AU630600B2 - New alpha-mono-olefin based graft copolymer - Google Patents

New alpha-mono-olefin based graft copolymer Download PDF

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AU630600B2
AU630600B2 AU31708/89A AU3170889A AU630600B2 AU 630600 B2 AU630600 B2 AU 630600B2 AU 31708/89 A AU31708/89 A AU 31708/89A AU 3170889 A AU3170889 A AU 3170889A AU 630600 B2 AU630600 B2 AU 630600B2
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ethylene
graft copolymer
copolymer
polyamide
propylene
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Patrick Abadie
Michel Glotin
Roland Parsy
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Arkema France SA
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Atochem SA
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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)

Description

:i I- I 9'.
S F Ref: 90313 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
Class Int Class Class Int Class FOR OFFICE USE: Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name and Address S' of Applicant: Atochem La Defense 10, 4 8 Cours Michelet 92800 Puteaux
FRANCE
Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Address for Service: t Complete Specification for the invention entitled: Newa -Mono-olefin Based Graft Copolymer The following statement is a full description of best method of performing it known to me/us this invention, including the 5845/5 -1 !i
ABSTRACT
O(-MONO-OLEFIN BASED GRAFT COPOLYMER The invention relates to a graft copolymer comprising at least one monoamino-substituted polyamide oligomer and an 3-mono-olefin polymer or copolymer grafted with a monomer which can react with the amine functional group of the oligomer. It is produced by free-radical grafting of the monomer and then by addition of the oligomer. The invention also relates to the use of this graft copolymer as a compatability agent for at least two mutually incompatible thermoplastic polymers for the production of alloys.
e e* la NEW a-MONO-OLEFIN BASED GRAFT COPOLYMER The present invention relates to an a-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.
5 It is known how to make two incompatible polymers I compatible, in certain specific mixtures, by combining them with a third polymer, which is partially compatible with both i of the polymers.
i Thus, for example, various third polymers have been proposed for a polypropylene/polyamide mixture: i In Japanese Patent No. 70-030943, a composition i comprising polypropylene, polyamide and polypropylene grafted I 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 w 2 propylene and a-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.
In 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 a-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 .20 derived from c-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.
-3- 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 a-mono-olefin polymer or copolymer.
The copolymer according to the invention comprises a graft copolymer represented by the expression A,MbXP, 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 a-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 a-mono-olefin containing from 2 to 8 carbon atoms, and preferably derived from S. ethylene, units derived from several a-mono-olefins as previously defined, which may be merely mixed together or may Sbe randomly copolymerized or block-copolymerized, and one of i these a-mono-olefins is preferably ethylene, units derived from a monomer which can be polymerized with one of the a-mono-olefins as previously 25 defined, for example an alkyl acrylate, provided that M does not represent a unit derived from a diene, 1 Q^ ,~z 'Ii the units A and M which form the said (co)polymer backbone are randomly copolymerized or block-copolymerized or are simply mixtures, X is a unit derived from a monomer which can be grafted by a free-radical mechanism onto an a-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: a, a *0 a.
0 R II 1 H N_(CH )?fC NH-(CB 2 -C g N 2 2E 2 9I .R6 in which f is a number from 3 to 11, g is a number from 5 to 80 and preferably from 15 to 15 Rs is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms,
R
6 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 _re numbers which correspond to the following definitions: a is from 0 to 5,000-and preferably from 350 to 2,-000.
5 The sum a b is from 350 to 45,000 and preferably from 500 to 10,000.
c is selected in such a way 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 preferably less than and more preferably from 5,000 ppm to most preferably from 5,000 ppm to 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: AMb in which a, b, A and M are as previously defined, means any polymer composed of A and M units derived from monomers which have been randomly polymerized 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 i carried out in accordance with known processes.
I: 20 For example, propylene and an a-olefin may be copolymerized in the presence of a Ziegler catalyst or a coordination catalyst.
The graft copolymer according to the invention can 6 be obtained by free-radical grafting onto the (co)polymer 25 backbone of a monomer which can react with an amine functional group and then by addition of the oligomer onto the previously grafted (co)polymer.
I I Ir I 'A 6 The 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: R 0 R
R
S/
2 R 0 H /0 R /3 OH C 2 0R in which: RI and R 2 are either hydrogen, or a linear or branched alkyl chain containing upto 8 carbon atoms, with at 10 least one of these symbols representing hydrogen,
R
3 is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms, R4 is a linear or branched alkenyl group containing 2 to 12 carbon atoms.
The preferred monomers X are citraconic anhydride, fumaric acid, mesaconic acid, the anhydride of 3allylsuccinic acid and, most preferably maleic anhydride.
The grafting of the monomer X onto the (co)polymer backbone carried out by a free-radical mechanism, takes place in the presence of a free-radical initiator which may be dicumyl peroxide, benzoyl peroxide or 9* 7 Normally the initiator is used in a proportion of x 10 4 to 4 x 10-2 in relation to the weight of the (co)polymer.
The free-radical grafting of the 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 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 2000C, and preferably from 110 to 1400C.
The technique of free-radical grafting of the monomer X onto the (co)polymer backbone in the molten state is particularly useful when a degree of 8 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 2500C, and preferably from 180 to 2000C.
The average residence time of the molten material in the extruder is normally selected from 15 seconds .0 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, V.
V
V
1 of formula: 0 0 R U 1 /5 H2N -(CR 2 -(CH2- fc
N
R R 6 in which f, g, R, and R 6 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: H N -(CR2) C
OH
9 or by polyaddition of a lactam of formula: (CH 2 f H 0 in which f has the meaning previously given, in the presence of a monofunctional polymerization regulator of the formula:
R
'NH
in which R5 and R. have the meaning previously given.
S: The amino acid or lactam monomers preferred for S* the synthesis of the monoamino-substituted oligomer *I ii 1 0 of the invention are caprolactum, 11-aminounderanoic i acid and dodecalactam.
l The preferred monofunctional polymerization regulators are laurylamine and oleylamine.
J The polycondensation defined above can be carried out in accordance with conventionally known processes, for example at a temperature generally of from 200 to i 300°C, under vacuum or in an ine atmosphere, with j 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 the monofunctional polymerization regulator.
-i
C
I
10 To calculate the average chain length, one molecule of chain regulator is normally counted for each oligomer chain.
The addition of the monoamino-substituted polyamine 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 one anhydride or acid functional group of the 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 0.
S* and the (co)polymer at a temperature generally of from 230 to 250 0 C in an extruder. The average residence time *:15 of the molten material in the extruder may be from .0 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 20 of the free polyamide oligomers, that is to say those which have not reacted to form the final graft copolymer.
The a-mono-olefin graft copolymers according to the invention have the following advantages over the t ird polymers referred to in the prior art.
It is possible to control the degree of grafting of the polyamide oligomer onto the graft (co)polymer and thus to have more complete control of the structure j a a..
a a. pC a 11 of the graft copolymer.
It is possible to adjust and control the average molecular mass of 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 20 (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.
9 a. a a a .a *a a a. a 9
SI
12 Examples of polymers or tnermoplastic resins which are compatible with the polyamide oligomers forming part of the composition of the graft copolymer, include: aliphatic polyam- ,es such as polyamides 6, 11 or 12, c .Rc.
C
SR CR
C
CR..
C C R C 4 C* Re *C C 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 6,),217,237 and 59,015,447.
10 block-copolymerized 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 poly- 15 para-vinylphenol.
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.
20 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 fiores, and pigments.
Examples of thermoplastic polymers which are compatible with the (co)polymer backbone, includepolypropylene, polethylene or Cc Sc CR r rR S
CR
Cc 1 13 r a r S* to a. S St ethylene-propylene copolymers.
By virtue of the compatibility agent according to the invention, it is possible to produce improved alloys such as: 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 Polypara-vinylphenol polypropylene or polyethylene or ethylene/propylene copolymer Block polyetheramide polypropylene or polyethylene or ethylene/propylene 20 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 thermo- ,S *S 5
S
AS 4
S
S.
L a 14 J S.
B. S B 0e 0
I
plastic polymers.
The morphology of a mixture of thermoplastic polymers without the graft copolymer according to the invention, examined by electron microscopy, is generally seen in the form of large nodules of one 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 size 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.
20 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 the component having the lowest performance.
The following examples further illustrate the 4* 55 *r I
S
*4 S d SB S BC invention.
s 15 EXAMPLE 1: A. Synthesis of the graft copolymer backbone X Into a WERNER extruder, 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 0
C),
1.6 parts of maleic anhydride and 1.7 parts of dissolved in one part of chlorobenzene.
10 The mixture is brought to 200 0 C and the rotational .4 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 an- 20 hydride is determined.
S
By gel permeation chromatography, it is determined that the number-average molecular mass is equal to 32,000.
B Synthesis of the polyamide oligomer (P) Into a 100-litre stainless steel reactor, are introduced 31 kg of caprolactam, 0.91 kg of laurylamine and 3.5 litres of water.
16 Having purged the reactor with nitrogen, it is heated in the closed state for 2 hours at 250°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 0 C then dried for 16 hours in a vacuum oven at 80 0
C.
In this way, a polyamide oligomer is obtained ooto eo whose number average molecular mass is 5,700, determined by potentiometric analysis of the terminal amine functional groups.
C Preparation of the graft copolymer 15 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 B in a WERNER extruder, is kneaded in the molten state.
The mixture is brought to 240 0
C.
20 The average residence time of the mixture in the i 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 KUMAGAWA type.
In this way the polyamide oligomers which have not reacted with the anhydride functional groups of the maleinated copolymer are selectively extracted with 17 formic acid. By this method, a degree of condensation of the polyamide oligomer onto the graft (co)polymer of is determined.
The graft copolymer obtained in this way can be represented by the expression: As 6 3
M
1 3 6 X3.78P2.45 in which A is a unit derived from propylene M is a unit derived from ethylene X is a unit derived from maleic anhydride 10 P is an oligomer of caprolactam for which Mn 5700 EXAMPLE 2: Into a WERNER extruder is continuously introduced a mixture comprising by weight 33 parts of polypropylene, 57 parts of polyamide 6 and 10 parts of the maleinated copolymer backbone described in Example 1.A (SAMPLE 1).
The material temperature along the barrel is between 255 and 270 0 C. The rotational speed of the screw is 150 revolutions/minute and the output of material is 20 kg/hour.
Under the 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 6 (SAMPLE 3).
i il l i i-i i ii-;i i~ii ii ri,;uL~ 18 In the 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 0 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 plaques of dimensions 100 X 100 X 3 mm from which are cut the half size ISO test pieces conforming to the standard NFT 51034.
Some test pieces are cut in the direction of injection flow (TEST PIECES others are cut perpendicularly to the direction of injection flow (TEST PIECES
B).
Some test pieces are also moulded from the 15 samples in accordance with the standard defined by the Institut FrangaiS du Caoutchouc (TEST PIECES C).
The test pieces A, B and C are evaluated by tensile elongation in accordance with the standard NFT 51034.
20 The test pieces from SAMPLE 3 (reference) are extremely brittle: they break at 5 to 6% elongation; this inLdicates 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 1 behave differently: the test pieces A and B have a more brittle behaviour than test piece C; this corresponds to an -19inhomogeneity of the sample as well as a susceptibility to orientation.
In the case of the three types of test pieces from SAMPLE 2, a homogeneous ductile behaviour is observed: this indicates a good homogeneity in SAMPLE 2 as well as a low susceptibility to transformation and orientation.
SAMPLES 1 and 2 are also tested for CHARPY impact strength at ambient temperature, after having been 10 injection-moulded into test pieces.
In the case of SAMPLE 1, a breakage rate of is observed.
In the case of SAMPLE 2, none of the test pieces broke under test.
EXAMPLE 3: A. Into a WERNER ZSK30 extruder, a mixture is continuously introduced containing by weight 100 parts of an ethylene-propylene block copolymer (containing 12% by weight of ethylene, having a melt index 5, and a 20 melting point 163 1.5 parts of maleic anhydride and S. 1.7 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane dissolved in one 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 1: 20 been grafted.
The number-average molecular mass M, determined by gel permeation chromatography is 19,700.
B. A monoamino-substituted polyamide oligomer is produced under the same conditions as those described in Example 1.B with a ratio by weight of caprolactam to laurylamine equal to 15.7. The number-average molecular mass M of the oligomer is 2,800.
C. In a WERNER ZSK30 extruder, there is kneaded 10 in the 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.
15 After the extrusion, the degree of condensation of the oligomer onto the graft copolymer backbone is Smeasured under the same conditions as those described in Example 1.C, this being 65.8%.
The graft copolymer obtained in this way can be 20 represented by the expression:
A
409 sM 4 X2.
05 P1.
3 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 21 EXAMPLE 4: A mixture comprising by weight 50 parts of polypropylene and 50 parts of hydrolysed ethylene-vinyl acetate copolymer (EVOH) is brought to 220 0 C and kneaded in the chamber of a BRABENDER 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 des- 10 cribed in Example 3.A, is kneaded under the same conditions as above (SAMPLE 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).
I In the case of SAMPLES 4, 5 and 6, the polypropylene used has a melt index equal to 5 and a melting point equal to 166 0 C and the EVOH used is such that its ethylene content is 38% (by moles).
20 SAMPLES 4, 5 and 6 are subsequently examined by i 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 um in the polypropylene matrix; moreover it is observed that the adhesion between these nodules of EVOH and the polypropylene matrix is very _9_L1Y^ I i 22 poor.
Examination of SAMPLE 5 shows a morphology which is quite coarse; nodules of EVOH are distinguished having a diameter between 5.7 and 7 pm, whose adhesion to the polypropylene matrix is poor.
Examination of SAMPLE 6 shows a fine morphology typified by nodules having a diameter of between 1.7 and 2.8 pm and whose adhesion to the polypropylene matrix is very good.
EXAMPLE A mixture comprising by weight 50 parts of polypropylene and 50 parts of polypara-vinylphenol (PPVP) Sis brought to 200 0 C and kneaded in the chamber of a S BRABENDER 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 1 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).
In the case of SAMPLES 7, 8 and 9, the polypropylene used has a melt index equal to 5 and a melting point equal fo 166 0 C and the polypara-vinylphenol is an oligomer -23whose weight-average molecular mass is 4,000 and whose melting point ranges between 160 and 200 0
C.
SAMPLES 7, 8 and 9 are subsequently examined by scanning electron microscopy (magnification: 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 pm, dispersed in a matrix of PP. The total incompatibility of the two polymers is shown by observing frac- 10 ture surfaces.
Examination of SAMPLE 8 shows an improved dispersion of the polypara-vinylphenol (PPVP) in the polypropy- I lene. The average size of the nodules of PPVP dispersed in the PP matrix is about 10 pm. 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 pm, dispersed in the matrix of PP and whose adhesion to this matrix is greatly improved in relation 20 to that of SAMPLES 7 and 8.
1: EXAMPLE 6 A mixture comprising by weight 50 parts of polypropylene and 50 parts of polyetheresteramide is brought to 200 0 c and kneaded in the chamber of a BRABENDER plastograph for 15 minutes with a stirring speed of revolutions/minute (SAMPLE 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 Sparts of polyetheresteramide and 2 parts of the graft s copolymer described in example 3.C (SAMPLE 12).
10 In the case of SAMPLES 10, 11 and 12, the poly- I "propylene used has a melt index equal to 5 and a melting I point equal to 166 0 C and the polyetheresteramide is obtained by copolycondensation of a,w-dicarboxyl-substituted polyamide 12 blocks having Mn 600, and a,wdihydroxyl-substituted polytetramethylene glycol blocks having Mn 2,000.
SAMPLES 10, 11 and 12 are subsequently examined by scanning electron microscopy (magnification: 2,500 X).
Examination of SAMPLE 10 shows a particularly 20 coarse morphology typified by a three-dimensional network.
Examination of SAMPLE 11 does not show any improvement in adhesion, nor any reduction in the size of the three-dimensional network in relation to the examination of SAMPLE When SAMPLE 12 is examined, a less coarse morphology is observed than that of SAMPLES 10 and 11. The -L I' 1;- 25 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 50 parts of polypropylene and 50 parts of amorphous semiaromatic polyamide is brought to 220 0 C and kneaded in the chamber of a BRABENDER plastograph for 30 minutes at a mixing speed of 50 revolutions/minute (SAMPLE 13).
10 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 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 In the case of SAMPLES 13, 14 and 15 the poly- 20 propylene used has a melt index equal to 5 and a melting "j point equal to 166 0 C and the amorphous semiaromatic polyamide used is based on terephthalic acid and 2,2,4trimethyl-1,6-diaminohexane and "2,4,4-trimethyl-1,6diaminohexane.
SAMPLES 13, 14 and 15 are subsequently examined by scanning electron microscopy (magnification: X 2,500).
i 26 Examination of SAMPLE 133 shows an incompatibility between the 2 polymers: nodules of amorphous semiaromatic polyamide are distinguished whose average diameter is 30 Am, dispersed in the matrix of polypropylene. Moreover, adhesion between the nodules of amorphous semiaromatic polyamide and the matrix of PP is non-existant.
SAMPLE 14 has quite a coarse morphology; nodules of amorphous semiaromatic polyamide having an average 10 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 15 shows a quite fine morphology characterized by nodules of amorphous semiaromatic polyamide having an average diameter equal to S* 3.3 pm and whose adhesion to the matrix of PP is good.
EXAMPLE 8 A mixture comprising by weight 50 parts of polypropylene and 50 parts of amorphous semiaromatic 20 polyamide is brought to 280 0 C and kneaded in the chamber I. 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 as above (SAMPLE 17).
L I qyl~ 27 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 18).
In the case of SAMPLES 16, 17 and 18 the polypropylene used has a melt index equal to 5 and a melting point equal to 166 0 C; the amorphous semiaromatic polyamide used is based on isophthalic acid, 4,4'-diamino-3,3'- 1 dimethyldicyclohexylmethane and lauryllactam.
I 10 SAMPLES 16, 17 and 18 are subsequently examined S. by scanning electron microscopy (magnification: X 2,500).
Examination of SAMPLE 16 shows an incompatibility between the 2 polymers: nodules of amorphous semiaromatic polyamide are distinguished whose average diameter is 20 Am dispersed in the matrix of polypropylene. Moreover, adhesion between the nodules of amorphous semiaromatic polyamide and the matrix of PP is nonexistant.
I Examination of SAMPLE 17 shows a quite coarse morphology: nodules of amorphous semiaromatic polyamide I 20 having an average diameter equal to 10 lm are dispersed in the matrix of polypropylene; there is moderate adi hesion of the nodules to the matrix.
Examination of SAMPLE 18 shows a quite fine morphology characterized by nodules of amorphous semiaromatic polyamide having an average diameter equal to Am and whose adhesion to the matrix of polypropylene is good.
L 1l 28 EXAMPLE 9: Into a WERNER extruder, a mixture is continuously introduced comprising by weight 26 parts of polypropylene, 67 parts of polyamide 6 and 7 parts of the maleinated ethylene-propylene copolymer described in example 3-A (SAMPLE 19).
The temperature of the material along the barrel is between 260°C and 290 0 C. The rotational speed of the S* screw is 150 revolutions/minute and the output of material 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 1.C (SAMPLE 15 A reference mixture is produced, also under the same conditions, containing (by weight) 32.7% of poly- I propylene and 67.3% of polyamide 6.
In the case of SAMPLES 19, 20 and 21, the polypropylene used is a polypropylene homopolymer having a 20 melt index of 12 and a melting point of 166 0 C, and the polyamide 6 is a homopolymer of caprolactam having a melting point of 218 0
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 0 C and at 40 0 C. The results of this evaluation are presented in the table 29 below.
IZOD IMPACT STRENGTH
SAMPLE
5 23 0 C 40 0
C
19 6 9 10.5 13 21 2 3 *t

Claims (17)

  1. 2. Graft copolymer according to claim 1, in which A is a unit derived from propylene.
  2. 3. Graft copolymer according to claims 1 or 2, in which M is a unit derived from ethylene.
  3. 4. Graft copolymer according to any one of claims 1 to 3, in which g is a number from 15 to Graft copolymer according to any one of claims 1 to 4, in which a is from 350 to 2000.
  4. 6. Graft copolymer according to any one of claims 1 to 5, in which the sum of a b is from 500 to 'A W- 32 10,000.
  5. 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%.
  6. 8. Graft copolymer according to claim 7, 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
  7. 9. Graft copolymer according to any one of claims 1 to 8, in which d is equal to at least 0.3c. Graft copolymer according to any one of claims 1 to 9, in which the monomer from which X is derived has the formula: u e 10 2 II R 2 S RcC 7 /oir \C O cl c a 0 1 C-~14 15 in which: RI 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, R 3 is hydrogen or a linear or branched alkyl group containing up to 10 carbon atoms, and -L 33 R 4 is a linear or branched alkenyl group containing 2 to 12 carbon atoms.
  8. 11. A mixture of two or more graft (co)polymers as claimed in any one of claims 1 to
  9. 12. Process for producing a graft copolymer as claimed in any one of claims 1 to 11, which comprises: free radical grafting a monomer which can react with an amine functional group onto a (co)polymer AMb backbone, and adding a polyamide oligomer onto the previously -grafted copolymer.
  10. 13. Process according to claim 12, in which the monomer which reacts with an amine functional group is citraconic anhydride, fumaric acid, mesaconic acid, the anhydride of 3-allyl-succinic acid or maleic anhydride.
  11. 14. Process according to claims 12 or 13, in which the polyamide oligomer of formula: r n h c g in which R 5 and R6 are as defined in claim 1 or 4, is obtained by polycondensation of an amino acid of the formula: 0 i 2N- (C 2) Cy- 0 or by polyaddition of a lactam of formula I i I _il 34 N--C R 0 with f as defined above, in the presence of a mono-functional polymerization regulator of the formula: R 6 in which R, and R, are as defined in claim 1. Process according to claim 14, in which the monomer for the synthesis of the polyamide oligomer is caprolactam, 11-aminoundecanoic acid or dodecalactam.
  12. 16. Process according to claim 14 or 15, in which the monofunctional polymerization regulator is either laurylamine or oleylamine. i 10 17. Graft copolymer according to any one of claims 1 to 11 produced by the process of any of claims 12 to 16.
  13. 18. Graft copolymer according to claim 1 substantially as described in any of the Examples 1 to 9. 15 19. An alloy of at least two incompatible thermoplastic polymers and a copolymer as claimed in any one of claims 1 to 11.
  14. 20. An alloy according to claim 19, which comprises the graft copolymer according to any one of claims 20 1 to 11 and one of the following pairs of thermoplastic polymers: aliphatic (co)polyamide (co)polymer of propylene and/or ethylene, semiaromatic (co)polyamide (co)polymer of 1' S ,ocm> 35 propylene and/or ethylene, block polyether amide (co)polymer of propylene and/or ethylene, vinylphenolic polymer (co)polymer of propylene and/or ethylene, hydrolysed (ethylene-vinyl acetate) copolymer (co)polymer of propylene and/or ethylene.
  15. 21. An alloy according to claim 20 wherein the pair of thermoplastic polymers is 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 Polyparavinylphenol polypropylene or polyethylene or ethylene/propylene copolymer 20 Semiaromatic polyamide polypropylene or polyethylene or ethylene/propylene copolymer
  16. 22. An alloy according to any one of claims 19 to 21 which contains from 0.1 to 30% by weight of the graft copolymer as defined in claims 1 to 11 in relation to the 25 weight of the mixture of thermoplastic resins.
  17. 23. An alloy according to claim 22, in which the weight of the graft copolymer is from 5 to -L 36 DATED this TWENTY SECOND day of MARCH 1989 Atochern Patent Attorneys for the Applicant SPRUSON FERGUSON *6 00 00so 0000 00 S. S 00 00 0 00 00 00 0 0 S E~S Al 0 0 00 0 o 00 0 06
AU31708/89A 1988-03-24 1989-03-23 New alpha-mono-olefin based graft copolymer Ceased AU630600B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8803877 1988-03-24
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

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AU3170889A AU3170889A (en) 1989-09-28
AU630600B2 true AU630600B2 (en) 1992-11-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US10605385B2 (en) 2013-02-18 2020-03-31 Arkema France Use of semi-aromatic copolyamide for transporting refrigerant fluid

Families Citing this family (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2628115B1 (en) * 1988-03-04 1990-07-13 Atochem COMPOSITION FOR MAKING COMPATIBLE WITH AT LEAST TWO INCOMPATIBLE THERMOPLASTIC POLYMERS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED
FR2651785B1 (en) * 1989-09-14 1991-12-06 Atochem ALLOYS BASED ON A VINYL ALCOHOL ETHYLENE COPOLYMER WITH GAS BARRIER PROPERTY, THERMOFORMABLE AND / OR RESISTANT TO REPEATED BENDING.
CA2033642A1 (en) * 1990-01-11 1991-07-12 Dilip R. Abayasekara Graft polymers of epsilon-caprolactam
FR2657070A1 (en) * 1990-01-15 1991-07-19 Atochem BARRIER FILM COMPRISING AN ALLOY BASED ON A VINYL ETHYLENE ALCOHOL COPOLYMER, ITS PREPARATION AND PARTICULAR USE IN PACKAGING
US5274030A (en) * 1990-01-15 1993-12-28 Atochem Hot water/superheated steam-resistance EVOH barrier films
JP2828300B2 (en) * 1990-02-01 1998-11-25 日本合成化学工業株式会社 Ethylene-vinyl acetate copolymer saponified composition having improved properties and use thereof
JP2892487B2 (en) * 1990-10-29 1999-05-17 日本合成化学工業株式会社 Polyolefin resin composition and use thereof
US5214090A (en) * 1990-02-01 1993-05-25 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Resin composition and use thereof
US5278229A (en) * 1990-02-01 1994-01-11 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Polyolefin composition and the use thereof
JP2860129B2 (en) * 1990-02-01 1999-02-24 日本合成化学工業株式会社 Manufacturing method of molded products with excellent impact resistance
JP2865352B2 (en) * 1990-02-01 1999-03-08 日本合成化学工業株式会社 Saponified ethylene-vinyl acetate copolymer composition and use thereof
US5177138A (en) * 1990-02-01 1993-01-05 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Resin composition including a saponified ethylene-vinyl acetate copolymer, polyolefin, a graft copolymer and hydrotalcite
US5280065A (en) * 1990-02-01 1994-01-18 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Saponified ethylene-vinyl acetate copolymer composition and the use thereof
US5298334A (en) * 1990-02-01 1994-03-29 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Saponified ethylene-vinyl acetate copolymer composition and the use thereof
JP2865353B2 (en) * 1990-02-01 1999-03-08 日本合成化学工業株式会社 Polyolefin resin composition and use thereof
US5160475A (en) * 1990-02-01 1992-11-03 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Method of producing shaped articles having excellent impact resistance
US5419861A (en) * 1990-02-15 1995-05-30 Elf Aquitaine Production Method for improving the paintability of objects fashioned from polyamide and polyolefin blends
FR2658115B1 (en) * 1990-02-15 1992-05-07 Elf Aquitaine PROCESS FOR IMPROVING THE ABILITY TO PAINT SHAPED OBJECTS FROM POLYAMIDE / POLYOLEFIN ALLOYS.
EP0506515B1 (en) * 1991-03-29 1996-08-14 Elf Atochem S.A. Polyamide/polyolefine blend release film for the production of sheet moulding compound and sheet moulding compound produced with such film
JP3063864B2 (en) * 1991-06-24 2000-07-12 日本合成化学工業株式会社 Process for producing saponified ethylene-vinyl acetate copolymer molded article
FR2697465A1 (en) * 1992-10-30 1994-05-06 Atochem Elf Sa Laminates based on polyamide / polyolefin alloys and coextrusion binders, objects obtained therefrom, coating methods therewith.
DE69419998T2 (en) * 1993-10-12 1999-12-02 Atochem Elf Sa Polyamide / polyolefin blend article with seam
FR2726345B1 (en) 1994-11-02 1996-12-27 Atochem Elf Sa POLYAMIDE AND POLYETHYLENE TUBES FOR DOMESTIC GAS DISTRIBUTION
FR2727124B1 (en) 1994-11-22 1996-12-20 Atochem Elf Sa POLYAMIDE-BASED FLEXIBLE TRANSLUCENT COMPOSITION, PROCESS FOR CONVERTING SAME, AND ARTICLES OBTAINED THEREFROM
EP0731308B1 (en) 1995-03-09 1999-04-14 Elf Atochem S.A. Polyamid based tubes for the transport of fuel
FR2731497B1 (en) 1995-03-10 1997-04-30 Atochem Elf Sa TUBE FOR TRANSPORTING DRINKING WATER
EP0766913B1 (en) * 1995-10-05 2001-01-03 Atofina Method for treating soils by fumigation
EP0780594A1 (en) 1995-12-21 1997-06-25 Elf Atochem S.A. Antistatic belts
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WO2000058403A1 (en) * 1999-03-31 2000-10-05 Atofina Polyamide and polypropylene mixtures and injected parts produced with said mixtures
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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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963799A (en) * 1974-11-13 1976-06-15 E. I. Du Pont De Nemours And Company Graft copolymer in polyamide polyethylene blends
GB1440030A (en) * 1972-09-19 1976-06-23 Basf Ag Promoting mixing or adhesion of incompatible thermoplastic polymers
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

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS507636B1 (en) * 1970-09-12 1975-03-27
JPS569925B2 (en) * 1974-06-19 1981-03-04
JPS51125466A (en) * 1974-11-13 1976-11-01 Du Pont Process for preparing graftcopolymer
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
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1440030A (en) * 1972-09-19 1976-06-23 Basf Ag Promoting mixing or adhesion of incompatible thermoplastic polymers
US3963799A (en) * 1974-11-13 1976-06-15 E. I. Du Pont De Nemours And Company Graft copolymer in polyamide polyethylene blends
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10023695B2 (en) 2013-02-18 2018-07-17 Arkema France Thermoplastic structure for transporting refrigerant fluid
US10605385B2 (en) 2013-02-18 2020-03-31 Arkema France Use of semi-aromatic copolyamide for transporting refrigerant fluid
US10914409B2 (en) 2013-02-18 2021-02-09 Arkema France Use of semi-aromatic copolyamide for transporting refrigerant fluid
US11209105B2 (en) 2013-02-18 2021-12-28 Arkema France Use of semi-aromatic copolyamide for transporting refrigerant fluid

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NO891061D0 (en) 1989-03-13
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JP2577334B2 (en) 1997-01-29
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FR2629090A1 (en) 1989-09-29
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JPH01284524A (en) 1989-11-15
PT90079A (en) 1989-11-10
CN1036586A (en) 1989-10-25
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AU3170889A (en) 1989-09-28
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NO173739C (en) 1994-01-26

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