CA1203035A - Polyamide moulding compositions - Google Patents
Polyamide moulding compositionsInfo
- Publication number
- CA1203035A CA1203035A CA000396031A CA396031A CA1203035A CA 1203035 A CA1203035 A CA 1203035A CA 000396031 A CA000396031 A CA 000396031A CA 396031 A CA396031 A CA 396031A CA 1203035 A CA1203035 A CA 1203035A
- Authority
- CA
- Canada
- Prior art keywords
- graft
- weight
- composition
- polyamide
- plasticiser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- 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)
Abstract
Polyamide moulding compositions ABSTRACT OF THE DISCLOSURE
Thermoplastic moulding compositions comprising I) 30 - 94 % by weight, based on the total moulding composition, of at least one polyamide, II) 70 - 3 % by weight, based on the total moulding composition, of a graft product prepared from cross-linked optionally substituted butadiene and as graft monomer ester of (meth)acrylic acid and optionally styrene and (meth)acrylonitrile and III) 20 - 3 % by weight based on the total moulding com-position, of a low molecular weight plasticiser.
Thermoplastic moulding compositions comprising I) 30 - 94 % by weight, based on the total moulding composition, of at least one polyamide, II) 70 - 3 % by weight, based on the total moulding composition, of a graft product prepared from cross-linked optionally substituted butadiene and as graft monomer ester of (meth)acrylic acid and optionally styrene and (meth)acrylonitrile and III) 20 - 3 % by weight based on the total moulding com-position, of a low molecular weight plasticiser.
Description
~33l:~3~
Polyamide Moulding Compositions This invention relates to thermopla~tic moulding com-positions obtained from polyamides, a polydiene-based yraft product and plasticisers, which are distlnguished by great toughness, excellent flexibility, resistance to alternating brea]~ing strength and durable surface characteristics.
It has already been disclosed in German Offenlegungs-schrift No. 2,7~2,176 that the impact strength and notched impact strength of polyamides can be increased by adding graft polymers of cross-linked polybutadienes and grafted (meth)acrylic acid ester units. Although these moulding compositions are very tough, they are unsuitable for certain purposes, e.g. for use in shoe soles and tubes~ because they do not always have the required elastic properties.
It is known that these properties may be improved by the addition of plasticisers. The usual low molecular weight plasti-cisexs diffuse relatively rapidly ~o the surface of moulded poly-amide products so that these products in time become brittle and they become unsightly owing to the deposition of plasticiser.
It has now surprisingly been found that if a plasticiser conventionally used for polyamides is added -to the polyamides which are modified with -the above mentioned graft polymers, not only a marked improvement in the elastic properties is obtained, in particular the reversible stretchability and resistance to alternating breaking strength, but the gloss and surface characteristics of the moulded products obtained can be preserved substantially unchanged even under prolonged storage.
~7 ~2~ 5 The present invention therefore provides a thermoplastic moulding composition comprising 30~94% by weight of at least one polyamide, 7-3% by weight o~ at leas-t one graft copolymer prepared from 50-95% by weight of a cross-linked butadiene polymer as graft substrate, 5-50% by weight of an ester of acrylic or methacrylic acid as graft monomer wherein the gel content of the graft sub-strate is ~ 70%, determined in toluene, the graft yield is ~ 0.15 and the average particle diameter of the graft copolymer is ~ 0.1 ~m; 20-3% by weight of a plasticiser for polyamide.
The polyamides used may be an~ thermoplastic polyamides, partially crystalline polyamides being preferred. The partially crystalline polyamides used for the moulding compositions accord-ing to the invention may be polyamide-6, polyamide-6,6 and copolymers of these two componentsO Partially crystalline poly-amides in which the acid component consists partially or com-pletely of terephthalic acid and/or isophthalic acid and/or suberic acid and/or sebacic ~2~
aci~ and/or azelaic acid and/or adipic acid and/or cyclohexanedicarboxylic acid, and the diamine component consists par-tially or comple-tely of m- and/or p-xylylene diamine and/or hexamethylene diamine and/or 2,2,~-trirnethyl-hexamethylene diamine and/or 2,~ trimethyl-hexamethylene diamine and/or isophorone diamine are also suitable;
the composition of these polyamides is known in the art.
Polyamides prepared partially or completely from lactams having 7 to 12 C-atoms, optionally with the addition of one or more of the abo~e mentioned starting components, should also be mentioned.
PGlyamide-6 and polyamide-6,6 are particularly pre-ferred partially crystalline pclyamides.
The polyamides should preferably have a relative vis-cosity ~determined on a 1~ by weight solution in m-cresol at 25C) of 2.0 to 5.0, most preferably from 2.5 to 4.5.
'l'he graft substrate used for the prep~ration of the graft products may consist of cross-linked diene rubbers of poly-butadiene and/or polyisoprene which may contain up to 40% by weight of styrene and/or acrylonitrile as comonomers.
The gel content of the polymers used as graft substrate be ~, 70% by weight and is preferably 7~ 80% by weight (determined in toluene).
The preferred graft substrate is a cross-linke~
polybutadiene.
The graft monomers used for the purpose o~ this invention include acrylonitrile, styrene, methacrylonitrile and aliphatic esters of acrylic acid and methacrylic acid having up to 22 C-atoms. Esters of acrylic and meth-acrylic acid are preferred graft monomers. Among the esters of acrylic and methacrylic acid, the methyl, ethyl, n-butyl, tert.-butyl, octyl and ethylhexyl esters are particularly preferred.
The graft products according to the invention may be prepared by any known polymerisation methods (emulsion, solution, bulk, suspension or precipitation polymer-Le A~20 753 .~
3L2~30;~5 isation) or by combinations of these me-thods.
To prepare the graft products, the monomer which is to be grafted is polymerised in the presence o~ -the previously formed graft substrate. Usually, some free homopolymer is formed in addi-tion to the graft polymer. The term graft products is used to de-note the sum of graft copolymers and free polymers. The quantity of the grafted monomer and its molecular weight may be influenced within wide limits by variation of the polymerisation conditions.
These include mainly the nature of the polymerisation process, the temperature, the activator system, the molecular weight regulators, the conditions of stirring and the method of addition of the monomer. According -to the inven-tion, the graft yield G should be ~ 0.15, preferably G ~ 0.40. The graft yield G is the proportion of grafted monomer to the total quantity of monomer in the graft-ing composi-tion and is dimensionless.
Emulsion polymerisation is the preferred method of poly-merisation for the graft polymers according to the invention4 The substances used as graft substrate for the preparation of graft products by emulsion polymerisation may be cross-linked butadiene polymers preferably obtained by emulsion polymerisation.
Accordi.ng to the invention, it is preferred to use graft products which have an "average particle diameter" d50 of 0.2 -to 0.6 ~m, preferably 0.3 to 0.5 ~m, in particular about 0.4 llm, (for deter-mination of this diameter, see W. Scholtan and H. Lange, Kolloid-Z.
and Z. Polymere 250 (1972) 782-796 of G. Kampf, H. Schuster~ Angew.
Makromolekulare Chemie _ (1970) pp.lll-129).
Instead of using only one graft substrate, mixtures of var-~0~
..b~
33~3Sa~a -ious graft substrates may be used for the preparation of graft pro-ducts. Furthermore, instead of mixirly the polyamides with only one graft product, they may be mixed with a mixture of several graft products according to the invention having different constituents.
The moulding compositions according to the invention are most preferably prepared from graft products obtained from a) 70-95% by weigh-t, preferably 75-90% by weight, of a cross-linked polymer oE butadiene and/or substituted butadiene as graft substrate consisting o~ at least 95% by weight of substituted or unsubstituted buta-diene units, and b) 5--3Q% by weight, preferably 10-25% by weight, of methyl methacrylate as graft monomer, wherein the gel content of the graEt substrate should be ~ 70% by weight, preferably ~80% by weight, measured in toluene, the graft yield G should be ?, 0.15, preferably ~ ~.40, and the average particle diameter of the graft copolymer should be 0.2 to 0.6 ~m, preferably 0~3 to 0.5 ~m, in particular about 0.4 ~
The plasticisers may be any of the usual, preferably low molecular weight compounds used for polyamides, in particular any substances which are capable of lowering the freezing point of the polyamides without altering the chemical nature of the polyamide macromoleculesO These include the ~ollowing substances or classes of substances:
Aromatic hydroxyl compounds, e.g. pwhydrGxybenzoic acid-
Polyamide Moulding Compositions This invention relates to thermopla~tic moulding com-positions obtained from polyamides, a polydiene-based yraft product and plasticisers, which are distlnguished by great toughness, excellent flexibility, resistance to alternating brea]~ing strength and durable surface characteristics.
It has already been disclosed in German Offenlegungs-schrift No. 2,7~2,176 that the impact strength and notched impact strength of polyamides can be increased by adding graft polymers of cross-linked polybutadienes and grafted (meth)acrylic acid ester units. Although these moulding compositions are very tough, they are unsuitable for certain purposes, e.g. for use in shoe soles and tubes~ because they do not always have the required elastic properties.
It is known that these properties may be improved by the addition of plasticisers. The usual low molecular weight plasti-cisexs diffuse relatively rapidly ~o the surface of moulded poly-amide products so that these products in time become brittle and they become unsightly owing to the deposition of plasticiser.
It has now surprisingly been found that if a plasticiser conventionally used for polyamides is added -to the polyamides which are modified with -the above mentioned graft polymers, not only a marked improvement in the elastic properties is obtained, in particular the reversible stretchability and resistance to alternating breaking strength, but the gloss and surface characteristics of the moulded products obtained can be preserved substantially unchanged even under prolonged storage.
~7 ~2~ 5 The present invention therefore provides a thermoplastic moulding composition comprising 30~94% by weight of at least one polyamide, 7-3% by weight o~ at leas-t one graft copolymer prepared from 50-95% by weight of a cross-linked butadiene polymer as graft substrate, 5-50% by weight of an ester of acrylic or methacrylic acid as graft monomer wherein the gel content of the graft sub-strate is ~ 70%, determined in toluene, the graft yield is ~ 0.15 and the average particle diameter of the graft copolymer is ~ 0.1 ~m; 20-3% by weight of a plasticiser for polyamide.
The polyamides used may be an~ thermoplastic polyamides, partially crystalline polyamides being preferred. The partially crystalline polyamides used for the moulding compositions accord-ing to the invention may be polyamide-6, polyamide-6,6 and copolymers of these two componentsO Partially crystalline poly-amides in which the acid component consists partially or com-pletely of terephthalic acid and/or isophthalic acid and/or suberic acid and/or sebacic ~2~
aci~ and/or azelaic acid and/or adipic acid and/or cyclohexanedicarboxylic acid, and the diamine component consists par-tially or comple-tely of m- and/or p-xylylene diamine and/or hexamethylene diamine and/or 2,2,~-trirnethyl-hexamethylene diamine and/or 2,~ trimethyl-hexamethylene diamine and/or isophorone diamine are also suitable;
the composition of these polyamides is known in the art.
Polyamides prepared partially or completely from lactams having 7 to 12 C-atoms, optionally with the addition of one or more of the abo~e mentioned starting components, should also be mentioned.
PGlyamide-6 and polyamide-6,6 are particularly pre-ferred partially crystalline pclyamides.
The polyamides should preferably have a relative vis-cosity ~determined on a 1~ by weight solution in m-cresol at 25C) of 2.0 to 5.0, most preferably from 2.5 to 4.5.
'l'he graft substrate used for the prep~ration of the graft products may consist of cross-linked diene rubbers of poly-butadiene and/or polyisoprene which may contain up to 40% by weight of styrene and/or acrylonitrile as comonomers.
The gel content of the polymers used as graft substrate be ~, 70% by weight and is preferably 7~ 80% by weight (determined in toluene).
The preferred graft substrate is a cross-linke~
polybutadiene.
The graft monomers used for the purpose o~ this invention include acrylonitrile, styrene, methacrylonitrile and aliphatic esters of acrylic acid and methacrylic acid having up to 22 C-atoms. Esters of acrylic and meth-acrylic acid are preferred graft monomers. Among the esters of acrylic and methacrylic acid, the methyl, ethyl, n-butyl, tert.-butyl, octyl and ethylhexyl esters are particularly preferred.
The graft products according to the invention may be prepared by any known polymerisation methods (emulsion, solution, bulk, suspension or precipitation polymer-Le A~20 753 .~
3L2~30;~5 isation) or by combinations of these me-thods.
To prepare the graft products, the monomer which is to be grafted is polymerised in the presence o~ -the previously formed graft substrate. Usually, some free homopolymer is formed in addi-tion to the graft polymer. The term graft products is used to de-note the sum of graft copolymers and free polymers. The quantity of the grafted monomer and its molecular weight may be influenced within wide limits by variation of the polymerisation conditions.
These include mainly the nature of the polymerisation process, the temperature, the activator system, the molecular weight regulators, the conditions of stirring and the method of addition of the monomer. According -to the inven-tion, the graft yield G should be ~ 0.15, preferably G ~ 0.40. The graft yield G is the proportion of grafted monomer to the total quantity of monomer in the graft-ing composi-tion and is dimensionless.
Emulsion polymerisation is the preferred method of poly-merisation for the graft polymers according to the invention4 The substances used as graft substrate for the preparation of graft products by emulsion polymerisation may be cross-linked butadiene polymers preferably obtained by emulsion polymerisation.
Accordi.ng to the invention, it is preferred to use graft products which have an "average particle diameter" d50 of 0.2 -to 0.6 ~m, preferably 0.3 to 0.5 ~m, in particular about 0.4 llm, (for deter-mination of this diameter, see W. Scholtan and H. Lange, Kolloid-Z.
and Z. Polymere 250 (1972) 782-796 of G. Kampf, H. Schuster~ Angew.
Makromolekulare Chemie _ (1970) pp.lll-129).
Instead of using only one graft substrate, mixtures of var-~0~
..b~
33~3Sa~a -ious graft substrates may be used for the preparation of graft pro-ducts. Furthermore, instead of mixirly the polyamides with only one graft product, they may be mixed with a mixture of several graft products according to the invention having different constituents.
The moulding compositions according to the invention are most preferably prepared from graft products obtained from a) 70-95% by weigh-t, preferably 75-90% by weight, of a cross-linked polymer oE butadiene and/or substituted butadiene as graft substrate consisting o~ at least 95% by weight of substituted or unsubstituted buta-diene units, and b) 5--3Q% by weight, preferably 10-25% by weight, of methyl methacrylate as graft monomer, wherein the gel content of the graEt substrate should be ~ 70% by weight, preferably ~80% by weight, measured in toluene, the graft yield G should be ?, 0.15, preferably ~ ~.40, and the average particle diameter of the graft copolymer should be 0.2 to 0.6 ~m, preferably 0~3 to 0.5 ~m, in particular about 0.4 ~
The plasticisers may be any of the usual, preferably low molecular weight compounds used for polyamides, in particular any substances which are capable of lowering the freezing point of the polyamides without altering the chemical nature of the polyamide macromoleculesO These include the ~ollowing substances or classes of substances:
Aromatic hydroxyl compounds, e.g. pwhydrGxybenzoic acid-
2-ethyihexyl esters, dihydroxybenzoic acid esters~ phenols and aromatic hydroxyaldehydes; aromatic sulphonamides, e.g. benzene sulphonic acid-N-monoethyl amide, benzene sulphonic acid-N-butyl amide, toluene sulphonic acid amide, toluene sulphonic acid ethyl amide and N~cyclohexyl-p-toluene sulphonamide, phthalic acid esters, e.g~ di-iso~
propyl-phthalate, di-tert.-butyl-phthalate, di-2~ethy1-hexyl-phthalate, di-isononyl-phthalate, and di-isononyl poly-triethylene glycol-phthalate; lactams, -caProlactam, laurin lactam; lactones; reaction products of hydroxycarboxylic acids and aIkylene oxides, acryl cyc]~h~n~1, abietyl ~lc~hnl,-te~rahydro-Le A 20 753 ~Z~3~)3~
furfuryl alcohol-carboxylic acid esters, pentane triol and its esters.
Suitable plasticisers for the purpose of this invention also include alkylsulphvnic acid esters prepared from alkyl sulphochlorides containing 1 to 4, preferably 1 to 2 S02 Cl groups statistically or uniformly distributed over the hydrocarbon chain, and phenols.
Suitable phenols include monophenols, e~g. derivatives of phenyl, diphenyl and naphthyl r and bisphenGls such as hydroquinone, resorcinol, dihydroxydiphenyl, bis-(hydroxy-phenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-~hydroxyphenyl)~sulphides, bis~(hydroxyphenyl)-ethers t bis-(hydroxyphenyl)~sulphonides and bis-(hydroxyphenyl)-sulphone.
The following are examples of suitable sulphonic acid esters:
(C12-C18)-alkyl-sulphonic acid-p-phenylesters, (C12-C18) alkyl di-(sulphonic acid-p-phenylesters), (C12-C18)-alkyl-sulphonic acid-p-phenyl-octyl esters, 0 (C12-C18)-alkyl-sulphonic acid-p~hydroxybenzoic acid-isobutylesters, 2,2-bis-((C12-C18)-alkylsulphonic acid-4-phenylester)-propane and 2~2-bis-((C12-C18)-alkylsulphonic acid 3,5-dichloro-4-phenylester)-propaneO
The plasticisers added to the mouldins compositions according to the invention are preferably aromatic sulph~n~Ps an~ lac~ams.
Preparation of the polyamide moulding compositions according to the invention may be carried out in the usual mixing apparatus such as rollers, kneaders or single shaft or multi-shaft extruders. Double shaft extruders are particularlysuitable.
The moulding compositions may be prepared on the above mentioned mixing apparatus by melting the three components I,II and III together and homogenizing them or by incorp~
orating the graft product II in the melt of the polyamide Le A 20 753 ~33~3S
I containing plasticiser ~(III) or by incorporating the plasticiser III in the molte:n mixture of polyamide I and graft product III.
The moulding compositions according to the invention may contain the usual additives such as lubricants and mould release agents, nucleating agents, stabilisers, flame protective agents and dyes. The additives are preferably added in the pure form or as concentrates when compounding the mixture.
The moulding compositions according to the invention are particularly suitable for the manufacture of shoe soles, seals or tubes by virtue Gf their excellent elastic properties.
Le ~ 20 753
propyl-phthalate, di-tert.-butyl-phthalate, di-2~ethy1-hexyl-phthalate, di-isononyl-phthalate, and di-isononyl poly-triethylene glycol-phthalate; lactams, -caProlactam, laurin lactam; lactones; reaction products of hydroxycarboxylic acids and aIkylene oxides, acryl cyc]~h~n~1, abietyl ~lc~hnl,-te~rahydro-Le A 20 753 ~Z~3~)3~
furfuryl alcohol-carboxylic acid esters, pentane triol and its esters.
Suitable plasticisers for the purpose of this invention also include alkylsulphvnic acid esters prepared from alkyl sulphochlorides containing 1 to 4, preferably 1 to 2 S02 Cl groups statistically or uniformly distributed over the hydrocarbon chain, and phenols.
Suitable phenols include monophenols, e~g. derivatives of phenyl, diphenyl and naphthyl r and bisphenGls such as hydroquinone, resorcinol, dihydroxydiphenyl, bis-(hydroxy-phenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-~hydroxyphenyl)~sulphides, bis~(hydroxyphenyl)-ethers t bis-(hydroxyphenyl)~sulphonides and bis-(hydroxyphenyl)-sulphone.
The following are examples of suitable sulphonic acid esters:
(C12-C18)-alkyl-sulphonic acid-p-phenylesters, (C12-C18) alkyl di-(sulphonic acid-p-phenylesters), (C12-C18)-alkyl-sulphonic acid-p-phenyl-octyl esters, 0 (C12-C18)-alkyl-sulphonic acid-p~hydroxybenzoic acid-isobutylesters, 2,2-bis-((C12-C18)-alkylsulphonic acid-4-phenylester)-propane and 2~2-bis-((C12-C18)-alkylsulphonic acid 3,5-dichloro-4-phenylester)-propaneO
The plasticisers added to the mouldins compositions according to the invention are preferably aromatic sulph~n~Ps an~ lac~ams.
Preparation of the polyamide moulding compositions according to the invention may be carried out in the usual mixing apparatus such as rollers, kneaders or single shaft or multi-shaft extruders. Double shaft extruders are particularlysuitable.
The moulding compositions may be prepared on the above mentioned mixing apparatus by melting the three components I,II and III together and homogenizing them or by incorp~
orating the graft product II in the melt of the polyamide Le A 20 753 ~33~3S
I containing plasticiser ~(III) or by incorporating the plasticiser III in the molte:n mixture of polyamide I and graft product III.
The moulding compositions according to the invention may contain the usual additives such as lubricants and mould release agents, nucleating agents, stabilisers, flame protective agents and dyes. The additives are preferably added in the pure form or as concentrates when compounding the mixture.
The moulding compositions according to the invention are particularly suitable for the manufacture of shoe soles, seals or tubes by virtue Gf their excellent elastic properties.
Le ~ 20 753
3~:~3~
Examples Preparation Gf the qraft product A solution o~ 80 parts by weight of sal-t-free water, 1.5 parts by w~ight of the sodium salt of disproportion~
ated abietic acid and 0.3 parts by weight o~ potassium peroxydisulphate is introduced into a pressure resis-tant stirrer vessel. Af-ter the air has been displaced by nitrogen and the reaction temperature adjusted to 55C, 0.35 parts by weight of dodecylmercaptan and x par-ts by weight of butadiene are added and the reaction mixture is polymerised~ As the reaction velocity falls with pro-gressive polymerisation, the temperature is slow]y raised to 68C~
When polymerisation has been terrninated, small quan~
~ities of unreacted butadiene are removed by stirring the resulting latex at reduced pressure.
175 parts by weight of water freed from salt and 0.3 parts by weight of potassium peroxydis~llphate are added.
Ater displacement of the air by nitroge~ and heating to 65Ct 2 parts by weight of emulsifier (sodium salt of disproportionated abietic acid or alkyl sulphonates~
dissolved in 25 parts by weight of water and y parts by weight of the monomers indicated in Table 1 are added.
The reactants are run in over a period of about 4 hours~
Stirring is then continued for a further 2 hours at 65C
to complete the reaction.
The graft product latex obtained as described above is coagulated with 2~ MgS04/acetic acid solution (mixed in proportions of 1~1 parts by weight) after the addition of 1 part by weight of a phenolic antioxidant (2,6-di-tert.-butyl~p-cresol), and the coagulate is separated off, washed free from salt and dried under vacuum at 70 C.
The composition of the graft products is entered in Table 1.
Le A 20 753 ~.
Table 1: Composition of graft products t~
~D
o Type Parts by weight Parts by weight of Average particle ~ o~ butadiene graft monomer dianeter ~m Ul X ~
A 80 20 n-B~/t-B~ 0.4 (8:2 (72/28) 0.4 C 80 20 MMA 0.4 D 60 40 MMA 0.4 n-BA = n-butyl acrylate t-BA = tert.butyl acrylate S = styrene AN = acrylonitrile M~A~ = methyl methacrylate Examples 1 19 Preparation of the moulding compositions Incorporation of yraft products A - D in the polyamide is carried out in a commercial continuously operatin~
double shaft extruder ZSK 32 oE Werner ~ Pfleiderer in which the po]yamide has previously been mel-ted at temper-atures of 270 to 290C.
The graft product is fed into the polyamide melt from a second ~ee~ tube, preferably under an atmosphere of nitrogen. The graft product becomes homogeneously distributed in the molten polyamide. The plasticiser is measured into the homogenised melt of polyamide and graft polymer from a separate pipe, using a metering pump.
It may be advantageous to degasify the melt before its exit from the nozzleO The cylinder temperatures are adjusted to ensure a reaction temperature of 270 to 290 C.
The mol~en strand of mixture of polyamide, graft product and plasticiser is cooled in water, granulated and dried.
Migration of plasticiser is determined on this granulate by measuring the weight losses after storage in water (24 hours at 60C3. The results are shown in Table 3.
The granulate was also used to extrude standard test rods 5according to DIN 53 453), flak rods (according to DIN 53 453) and tensile bars (according to DIN 53 455) from a conventional ejection moulding machine at 260C.
The standard test rods were used to test the notched impact strength ak 25 C (according to DIN 53 453), the flat rods were used to determine the resistance to alternating folding (on the basis of DIN 53 359) and the tensile bars were used to determine the relative reversible elongation (according to DIN 53 455).
The composition and properties of the moulding compositions are shown in Table 2 an~ 3.
Le A 20 753 3~
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t~ I o Il) ~ ~ !1.
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~ op ~1 ~~1~J r-l ~--1 r-l ~1 1-l rn a) H ~ H
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a oP ~ D 0 , 'C
--I a) r~ a~ a~ r~ r~ rJ~ rJ~ ~ r~ rs~ rJ~ a~ rJ~ O O
O S~ , O
P~ ~ rf) r~ ~ r~7 r~ r~ ~ r~7 r~) ~ r~ r~ ~7 r~) r~
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r:n O
a OOOOOOOOOOOOOOOr~l~,,c ~:4 0~ r~ r~ r~ r ~ ~ r~ r L~ r~) ~ r~
a rJ~ ~ rn C U
rr~ a S~ ~ E ~ ~ ~
~ m c~ a ~ m c~ a o ~o o u c) ~ L ; r~ a ~ ~ _ C
a) al ~ r~ Q
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X ~3 # # # ~ o --I r~l rY~ ~ _ ~ H
E~ ~ 0 ,~ rJ~ ~ ~ H * H
Lr~ A 20 753 Table 3: ~xperiments to determine plasticiser migration t~
O Ex- Graft product Polyamide Plasticiser Quantity Plasticiser ample Type ~ by wt. Type ~ % by wt. migrated content rel ~ by wt. Type after 5 after 10 days/~ by days/~ by weight weight 17*) - - PA-6 3.95 90 I 10 2~8 3.1 18*3 ~ ~ PA-6 3.95 90 II 10 1.6 1.9 I C
12 C 40 PA-6 3.95 50 I 10 1.6 1.95~i 13 C 30 PA 6 3.95 60 I 10 1.8 2.1 19 C 40 PA-6 3.95 50 II 10 0.57 0.95 ~:,
Examples Preparation Gf the qraft product A solution o~ 80 parts by weight of sal-t-free water, 1.5 parts by w~ight of the sodium salt of disproportion~
ated abietic acid and 0.3 parts by weight o~ potassium peroxydisulphate is introduced into a pressure resis-tant stirrer vessel. Af-ter the air has been displaced by nitrogen and the reaction temperature adjusted to 55C, 0.35 parts by weight of dodecylmercaptan and x par-ts by weight of butadiene are added and the reaction mixture is polymerised~ As the reaction velocity falls with pro-gressive polymerisation, the temperature is slow]y raised to 68C~
When polymerisation has been terrninated, small quan~
~ities of unreacted butadiene are removed by stirring the resulting latex at reduced pressure.
175 parts by weight of water freed from salt and 0.3 parts by weight of potassium peroxydis~llphate are added.
Ater displacement of the air by nitroge~ and heating to 65Ct 2 parts by weight of emulsifier (sodium salt of disproportionated abietic acid or alkyl sulphonates~
dissolved in 25 parts by weight of water and y parts by weight of the monomers indicated in Table 1 are added.
The reactants are run in over a period of about 4 hours~
Stirring is then continued for a further 2 hours at 65C
to complete the reaction.
The graft product latex obtained as described above is coagulated with 2~ MgS04/acetic acid solution (mixed in proportions of 1~1 parts by weight) after the addition of 1 part by weight of a phenolic antioxidant (2,6-di-tert.-butyl~p-cresol), and the coagulate is separated off, washed free from salt and dried under vacuum at 70 C.
The composition of the graft products is entered in Table 1.
Le A 20 753 ~.
Table 1: Composition of graft products t~
~D
o Type Parts by weight Parts by weight of Average particle ~ o~ butadiene graft monomer dianeter ~m Ul X ~
A 80 20 n-B~/t-B~ 0.4 (8:2 (72/28) 0.4 C 80 20 MMA 0.4 D 60 40 MMA 0.4 n-BA = n-butyl acrylate t-BA = tert.butyl acrylate S = styrene AN = acrylonitrile M~A~ = methyl methacrylate Examples 1 19 Preparation of the moulding compositions Incorporation of yraft products A - D in the polyamide is carried out in a commercial continuously operatin~
double shaft extruder ZSK 32 oE Werner ~ Pfleiderer in which the po]yamide has previously been mel-ted at temper-atures of 270 to 290C.
The graft product is fed into the polyamide melt from a second ~ee~ tube, preferably under an atmosphere of nitrogen. The graft product becomes homogeneously distributed in the molten polyamide. The plasticiser is measured into the homogenised melt of polyamide and graft polymer from a separate pipe, using a metering pump.
It may be advantageous to degasify the melt before its exit from the nozzleO The cylinder temperatures are adjusted to ensure a reaction temperature of 270 to 290 C.
The mol~en strand of mixture of polyamide, graft product and plasticiser is cooled in water, granulated and dried.
Migration of plasticiser is determined on this granulate by measuring the weight losses after storage in water (24 hours at 60C3. The results are shown in Table 3.
The granulate was also used to extrude standard test rods 5according to DIN 53 453), flak rods (according to DIN 53 453) and tensile bars (according to DIN 53 455) from a conventional ejection moulding machine at 260C.
The standard test rods were used to test the notched impact strength ak 25 C (according to DIN 53 453), the flat rods were used to determine the resistance to alternating folding (on the basis of DIN 53 359) and the tensile bars were used to determine the relative reversible elongation (according to DIN 53 455).
The composition and properties of the moulding compositions are shown in Table 2 an~ 3.
Le A 20 753 3~
;, ~ C~
,) lli 1) 0 J -I (~) a) ~
t~ I o Il) ~ ~ !1.
~r OOOOOOOOOOOOOOOO
U ~ C ) O O O O O O O L ) O 1~) 0 0 0 0 0 U~) " ~ n ~ ~ ~ ~ ~' a~
s U Q
' OOOOOOOOOOOOOO~O
~ op ~1 ~~1~J r-l ~--1 r-l ~1 1-l rn a) H ~ H
H H H H I I I I H I I H I H H
' ' rC
O O O O O O O O O O O O O O ~ l~
a oP ~ D 0 , 'C
--I a) r~ a~ a~ r~ r~ rJ~ rJ~ ~ r~ rs~ rJ~ a~ rJ~ O O
O S~ , O
P~ ~ rf) r~ ~ r~7 r~ r~ ~ r~7 r~) ~ r~ r~ ~7 r~) r~
r ~
r:n O
a OOOOOOOOOOOOOOOr~l~,,c ~:4 0~ r~ r~ r~ r ~ ~ r~ r L~ r~) ~ r~
a rJ~ ~ rn C U
rr~ a S~ ~ E ~ ~ ~
~ m c~ a ~ m c~ a o ~o o u c) ~ L ; r~ a ~ ~ _ C
a) al ~ r~ Q
R I ~ ~ *
X ~3 # # # ~ o --I r~l rY~ ~ _ ~ H
E~ ~ 0 ,~ rJ~ ~ ~ H * H
Lr~ A 20 753 Table 3: ~xperiments to determine plasticiser migration t~
O Ex- Graft product Polyamide Plasticiser Quantity Plasticiser ample Type ~ by wt. Type ~ % by wt. migrated content rel ~ by wt. Type after 5 after 10 days/~ by days/~ by weight weight 17*) - - PA-6 3.95 90 I 10 2~8 3.1 18*3 ~ ~ PA-6 3.95 90 II 10 1.6 1.9 I C
12 C 40 PA-6 3.95 50 I 10 1.6 1.95~i 13 C 30 PA 6 3.95 60 I 10 1.8 2.1 19 C 40 PA-6 3.95 50 II 10 0.57 0.95 ~:,
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A thermoplastic moulding composition comprising I) 30-94% by weight of at least one polyamide II) 70-3% by weight of at least one graft copolymer prepared from a) 50-95% by weight of a cross-linked butadiene polymer as graft substrate b) 5-50% by weight of an ester of acrylic or methacrylic acid as graft monomer wherein the gel content of the graft sub-strate is ? 70%, determined in toluene, the graft yield is ? 0.15 and the average particle diameter of the graft copolymer is ?
0.1µm;
III) 20-3% by weight of a plasticiser for polyamide.
0.1µm;
III) 20-3% by weight of a plasticiser for polyamide.
2. A composition as claimed in claim 1, comprising 50 to 90%
by weight of component I, 50 to 5% by weight of component II and 15 to 5% by weight of component III.
by weight of component I, 50 to 5% by weight of component II and 15 to 5% by weight of component III.
3. A composition as claimed in claim 1, wherein the graft product is prepared from 70 to 90% by weight of component (a) and 30 to 10% by weight of component (b).
4. A composition as claimed in claim 1, wherein the gel content of the graft substrate is ?80%, the graft yield is ? 0.40 and the average particle diameter of the graft polymer is from 0.2 to 0.6µm.
5. A moulded product prepared from a composition as claimed in claim 1.
6. A composition as claimed in claim 1, wherein the graft monomer is an ester of acrylic or methacrylic acid and an alcohol with Cl-C8.
7. A composition as claimed in claim 6, wherein the graft monomer is methyl methacrylate and the graft substrate a cross-linked polybutadiene.
8. A composition as claimed in claim 1, wherein the plasticiser is an aromatic sulphonamide.
9. A composition as claimed in claim 1, wherein the plasticiser is a lactam.
10. A composition as claimed in claim 1 where the graft substrate includes copolymerized styrene, acrylonitrile or mixtures thereof.
11. A composition as claimed in claim 1 wherein the graft monomer includes up to 80% by weight styrene and up to 80% by weight acrylonitrile.
12. A composition as claimed in claim 1 including additives selected from lubricants, mould release agents, nucleating agents, stabilizers, flame protective agents, dyes and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813105364 DE3105364A1 (en) | 1981-02-13 | 1981-02-13 | POLYAMIDE MOLDS |
| DEP3105364.5 | 1981-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1203035A true CA1203035A (en) | 1986-04-08 |
Family
ID=6124844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000396031A Expired CA1203035A (en) | 1981-02-13 | 1982-02-11 | Polyamide moulding compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0058331B1 (en) |
| JP (1) | JPS57149353A (en) |
| CA (1) | CA1203035A (en) |
| DE (2) | DE3105364A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4785050A (en) * | 1985-09-25 | 1988-11-15 | Bayer Aktiengesellschaft | High impact strength, readily flowing polyamide moulding materials |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3339000A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC POLYAMIDE MOLDS WITH HIGH TOUGHNESS |
| US4659766A (en) * | 1983-12-19 | 1987-04-21 | Borg-Warner Chemicals, Inc. | Graft copolymer - plasticized PVC blends as thermoplastic elastomers |
| DE3405532A1 (en) * | 1984-02-16 | 1985-08-22 | Bayer Ag, 5090 Leverkusen | MOLDINGS FROM THERMOPLASTIC POLYAMIDE AND GRAFT RUBBER |
| EP0154037A3 (en) * | 1984-02-29 | 1987-02-04 | The Dow Chemical Company | Blends of aromatic-aliphatic polyamides and impact modifiers |
| DE3441547A1 (en) * | 1984-11-14 | 1986-05-15 | Basf Ag, 6700 Ludwigshafen | IMPACT TOE POLYOXYMETHYLENE MOLDING MATERIALS AND A METHOD FOR THE PRODUCTION THEREOF |
| DE3544761A1 (en) * | 1985-12-18 | 1987-06-19 | Basf Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON POLYAMIDES AND STYRENE-CONTAINING POLYMERS |
| CH672495A5 (en) * | 1987-07-17 | 1989-11-30 | Inventa Ag | |
| DE3827669A1 (en) * | 1988-08-16 | 1990-02-22 | Bayer Ag | THERMOPLASTIC INTERPOLYMERS AND THEIR USE IN MIXTURES OF POLYAMIDE AND STYRENE CO- AND / OR GRAFT POLYMERISAT |
| DE19543186A1 (en) | 1995-11-20 | 1997-05-22 | Bayer Ag | Flame-retardant themoplastic moldings with improved properties |
| US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| CA2492839C (en) | 2002-08-12 | 2011-02-01 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
| US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
| US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
| ATE555166T1 (en) | 2005-07-15 | 2012-05-15 | Exxonmobil Chem Patents Inc | ELASTOMERIC COMPOSITIONS |
| JP2009299746A (en) * | 2008-06-11 | 2009-12-24 | Hiroyasu Minayoshi | Hole blocking-up embedded plug and hole blocking-up method using hole blocking-up embedded plug |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4173556A (en) * | 1976-03-03 | 1979-11-06 | Monsanto Company | Elastoplastic compositions of rubber and polyamide |
| EP0001245B1 (en) * | 1977-09-20 | 1982-01-27 | Bayer Ag | Impact-resistant polyamide masses and their use in mouldings |
| DE2742176A1 (en) * | 1977-09-20 | 1979-03-29 | Bayer Ag | Impact-resistant polyamide moulding compsns. - contain added butadiene! (co)polymer substrate grafted with (meth)acrylic! acid ester and opt. (meth)acrylaminde! and (meth)acrylonitrile! |
| DE2962485D1 (en) * | 1978-12-16 | 1982-05-19 | Bernard Ingrid | Infusion device |
-
1981
- 1981-02-13 DE DE19813105364 patent/DE3105364A1/en not_active Withdrawn
-
1982
- 1982-02-02 EP EP82100695A patent/EP0058331B1/en not_active Expired
- 1982-02-02 DE DE8282100695T patent/DE3264099D1/en not_active Expired
- 1982-02-09 JP JP57018303A patent/JPS57149353A/en active Granted
- 1982-02-11 CA CA000396031A patent/CA1203035A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4785050A (en) * | 1985-09-25 | 1988-11-15 | Bayer Aktiengesellschaft | High impact strength, readily flowing polyamide moulding materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0212263B2 (en) | 1990-03-19 |
| DE3264099D1 (en) | 1985-07-18 |
| JPS57149353A (en) | 1982-09-14 |
| EP0058331B1 (en) | 1985-06-12 |
| DE3105364A1 (en) | 1982-09-02 |
| EP0058331A1 (en) | 1982-08-25 |
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