or alkenyl group containing up to 20 carbon atoms, a. cycloaliphatic radical# which may or may not be saturated, an aromatic radical or a combination of the abovementioned# a, b, c and d are numbers which correspond to the following definitionss a is from 0 to 5,000-and preferably from 350 to 2,000.
The sum a + b is from 350 to 45,000 and preferably from 500 to 10,000.
c is selected is such a way that the ratio by weight of th® monomer X grafted onto the (co)polymer backbone to the copolymer grafted with X is from 500 ppm to 10%, preferably less than 2%, and most preferably from 5,000 ppm to 1.5%.
d is above zero and less than or equal to c, and preferably at least equal to 0.3 c.
A (Co)polymer backbone of the formula:
Aa -M-b in which a, b, A and M are as previoualv defined, means any polymer composed of A and M units derived from monomers which have been randomly polymerised or block-polymerized, or as the case may be any mixture of polymers obtained by separate polymerizations of monomers from which the A and M units are derived.
This copolymerization or this mixing may be carried out in accordance with known processes.
For example, propylene and an e-olefin, may be copolymerized in the presence of a Ziegler catalyst or a coordination catalyst.
The graft copolymer according to the invention can be obtained by free-radical grafting onto the (co)polymer backbone of a monomer which can react with an amine functional group and than by addition of the oligomer onto the previously grafted (co)polymer.
Th© monomer X which can oe grafted by a free-radical mechanism onto the (co)polymer backbone and which has a functional group which can react with an amine functional group typically corresponds to one of the following formulae:
in whichs
Rj_ and R, are either hydrogen, or a linear or branched alkyl chain containing upto 8 carbon atoms, with at least one of these symbols representing hydrogen,
R3 is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms,
R^ is a linear or branched alkenyl group containing to 12 carbon atoms.
Th© preferred monomers Z ar© citraconic anhydride, fumaric acid, mesaconic acid, the anhydride of 3allylsuccinic acid and, most preferably maleic anhydride.
Th© grafting of th© monomer Z onto the (co)20 polymer backbone carried out by a free-radical mechanism, takes place in th© presence of a free-radical initiator which may be dicwnyl peroxide, benzoyl peroxide or 2,5dimethyl-2,5~di (texx-butylperoxy) hexane.
Normally the Initiator is used in a proportion of 2.5 x 10“* to 4 x 10’2 in relation to the weight ox the (co)polymer.
The free-radical grafting of th© monomer X onto the (co)polymer backbone may be carried out in the molten state or in solution in a solvent for the (co)polymer backbone. Examples of solvents of this type include toluene, xylene and chlorobenzene.
The solution grafting technique is particularly recommended when a degree of grafting greater than 1.5% is desired. (Ratio by weight of the grafted, monomer X to the (co)polymer backbone grafted with X).
The (co)polymer backbone, the monomer X and the free-radical polymerization Initiator are mixed with solvent for the (co)polymer, The mixture is brought to a temperature such that thermal decomposition of the freeradical initiator takes place so that the grafting reaction occurs. Generally, the duration of this reaction is from 0.5 to 10 times, and preferably from 1 to 4 times,the duration of the half-life of the free-radical initiator at the reaction temperature.
Generally the temperature of thermal decomposition of the free-radical initiator is from 90 to 200°C, and preferably from 110 to 140°C.
The technique of free-radical grafting of the monomer X onto the (co)polymer backbone in th® molten state Is particularly useful when a degree of grafting of from 500 ppm to 1.5% is required.
Free-radical grafting in the molten state consists in mixing the (co)polymer backbone with the required quantities of monomer X and free-radical initiator, for example in an extruder. The mixture is brought to a temperature which is generally from 170 to 250°C, and preferably from 180 to 200°C.
The average residence time of the molten material in the extruder is normally .selected from 15 seconds to 3 minutes, and preferably from 40 to 80 seconds.
The degree of grafting of the monomer X onto the (co)polymer backbone can be measured by analysis of the anhydride functional groups by infrared spectrophotometry
The monoamino-substituted polyamide oligomer, P, •j 5 of formulas
- 0 . Rc
H2N ~(CR2^—c-NH /•N \
R, in which f, g, Rs and Rg are as previously defined, is subsequently added to the graft (co)polymer.
This monoamino-substituted polyamide oligomer can be obtained by polycondensation of an amino acid of the formula:
V-(CH2)r :/ “OH ,0 or by polyaddition of a lactam of formula:
in which £ has the meaning previously given, in the presence of a monofunctional polymerisation regulator of the formula:
R, in which R3 and have the meaning previously given.
The amino acid or lactam monomers preferred for the synthesis of the monoamino-substituted oligomer of the invention are caprolactumf ^'-aminounde^anoic acid and dodecalactam.
The preferred monofunctional polymerization regulators are laurylamine and oleylamine.
Th© polycondensation defined above can be carried out in accordance with conventionally known processes, for example at a temperature generally of from 200 to 300°C, under vacuum or in an inert atmosphere, with stirring of the reaction mixture.
The average chain length of the oligomer Is determined by the initial molar ratio between the polycondensable monomer or the lactam and th© monofunctional polymerization regulator.
To calculate th® average chain length., on® molecule of chain regulator is normally counted for each oligomer chain.
The addition of the mo noamino-substituted poly5 amine oligomer onto the (co)polymer backbone grafted with a monomer X is carried out by reacting an amine functional group of the oligomer with at least on© anhydride or acid functional group of th® graft (co)polymer. Amide or imide linkages are thus created.
The addition of the oligomer P onto the graft (co)polymer backbone is preferably carried out in the molten state. Thus, it is possible to knead the oligomer and the (co)polymer at a temperature generally of from 230 to 250°C in an extruder. Th® average residence time of the molten material in the extruder may be from 15 seconds to 5 minutes, and preferably from 1 to 3 minutes.
The addition of the oligomer onto the graft (co)polymer backbone is evaluated by selective extraction of the free polyamide oligomers, that Is to say those which have not reacted fo form the final graft copolymer.
The cs-mono-olefin graft copolymers according to the Invention have th® following advantages over the third polymers referred to in the prior art.
- If is possible to control th® degree of grafting of the polyamide oligomer onto the graft (co)polymer and thus to have mor® complete control of the structure of the graft copolymer.
- It is possible to adjust and control the average molecular mass ot the monoamino-substituted polyamide oligomer. Indeed, the average molecular mass of the polyamide oligomer is a determining factor for the action and the effectiveness of the graft copolymer according to the invention as a compatibility agent for alloys of Incompatible polymers.
- The graft copolymers according to the invention do not have any chain ends which are reactive in the context of polycondensation, and during the kneading of the components of the alloy with the graft copolymer according to the invention# the said chain ends will not react in an uncontrolled manner.
The graft copolymer according to the invention particularly enables at least two mutually incompatible thermoplastic polymers, one of which, however, Is compatible with the polyamide oligomer component of the said copolymer and the other of which is compatible with the (co)polymer backbone# to be combined homogeneously»
The graft copolymer may be incorporated in the usual manner into a mixture of thermoplastic resins, in the molten state, in a kneading device. The quantity of copolymer introduced is typically from 0.1 to 30% and preferably from 5 to 15% by weight in relation to the weight of the mixture of thermoplastic resins.
Examples of polymers or tnermoplastic resins which are compatible with the polyamide oligomers forming part of the composition, of the graft copolymer, include:
- aliphatic polyamides such as polyamides 6, 11 or
12, . .
semiaromatic polyamides, for example those defined in French Patents FR 1,588,130, 2,324,672 and 2,575,756, in European Patent EP 53,876, and in Japanese Patents 60,217,237 and 59,015,447.
- block-copolymerised polyetheresteramides or block-copolymerized polyetheramides, for example the products described in US Patents 4,332,920 and 4,331,786.
~ hydrolysed ethylene-vinyl acetate copolymers,
- resins comprising phenolic units such as poly15 para-vinyIphenol.
It is to be understood that the term polymers also includes copolymers to the extent that the content of compatible units of the copolymer is adequate to maintain compatibility.
It is also appropriate to use the term ’polymers™ to include the mixture of polymers, or copolymers, with various additives, for example impact modifiers, inorganic fillers, glass flores, and pigments.
Examples of thermoplastic polymers which are 25 compatible with th© (co)polymer backbone, include ·· polypropylene, polethylene or ethylene-propylene copolymers.
By virtue of th© compatibility agent according to the invention, it is possible to produce improved alloys such as:
Polyamide 6 - polypropylene
Polyamide 6 - polye thylene Polyamide 6 ethylene/propylene copolymer Polyamide 11 or 12 polypropylene or polyethylene or ethylene/propylene copolymer
Hydrolysed ethylene-vinyl acetate copolymer
polypropylene or polyethylene or ethylene/propylene copolymer Polypara-viny Iphenol polypropylene or polyethylene or ethylene/propylene copolymer Block polyetheramide polypropylene or polyethylene or ethylene/propylene copolymer Semiaromatic polyamide - - polypropylene or polyethylene or ethylene/propylene
copolymer
The compatibility caused by the graft copolymer according to the invention is demonstrated by electron microscopy and by the mechanical properties of the product resulting from the mixture of the Incompatible thermo14 plastic polymers.
The morphology of a mixture of thermoplastic polymers without th® graft copolymer according to the invention, examined by electron microscopy, Is generally seen in the form of large nodules of on© polymer surrounded by the matrix formed by the other polymer, the adhesion between the nodules and the matrix being substantially nonexistent. The addition of the graft copolymer causes a significant diminution in the siae of the nodules. A strong adhesion between the visible phases is also observed as the nodules being coated by the matrix. Under these conditions, there is formed what may be called an alloy, by analogy with metallurgical structures, as distinct from simple mixtures»
The mechanical properties of thermoplastic alloys of this kind are at least equal to those of the components, weighted by the volume fraction of each component, and in certain cases greater than those of the two components, for example in impact strength.
In contrast with these alloys according to the invention, simple mixtures of the same mutually incompatible polymers, without the effect of the graft copolymer according to the invention, have mechanical properties which are generally close to those of th® component having the lowest performance.
The following examples further illustrate the invention.
EXAMPLE Is
A. - Synthesis of the graft copolymer backbone X
Into a WERNER extrudert a mixture is continuously introduced which comprises by weight 100 parts of propylene-ethylene block copolymer (containing 12% by weight of ethylene, of melt index = 5, of melting point 163°C), 1.6 parts of maleic anhydride and 1.7 parts of 2,5dimethyl-2,5-di(tert-butylperoxy)hexane dissolved in one part of chlorobenzene.
The mixture is brought to 200°C and the rotational speed of the screw is 100 revolutions/minute.
Devolatilization of the mixture is then carried out before the die entry in order to remove chlorobenzene and the maleic anhydride which has not reacted.
At the die exit, a sample of the graft polymer is taken, which is dissolved in xylene and then precipitated in acetone In order to be purified.
By analysis of the anhydride functions by infrared spectrophotometry, 1.16% by weight of grafted anhydride is determined.
By gel permeation chromatography, it Is determined that the number-average molecular mass is equal to 32,000.
B - Synthesis of.the polyamide olioomer (?)
Into a 100-litre stainless steel reactor, are introduced 31 kg of caprolactam, 0.91 kg of laurylamine and 3.5 litres of water.
Having purged the reactor with nitrogen, it is heated in the closed state for 2 hours at 25Q°C, while stirring at 35 revolutions/minute. The pressure of the atmosphere in the reactor is subsequently reduced over 1 hour.
After the reactor has been swept with nitrogen for 15 minutes, the oligomer is poured into water, centrifuged, washed with water at 80°C then dried for 16 hours in a vacuum oven at 80°C.
In this way, a polyamide oligomer is obtained whose number average molecular mass is 5,700, determined by potentiometric analysis of the terminal amine functional groups.
C - Preparation of the graft copolymer
A mixture comprising by weight 59.8 parts of the graft copolymer backbone described under A and 40.2 parts of the oligomer described under 8 in a WERNBR SSK30 extruder, is kneaded In the molten state.
The mixture is brought to 240°C.
The average residence time of the mixture in the extruder is about 3 minutes.
At the outlet from the extruder, a sample of material is taken which is introduced to an extractor of the KtJM&GAWA type.
In this way the polyamide oligomers which have not reacted with the anhydride functional groups of the malein&ted copolymer ar® selectively extracted with formic acid. 3y this method, a degree of condensation of the polyamide oligomer onto the graft (co)polymer of 55% is determined.
The graft copolymer obtained in this way can be represented by the expressions •^663^136^3.78® 2. «3 in which A is a unit derived from propylene M is a unit derived from ethylene X is a unit derived from maleic anhydride p is an oligomer of caprolactam for which Mn ~ 5700
EXAMPLE 2 s
Into a WERNER extruder is continuously introduced a mixture comprising by weight 33 parts of polypropylene, 57 parts of polyamide 5 and 10 parts of the maleinated copolymer backbone described in Example l.A (SAMPLE 1).
The material temperature along the barrel is between 255 and 270°C. The rotational speed of the screw is 150 revolutions/minute and the output of material is 20 kg/hour.
Under th® same conditions a mixture Is extruded containing by weight 33 parts of polypropylene, 57 parts of polyamide 6 and 10 parts of the graft copolymer described in Example 1. C (SAMPLE 2).
Also under the same conditions# a reference mixture is produced containing (by weight) 36.7 parts of polypropylene and 63.3 parts of polyamide S (SAMPLE 3).
In th© case of the SAMPLES 1„ 2 and 3, the polypropylene used is a propylene homopolymer having a melt index = 3 and a melting point = 166°C, and. the polyamide 6 used is a homopolymer of caprolactam having a melting point - 218°C.
Samples 1, 2 and 3 are injection-moulded in the form of plagues of dimensions 100 I 100 1 3 ram from which are cut the half size ISO test pieces conforming to th® standard NET 51034.
Some test pieces are cut In th® direction of injection flow (TEST PIECES A); others are cut perpendicularly to the direction of injection flow (TEST PIECES
B).
Some test pieces are also moulded from the samples in accordance with th® standard defined by the Institut Frangais du Caoutchouc (TEST PIECES C).
The test pieces A, B and C ar® evaluated by tensile elongation in accordance with the standard NFT
51034.
The test pieces from SAMPLE 3 (reference) are extremely brittle s they break at 5 to 6% elongation j this Indicates a coarse and inhomogeneous morphology as well as a lack of adhesion between, the two components of REFERENCE SAMPLE 3«
The test pieces A, B and C from SAMPLE I behave differently: the test pieces A and B have a more brittle behaviour than test piece C; this corresponds to an inhomogeneity of th® sample as well as a susceptibility to orientation.
In the case of th® three types of test pieces from SAMPLE 2, a homogeneous ductile behaviour is observed s this indicates a good homogeneity in SAMPLE 2 as well as a low susceptibility to transformation and orientation.
SAMPLES 1 and 2 axe also tested for CHARPT impact strength at ambient temperature, after having been injection-moulded Into test pieces.
In th® case of SAMPLE 1, a breakage rate of 60%
Is observed.
In the case of SAMPLE 2, none of the test pieces broke under test.
EXAMPLE 3s
A. Into a WERNER ZSS30 extruder, a mixture is continuously introduced containing by weight 100 parts of an ethylene-propylene block copolymer (containing 12% byweight of ethylene, having a melt index = 5, and a melting point = 163°C), 1.5 parts of maleic anhydride and 1.7 parts of 2,5-dimethy1-2,5-di(tert-butyIperoxy)hexane dissolved In. on® part of chlorobenzene.
The extrusion conditions and purification conditions are identical with those described in Example l.A.
The analysis of the anhydride functional groups by infrared spectrophotometry of a sample of graft copolymer shows that 1.02% by weight of anhydride has been grafted.
The number-average molecular mass M* determined by gel permeation chromatography is 19,700«
B. A monoamine-substituted polyamide oligomer is produced under the same conditions as those described in Example l.B with a ratio by weight of caprolactam to laurylamine equal to 15.7. The number-average molecular mass of the oligomer is 2,800.
C. In a WERNER ZSK30 extruder, there is kneaded in th© molten state, under the same conditions as those described in Example l.C, a mixture comprising by weight 77 parts of the graft copolymer described above and 23 parts of the polyamide oligomer such as previously described.
After the extrusion, the degree of condensation of the oligomer onto the graft copolymer backbone is measured under the same conditions as those described in Example l.C, this being 65.8%.
The graft copolymer obtained in this way can be represented by the expressions
AsOgMg .03-^1.35 in which A represents a unit derived from propylene M represents a unit derived from ethylene X represents a unit derived from maleic anhydride and
P represents a unit derived from an oligomer of caprolactam having Mn = 2,800
EXAMPLE 4s
A mixture comprising by weight 50 parts of polypropylene and 50 parts of hydrolysed ethylene-vinyl acetate copolymer (EVOH) is brought to 220°C and kneaded in the chamber of a SRABENDBR plastograph for 30 minutes with a mixing speed of 50 revolutions /minute (SAMPLE 4).
A mixture comprising by weight 49 parts of polypropylene, 49 parts of EVOH and 2 parts of the maleinated ethylene-propylene copolymer backbone described In Example 3 .A, is kneaded under the same conditions as above (SAMPLE 5).
A mixture is also produced under the same conditions, containing by weight 49 parts of polypropylene, 49 parts of EVOH and 2 parts of the graft copolymer described In Example 3.C (SAMPLE 6).
In the case of SAMPLES 4, 5 and S, the polypropylene used has a melt index equal to 5 and a melting point ©qual to 1SS°C and the EVOH used is such that its ethylene content is 38% (by moles).
SAMPLES 4, 5 and 6 are subsequently examined by scanning electron microscopy (magnification: 2,500 X).
Examination of SAMPLE 4 shows that the two polymers have very little compatibility; very disparate nodules of EVOH are distinguished, the diameter of which varies from 11 to 27 μΆ in the polypropylene matrix; moreover it is observed that the adhesion between these nodules of EVOH and th® polypropylene matrix is very poor.
Examination of SAMPLE 5 shows a morphology which is quite coarse; nodules of SVOH are distinguished having a diameter between 5.7 and 7 whose adhesion to the polypropylene matrix is poor.
Examination of SAMPLE 6 shows a fin® morphology typified by nodules having a diameter of between 1.7 and 2.8 μ» and whose adhesion to the polypropylene matrix is very good.
EXAMPLE 5
A mixture comprising by weight 50 parts of polypropylene and 50 parts of polypara-vinylphenol (PPVP) is brought to 200°C and kneaded in the chamber of a 3RABENDER plastograph for 15 minutes with a mixing speed of 50 revolutions/minute (SAMPLE 7).
A mixture comprising by weight 49 parts of propylene, 49 parts of polypara-vinylphenol and 2 parts of the maleinated ethylene-propylene copolymer described in Example 3 .A, is kneaded under the same conditions as above (SAMPLE 8).
A mixture is also prepared under the same conditions comprising by weight 49 parts of polypropylene, 49 parts of polypara-vinylphenol and 2 parts of the graft copolymer described in example 3. C (SAMPLE 9).
la the case of SAMPLES 7# 8 and 9, the polypropylene used has a melt index equdl to 5 and a melting point equal to 166°C and the polypara-vinylphenol is an oligomer whose weight-average molecular mass Is 4,000 and whose melting point ranges between 160 and 200°C.
SAMPLES 7, 8 and 9 are subsequently examined by scanning electron microscopy (magnifications 2,500 X) Examination of SAMPLE 7 shows a coarse morphology in which localized cocontinuous phases are found or ovoid nodules of PPVP having an average diameter equal to 30 /nn, dispersed in a matrix of PP. The total incompatibility of the two polymers is shown by observing fracture surfaces.
Examination of SAMPLE 8 shows an improved dispersion of the polypara-vinylphenol (PPVP) in the polypropylene- The average size of the nodules of PPVP dispersed in the PP matrix is about 10 μπι. The adhesion between the phases is unimproved In relation to SAMPLE 7.
Examination of SAMPLE 9 shows a fine morphology, typified by nodules of PPVP having an average diameter equal to 2 dispersed in the matrix of PP and whose adhesion to this matrix is greatly improved in relation to that of SAMPLES 7 and 8.
EXAMPLE 6
A mixture comprising by weight 50 parts of polypropylene and 50 parts of polyetheresteramide Is brought to 200°c and kneaded In the chamber of a BRABENDER plastograph for 15 minutes with a stirring speed of 50 revolutions/minute (SAMPLE 10)24
A mixture comprising by weight 49 parts of propylene, 49 parts of polyetheresteramide and 2 parts of the maleinated ethylene-propylene copolymer described in
Example 3.A, is kneaded under the same conditions as above (SAMPLE 11).
A mixture is also produced under the same conditions comprising by weight 49 parts of polypropylene, 49 parts of polyetheresteramide and 2 parts of the graft copolymer described in example 3.C (SAMPLE 12).
In the case of SAMPLES 10, 11 and 12, the polypropylene used has a melt index equal to 5 and a melting point equal to 166°C and the polyetheresteramide is obtained by copolycondensation of ©,w-dicarboxyl-substituted polyamide 12 blocks having Μη β SOO, and e,wdihydroxyl-substituted polytetramethylene glycol blocks having Si ~ 2,000.
SAMPLES 10, 11 and 12 are subsequently examined by scanning electron microscopy (magnification: 2,500 Σ).
Examination of SAMPLE 10 shows a particularly coarse morphology typified by a three-dimensional network.
Examination of SAMPLE 11 does not show any improvement in adhesion, nor any reduction in the sis® of the three-dimensional network in relation to the examination of SAMPLE 10.
When SAMPLE 12 is examined, a less coarse morphology is observed than that of SAMPLES 10 and 11. The morphology of SAMPLE 12 is no longer typified by a threedimensional network but by the dispersion of nodules of polyetheresteramide In a matrix of polypropylene.
EXAMPLE 7
A mixture comprising by weight SO parts of polypropylene and SO parts of amorphous semiaromatic polyamide is brought to 220°C and kneaded In the chamber of a BRABENDER plastograph for 30 minutes at a mixing speed of 50 revolutions/minute (SAMPLE 13).
A mixture comprising by weight 49 parts of polypropylene, 49 parts of amorphous semiaromatic polyamide and 2 parts of the xnaleinated ethylene-propylene copolymer described in Example 3.A, is kneaded under the same conditions as above (SAMPLE 14).
A mixture Is also produced under the same conditions containing by weight 49 parts of polypropylene, 49 parts of amorphous semiaromatic polyamide and 2 parts of the graft copolymer described In example 3.C (SAMPLE 15).
Xn the case of SAMPLES 13, 14 and 15 the poly20 propylene used has a melt index equal to 5 and a melting point equal to 166°C and the amorphous semiaromatic polyamide used is based on terephthalic acid and 2,2,4tr imethvl -1, S -diaminohexane and '2,4,4 - tr imethv 1 -1,6diaminohexane.
SAMPLES 13, 14 and 15 are subsequently examined by scanning electron microscopy (magnification: X 2,500).
Examination of SAMPLE 133 shows an incompatibility between the 2 polymers s nodules of amorphous semiaromatic polyamide ar® distinguished whose average diameter is 30 /un, dispersed in the matrix of polypropylene. Moreover, adhesion between th® nodules of amorphous semiaromatic polyamide and the matrix of PP is non-existant.
SAMPLE 14 lias quite a coarse morphology; nodules of amorphous semiaromatic polyamide having an average diameter equal to 5 pm, are dispersed in the matrix of polypropylene; there is moderate adhesion of the nodules to the matrix.
Examination of SAMPLE IS shows a quite fine morphology characterized by nodules of amorphous semiaromatic polyamide having an average diameter equal to 3.3 /*m and whose adhesion to the matrix of PP is good,
EX^LE_8
A mixture comprising by weight 50 parts of polypropylene and 50 parts of amorphous semiaromatic polyamide is brought to 280°C and kneaded in the chamber of a HAAKE plastograph for 20 minutes with a mixing speed of 50 revolutions/minute (SAMPLE 16).
A mixture comprising by weight 49 parts of polypropylene, 49 parts of amorphous semiaromatic polyamide and 2 parts of the maleinated ethylene-propylene copolymer described in example 3.A, is kneaded under the same conditions aa above (SAMPLE 17).
A mixture is also produced under the same conditions containing by weight 49 parts of polypropylene, 49 parts ox amorphous semiaromatic polyamide and 2 parts of the graft copolymer described in example 3.C (SAMPLE 18).
In the case of SAMPLES 16, 17 and 18 th© polypropylene used has a melt index equal to 5 and a melting point equal to 16S°C; the amorphous semiaromatic polyamide used is based on isophthalic acid, 4,4'-diamino-3,3'dimethyldicyclohexylmethane and lauryllactam.
SAMPLES IS, 17 and 18 are subsequently examined by scanning electron microscopy (magnifications X 2,500).
Examination of SAMPLE 16 shows an incompatibility between th© 2 polymers: nodules of amorphous semiaromatic polyamide are distinguished whose average diameter is
μ®. dispersed in the matrix of polypropylene. Moreover, adhesion between the nodules of amorphous semiaromatic polyamide and the matrix of PP is nonexistent.
Examination of SAMPLE 17 shows a quite coarse morphology: nodules of amorphous semiaromatic polyamide having an average diameter equal to 10 are dispersed In the matrix of polypropylene; there is moderate adhesion of the nodules to th® matrix.
Examination of SAMPLE 18 shows a quite fine morphology characterized by nodules of amorphous semi25 aromatic polyamide having an average diameter equal to
3.5 μ» and whose adhesion to the matrix of polypropylene
Is good.
EXAMPLE 9;
Into a WERNER extruder, a mixture is continuously introduced comprising by weight 26 parts of polypropylene, 67 parts of polyamide S and 7 parts of the maleinated ethylene-propylene copolymer described in example 3-A (SAMPLE IS).
The temperature of the material along the barrel is between 260°C and 290°C. The rotational speed of the screw is 150 revolutions/minute and the output of mater10 ial is 20 kg/hour.
A mixture is extruded under the same conditions comprising by weight 26 parts of polypropylene, 67 parts of polyamide 6 and 7 parts of the graft copolymer described In Example l.C (SAMPLE 20).
A reference mixture is produced, also under the same conditions, containing (by weight) 32.7% of polypropylene and 67.3% of polyamide 6»
In th® case of SAMPLES 19, 20 and 21, the polypropylene used Is a polypropylene homopolymer having a melt index of 12 and a melting point of 166°C, and the polyamide 6 is a homopolymer of caprolactam having a melting point of 218°C.
Samples 19, 20 and 21 are injection-moulded in the form of test pieces having dimensions 127 X 12.7 X
6.4 mm and their IZOD impact strength is evaluated in accordance with ISO standard at 23®C and at 40°C. The results of this evaluation are presented in th® table below.
IS’OD IMPACT STRENGTH C&SZPT & 7 3°C 40°C IS 6 6 20 10.5 13 21 2 3
Claims (22)
1. Graft copolymer of the formula: A.,M b X c P d in which: A a M b represents the (co)polymer backbone, and X c P d represents polymer grafted onto the (co)polymer backbone, and in which A is a unit derived from an a-mono~olefin of 2 to 8 carbon atoms, M is a unit derived from either an α-mono-olefin of
2. To 8 carbon atoms, or two or more said mono-olefins which have been randomly or block-copolymerized, or a monomer which can be polymerized with a said α-mono-olefin, provided that M does not represent a unit derived from a diene, with the units A and M which form the said (co)polymer backbone being formed by random copolymerization or block copolymerization, X is a unit derived from a monomer which can be grafted onto an α-mono-olefin homo- or copolymer and contains a group which is capable of reacting with an amino-group, P is derived from a polyamide oligomer of formula: in which each f is a number from 3 to 11, g is a number from 5 to 80, is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms, Rg is a linear or branched alkyl or alkenyl group containing up to 20 carbon atoms, a cycloaliphatic group, which may or may not be saturated, an aromatic group or a combination of the abovementioned. a is from 0 to 5,000, the sum a + b is from 350 to 45,000, c is a number such that the ratio by weight of the monomer X grafted onto the (co)polymer backbone to the copolymer grafted with X is from 500 ppm to 10%, and d is greater than zero and less than or equal to c. 2, which A is a
3. in which M is
4. . claims 1 to 3
5. . claims 1 to 4
6. claims 1 to 5 Graft copolymer according to claim 1, in unit derived from propylene. Graft copolymer according to claims 1 or a unit derived from ethylene. Graft copolymer according to any one of , in which g is a number from 15 to 55. Graft copolymer according to any one of , in which a is from 350 to 2000. Graft copolymer according to any one of , in which the sum of a -r b is from 500 to 10,000.
7. Graft copolymer according to any one of claims 1 to 6, in which c is a number such that the ratio by weight of the monomer X grafted onto the (co)polymer backbone to the copolymer grafted with X is from 5000 ppm to 2%.
8. Graft copolymer according to any one of claims 1 to 7, in which d is equal to at least 0.3c.
9. Graft copolymer according to any one of claims 1 to 8, in which the monomer from which X is derived has the formula: in which: R^ and R 2 are independently hydrogen, or a linear or branched alkyl chain containing up to 8 carbon atoms, at least one of these being hydrogen, Rg is hydrogen or a linear or branched alkyl group containing up to 10 carbon atoms, and R d is a linear or branched alkenyl group containing up to 12 carbon atoms.
10. A mixture of two or more graft (co)polymers as claimed in any one of claims 1 to 9.
11. Process for producing a graft copolymer as claimed in any one of claims 1 to 10, which comprises; grafting a monomer which can react with an amine functional group onto a (co)polymer backbone, and 5 adding a polyamide oligomer onto the previously grafted copolymer.
12. Process according to claim 11, in which the monomer which reacts with an amine functional group is citraconic anhydride, fumaric acid, mesaconic acid, the 10 anhydride of 3-allyl-succinic acid or maleic anhydride.
13. Process according to claims 11 or 12, in which the polyamide oligomer of formula: -(CH) — 2 2 ΐ -ΝΗ-(CEL) R„ / 3 'S % in which f, g, and Rg are as defined in claims 1 or 4, is 15 obtained by polycondensation of an amino acid of the formula: ΌΗ or by polyaddition of a lactam of formula with f as defined above, in the presence of a monofunctional polymerization regulator of the formula: NE in which R e and R r are as defined in claim 1. 5 δ
14. Process according to claim 13, in which the monomer for the synthesis of the polyamide oligomer is caprolactam, 11-aminoundecanoic acid or dodecalactam.
15. Process according to any one of claims 13 or 14, in which the monofunctional polymerization regulator is either laurylamine or oleylamine.
16. Graft copolymer according to any one of claims 1 to 10 produced by the process of any of claims 11 to 15.
17. Graft copolymer according to claim 1 substantially as described in any of the Examples 1 to 9.
18. An alloy (as hereinbefore defined) of at least two incompatible thermoplastic polymers and a compound described in any one of claims 1 to 10.
19. An alloy according to claim 18, which comprises the graft copolymer according to any one of claims 1 to 10 and one of the following pairs of thermoplastic polymers: aliphatic (co)polyamide - (co)polymer or propylene and/or ethylene, semiaromatic (co)polyamide - (co)polymer of propylene and/or ethylene, block polyether amide (co)polymer of propylene and/or ethylene, vinylphenolic 35 polymer - (co)polymer of propylene and/or ethylene, hydrolysed (ethylene-vinvl acetate) copolymer - (co)polymer of propylene and/or ethylene.
20. An alloy according to claim 19 selected from pairs: Polyamide 6 polypropylene Polyamide 6 polyethylene Polyamide 6 - ethylene/propylene copolymer Polyamide 11 or 12 polypropylene or polyethylene or ethylene/propylene copolymer Hydrolysed ethylene-vinyl acetate copolymer polypropylene or polyethylene or ethylene/propylene copolymer Block polyether amide polypropylene or polyethylene or ethylene/propylene copolymer PolyparavinyIphenol polypropylene or polyethylene or ethylene/propylene copolymer Semiaromatic polyamide polypropylene or polyethylene or ethylene/propylene copolymer
21. An alloy according to any one of claims 18 to 20 which contains from 0.1 to 30% by weight of the graft copolymer as defined in claims 1 to 10 in relation to the weight of the mixture of thermoplastic resins.
22. An alloy according to claim 21, in which the weight of the graft copolymer is from 5 to 15%.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8803877A FR2629090B1 (en) | 1988-03-24 | 1988-03-24 | GRAFT COPOLYMER BASED ON ALPHA-MONO-OLEFIN, ITS MANUFACTURING PROCESS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE890945L IE890945L (en) | 1989-09-24 |
| IE72214B1 true IE72214B1 (en) | 1997-04-09 |
Family
ID=9364609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE94589A IE72214B1 (en) | 1988-03-24 | 1989-03-23 | New alpha-mono-olefin based graft copolymer |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0342066A1 (en) |
| JP (1) | JP2577334B2 (en) |
| KR (1) | KR940007026B1 (en) |
| CN (2) | CN1032219C (en) |
| AU (1) | AU630600B2 (en) |
| CA (1) | CA1332252C (en) |
| DE (1) | DE3909273C2 (en) |
| DK (1) | DK143189A (en) |
| FI (1) | FI96618C (en) |
| FR (1) | FR2629090B1 (en) |
| IE (1) | IE72214B1 (en) |
| NL (1) | NL8900661A (en) |
| NO (1) | NO173739C (en) |
| PT (1) | PT90079A (en) |
| ZA (1) | ZA892223B (en) |
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| CN116355139A (en) * | 2023-02-28 | 2023-06-30 | 杭州师范大学 | Modified polypropylene with adjustable grafting, crosslinking and degradation, preparation method and application thereof |
| CN116444984A (en) * | 2023-05-15 | 2023-07-18 | 链行走新材料科技(广州)有限公司 | Functionalized low-temperature heat sealing material and application thereof |
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| JPS507636B1 (en) * | 1970-09-12 | 1975-03-27 | ||
| DE2245957A1 (en) * | 1972-09-19 | 1974-03-28 | Basf Ag | THERMOPLASTIC MOLDING COMPOUNDS AND LAMINATES |
| JPS569925B2 (en) * | 1974-06-19 | 1981-03-04 | ||
| JPS51125466A (en) * | 1974-11-13 | 1976-11-01 | Du Pont | Process for preparing graftcopolymer |
| US3963799A (en) * | 1974-11-13 | 1976-06-15 | E. I. Du Pont De Nemours And Company | Graft copolymer in polyamide polyethylene blends |
| JPS5247052A (en) * | 1975-10-13 | 1977-04-14 | Mitsubishi Chem Ind Ltd | Thermoplastic resin compositions |
| JPS5286242A (en) * | 1976-01-12 | 1977-07-18 | Hitachi Shipbuilding Eng Co | Muddy water shield facing breaking detector |
| US4225476A (en) * | 1976-05-14 | 1980-09-30 | E. I. Du Pont De Nemours And Company | Adhesive blend of wood rosin and thermoplastic graft copolymer |
| US4154646A (en) * | 1977-07-22 | 1979-05-15 | Hercules Incorporated | Preparation of hydrophilic styrene maleic anhydride copolymer fibers for use in papermaking |
| US4154647A (en) * | 1977-07-27 | 1979-05-15 | Hercules Incorporated | Preparation of hydrophilic polyolefin fibers for use in papermaking |
| JPS5432557A (en) * | 1977-08-17 | 1979-03-09 | Cosmo Co Ltd | Stabilized polypropylene resin composition |
| JPS5847421A (en) * | 1981-09-16 | 1983-03-19 | 小林 博行 | Horn fishing hook |
| JPS58122950A (en) * | 1982-01-19 | 1983-07-21 | Idemitsu Kosan Co Ltd | Polypropylene composition having improved rigidity |
| JPS59197459A (en) * | 1983-04-26 | 1984-11-09 | Ube Ind Ltd | Production of polyamide composition |
| US4537929A (en) * | 1984-01-20 | 1985-08-27 | Plastic Specialties And Technologies, Inc. | High impact nylon composition |
| JPS60233131A (en) * | 1984-05-04 | 1985-11-19 | Toagosei Chem Ind Co Ltd | Modifier for polyolefinic resin |
| JPS61152782A (en) * | 1984-12-27 | 1986-07-11 | Ube Ind Ltd | Polyamide adhesive composition and laminate |
| DE3507657A1 (en) * | 1985-03-05 | 1986-09-11 | Hüls AG, 4370 Marl | COLD IMPACT TOE, THERMOPLASTICALLY PROCESSABLE MOLDS |
| JPS62241946A (en) * | 1986-04-14 | 1987-10-22 | Tonen Sekiyukagaku Kk | Thermoplastic resin composition |
-
1988
- 1988-03-24 FR FR8803877A patent/FR2629090B1/en not_active Expired - Lifetime
-
1989
- 1989-03-09 EP EP19890400658 patent/EP0342066A1/en not_active Ceased
- 1989-03-13 NO NO891061A patent/NO173739C/en unknown
- 1989-03-17 NL NL8900661A patent/NL8900661A/en active Search and Examination
- 1989-03-21 DE DE3909273A patent/DE3909273C2/en not_active Expired - Lifetime
- 1989-03-22 DK DK143189A patent/DK143189A/en not_active Application Discontinuation
- 1989-03-22 CA CA000594464A patent/CA1332252C/en not_active Expired - Fee Related
- 1989-03-22 PT PT90079A patent/PT90079A/en not_active Application Discontinuation
- 1989-03-23 IE IE94589A patent/IE72214B1/en not_active IP Right Cessation
- 1989-03-23 CN CN89101611A patent/CN1032219C/en not_active Expired - Lifetime
- 1989-03-23 AU AU31708/89A patent/AU630600B2/en not_active Ceased
- 1989-03-23 FI FI891424A patent/FI96618C/en not_active IP Right Cessation
- 1989-03-23 ZA ZA892223A patent/ZA892223B/en unknown
- 1989-03-24 KR KR1019890003755A patent/KR940007026B1/en not_active IP Right Cessation
- 1989-03-24 JP JP1073711A patent/JP2577334B2/en not_active Expired - Lifetime
-
1995
- 1995-07-21 CN CN95109008A patent/CN1061059C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036586A (en) | 1989-10-25 |
| PT90079A (en) | 1989-11-10 |
| KR890014600A (en) | 1989-10-24 |
| EP0342066A1 (en) | 1989-11-15 |
| FR2629090B1 (en) | 1990-11-23 |
| NO173739C (en) | 1994-01-26 |
| KR940007026B1 (en) | 1994-08-03 |
| FI96618C (en) | 1996-07-25 |
| AU3170889A (en) | 1989-09-28 |
| JP2577334B2 (en) | 1997-01-29 |
| FI891424A0 (en) | 1989-03-23 |
| ZA892223B (en) | 1989-11-29 |
| FI96618B (en) | 1996-04-15 |
| FR2629090A1 (en) | 1989-09-29 |
| FI891424A (en) | 1989-09-25 |
| NL8900661A (en) | 1989-10-16 |
| NO891061L (en) | 1989-09-25 |
| IE890945L (en) | 1989-09-24 |
| CN1121088A (en) | 1996-04-24 |
| DK143189A (en) | 1989-09-25 |
| DE3909273C2 (en) | 2001-02-15 |
| CA1332252C (en) | 1994-10-04 |
| CN1032219C (en) | 1996-07-03 |
| DE3909273A1 (en) | 1989-10-05 |
| JPH01284524A (en) | 1989-11-15 |
| CN1061059C (en) | 2001-01-24 |
| NO173739B (en) | 1993-10-18 |
| NO891061D0 (en) | 1989-03-13 |
| AU630600B2 (en) | 1992-11-05 |
| DK143189D0 (en) | 1989-03-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |