CA1322797C - Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereof - Google Patents
Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereofInfo
- Publication number
- CA1322797C CA1322797C CA000545946A CA545946A CA1322797C CA 1322797 C CA1322797 C CA 1322797C CA 000545946 A CA000545946 A CA 000545946A CA 545946 A CA545946 A CA 545946A CA 1322797 C CA1322797 C CA 1322797C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- per cent
- block
- copolymer
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A B S T R A C T
IMPACT RESISTANT BLENDS OF THERMOPLASTIC POLYAMIDES, POLYOLEFINS
AND ELASTOMERS AND PROCESS FOR THE PREPARATION THEREOF
Impact resistant polymeric composition comprising 1-95 %wt of a polyamide, 1-95 %wt of a functionalized polyolefin and 1-50 %wt of an elastomer and process for the preparation thereof by melt-blending.
K4840.TXT
IMPACT RESISTANT BLENDS OF THERMOPLASTIC POLYAMIDES, POLYOLEFINS
AND ELASTOMERS AND PROCESS FOR THE PREPARATION THEREOF
Impact resistant polymeric composition comprising 1-95 %wt of a polyamide, 1-95 %wt of a functionalized polyolefin and 1-50 %wt of an elastomer and process for the preparation thereof by melt-blending.
K4840.TXT
Description
~322797 The present invention relates to an impact resistank polymeric composi~ion comprising a polyamide, a functionalized polyolefin and an elastomerO The inv&ntion also relates to a process for the preparation therefor.
This application is related to Canadian patent application 545,938 and to Canadian patent application 545,952.
Thermoplastic polyamides, such as nylon 6,6, are a class of materials ~hich possess a good balance of properties comprising strength and stiffness which make them useful as structural materials. However, for a par~icular application, a ~hermoplas~ic polyamide may no~ offar the combination o~ properties desired, and therefor~ means to correct this deficieny are of interest.
One major deficiency of thermoplastic polyamides is their poor resistance ~o impact, especially when dry.
particularly appealing route to achieving improved impact resistance in a thermoplastic is by blending it with another polymer. It is well known that stif~ plastics can often be impact modified by addition of an immiscible lo~ modulus elastomer.
~owever, in general, physical blending of polymers has not been a successful route to toughen thermoplastic polyamides. This is due to the poor adhesion immiscibl~ polymers typically exhibit wlth each other. As a result, interfaces between blend component domains represent areas of severe weaknesses, providing natural flows which result in facile mechanical Eailure.
A route to achieve inter~acial adhesion between dissimilar materials is by chemically attaching to one or more of .
, .
~3227~7 the materials functional moieties which enhance their interaction.
Such lnteractions include chemical reaction, hydrogen bondiny, and dipole-dipole lnteractions.
.
~ ~ .
: :
.
20 ~
: :::: ~ :
:
:
: :
la .~ ' .
132~7~7 It has been previously proposed to increase the impact strength of polyamides by addition of a modified block copolymer. Hergenrother et al in U.S. Patent 4,427,828 and Shiraki et al in International KoXai ApplicatLon No. W083/004g2 disclose blends of thermoplastic polyamide with a modified block copolymer. These blends are deficient, however, because the blended components, especially the block copolymer, are relatively expensive. Also, polyamides have a tendency to absorb water and consequently properties are degraded.
Blending polyolefins with polyamides would decrease the water absorption for the blend since a portion of the polyamide which absorbs water would be replaced by polyolefin which absorbs relatively little water. In the past atte~pts to extend impact modified polyamides with polyolefins have been unsuccessful because the polyamides were incompatible with the polyolefins.
It has been discovered that by functionalizing various components in a polyamide, polyolefin elastomer blend a desirable combination of properties and cost can be obtained.
According to the present invention, there is provided an impact resistant blend of a thermoplastic polyamide, a functionalized polyolefin and an elastomer. Nore particularly there is provided impact resistant polymeric compositions comprising (a) from 1 to 95 per cent by weight of a polyamide having a number average molecular weight of at least 5000;
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1-50 per cent by weight of an elas~omer, calculated on the total of (a), ~b) and (c), said total being 100 per cent.
The polya~ide matrix resin of the toughened compositions of this invention is well known ln the art and embraces those semi-crystalline and amorphous r~sins having a molecular weight of at least 5000 and commonly referred to as nylons. Suitable polyamides include those described in U S. Patent Nos. 2,071,250; 2,071,251;
2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; and 3,393,210.
The polyamide resin can be produced by condensation of equimolar amounts uf a saturated dlcarboxylic acid containing from 4 to 12 `` ~ 322~97 carbon atoms with a diamine, in which the diamine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide.
Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene isophthalamlde, polyhexa-methylene tere-co~isophthalamide and polyhexamethylene dodecanoamide (nylon 612), the polyamide produced by ring opening of lactams, i.e., polycaprolactam, polylauric lactam, poly-ll-aminoundecanoic 1~ acid, bis(paraaminocyclohexyl~ methane dodecanoamide. It is also possible to use in this invention polyamides prepared by the copolymerization of two of the above poly~ers or terpolymerization of the above polymers or their components, e.g., for example, an adipic isophthalic acid hexamethylene diamine copolymer. Preferably the polyamides are linear with a melting point in excess of 200DC.
As great as 99 percent by weight of the composition can be composed of polyamide; however, preferred compositions contain from 60 to 99 percent, and more narrowly 80 to 95 percent, by weight oi polyamide.
The polyolefins employed in the instant invention are cyrstalline or crystallizable poly(alpha-olefins) and their copolymers. The alpha-olefin or l-olefin monomers employed in the instant invention have 2 to 5 carbcn atoms.
Examples of suitable polyolefins, both plastic and elastomeric, include low density polyethylene, high density polyethylene, polypropylene, poly-l-butene, poly-3-methyl-1-butene, poly-4-methyl-l-pentene, copolymers of monoolefins with other olefins (mono- or diolefins~ or vinyl monomers such as ethylene-propylene copolymers or with one or more additional monomers, i.e., EPDN, ethylene/butylene copoIymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, propylene/4-methyl-1-pentene copolymer, ethylene/
methacrylic acid, ethylene/acrylic acid and their lonomers and the like. The number average molecular weight of ~he polyolefins is preferably above about lO,000, more preferably above about 50,000.
In addition, it is preferred that the apparent crystalline melting point be above about 100C, pr~ferably between about 100C and about 250C, and more preferably between about 140C and about 250C. The preparation of these various polyolefins are well ~ 322~ ~
~ 3293-2847 known. See generally "Olefin Polymers," Volume 14, Kirk-Othmer Encyclopedla of Chemical Technology, pages 217-335 (1967).
The high density polyethylene employed has an approximate crystallinity of over about 75% and a density in grams per cubic centlmeter (g/cm2) of between about 0.94 and 1.0 while the low densi~y polyethylene employed has an approximate crys~allinlty of over about 35~ and a density of betwaen about 0.90 g/cm2 and 0.94 g~cm2. Mosk commercial polyethylenes have a number average molecular weight of ahout 50,000 to about 500,000.
The polypropylene employed is the ~o-called i~otactic polypropylene as opposed to atactic polypropylene. This poly-propylene is described in the above Kirk-Oth~er re~erenca and in United Sta~es Patent No. 3,112,300. The number average molecular weigh~ of ~he polypropylene employed is typically in excess of about 100,000. The polypropylene suitable for ~his invention may be prepared using methods of the pri.or art. Depending on the specific catalyst and polymerizatlon condi~ions employed, the polymer produced may contain a~actic as well as iso~actic, syndio-; tactic or so-called s~ereo-block molecules. These may be separa~ed, if desired, by selective solvent extraction to yield products of low atactic content thak crystallize more completely.
The preferrsd commercial polypropylenes are generally prepared using a solid, crystalline, hydrocarbon-insoluble cataly~t made from a titanium trichloride composition and an alumlnum alkyl compound, e.g., triethyl aluminum or diethyl aluminum chloride.
If desired, the polypropylene employed may be a copolymer containing minor (1 to 20 per cent by weight) amountæ of ethylene ~' ,,.~
~ , , ~ , .
~32~7~7 or other alpha-olefin comonomers.
The poly(1-butene~ preferably has an isotactic structure. The catalysts used in prepariny the poly(1-butene) are typically organometallie compounds commonly referred to as Ziegler-Natta catalysts. A typical catalyst is the interacted produc~ resulting irom mixing equimolar quantities o~ ~itanium tetrachloride and triethylaluminum. The manufacturing process is normally carried out in an inert diluent such as hexane.
Manufacturing operation, in all phases of polymer formation, is conduated in such a manner as to guarantee rigorous exclusion of water even in traee amounts.
.
4a ! ~
~, ~
~3~97 One very suitable polyolefin is poly(4-methyl-1-pentene).
Poly(4-methyl-1-pentene) typically has an apparent crystalline melting point of between about 240 and 250~C and a relative density of between about 0.80 and 0.85. Monomeric 4-methyl-1-pentene is com~ercially manufactured by the alkali-metal catalyst dimerization of propylene. The homopolymerization of 4-methyl-l-pentene with Ziegler-Natta ca~alysts is described in the Kirk-Othmer ~ncyclopedia of Chemical Technology, Supplement volume, pages 789-792 (second edition, 1971). However, the isotactic homopolymer of 4-methyl-1-pentene has certain technical defects, such as brittleness and inadequate transparency. Therefore, commercially available poly(4-methyl-1-pentene) is actually a copolymer with minor proportions of other alpha-olefins, together with the addition of suitable oxidation and melt stabilizer systems.
These copolymers are described in the Kirk-Othmer Encyclopedia of Chemical Technology, Supplement ~olume, pages 792-907 (second edition, 1971), and are available from Mitsui Chemical ~ompany under the tradename TPX. resin. Typical alpha-olefins are linear alpha-olefins having from 4 to 18 carbon atoms. Suitable resins are copolymers of 4-methyl-1-pentene with from about 0.5 to about 30% by weight of a linear alpha-olefin.
If desired, the polyolefin may be a mixture of ~arious polyolefins. However, the much preferred polyolefin is isot~ctic polypropylene.
The modified polyole~ins suitable for use in the present invention are prepared by reacting a polyolefin with, for example, an unsat~rated mono or polycarboxylic acid, or derivatives thereof.
The modified polyolefins are readily prepared according to the procedure described in U.S. Patent No. 3,480,580 or U.S. Patent No.
This application is related to Canadian patent application 545,938 and to Canadian patent application 545,952.
Thermoplastic polyamides, such as nylon 6,6, are a class of materials ~hich possess a good balance of properties comprising strength and stiffness which make them useful as structural materials. However, for a par~icular application, a ~hermoplas~ic polyamide may no~ offar the combination o~ properties desired, and therefor~ means to correct this deficieny are of interest.
One major deficiency of thermoplastic polyamides is their poor resistance ~o impact, especially when dry.
particularly appealing route to achieving improved impact resistance in a thermoplastic is by blending it with another polymer. It is well known that stif~ plastics can often be impact modified by addition of an immiscible lo~ modulus elastomer.
~owever, in general, physical blending of polymers has not been a successful route to toughen thermoplastic polyamides. This is due to the poor adhesion immiscibl~ polymers typically exhibit wlth each other. As a result, interfaces between blend component domains represent areas of severe weaknesses, providing natural flows which result in facile mechanical Eailure.
A route to achieve inter~acial adhesion between dissimilar materials is by chemically attaching to one or more of .
, .
~3227~7 the materials functional moieties which enhance their interaction.
Such lnteractions include chemical reaction, hydrogen bondiny, and dipole-dipole lnteractions.
.
~ ~ .
: :
.
20 ~
: :::: ~ :
:
:
: :
la .~ ' .
132~7~7 It has been previously proposed to increase the impact strength of polyamides by addition of a modified block copolymer. Hergenrother et al in U.S. Patent 4,427,828 and Shiraki et al in International KoXai ApplicatLon No. W083/004g2 disclose blends of thermoplastic polyamide with a modified block copolymer. These blends are deficient, however, because the blended components, especially the block copolymer, are relatively expensive. Also, polyamides have a tendency to absorb water and consequently properties are degraded.
Blending polyolefins with polyamides would decrease the water absorption for the blend since a portion of the polyamide which absorbs water would be replaced by polyolefin which absorbs relatively little water. In the past atte~pts to extend impact modified polyamides with polyolefins have been unsuccessful because the polyamides were incompatible with the polyolefins.
It has been discovered that by functionalizing various components in a polyamide, polyolefin elastomer blend a desirable combination of properties and cost can be obtained.
According to the present invention, there is provided an impact resistant blend of a thermoplastic polyamide, a functionalized polyolefin and an elastomer. Nore particularly there is provided impact resistant polymeric compositions comprising (a) from 1 to 95 per cent by weight of a polyamide having a number average molecular weight of at least 5000;
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1-50 per cent by weight of an elas~omer, calculated on the total of (a), ~b) and (c), said total being 100 per cent.
The polya~ide matrix resin of the toughened compositions of this invention is well known ln the art and embraces those semi-crystalline and amorphous r~sins having a molecular weight of at least 5000 and commonly referred to as nylons. Suitable polyamides include those described in U S. Patent Nos. 2,071,250; 2,071,251;
2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; and 3,393,210.
The polyamide resin can be produced by condensation of equimolar amounts uf a saturated dlcarboxylic acid containing from 4 to 12 `` ~ 322~97 carbon atoms with a diamine, in which the diamine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide.
Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene isophthalamlde, polyhexa-methylene tere-co~isophthalamide and polyhexamethylene dodecanoamide (nylon 612), the polyamide produced by ring opening of lactams, i.e., polycaprolactam, polylauric lactam, poly-ll-aminoundecanoic 1~ acid, bis(paraaminocyclohexyl~ methane dodecanoamide. It is also possible to use in this invention polyamides prepared by the copolymerization of two of the above poly~ers or terpolymerization of the above polymers or their components, e.g., for example, an adipic isophthalic acid hexamethylene diamine copolymer. Preferably the polyamides are linear with a melting point in excess of 200DC.
As great as 99 percent by weight of the composition can be composed of polyamide; however, preferred compositions contain from 60 to 99 percent, and more narrowly 80 to 95 percent, by weight oi polyamide.
The polyolefins employed in the instant invention are cyrstalline or crystallizable poly(alpha-olefins) and their copolymers. The alpha-olefin or l-olefin monomers employed in the instant invention have 2 to 5 carbcn atoms.
Examples of suitable polyolefins, both plastic and elastomeric, include low density polyethylene, high density polyethylene, polypropylene, poly-l-butene, poly-3-methyl-1-butene, poly-4-methyl-l-pentene, copolymers of monoolefins with other olefins (mono- or diolefins~ or vinyl monomers such as ethylene-propylene copolymers or with one or more additional monomers, i.e., EPDN, ethylene/butylene copoIymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, propylene/4-methyl-1-pentene copolymer, ethylene/
methacrylic acid, ethylene/acrylic acid and their lonomers and the like. The number average molecular weight of ~he polyolefins is preferably above about lO,000, more preferably above about 50,000.
In addition, it is preferred that the apparent crystalline melting point be above about 100C, pr~ferably between about 100C and about 250C, and more preferably between about 140C and about 250C. The preparation of these various polyolefins are well ~ 322~ ~
~ 3293-2847 known. See generally "Olefin Polymers," Volume 14, Kirk-Othmer Encyclopedla of Chemical Technology, pages 217-335 (1967).
The high density polyethylene employed has an approximate crystallinity of over about 75% and a density in grams per cubic centlmeter (g/cm2) of between about 0.94 and 1.0 while the low densi~y polyethylene employed has an approximate crys~allinlty of over about 35~ and a density of betwaen about 0.90 g/cm2 and 0.94 g~cm2. Mosk commercial polyethylenes have a number average molecular weight of ahout 50,000 to about 500,000.
The polypropylene employed is the ~o-called i~otactic polypropylene as opposed to atactic polypropylene. This poly-propylene is described in the above Kirk-Oth~er re~erenca and in United Sta~es Patent No. 3,112,300. The number average molecular weigh~ of ~he polypropylene employed is typically in excess of about 100,000. The polypropylene suitable for ~his invention may be prepared using methods of the pri.or art. Depending on the specific catalyst and polymerizatlon condi~ions employed, the polymer produced may contain a~actic as well as iso~actic, syndio-; tactic or so-called s~ereo-block molecules. These may be separa~ed, if desired, by selective solvent extraction to yield products of low atactic content thak crystallize more completely.
The preferrsd commercial polypropylenes are generally prepared using a solid, crystalline, hydrocarbon-insoluble cataly~t made from a titanium trichloride composition and an alumlnum alkyl compound, e.g., triethyl aluminum or diethyl aluminum chloride.
If desired, the polypropylene employed may be a copolymer containing minor (1 to 20 per cent by weight) amountæ of ethylene ~' ,,.~
~ , , ~ , .
~32~7~7 or other alpha-olefin comonomers.
The poly(1-butene~ preferably has an isotactic structure. The catalysts used in prepariny the poly(1-butene) are typically organometallie compounds commonly referred to as Ziegler-Natta catalysts. A typical catalyst is the interacted produc~ resulting irom mixing equimolar quantities o~ ~itanium tetrachloride and triethylaluminum. The manufacturing process is normally carried out in an inert diluent such as hexane.
Manufacturing operation, in all phases of polymer formation, is conduated in such a manner as to guarantee rigorous exclusion of water even in traee amounts.
.
4a ! ~
~, ~
~3~97 One very suitable polyolefin is poly(4-methyl-1-pentene).
Poly(4-methyl-1-pentene) typically has an apparent crystalline melting point of between about 240 and 250~C and a relative density of between about 0.80 and 0.85. Monomeric 4-methyl-1-pentene is com~ercially manufactured by the alkali-metal catalyst dimerization of propylene. The homopolymerization of 4-methyl-l-pentene with Ziegler-Natta ca~alysts is described in the Kirk-Othmer ~ncyclopedia of Chemical Technology, Supplement volume, pages 789-792 (second edition, 1971). However, the isotactic homopolymer of 4-methyl-1-pentene has certain technical defects, such as brittleness and inadequate transparency. Therefore, commercially available poly(4-methyl-1-pentene) is actually a copolymer with minor proportions of other alpha-olefins, together with the addition of suitable oxidation and melt stabilizer systems.
These copolymers are described in the Kirk-Othmer Encyclopedia of Chemical Technology, Supplement ~olume, pages 792-907 (second edition, 1971), and are available from Mitsui Chemical ~ompany under the tradename TPX. resin. Typical alpha-olefins are linear alpha-olefins having from 4 to 18 carbon atoms. Suitable resins are copolymers of 4-methyl-1-pentene with from about 0.5 to about 30% by weight of a linear alpha-olefin.
If desired, the polyolefin may be a mixture of ~arious polyolefins. However, the much preferred polyolefin is isot~ctic polypropylene.
The modified polyole~ins suitable for use in the present invention are prepared by reacting a polyolefin with, for example, an unsat~rated mono or polycarboxylic acid, or derivatives thereof.
The modified polyolefins are readily prepared according to the procedure described in U.S. Patent No. 3,480,580 or U.S. Patent No.
3,481,910. The polyolefins which can be modified ara prepared from monoolefins containing at least 2 carbon atoms. Such polyolefins lnclude homopolymers and copolymers of, for example, propylene, l-butene, 4-methyl-1-pentene, 3-methyl-l-butene, 4,4-dimethyl-l-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 5-ethyl-1-hexene, 6-methyl-1-heptene, l-hexene, l-heptene, l-octene, l-nonene, l-decene, and l-dodecene and the like.
, ~ 3227~7 Examples of suitable polyolefins, both plastic and elastomeric, include low density polyethylene, high density polyethylene, polypropylene, poly-l-butene, poly-3-methyl-l-butene, poly-4-methyl-l-pentene, ethylene-propylene copolymers or with one or more additional monomers, for ~xample, EPDM, ethylene-butylene copolymers, ethylene-vinyl ace~ate copolymers, ethylene/ethyl acrylate copolymers, propylene/4-methyl-1-pentene copolymers and the like.
The reaction of the polyolefin, which for ease of reaction is generally a low viscosity polyolefin, with an unsaturated mono or polycarboxylic acid, and deri~atives thereof, can be carried out in the presence of a free radical source. These homopolymeric or copolymeric low viscosity poly-~-olefins are prepared by thermally degrading conventional high molecular weight ~-olefin polymers prepared by conventional polymerization processes. For example, one such suitable conventional polymer is the highly crystalline polypropylene prepared according to U.S. Patent No. 2,969,345.
Thermal degradation of conventional homopolymers or copolymers is accomplished by heating them at elevated temperatures causing the polymer chain to rupture apparently at the points of chain branching of the polymeric material. The degree of degradation is controlled by reaction time and temperature to give a ~hermally degraded low molecular weight crystallizable polymeric material having a melt viscosity range from about 100-5,000 cp. at 190C (ASTND12 38-57T
using 0.04+0.0002 inch orifice) and an inherent viscosity of about 25 0.1 to 0.5, [Schulken and Sparks, Journal Polymer Science 26 227, (1957)]. By carefully controlling the time, temperature and agitation, a thermally degraded poly-~-olefin of relatively narrower molecular weight range than the starting high molecular weight polymer is obtained. The degradation is ¢arried out at a temperature 30 from 290C to about 4~5C.
The low viscosity poly-~-olefins are characterized by having a melt viscosity of less than about lO0 to 5,000 cp. as ~easured at 190C (ASTM-D12 38-57T using 0.04+0.C002 inch orifice). These low viscosity poly-~-olefins are reacted with unsaturated mono or polycarboxylic a¢ids, and derivatives thereof, at temperatures ~ 3~9~
generally less than 300C, preferably from about 150-250C in the presence of free radical sources. ~uitable free radical sources are, for example peroxides such as ditertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, p-menthane peroxide, p-menthane hydroperoxide compounds or azo compounds, such as azobis(isobutyronitrile~, or irradiation sources. Suitable irradiation sources include, for example, those from cobalt, uranium, thorium, and the like and ultraviolet light. Preferably, about 1 to 10 percent organic unsaturated polycarboxylic acid, anhydride or esters thereof, hased on the weight of the low viscosity polyolefin, ~an be used. The amount of peroxide or free radical agent used is generally quite low being o the order of about 0.01 to about 0.5 percent based on the weight of the low viscosity poly-~-olefin. The reaction may be carried out either in a batchwise or in a ~ontinuous manner with contact times in the order of about 10 minutes to about 2 hours. Suitable unsaturated mono or poly-carboxylic acids and derivatives thereoi are described later in the section entitled Functionalized Block Copolymers and include maleic acid, maleic anhydride, fumaric acid, citaconic anhydride, aconitric anhydrlde, itaconic anhydride, the half or full esters derived from methyl, ethyl, dimethyl maleate, dimethyl fumarate, methyl ethyl maleate, dibutyl maleate, dipropyl maleate, and the like, or those compounds which form these compounds at elevated reaction temperatures such as citric acid, i`or example. These modified low molecular 25 weight poly-~-olefin compositions have a meIt viscosity of 100-5,000 - centipoise at 190C and a saponification number of from at least 6 to about 60, preferably about 7-30. It has ~een observed that the melt viscosity of the product increases slightly. This increase in melt viscosity may be due to a slight degree of crosslinklng or to copolymerization of the wax material with maleic anhydride.
The reaction of the polyolefin can also be carried out in an extruder or a Banbury mixer. This process can be used for reacting polyolefins having a melt viscosity greater than 5,000 cp. at 190C
up to a viscosity of 500,000 cp. at 190C. The modified polyolefins prepared in this manner, such as polypropylene, can have a melt ~ 3~27~7 viscosity of 150,000 or higher cp. at 190C and a saponiflcation number of up to 60.
One method for the determination of saponification number of maleated polypropylene is as follows: Ueigh approximately 4g of the sample into a 500 ml alkali-resistant Erlenmeyer flask and add 1,000 ml distilled xylene. Heat under a reflux condenser for 1 hour. Cool the solution to 75C or less, and add from a buret 30 ml standardized 0.10 N KOH in ethyl alcohol. Heat under reflux for 45 min. Cool, and add from a buret standardized O.10 N CH3COOH in xylene until the mixture is a(id to phenolphthalein. Add at least 1 ml excess CH3COOH. Reheat the solution under reflux for 15 min.
Remove from heat, add 5 ml water, and titrate to a faint pink end point with O.10 N KOH in ethyl alcohol. Run a blank in this manner using the same amounts of resgents and the same heating times.
Calculation:
For Sample For Blank (ml.KOHxN)(ml.CH3COOHxN~ -[~ml.KOHxN)(ml.CH3COOHxN)lx56.1 g. Sample ~ Sap.No.
The unreacted, unsaturated polycarboxylic acid can be separated from the reaction mixture by purging the reaction mixture with an inert gas while the melt temperature is between 200 and 300C.
After the unreacted unsaturated polycarboxylic acid has been removed, the modified poly-~-olefin can be further purified by vacuum stripping, solvent extraction, or dissolving in a hydrocarbon medium and isolated by precipitation with a nonsolvent such as acetone.
It may be desirable to use an effective polyolefin stabilizer in order to prevent gelation or degrsdation of blend properties.
Some suitable stabilizers lnclude dilauryl thiodipropionate, butylated hydroxytoluene, dioctadecyl p-cresol,~pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4 hydroxyphenyl)propionatel, dodecyl stearyl thiodipropionate, 2,2'-methylene bis(6-tert-butyl-p-cresol) and the like or comblnations of such stabilizers. Desirable :~3~97 g stabilizer concentrations include about 0.05 to about 1.0 percent of stabilizer, by weight, to the blend.
If desired, the functionalized polyolefin may be mixed with unfunctionalized polyolefins, for example, a highly functionalized polyolefin may be diluted with unfunctionalized polyolefin to improve properties or reduce cost.
Elastomers useful in the blends of the present invention may include elastomeric olefin copolymers, selectively hydrogenated block copolymers and elastomeric acrylic containing polymers made by the emulsion process. The~e elastomers may or may nct be functionalized.
Elastomeric acrylic containing polymers are well known in the art and are described in U.S. Patents 3,668,274 and 4,5~4,344.
Elastomeric copolymers of ethylene, at least one C3 to C6 ~-monoolefin, and at least one nonconjugated diene are well known in the art. These copolymers have a substantially saturated hydro-carbon backbone chain which causes the copolymer to be relatively inert to ozone attack and oxidative degradation and have side-chain unsaturation available for sulfur curing.
These copolymers are conveniently prepared by copolymerizing the monomers in the presence of a coordination catalyst system such as diisobutylaluminum chloride and vanadium oxytrichloride.
Copolymerization may be conducted in an inert solvent or in a slurry or particle form reactor. Details of their preparation are 25 given, for example, in U.S. Patent Nos. 2,~33,4~0; 2,962,451;
3,000,866; 3,093,620; 3,093,621; 3,063,973; 3,147,230; 3,154,528;
3,~60,708; and M. Sittig, "Stereo Rubber and Other Elastomer Processes," Noyes Development Corporation, Park Ride, N.J., 1967.
Propylene is normally selected as the ~-monoolefin in preparing such copolymers because of its availability and for reasons of economics. Other lower ~-monoolefins, such as l-butene, l-pentene, and l-hexene can be selected in place of or in addition to ~ropylene in preparing elastomeric copolymers which are useful in practicing the invention. The term EPDM as used herein r~fers to ~he preferred copolymers of ethylene, propylene, and at least one noncon~ugated diene.
, ~ ~ , " , .,~ , , ~322~7 An espscially preferred class of EPDM is that in which the nonconjugated diene is monoreactive. Monoreactive nonconjugated dienes have one double bond which readily enters the copolymerization reaction with ethylene and propylene, and a second double bond which does not, to any appreciable extent, enter the copolymerization reaction. Copolymers of this class have maximum side chain unsaturation for a given diene content, which unsaturation is available for adduct formation. Gel content of these copolymers is also minimal since there is minimal cross-linking during copolymerization.
Monoreactive nonconjugated dienes which can be selected in preparing this preferred class of EPDM copolymer include linear aliphatic dienes of at least six carbon atoms which have one terminal double bond and one internal double bond, and cyclic dienes wherein one or both of the carbon-to-carbon double bonds are part of a carbocyclic ring. Of the linear dienes, copolymers of ethylene, propylene, and 1,4-hexadiene having an inherent viscosity of at least about l.S are especially preEerred.
Classes of cyclic dienes useful in preparing the preferred class of EPDM copolymers for adduct formation include alkylidene bicycloalkenes, alkenyl bicycloalkenes, bicycloalkadienes, and alkenyl cycloalkenes. Representative of alkylidene bicycloalkenes are 5-alkylidene-2-norbornenes such as 5-ethylidene-2-norbornene and 5~methylene-2-norbornene. Representative of alkenyl bicyclo-alkenes are 5-alkenyl-2-norbornenes such as 5-(1'-propenyl)-2-norbornene, 5-(2'-butenyl)-2-norbornene, and 5-hexenyl-2-norbornene.
D~cyclopentadiene and 5-ethyl-~,5-norbornadiene are illustrative of bicycloalkadienes, and vinyl cyclohexane is representative of alkenyl cycloalkenes which may be selected as the diene monomer.
EPDM copolymers prepared from cyclic dienes preferably have an inherent viscosity within the range of about 1.5 to 3.0, as measured on 0.1 gram copolymer dissolved in 103 milliliters of perchloro-ethylene at 30C, for optimum processing propert~es. Of the cyclic dienes, S-ethylidene-2-norbornene ~s preferred.
~322~
Another class of preferred copolymers includes branched tetrapolymers made from ethylene, at least one C3 to C5 ~-monoolefin with propylene being preferred, at least one monoreactive non-conjugated diene, and at least one direactive nonconjugated diene such as 2,5-norbornadiene or 1,7-octadiene. By "direactive" i5 meant that both double bonds are capable of polymeri~ing during preparation of the copolymer. Tetrapolymers of thls class preferably have an inherent viscosity of about 1.2 to 3.0, as measured on 0.1 gram copolymer dissolved in 100 milliliters of perchloroethylene at 30C, for optimum processing properties. A preferred copolymer of this class ls a tetrapolymer of ethylene, propylene, 1,4-hexadiene, and 2,5-norbornadiene. Such copolymers are described in Canadian Patents Nos. 855,774 and 897,895.
Copolymers of the classes defined above have low gel content, a substantia:Lly saturated hydrocarbon backbone which is resistant to o70ne and oxidative degradation, and hydrocarbon side-chain unsaturation which presents sites for the thermal addition of maleic anhydride, fumaric acid, and other species capable of thermal addition to the above mentioned side-chain unsaturation.
Low gel content is indicative of a polymer having favorable processing properties.
Although the present invention will be discussed în relationship to thermal addition of maleic anhydride to from a graft, it is understood that in the present inventîon maleic acid or f~maric acid may be directly substituted for maleic anhydride to form the same adduct. The adduct containing succinic groups attached to the elastomeric copolymer contains these groups with use of a starting material of maleic anhydride, maleic acid or fumaric acid. Maleic anhydride, maleic acid and iumaric acid are equivalents to one another to produce thc same type of graft containing the same succinic groups. Therefore, the remarks made herein in use of maleic anhydride also refer to maleic acid and fumaric acid. Also, the use of other thermal reactions with this hydrocarbon side-chain unsaturation may be used for the present invention.
~ 3~2~
Using a copolymer of ethylene, propylene, and 1,4-hexadiene, thermal addition of maleic anhydride to the copolymsr is theorized to occur by the following equation:
Polymer Backbone Polymer Backbone CH CH = CH ______~ CH fH2-C
H + l~ / C~ HC - CH -C
A molecule of maleic anhydride adds to the polymer at the site of side chain unsAturation to give a succinic anhydride radical bonded to the side chain. Said chain uncaturation shifts by one carbon atom. It will be understood that side chain unsaturation can also shift away fro~ the backbone chain when the unsaturation is several carbon atoms removed from the terminal side chain carbon atom, as in copolymers of ethylene, propylene, and 1,4-octadiene.
However, it has been further found that in addition to the adduct containing succinic anhydride att:ached to the elastomeric copolymer, succinic acid groups can alscl be attached to the copolymer.
Generally the adduct will contain succinic groups attached to the copolymer as a mix~ure of succinic anhyclride and succinic acid.
In this disclosure "succinic groups" will include succinic anhydride, succinic acid or a combination of succinic anhydride and succinic acid.
The adducts of this invention can be prepared by any process which intimately mixes ~aleic anhydride ~ith the copolymer without appreciable generation of free radicals, and which concurrently or subsequently heats the mixture to a temperature whereat thermal addition occurs. Selected temperature~ will generally be 2t least 225C to obtain adduct i`or~ation at acceptable rates and less than about 350C to avoid any significant polymer breakdown. Preferred temperature ranges will vary with the particular polymer and can readily be determined by one skilled in the art.
Mixing of the maleic anhydride and copolymer can be by blending molten anhydride with copolymer in an internal mixer or extruder, or by blending finely divided dry maleic anhydride with copolymer on a well-ventilated rubber mill with concurrent or subsequent heating, such as in a hot press or mold. Temperatures necessary to achieve thermal grafting are sufficiently high to dehydrate maleic acid, forming maleic anhydride in situ. Thus, maleic acid can be compounded with the copolymer instead of maleic anhydride when such is desired. The maleic al~ydride can be substituted with groups, such as bromine or chlorine, which do not unduly interfere with the graft reaction.
~referred copolymers of ethylene, propylene, and 1,4-hexadiene are very resistant to free radical formation under high shear stress conditions and are readily mixed on conventional bul~
processing equipment without gel formation. Care must be exercised, however, in selecting the mixing conditions for copolymers derived from strained ring dienes such as ethylidene norbornene. Such copolymers will readily generate free radicals when sheared at low temperatures, and are preferably mixed with maleic anhydride at high temperature, such as above 90C to avoid appreciable gel formation.
It is generally desired to form adducts containing about 0.02 to 20~, and preferably about 0.1 to 10~, by weight maleic anhydride.
Adducts containing such quantities of m~leic anhydride have sufficient carboxylated sites for ionic curing or grafting of the copolymer.
To achieve a desired degree of adduct formation within a reasonable time, high concentrations of reactants are help~`ul. One will generally select a polymer having about twice the amount of side-chain unsaturation as is stoichiometrically required ~or the desired amount of maleic anhydride incorporation. S~milarly, about twice as much maleic anhydride is added as is desired ln the polymer adduct. Conversion o~ about 40 to 50% of the maleic :L32~7~
-14- $3293-~847 anhydride will resul~ in copolymer adduct having ~he desired compo~ition. For example, if one desires to obtain an ethylene/propyleneJl,4-hexadiene copolymer having 2.2 weight percent maleic anhydride content, he could conveniently mix a copolymer having 0.49 moles side~chain unsaturation per kilogram of polymer with 0.49 moles maleic anhydride and heat the mixture to convert 45~ of the anhydride, thereby obtai.ning the desired product.
It is often desirable to perform further reactions on the derivatized elastomeric olefin copolymer. For example, a copolymer containing succinic groups may be esterified with hydroxy-containing compounds.
Block copolymers of conjugated dienes and vinyl aromatic hydrocarbons which may be utilized include any of those which exhibit elastomeric properties and those which have 1,2-microstructure con~ents prior ~o hydrogenation of from about 7% to about 100% and preferably from about 35 to 50% of the condensed butadiene units. Such block copolymers may be multiblock copolymers of varying structures containing various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up ko about 60 percent by weight o~ vinyl aromatic hydrocarbon. Thus, multiblock copolymers may be utilized which are linear or radial symmetric or asymmetric and which have structures represented by the formula Bn~AB)oAp where n = 0 or 1, o = 1 to 100 and p-0 or 1, to which has been grafted an acid compound or its derivative wherein, (1) each A is predominantly a polymerized monoalkenyl aromatic hydrocarbon block havin~ an average molecular weight of 2,000 ~ ~22~7 -l~a- 63293-28~7 to 115,000;
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
, ~ 3227~7 Examples of suitable polyolefins, both plastic and elastomeric, include low density polyethylene, high density polyethylene, polypropylene, poly-l-butene, poly-3-methyl-l-butene, poly-4-methyl-l-pentene, ethylene-propylene copolymers or with one or more additional monomers, for ~xample, EPDM, ethylene-butylene copolymers, ethylene-vinyl ace~ate copolymers, ethylene/ethyl acrylate copolymers, propylene/4-methyl-1-pentene copolymers and the like.
The reaction of the polyolefin, which for ease of reaction is generally a low viscosity polyolefin, with an unsaturated mono or polycarboxylic acid, and deri~atives thereof, can be carried out in the presence of a free radical source. These homopolymeric or copolymeric low viscosity poly-~-olefins are prepared by thermally degrading conventional high molecular weight ~-olefin polymers prepared by conventional polymerization processes. For example, one such suitable conventional polymer is the highly crystalline polypropylene prepared according to U.S. Patent No. 2,969,345.
Thermal degradation of conventional homopolymers or copolymers is accomplished by heating them at elevated temperatures causing the polymer chain to rupture apparently at the points of chain branching of the polymeric material. The degree of degradation is controlled by reaction time and temperature to give a ~hermally degraded low molecular weight crystallizable polymeric material having a melt viscosity range from about 100-5,000 cp. at 190C (ASTND12 38-57T
using 0.04+0.0002 inch orifice) and an inherent viscosity of about 25 0.1 to 0.5, [Schulken and Sparks, Journal Polymer Science 26 227, (1957)]. By carefully controlling the time, temperature and agitation, a thermally degraded poly-~-olefin of relatively narrower molecular weight range than the starting high molecular weight polymer is obtained. The degradation is ¢arried out at a temperature 30 from 290C to about 4~5C.
The low viscosity poly-~-olefins are characterized by having a melt viscosity of less than about lO0 to 5,000 cp. as ~easured at 190C (ASTM-D12 38-57T using 0.04+0.C002 inch orifice). These low viscosity poly-~-olefins are reacted with unsaturated mono or polycarboxylic a¢ids, and derivatives thereof, at temperatures ~ 3~9~
generally less than 300C, preferably from about 150-250C in the presence of free radical sources. ~uitable free radical sources are, for example peroxides such as ditertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, p-menthane peroxide, p-menthane hydroperoxide compounds or azo compounds, such as azobis(isobutyronitrile~, or irradiation sources. Suitable irradiation sources include, for example, those from cobalt, uranium, thorium, and the like and ultraviolet light. Preferably, about 1 to 10 percent organic unsaturated polycarboxylic acid, anhydride or esters thereof, hased on the weight of the low viscosity polyolefin, ~an be used. The amount of peroxide or free radical agent used is generally quite low being o the order of about 0.01 to about 0.5 percent based on the weight of the low viscosity poly-~-olefin. The reaction may be carried out either in a batchwise or in a ~ontinuous manner with contact times in the order of about 10 minutes to about 2 hours. Suitable unsaturated mono or poly-carboxylic acids and derivatives thereoi are described later in the section entitled Functionalized Block Copolymers and include maleic acid, maleic anhydride, fumaric acid, citaconic anhydride, aconitric anhydrlde, itaconic anhydride, the half or full esters derived from methyl, ethyl, dimethyl maleate, dimethyl fumarate, methyl ethyl maleate, dibutyl maleate, dipropyl maleate, and the like, or those compounds which form these compounds at elevated reaction temperatures such as citric acid, i`or example. These modified low molecular 25 weight poly-~-olefin compositions have a meIt viscosity of 100-5,000 - centipoise at 190C and a saponification number of from at least 6 to about 60, preferably about 7-30. It has ~een observed that the melt viscosity of the product increases slightly. This increase in melt viscosity may be due to a slight degree of crosslinklng or to copolymerization of the wax material with maleic anhydride.
The reaction of the polyolefin can also be carried out in an extruder or a Banbury mixer. This process can be used for reacting polyolefins having a melt viscosity greater than 5,000 cp. at 190C
up to a viscosity of 500,000 cp. at 190C. The modified polyolefins prepared in this manner, such as polypropylene, can have a melt ~ 3~27~7 viscosity of 150,000 or higher cp. at 190C and a saponiflcation number of up to 60.
One method for the determination of saponification number of maleated polypropylene is as follows: Ueigh approximately 4g of the sample into a 500 ml alkali-resistant Erlenmeyer flask and add 1,000 ml distilled xylene. Heat under a reflux condenser for 1 hour. Cool the solution to 75C or less, and add from a buret 30 ml standardized 0.10 N KOH in ethyl alcohol. Heat under reflux for 45 min. Cool, and add from a buret standardized O.10 N CH3COOH in xylene until the mixture is a(id to phenolphthalein. Add at least 1 ml excess CH3COOH. Reheat the solution under reflux for 15 min.
Remove from heat, add 5 ml water, and titrate to a faint pink end point with O.10 N KOH in ethyl alcohol. Run a blank in this manner using the same amounts of resgents and the same heating times.
Calculation:
For Sample For Blank (ml.KOHxN)(ml.CH3COOHxN~ -[~ml.KOHxN)(ml.CH3COOHxN)lx56.1 g. Sample ~ Sap.No.
The unreacted, unsaturated polycarboxylic acid can be separated from the reaction mixture by purging the reaction mixture with an inert gas while the melt temperature is between 200 and 300C.
After the unreacted unsaturated polycarboxylic acid has been removed, the modified poly-~-olefin can be further purified by vacuum stripping, solvent extraction, or dissolving in a hydrocarbon medium and isolated by precipitation with a nonsolvent such as acetone.
It may be desirable to use an effective polyolefin stabilizer in order to prevent gelation or degrsdation of blend properties.
Some suitable stabilizers lnclude dilauryl thiodipropionate, butylated hydroxytoluene, dioctadecyl p-cresol,~pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4 hydroxyphenyl)propionatel, dodecyl stearyl thiodipropionate, 2,2'-methylene bis(6-tert-butyl-p-cresol) and the like or comblnations of such stabilizers. Desirable :~3~97 g stabilizer concentrations include about 0.05 to about 1.0 percent of stabilizer, by weight, to the blend.
If desired, the functionalized polyolefin may be mixed with unfunctionalized polyolefins, for example, a highly functionalized polyolefin may be diluted with unfunctionalized polyolefin to improve properties or reduce cost.
Elastomers useful in the blends of the present invention may include elastomeric olefin copolymers, selectively hydrogenated block copolymers and elastomeric acrylic containing polymers made by the emulsion process. The~e elastomers may or may nct be functionalized.
Elastomeric acrylic containing polymers are well known in the art and are described in U.S. Patents 3,668,274 and 4,5~4,344.
Elastomeric copolymers of ethylene, at least one C3 to C6 ~-monoolefin, and at least one nonconjugated diene are well known in the art. These copolymers have a substantially saturated hydro-carbon backbone chain which causes the copolymer to be relatively inert to ozone attack and oxidative degradation and have side-chain unsaturation available for sulfur curing.
These copolymers are conveniently prepared by copolymerizing the monomers in the presence of a coordination catalyst system such as diisobutylaluminum chloride and vanadium oxytrichloride.
Copolymerization may be conducted in an inert solvent or in a slurry or particle form reactor. Details of their preparation are 25 given, for example, in U.S. Patent Nos. 2,~33,4~0; 2,962,451;
3,000,866; 3,093,620; 3,093,621; 3,063,973; 3,147,230; 3,154,528;
3,~60,708; and M. Sittig, "Stereo Rubber and Other Elastomer Processes," Noyes Development Corporation, Park Ride, N.J., 1967.
Propylene is normally selected as the ~-monoolefin in preparing such copolymers because of its availability and for reasons of economics. Other lower ~-monoolefins, such as l-butene, l-pentene, and l-hexene can be selected in place of or in addition to ~ropylene in preparing elastomeric copolymers which are useful in practicing the invention. The term EPDM as used herein r~fers to ~he preferred copolymers of ethylene, propylene, and at least one noncon~ugated diene.
, ~ ~ , " , .,~ , , ~322~7 An espscially preferred class of EPDM is that in which the nonconjugated diene is monoreactive. Monoreactive nonconjugated dienes have one double bond which readily enters the copolymerization reaction with ethylene and propylene, and a second double bond which does not, to any appreciable extent, enter the copolymerization reaction. Copolymers of this class have maximum side chain unsaturation for a given diene content, which unsaturation is available for adduct formation. Gel content of these copolymers is also minimal since there is minimal cross-linking during copolymerization.
Monoreactive nonconjugated dienes which can be selected in preparing this preferred class of EPDM copolymer include linear aliphatic dienes of at least six carbon atoms which have one terminal double bond and one internal double bond, and cyclic dienes wherein one or both of the carbon-to-carbon double bonds are part of a carbocyclic ring. Of the linear dienes, copolymers of ethylene, propylene, and 1,4-hexadiene having an inherent viscosity of at least about l.S are especially preEerred.
Classes of cyclic dienes useful in preparing the preferred class of EPDM copolymers for adduct formation include alkylidene bicycloalkenes, alkenyl bicycloalkenes, bicycloalkadienes, and alkenyl cycloalkenes. Representative of alkylidene bicycloalkenes are 5-alkylidene-2-norbornenes such as 5-ethylidene-2-norbornene and 5~methylene-2-norbornene. Representative of alkenyl bicyclo-alkenes are 5-alkenyl-2-norbornenes such as 5-(1'-propenyl)-2-norbornene, 5-(2'-butenyl)-2-norbornene, and 5-hexenyl-2-norbornene.
D~cyclopentadiene and 5-ethyl-~,5-norbornadiene are illustrative of bicycloalkadienes, and vinyl cyclohexane is representative of alkenyl cycloalkenes which may be selected as the diene monomer.
EPDM copolymers prepared from cyclic dienes preferably have an inherent viscosity within the range of about 1.5 to 3.0, as measured on 0.1 gram copolymer dissolved in 103 milliliters of perchloro-ethylene at 30C, for optimum processing propert~es. Of the cyclic dienes, S-ethylidene-2-norbornene ~s preferred.
~322~
Another class of preferred copolymers includes branched tetrapolymers made from ethylene, at least one C3 to C5 ~-monoolefin with propylene being preferred, at least one monoreactive non-conjugated diene, and at least one direactive nonconjugated diene such as 2,5-norbornadiene or 1,7-octadiene. By "direactive" i5 meant that both double bonds are capable of polymeri~ing during preparation of the copolymer. Tetrapolymers of thls class preferably have an inherent viscosity of about 1.2 to 3.0, as measured on 0.1 gram copolymer dissolved in 100 milliliters of perchloroethylene at 30C, for optimum processing properties. A preferred copolymer of this class ls a tetrapolymer of ethylene, propylene, 1,4-hexadiene, and 2,5-norbornadiene. Such copolymers are described in Canadian Patents Nos. 855,774 and 897,895.
Copolymers of the classes defined above have low gel content, a substantia:Lly saturated hydrocarbon backbone which is resistant to o70ne and oxidative degradation, and hydrocarbon side-chain unsaturation which presents sites for the thermal addition of maleic anhydride, fumaric acid, and other species capable of thermal addition to the above mentioned side-chain unsaturation.
Low gel content is indicative of a polymer having favorable processing properties.
Although the present invention will be discussed în relationship to thermal addition of maleic anhydride to from a graft, it is understood that in the present inventîon maleic acid or f~maric acid may be directly substituted for maleic anhydride to form the same adduct. The adduct containing succinic groups attached to the elastomeric copolymer contains these groups with use of a starting material of maleic anhydride, maleic acid or fumaric acid. Maleic anhydride, maleic acid and iumaric acid are equivalents to one another to produce thc same type of graft containing the same succinic groups. Therefore, the remarks made herein in use of maleic anhydride also refer to maleic acid and fumaric acid. Also, the use of other thermal reactions with this hydrocarbon side-chain unsaturation may be used for the present invention.
~ 3~2~
Using a copolymer of ethylene, propylene, and 1,4-hexadiene, thermal addition of maleic anhydride to the copolymsr is theorized to occur by the following equation:
Polymer Backbone Polymer Backbone CH CH = CH ______~ CH fH2-C
H + l~ / C~ HC - CH -C
A molecule of maleic anhydride adds to the polymer at the site of side chain unsAturation to give a succinic anhydride radical bonded to the side chain. Said chain uncaturation shifts by one carbon atom. It will be understood that side chain unsaturation can also shift away fro~ the backbone chain when the unsaturation is several carbon atoms removed from the terminal side chain carbon atom, as in copolymers of ethylene, propylene, and 1,4-octadiene.
However, it has been further found that in addition to the adduct containing succinic anhydride att:ached to the elastomeric copolymer, succinic acid groups can alscl be attached to the copolymer.
Generally the adduct will contain succinic groups attached to the copolymer as a mix~ure of succinic anhyclride and succinic acid.
In this disclosure "succinic groups" will include succinic anhydride, succinic acid or a combination of succinic anhydride and succinic acid.
The adducts of this invention can be prepared by any process which intimately mixes ~aleic anhydride ~ith the copolymer without appreciable generation of free radicals, and which concurrently or subsequently heats the mixture to a temperature whereat thermal addition occurs. Selected temperature~ will generally be 2t least 225C to obtain adduct i`or~ation at acceptable rates and less than about 350C to avoid any significant polymer breakdown. Preferred temperature ranges will vary with the particular polymer and can readily be determined by one skilled in the art.
Mixing of the maleic anhydride and copolymer can be by blending molten anhydride with copolymer in an internal mixer or extruder, or by blending finely divided dry maleic anhydride with copolymer on a well-ventilated rubber mill with concurrent or subsequent heating, such as in a hot press or mold. Temperatures necessary to achieve thermal grafting are sufficiently high to dehydrate maleic acid, forming maleic anhydride in situ. Thus, maleic acid can be compounded with the copolymer instead of maleic anhydride when such is desired. The maleic al~ydride can be substituted with groups, such as bromine or chlorine, which do not unduly interfere with the graft reaction.
~referred copolymers of ethylene, propylene, and 1,4-hexadiene are very resistant to free radical formation under high shear stress conditions and are readily mixed on conventional bul~
processing equipment without gel formation. Care must be exercised, however, in selecting the mixing conditions for copolymers derived from strained ring dienes such as ethylidene norbornene. Such copolymers will readily generate free radicals when sheared at low temperatures, and are preferably mixed with maleic anhydride at high temperature, such as above 90C to avoid appreciable gel formation.
It is generally desired to form adducts containing about 0.02 to 20~, and preferably about 0.1 to 10~, by weight maleic anhydride.
Adducts containing such quantities of m~leic anhydride have sufficient carboxylated sites for ionic curing or grafting of the copolymer.
To achieve a desired degree of adduct formation within a reasonable time, high concentrations of reactants are help~`ul. One will generally select a polymer having about twice the amount of side-chain unsaturation as is stoichiometrically required ~or the desired amount of maleic anhydride incorporation. S~milarly, about twice as much maleic anhydride is added as is desired ln the polymer adduct. Conversion o~ about 40 to 50% of the maleic :L32~7~
-14- $3293-~847 anhydride will resul~ in copolymer adduct having ~he desired compo~ition. For example, if one desires to obtain an ethylene/propyleneJl,4-hexadiene copolymer having 2.2 weight percent maleic anhydride content, he could conveniently mix a copolymer having 0.49 moles side~chain unsaturation per kilogram of polymer with 0.49 moles maleic anhydride and heat the mixture to convert 45~ of the anhydride, thereby obtai.ning the desired product.
It is often desirable to perform further reactions on the derivatized elastomeric olefin copolymer. For example, a copolymer containing succinic groups may be esterified with hydroxy-containing compounds.
Block copolymers of conjugated dienes and vinyl aromatic hydrocarbons which may be utilized include any of those which exhibit elastomeric properties and those which have 1,2-microstructure con~ents prior ~o hydrogenation of from about 7% to about 100% and preferably from about 35 to 50% of the condensed butadiene units. Such block copolymers may be multiblock copolymers of varying structures containing various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up ko about 60 percent by weight o~ vinyl aromatic hydrocarbon. Thus, multiblock copolymers may be utilized which are linear or radial symmetric or asymmetric and which have structures represented by the formula Bn~AB)oAp where n = 0 or 1, o = 1 to 100 and p-0 or 1, to which has been grafted an acid compound or its derivative wherein, (1) each A is predominantly a polymerized monoalkenyl aromatic hydrocarbon block havin~ an average molecular weight of 2,000 ~ ~22~7 -l~a- 63293-28~7 to 115,000;
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
(4) ~he unsaturation of the block B is less than 10% of the original unsaturation.
Preferred copolymers have structures represented by formulae A-B, A-B-A, A-B-A~B, B-A-B, (AB)o 1 2 BA and the like wherein A is a polymer block o~ a vinyl aromatic hydrocarbon or a conjuga~ed diene/vinyl aromakic hydrocarbon tapered copolymer block and B is a polymer block of a conjugated diene.
The block copolymers may be produced by any well known block polymerization or copolymerizati~on procedures i.ncluding the well~known sequential addition of monomer techniques, incremental addition of monomer technique or coupling technique as illustrated in, for example, U.S. Patent Nos. 3,251,905; 3,390,207; 3,598,887 ar~d 4,219,627. As i5 well known in the hlock copolymer art, tapered copolymer blocks can be incorporated in the multiblock .
copolymer by copolymeri~ing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers utilizing the difference in their copolymerization reactivity rates. Various patents describe : the , 1 ~ ~ 2 l 9 7 6~293-2847 preparation of mul~lblock copolymers containing tapered copolymer blocks including Uni~ed States Patent Nos. 3,251,905; 3,265,765;
3,639,521 and 4,208,356.
Con~ugated dienes which may be utllized to prepare the polymers and copolymers are those having from 4 to 8 carbon atoms and include 1,3-butadiene, 2-methyl-1,3-butadlene (isoprene), 2,3 dimethyl-1,3-butadiene~ 1,3-pentadiene, 1,3-hexadiene, and the like. Mixtures of such conjugated dienes may also be used. The preferred conjugated diene is 1,3-butadiene.
Vinyl aromatic hydrocarbons which may be utilized to prepare copolymers include styrene, o-methylstyrene, p-methyl-styrene, p-tert-butylstyrene, 1,3-dimethylstryrene, alpha~
methylstyrene, vinyl-naphthalene, vinylanthracene and the like.
The preferred vinyl aromatic hydrocarbon is styrene.
It should be observed that the above-described polymers and copolymers may, if desired, be readily prepared by the methods set ~orth hereinbe~ore. However, s:Lnce many of these polymers and copolymers are commerclally avallable, it is usually pre~erred to employ the commercially available polymer as this serves to reduce the number of processing s~eps involved in the overall process.
; The hydrogenatlon of these polymers and copolymers may be carried out by a variety of well established processes including hydro genation in the presence oi such catalysts as Raney Nickel, noble metals ~uch as platinum, palladium and the like and soluble transition metal catalysts. Sultable hydrogenation processes which can be used are ones wherein ~he diene-con~aining polymer or copolymer ls dissolved in ~n inert hydrocarbon diluent such as ~5 A
~ ~227~
cyclohexane and hydrogenated by reaction with hydrogen in the presence of a sol~ble hydrogenation catalyst. Such processes are disclosed in United 5tates Paten~ Nos. 3,113,986 and ~,226,952.
The polymers and copolymers are hydrogenated in such a manner as to produce hydrogenated polymers and copolymers having a residual unsaturation content in the polydiene block of from ahout 0O5 to about 20 per cent of their original l~nsaturation content prior to hydrogenation. It is preferred that less than 10% of the monoalkenyl aromatic hydrocarbon units in block A are hydrogenated. It is, however, not excluded that an average from 25~ ~o 50% of the monoalkenyl aromatic hydrocarbon units are hydrogenated. The average unsaturatlon of the hydrogenated block copolymer is preferably reduced to less than 20% of it~ original value.
Block A pre~erably has an average molecular weight in the range of from 4~000 to 60,000 and block B has an average molecular weight in the range of from 35,000 to 150,00Q.
In general, any materials having the ability to react with the block copolymer in que~tion, in free radi~al initiated reactions or thermal addition reaGtions are operable for the purposes of the lnvention.
Monomers may be polymerizable or nonpolymerizable, however, preferred monomers are nonpolymerizable or slowly poly-merlzing. United States Patent 4,427,828 dlscloses block co polymers made by the thermal addition reaction. Free radically produced block copolymers and free radical me~hods are disclosed in Canadlan patent application Nos. 488,172 and 488,156.
In free radical reactions the monomers must be .~
~2~7~7 ethylenically unsaturated in order to be graftable. We have found that by grafting unsaturated monomers which have a slow polymerization rate the resulting graft copolymers contain little or no homopolymer of the unsa~urated monomer and contain only short graf~ed ~onomer chains which do not phase separate into separate domains.
The class of preferred monomers which will form graft polymers within the scope o~ the present invention have one or more functional groups or their derivatives such as carboxylic acid groups and ~heir salts, anhydrides, es~ers, imide groups, amide groups, acid chlorides and the like in addition to at least one point of unsaturation.
These ~unctionalities can be subsequently reacted with other modifying material~ to produce new functional groups. For example .
;:
ZO
16a .¢,,'~ .
.
322'~
a graft of an acid-containing monomer could be suitably modified by esterifying the resulting acid groups in the graft with appropriate reaction with hydroxy-containing compounds of varying carbon atoms lengths. The reaction could take place simultaneously with the grafting or in a subsequent post modification reaction.
The grafted polymer will usually contain from 0.02 to 20, preferably 0.1 to 10, and most preferably 0.2 to 5 weight percent of grafted portion.
The preferred modifying monomers are unsaturated mono- and polycarboxylic-containing acids tG3-Clo) with pre~erably at least one olefinic unsaturation, and anhydrides, salts, esters, ethers, amides, nitriles, thiols, thioacids, glycidyl, cyano, hydroxy, glycol, and other substituted derivatives from said acids.
Examples of such acids, anhydrides and derivatives thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic aci~, glycidyl acrylate, cyanoacrylates, hydroxy Cl-C20 alkyl methacrylates, acrylic polyethers, acrylic anhydride, methacryllc acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, acrylonitrile, methacrylonitrile, sodium acrylate, calcium acrylate, and magnesium acrylate.
Other monomers which can be used either by themselves or in combination with one or more o the carboxylic acids or derivatives therPof include C2-C50 vinyl monomers such as acrylamide, acrylo-nitrile and monovinyl aromatic compounds, i.e. styrene, chloro-styrenes, bromostyrenes, ~-methyl styrene, vinyl pyridines and the like.
Other monomers which can he used are C4 to C50 vinyl esters, vinyl ethers and allyl esters, such as vinyl butyrate, vinyl laurate, vinyl stearate, vinyl adipate and the like, and monomers having two or more vinyl groups, such as divinyl benzene, ethylene dimethacrylate, triallyl phosphite, dialkylcyanurate and triallyl cyanurate.
The preferred monomers to be grafted to the block copolymers according to the present invention are maleic anhydride, maleic ~ 3 ~ 7 acid, fumaric acid and their derivatives. It is well known in the art that these monomers do not polymerize easily.
The block copolymer may also be grafted with a sulphonic acid or a derivatlve thereof.
Of course, mixtures of monomer can be also added so as to achieve graft copolymers in which the graft chains originate from at least two different Monomers therein (in addition to the base polymer monomers).
The modified block copolymer for blending according to the present invention may be prepared by any means known in the art, for example, graft-reacting an acid moiety or its derivative with an aromatic vinyl cGmpound-conjugated diene compound block copolymer containing at least one polymer block AB mainly composed of a conjugated diene compound at least one polymer block BA mainly composed of an aromatic vinyl compound, wherein said graft reaction is carried out by melt or solution mixing said block copolymer and said acid moiety in the presence of a free radical initiator and wherein each A is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 2,000 to 115,000;
each B is a polymerized con~ugated diene hydrocarbon block having an average molecular weight of about 20,000 to 450,000; the blocks A constitute 5-95 weight percent of the copolymer; 40-55 mol percent of the condensed butadiene units in block B have a 1,2-configuration; the unsaturation oi the block B is reduced to less than 10~ of the original unsaturation; and the unsaturation of the A blocks is above 50% of the original unsaturation.
The toughened compositions of this invention can be prepared by melt blending, in a closed system, a polyamide, a functionalized polyolefin and an elastomer into a uniform mixture in a multi-screw extruder such as a ~erner Pfleiderer extruder having generally 2-5 - kneading blocks and at least one reverse pitch to generate high shear, or other conventional plasticating devices such as a Brabender, Banbury mill, or the like. Alternatively, the blends may be made by coprecipitation from solution, blending or by dry mi~ing together of the components followed by melt fabrication of the dry mixture by extrusion.
63293-2~47 Another method of preparing the blend would be to func~ionalize the elastomer in the presence of the polyolefin as described in Canadian patent application 545,938.
The impact resis~ant polymeric composition may be prepared by melt-blending from 1 per cent to 95 per cent by weight pre~erably from 10 per cent to 70 per cent or more pre~erably 15 per cent to 45 per cent of the polyamide, from 1 per cent to 95 per cent by weight, preferably from 10 to 70 and particularly from 15 to 45 per cent of a functionalized polyolefin, and from 1 per cent to 50 per cen~ by weight, preierably from 15 per cent to 35 per cent or more preferably 10 per cent to 25 per cent of an elastomer.
The compositions of the invention may be modified by one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation;
lubricants and mold release agents, colorants including dyes and pigments, f1brous and particulate i-illers and reinforcements, nucleating agents, plasticizers, etc.
The stabili7ers can be incorporated into the composition at any stage in the pr~para~ion of khe thermoplastic composi~ion.
Pre~erably the stabilizers are included early to preclude the i~itiation of degradation be~ore the composition can be protected.
Such stabili~ers must be compatible with the composition.
The oxidative and thermal stabilizers useful in the materials of the present invention include those used in addition polymers generally. They include, for example, up to 1 per cent by weight, based on the ~eight o~ polyamide of Group I metal 19.
~3~97 63293-2~47 halides, e.g., sodium, potassium, llthium with cuprous halides, e.g., chloride, bromide, iodide, hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
The ultraviolet light stabilizers, e.g., up to 2.0 per cent, based on the weight of polyamide, can also be those used in addition polymers generally. Examples of ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles, beDzophenones, and the like.
:
.
:
.
l9a .~.
:L3227~
Suitable lubricants and mold release agents, e.g., up to l.0 per cent, based on the weight of the composition, are stearic acid, stearic alcohol, stearamides, organic dyes such as nigrosine, etc., pigments, e.g., titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyamines, ultramarine blue, carbon black, PtC up to 50 per cent, based on the weight of the composition, of fibrous and particulate fillers and reinforcements, e.g., carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, fildspar, etc.; nucleating agent, e.g., talc, calcium fluoride, sodium phenyl phosphinate, alumina, and finely diYided polytetra-fluoroethylene, etc.; plasticizers; up to about 20 per cent, based on the weight of the composition, e.g., dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-normal butyl benzene sulfonamide, ortho and para toluene ethyl sulfonamide, etc.
The colorants (dyes and pigments) can be present in an amount of up to about 5.0 per cent by weight, based on the weight of the composition.
It is to be understood that in the specification and claims ~ herein, unless othen~ise indicated, when in connection with melt-blending, the amount oi the polyamide or block copolymer is expressed in terms of percent by weight it is meant percent by weight based on the total amount of these materials whlch is employed in the melt-blending.
EX~MPLES
To assist those skilled in the art in the practice Df this invention, the following Examples are set forth BS illustrations, parts and percentages being by weight unless otherwise specifically noted. The moulded bars were tested using the following test procedures in the dry-as-moulded state:
Notched Izod toughness: at each end ASTM D-256~56 Flexural Modulus: hSTM D-790-58T
Examples 1 and 2 and Comparative Experiments A-C
Preparation of Modi ied Block Copolymer by Solution Process The block copolymer used was a styrene-ethylene/butylene-styrene ' ''. ' ' '','.'' ' ~ ' .
"
. .
~ 32~7~7 block copolymer containing 29 weight ~ styrene with a molecular weight of 54,000. This polymer was modified with maleic anhydride in a solution free L-adical initiated reaction, because it cannot be melt-processed in the pure form maleic anhydride (104.5 g) and benzoyl peroxide initator (104.5 g) were dissolved in 32 kg of cyclohexane. This mixture was transferred to a 57 1 stainless steel stirre~ pressure reactor with an oil jacket heater. The reactor contents were heated from ambient temperature to the boiling point of cyclohexane (81C) over a two hour time period.
The heaters were turned off and the reactor contents were allowed to cool to about 40C. Water (0.95 1) and 10 g of antioxidant Ethyl 330 were then added to the vessel. The mixture was then transferred to a Binks vessel and coagulated by steam stripping.
Colorometric titration with potassium methoxide and phenolphthalein indicator was used to determine the maleic anhydride content of the polymer. This modified copolymer was found to contain 0.5~ by weight of grafted maleic anhydride.
Blending of N66 and Solution Modified Block Copolymer Prior to blending, the modified block copolymer was dried at 100C at sub-atmospheric pressure with a nitrogen purge for four hours. The thermoplastic polyamide used in this example was a commercial nylon 65 moulding grade having the trade name Zytel 101 and obtained from E. I. DuPont Company. Prior to all processing steps, the nylon 66 and its blends were dried at 120C for four hours at sub-atmospheric pressure with a nitrogen purge.
Blends of nylon 66 with both unmodified and modified block copolymer were prepared in a 30 mm diameter corotating twin screw extruder. The blend components were premixed by tumbling in polyethylene bags. A stabilizer package, O.5wt~ of the total material, made up of a 3:1 ratio of a phosphite and sterically hindered phenol antioxidant was inclu~ed in the composition. The extruder melt temperature prGfile varied from 270C in the feed zone to 285C at the die. The screw rotated at 300 revolutions per minute (rpm). The extrudate was pelletized and injection molded into test specimens. The formulations and physical properties are shown in Table 1.
, 1322 ~97 Composition (parts by wei~ht) Comparative Experiment A B C
Example 1 2 Nylon 66 100 80 70 80 70 Unmodified Block Copolymer -- 20 30 -- --Modified Block Copolymer -- -- -- 20 30 0.32 cm Dry as Moulded Room 43 80 80 1050 1430 Temperature Notched Izod (J/m) Compari.son of Experiments A, B and C with Examples 1 and 2 shows that blends of modified block copolymer and Nylon 66 have a considerably higher impact strength than the Nylon 66 alone or blends of Nylon 66 with unmodified block copolymer.
Examples 3-8 and Comparative Experiments D-~Preparation of Modified Block Copolymer by Melt Process The block copolymer used in the following example was KRATON
G-1652 Rubber, a commercial S-EB-S materialj which can be melt processed neat. This polymer was melt~reacted with maleic anhydride and Lupersol 101 in a 30mm diameter corotating twin screw extruder.
"Lupersol 101" is a trade name for 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane.
e reactants were premixed by tumbling in polyethylene bags, ~and then fed into the extruder. AlI extrusion conditions except 15 for reactan~ concentrations were kept constant. The melt temperature was varied from 150C in the feed zone to 260C at the die. A
~ screw speed of 350 rpm was used.
;~ Samples prepared in the above manner were analyzed for bound maleic by extracting the soluble fraction in refluxing tetrahydro-furan, recovering the soluble fraction by precipitation of the extractant into isopropyl alcohol, and titrating the dried precipitate using the method described in Example 1. Table 2 shows the reactant concentrations examined, as well as analytical results for the material prepared.
~ 3227~7 Wt.~ Maleic Wt.~ Wt.% Maleic Anhydride Lupersol 101 Anhydride grafted Polymer _ added added onto THF Solubles X 3 0.01 ~.2 Y 3 0.10 1.6 Blendin~ of Nylon 66 and Modified Block Copolymers_Prepared by Melt Process Blends of Nylon 66 with both modified and unmodified block copoly~er, were prepared in the manner described in Examples 1-2.
The formulations and physical properties are shown in Table 3. The physical propertles are for dry as moulded material.
`
~: ~
::
:
' .
.
-~32~7~7 O ~
o o I o o ~ oo ~
o , , o o ~ ~ o ~D I~ I I ~ C~l o , o o 1~r~
U~ o,~ o ,~ C~l ,............. ... ..
o I o v ~ ¦ ~
~: 3 c~l o o . I o:
~1 ~
0 ~
:: ` ~3 O O ~ O~ I I I ~i JJ
~ o: - ~ I~
o ~ ~ -`
: : ~: g ~
; ~ ~ NO ~ S~ o 0: 0 H O ~~:) O
X :~ o ~ ~: ~
G) O ~ ~:: 0 C~ , E~ ; V O ~ : , ~I E3 0 0 ~1 r~ ~ t O
~ ~ O ~ ~ ~
~ O ~ ~
' :' :
:
~3~2797 Comparison of Experiments D-G with Examples 3-8 shows that blends of modified block copolymer used have a considerably higher impact strength than the Nylon 66 or blends of Nylon 66 and unmodified block copolymer.
Blends According to the Present Invention Examples 9-19 and Comparative Experiments H-K
In the following examples Block copolymer 1 - S-EB-S 33~ styrene M.W. 181,000 PP 5520 - Injection moulding grade propylene homopolymer from Shell Chemical PP MA 0.16 and Maleic anhydride grafted polypropylenes with PP MA 1.0 functionalization given in weight percent.
Dry as moulded physical properties of blends exemplifying the present invention are given in Table 4.
~32~797 , , C`l I o C~ .
C~l C~U~
U~ o , , U~~ ~ o ,~
~D
I O IU~
u) I,~ I ~ I,~ r~
~1 ~ 1~ N
L~ I O Irl ~1 ~1 ~
U~ I U~ I ~ ~I` U~ ~D 1`.
''I cr~ c~
O I O O I I U~ I' ~ O
;t u l I c~l ~ I Icr~ O ~ u~
~1 ~ 0 ,~ 1 I I I I o~
~ ~D1~ 00 : ~ ~ O ~ I O I r~
~4 '711'7 1 1 1 u~ I ~ cn . .
0~
O I I O I I
~ O ~D
:~ ~ ~
O i I ~ O C~l ~ ~ O
0 0 0 1 C:~ IO _IC~l ~t -I ~ ~
0~ ~ O I 1~ ~ ~ ~
,_1 : C~ ~1C~O ' O, I O I O IC~ ~ ~ ~
1 ~ I 0~ 0 ~
O O I 1 0 1 ~ O~
0 ~0 1 0 1 1 ~ ~ ~ 00 U~
pO ~ N
0~ B ~
a ~ ~ ~ ~ ~ ~ ~ æ ~ ~ ~4 ~ ~ ~
~3227~7 - 27 - 63293-20~7 Examples 20 and 21 In the following examples Zy~el ST B01, an EPDM anhydride toughened nylon b3end manufactured by duPont was used.
Example 20 21 S'l' ~01 50 50 Block Copolymer 1 10 10 PP MA 0.16 -- 40 Tested Dry As Moulded:
Notchcd Izod (MN/m ) ?03 657 Flexural Modulus (MN/m ) 1393 12B2 Examples 22-24 S In the following examples modified block copolymer Z is an S-EB-S block copolymer modified with maleic anhydricle and poly-propylene as described in co-pending Canadian application Sr # 545,9.38.The ratio of polypropylsne Co block copolymer in che starting material was 1:3.
Examples 22 23 24 : Nylon 6S 40 40 40 Modlfied Block Copolymer Z 29 29 29 PP ~520 31 16 --PP MA 0.16 -- 15 31 Tested Dry As Moulded:
Nocclled Izocl (MN/m ) 262 46~l 673 F'lexl~rn3. Moclulu (MN~m2)1145 10~9 1083 t ~
~32~7~7 Comparative Experiments H-K and examples 9-19 show that in nylon blends containin~ polyolefins and block copolym2rs, when one or both of the polyolefin or block copolymers are functlonalized, the balance of ultimate and low strain properties are significantly improved.
Examples 20 and 21 show that similar improved properties are obtained when the elastomer is maleic anhydride functionalized olefin copolym~r.
Examples 22-24 show that improved properties can be also obtained by blending with a modified mixture of polyolefin and elastomer which has been prepared by simultaneously subjecting both components to a functionalization reaction.
Preferred copolymers have structures represented by formulae A-B, A-B-A, A-B-A~B, B-A-B, (AB)o 1 2 BA and the like wherein A is a polymer block o~ a vinyl aromatic hydrocarbon or a conjuga~ed diene/vinyl aromakic hydrocarbon tapered copolymer block and B is a polymer block of a conjugated diene.
The block copolymers may be produced by any well known block polymerization or copolymerizati~on procedures i.ncluding the well~known sequential addition of monomer techniques, incremental addition of monomer technique or coupling technique as illustrated in, for example, U.S. Patent Nos. 3,251,905; 3,390,207; 3,598,887 ar~d 4,219,627. As i5 well known in the hlock copolymer art, tapered copolymer blocks can be incorporated in the multiblock .
copolymer by copolymeri~ing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers utilizing the difference in their copolymerization reactivity rates. Various patents describe : the , 1 ~ ~ 2 l 9 7 6~293-2847 preparation of mul~lblock copolymers containing tapered copolymer blocks including Uni~ed States Patent Nos. 3,251,905; 3,265,765;
3,639,521 and 4,208,356.
Con~ugated dienes which may be utllized to prepare the polymers and copolymers are those having from 4 to 8 carbon atoms and include 1,3-butadiene, 2-methyl-1,3-butadlene (isoprene), 2,3 dimethyl-1,3-butadiene~ 1,3-pentadiene, 1,3-hexadiene, and the like. Mixtures of such conjugated dienes may also be used. The preferred conjugated diene is 1,3-butadiene.
Vinyl aromatic hydrocarbons which may be utilized to prepare copolymers include styrene, o-methylstyrene, p-methyl-styrene, p-tert-butylstyrene, 1,3-dimethylstryrene, alpha~
methylstyrene, vinyl-naphthalene, vinylanthracene and the like.
The preferred vinyl aromatic hydrocarbon is styrene.
It should be observed that the above-described polymers and copolymers may, if desired, be readily prepared by the methods set ~orth hereinbe~ore. However, s:Lnce many of these polymers and copolymers are commerclally avallable, it is usually pre~erred to employ the commercially available polymer as this serves to reduce the number of processing s~eps involved in the overall process.
; The hydrogenatlon of these polymers and copolymers may be carried out by a variety of well established processes including hydro genation in the presence oi such catalysts as Raney Nickel, noble metals ~uch as platinum, palladium and the like and soluble transition metal catalysts. Sultable hydrogenation processes which can be used are ones wherein ~he diene-con~aining polymer or copolymer ls dissolved in ~n inert hydrocarbon diluent such as ~5 A
~ ~227~
cyclohexane and hydrogenated by reaction with hydrogen in the presence of a sol~ble hydrogenation catalyst. Such processes are disclosed in United 5tates Paten~ Nos. 3,113,986 and ~,226,952.
The polymers and copolymers are hydrogenated in such a manner as to produce hydrogenated polymers and copolymers having a residual unsaturation content in the polydiene block of from ahout 0O5 to about 20 per cent of their original l~nsaturation content prior to hydrogenation. It is preferred that less than 10% of the monoalkenyl aromatic hydrocarbon units in block A are hydrogenated. It is, however, not excluded that an average from 25~ ~o 50% of the monoalkenyl aromatic hydrocarbon units are hydrogenated. The average unsaturatlon of the hydrogenated block copolymer is preferably reduced to less than 20% of it~ original value.
Block A pre~erably has an average molecular weight in the range of from 4~000 to 60,000 and block B has an average molecular weight in the range of from 35,000 to 150,00Q.
In general, any materials having the ability to react with the block copolymer in que~tion, in free radi~al initiated reactions or thermal addition reaGtions are operable for the purposes of the lnvention.
Monomers may be polymerizable or nonpolymerizable, however, preferred monomers are nonpolymerizable or slowly poly-merlzing. United States Patent 4,427,828 dlscloses block co polymers made by the thermal addition reaction. Free radically produced block copolymers and free radical me~hods are disclosed in Canadlan patent application Nos. 488,172 and 488,156.
In free radical reactions the monomers must be .~
~2~7~7 ethylenically unsaturated in order to be graftable. We have found that by grafting unsaturated monomers which have a slow polymerization rate the resulting graft copolymers contain little or no homopolymer of the unsa~urated monomer and contain only short graf~ed ~onomer chains which do not phase separate into separate domains.
The class of preferred monomers which will form graft polymers within the scope o~ the present invention have one or more functional groups or their derivatives such as carboxylic acid groups and ~heir salts, anhydrides, es~ers, imide groups, amide groups, acid chlorides and the like in addition to at least one point of unsaturation.
These ~unctionalities can be subsequently reacted with other modifying material~ to produce new functional groups. For example .
;:
ZO
16a .¢,,'~ .
.
322'~
a graft of an acid-containing monomer could be suitably modified by esterifying the resulting acid groups in the graft with appropriate reaction with hydroxy-containing compounds of varying carbon atoms lengths. The reaction could take place simultaneously with the grafting or in a subsequent post modification reaction.
The grafted polymer will usually contain from 0.02 to 20, preferably 0.1 to 10, and most preferably 0.2 to 5 weight percent of grafted portion.
The preferred modifying monomers are unsaturated mono- and polycarboxylic-containing acids tG3-Clo) with pre~erably at least one olefinic unsaturation, and anhydrides, salts, esters, ethers, amides, nitriles, thiols, thioacids, glycidyl, cyano, hydroxy, glycol, and other substituted derivatives from said acids.
Examples of such acids, anhydrides and derivatives thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic aci~, glycidyl acrylate, cyanoacrylates, hydroxy Cl-C20 alkyl methacrylates, acrylic polyethers, acrylic anhydride, methacryllc acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, acrylonitrile, methacrylonitrile, sodium acrylate, calcium acrylate, and magnesium acrylate.
Other monomers which can be used either by themselves or in combination with one or more o the carboxylic acids or derivatives therPof include C2-C50 vinyl monomers such as acrylamide, acrylo-nitrile and monovinyl aromatic compounds, i.e. styrene, chloro-styrenes, bromostyrenes, ~-methyl styrene, vinyl pyridines and the like.
Other monomers which can he used are C4 to C50 vinyl esters, vinyl ethers and allyl esters, such as vinyl butyrate, vinyl laurate, vinyl stearate, vinyl adipate and the like, and monomers having two or more vinyl groups, such as divinyl benzene, ethylene dimethacrylate, triallyl phosphite, dialkylcyanurate and triallyl cyanurate.
The preferred monomers to be grafted to the block copolymers according to the present invention are maleic anhydride, maleic ~ 3 ~ 7 acid, fumaric acid and their derivatives. It is well known in the art that these monomers do not polymerize easily.
The block copolymer may also be grafted with a sulphonic acid or a derivatlve thereof.
Of course, mixtures of monomer can be also added so as to achieve graft copolymers in which the graft chains originate from at least two different Monomers therein (in addition to the base polymer monomers).
The modified block copolymer for blending according to the present invention may be prepared by any means known in the art, for example, graft-reacting an acid moiety or its derivative with an aromatic vinyl cGmpound-conjugated diene compound block copolymer containing at least one polymer block AB mainly composed of a conjugated diene compound at least one polymer block BA mainly composed of an aromatic vinyl compound, wherein said graft reaction is carried out by melt or solution mixing said block copolymer and said acid moiety in the presence of a free radical initiator and wherein each A is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 2,000 to 115,000;
each B is a polymerized con~ugated diene hydrocarbon block having an average molecular weight of about 20,000 to 450,000; the blocks A constitute 5-95 weight percent of the copolymer; 40-55 mol percent of the condensed butadiene units in block B have a 1,2-configuration; the unsaturation oi the block B is reduced to less than 10~ of the original unsaturation; and the unsaturation of the A blocks is above 50% of the original unsaturation.
The toughened compositions of this invention can be prepared by melt blending, in a closed system, a polyamide, a functionalized polyolefin and an elastomer into a uniform mixture in a multi-screw extruder such as a ~erner Pfleiderer extruder having generally 2-5 - kneading blocks and at least one reverse pitch to generate high shear, or other conventional plasticating devices such as a Brabender, Banbury mill, or the like. Alternatively, the blends may be made by coprecipitation from solution, blending or by dry mi~ing together of the components followed by melt fabrication of the dry mixture by extrusion.
63293-2~47 Another method of preparing the blend would be to func~ionalize the elastomer in the presence of the polyolefin as described in Canadian patent application 545,938.
The impact resis~ant polymeric composition may be prepared by melt-blending from 1 per cent to 95 per cent by weight pre~erably from 10 per cent to 70 per cent or more pre~erably 15 per cent to 45 per cent of the polyamide, from 1 per cent to 95 per cent by weight, preferably from 10 to 70 and particularly from 15 to 45 per cent of a functionalized polyolefin, and from 1 per cent to 50 per cen~ by weight, preierably from 15 per cent to 35 per cent or more preferably 10 per cent to 25 per cent of an elastomer.
The compositions of the invention may be modified by one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation;
lubricants and mold release agents, colorants including dyes and pigments, f1brous and particulate i-illers and reinforcements, nucleating agents, plasticizers, etc.
The stabili7ers can be incorporated into the composition at any stage in the pr~para~ion of khe thermoplastic composi~ion.
Pre~erably the stabilizers are included early to preclude the i~itiation of degradation be~ore the composition can be protected.
Such stabili~ers must be compatible with the composition.
The oxidative and thermal stabilizers useful in the materials of the present invention include those used in addition polymers generally. They include, for example, up to 1 per cent by weight, based on the ~eight o~ polyamide of Group I metal 19.
~3~97 63293-2~47 halides, e.g., sodium, potassium, llthium with cuprous halides, e.g., chloride, bromide, iodide, hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
The ultraviolet light stabilizers, e.g., up to 2.0 per cent, based on the weight of polyamide, can also be those used in addition polymers generally. Examples of ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles, beDzophenones, and the like.
:
.
:
.
l9a .~.
:L3227~
Suitable lubricants and mold release agents, e.g., up to l.0 per cent, based on the weight of the composition, are stearic acid, stearic alcohol, stearamides, organic dyes such as nigrosine, etc., pigments, e.g., titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyamines, ultramarine blue, carbon black, PtC up to 50 per cent, based on the weight of the composition, of fibrous and particulate fillers and reinforcements, e.g., carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, fildspar, etc.; nucleating agent, e.g., talc, calcium fluoride, sodium phenyl phosphinate, alumina, and finely diYided polytetra-fluoroethylene, etc.; plasticizers; up to about 20 per cent, based on the weight of the composition, e.g., dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-normal butyl benzene sulfonamide, ortho and para toluene ethyl sulfonamide, etc.
The colorants (dyes and pigments) can be present in an amount of up to about 5.0 per cent by weight, based on the weight of the composition.
It is to be understood that in the specification and claims ~ herein, unless othen~ise indicated, when in connection with melt-blending, the amount oi the polyamide or block copolymer is expressed in terms of percent by weight it is meant percent by weight based on the total amount of these materials whlch is employed in the melt-blending.
EX~MPLES
To assist those skilled in the art in the practice Df this invention, the following Examples are set forth BS illustrations, parts and percentages being by weight unless otherwise specifically noted. The moulded bars were tested using the following test procedures in the dry-as-moulded state:
Notched Izod toughness: at each end ASTM D-256~56 Flexural Modulus: hSTM D-790-58T
Examples 1 and 2 and Comparative Experiments A-C
Preparation of Modi ied Block Copolymer by Solution Process The block copolymer used was a styrene-ethylene/butylene-styrene ' ''. ' ' '','.'' ' ~ ' .
"
. .
~ 32~7~7 block copolymer containing 29 weight ~ styrene with a molecular weight of 54,000. This polymer was modified with maleic anhydride in a solution free L-adical initiated reaction, because it cannot be melt-processed in the pure form maleic anhydride (104.5 g) and benzoyl peroxide initator (104.5 g) were dissolved in 32 kg of cyclohexane. This mixture was transferred to a 57 1 stainless steel stirre~ pressure reactor with an oil jacket heater. The reactor contents were heated from ambient temperature to the boiling point of cyclohexane (81C) over a two hour time period.
The heaters were turned off and the reactor contents were allowed to cool to about 40C. Water (0.95 1) and 10 g of antioxidant Ethyl 330 were then added to the vessel. The mixture was then transferred to a Binks vessel and coagulated by steam stripping.
Colorometric titration with potassium methoxide and phenolphthalein indicator was used to determine the maleic anhydride content of the polymer. This modified copolymer was found to contain 0.5~ by weight of grafted maleic anhydride.
Blending of N66 and Solution Modified Block Copolymer Prior to blending, the modified block copolymer was dried at 100C at sub-atmospheric pressure with a nitrogen purge for four hours. The thermoplastic polyamide used in this example was a commercial nylon 65 moulding grade having the trade name Zytel 101 and obtained from E. I. DuPont Company. Prior to all processing steps, the nylon 66 and its blends were dried at 120C for four hours at sub-atmospheric pressure with a nitrogen purge.
Blends of nylon 66 with both unmodified and modified block copolymer were prepared in a 30 mm diameter corotating twin screw extruder. The blend components were premixed by tumbling in polyethylene bags. A stabilizer package, O.5wt~ of the total material, made up of a 3:1 ratio of a phosphite and sterically hindered phenol antioxidant was inclu~ed in the composition. The extruder melt temperature prGfile varied from 270C in the feed zone to 285C at the die. The screw rotated at 300 revolutions per minute (rpm). The extrudate was pelletized and injection molded into test specimens. The formulations and physical properties are shown in Table 1.
, 1322 ~97 Composition (parts by wei~ht) Comparative Experiment A B C
Example 1 2 Nylon 66 100 80 70 80 70 Unmodified Block Copolymer -- 20 30 -- --Modified Block Copolymer -- -- -- 20 30 0.32 cm Dry as Moulded Room 43 80 80 1050 1430 Temperature Notched Izod (J/m) Compari.son of Experiments A, B and C with Examples 1 and 2 shows that blends of modified block copolymer and Nylon 66 have a considerably higher impact strength than the Nylon 66 alone or blends of Nylon 66 with unmodified block copolymer.
Examples 3-8 and Comparative Experiments D-~Preparation of Modified Block Copolymer by Melt Process The block copolymer used in the following example was KRATON
G-1652 Rubber, a commercial S-EB-S materialj which can be melt processed neat. This polymer was melt~reacted with maleic anhydride and Lupersol 101 in a 30mm diameter corotating twin screw extruder.
"Lupersol 101" is a trade name for 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane.
e reactants were premixed by tumbling in polyethylene bags, ~and then fed into the extruder. AlI extrusion conditions except 15 for reactan~ concentrations were kept constant. The melt temperature was varied from 150C in the feed zone to 260C at the die. A
~ screw speed of 350 rpm was used.
;~ Samples prepared in the above manner were analyzed for bound maleic by extracting the soluble fraction in refluxing tetrahydro-furan, recovering the soluble fraction by precipitation of the extractant into isopropyl alcohol, and titrating the dried precipitate using the method described in Example 1. Table 2 shows the reactant concentrations examined, as well as analytical results for the material prepared.
~ 3227~7 Wt.~ Maleic Wt.~ Wt.% Maleic Anhydride Lupersol 101 Anhydride grafted Polymer _ added added onto THF Solubles X 3 0.01 ~.2 Y 3 0.10 1.6 Blendin~ of Nylon 66 and Modified Block Copolymers_Prepared by Melt Process Blends of Nylon 66 with both modified and unmodified block copoly~er, were prepared in the manner described in Examples 1-2.
The formulations and physical properties are shown in Table 3. The physical propertles are for dry as moulded material.
`
~: ~
::
:
' .
.
-~32~7~7 O ~
o o I o o ~ oo ~
o , , o o ~ ~ o ~D I~ I I ~ C~l o , o o 1~r~
U~ o,~ o ,~ C~l ,............. ... ..
o I o v ~ ¦ ~
~: 3 c~l o o . I o:
~1 ~
0 ~
:: ` ~3 O O ~ O~ I I I ~i JJ
~ o: - ~ I~
o ~ ~ -`
: : ~: g ~
; ~ ~ NO ~ S~ o 0: 0 H O ~~:) O
X :~ o ~ ~: ~
G) O ~ ~:: 0 C~ , E~ ; V O ~ : , ~I E3 0 0 ~1 r~ ~ t O
~ ~ O ~ ~ ~
~ O ~ ~
' :' :
:
~3~2797 Comparison of Experiments D-G with Examples 3-8 shows that blends of modified block copolymer used have a considerably higher impact strength than the Nylon 66 or blends of Nylon 66 and unmodified block copolymer.
Blends According to the Present Invention Examples 9-19 and Comparative Experiments H-K
In the following examples Block copolymer 1 - S-EB-S 33~ styrene M.W. 181,000 PP 5520 - Injection moulding grade propylene homopolymer from Shell Chemical PP MA 0.16 and Maleic anhydride grafted polypropylenes with PP MA 1.0 functionalization given in weight percent.
Dry as moulded physical properties of blends exemplifying the present invention are given in Table 4.
~32~797 , , C`l I o C~ .
C~l C~U~
U~ o , , U~~ ~ o ,~
~D
I O IU~
u) I,~ I ~ I,~ r~
~1 ~ 1~ N
L~ I O Irl ~1 ~1 ~
U~ I U~ I ~ ~I` U~ ~D 1`.
''I cr~ c~
O I O O I I U~ I' ~ O
;t u l I c~l ~ I Icr~ O ~ u~
~1 ~ 0 ,~ 1 I I I I o~
~ ~D1~ 00 : ~ ~ O ~ I O I r~
~4 '711'7 1 1 1 u~ I ~ cn . .
0~
O I I O I I
~ O ~D
:~ ~ ~
O i I ~ O C~l ~ ~ O
0 0 0 1 C:~ IO _IC~l ~t -I ~ ~
0~ ~ O I 1~ ~ ~ ~
,_1 : C~ ~1C~O ' O, I O I O IC~ ~ ~ ~
1 ~ I 0~ 0 ~
O O I 1 0 1 ~ O~
0 ~0 1 0 1 1 ~ ~ ~ 00 U~
pO ~ N
0~ B ~
a ~ ~ ~ ~ ~ ~ ~ æ ~ ~ ~4 ~ ~ ~
~3227~7 - 27 - 63293-20~7 Examples 20 and 21 In the following examples Zy~el ST B01, an EPDM anhydride toughened nylon b3end manufactured by duPont was used.
Example 20 21 S'l' ~01 50 50 Block Copolymer 1 10 10 PP MA 0.16 -- 40 Tested Dry As Moulded:
Notchcd Izod (MN/m ) ?03 657 Flexural Modulus (MN/m ) 1393 12B2 Examples 22-24 S In the following examples modified block copolymer Z is an S-EB-S block copolymer modified with maleic anhydricle and poly-propylene as described in co-pending Canadian application Sr # 545,9.38.The ratio of polypropylsne Co block copolymer in che starting material was 1:3.
Examples 22 23 24 : Nylon 6S 40 40 40 Modlfied Block Copolymer Z 29 29 29 PP ~520 31 16 --PP MA 0.16 -- 15 31 Tested Dry As Moulded:
Nocclled Izocl (MN/m ) 262 46~l 673 F'lexl~rn3. Moclulu (MN~m2)1145 10~9 1083 t ~
~32~7~7 Comparative Experiments H-K and examples 9-19 show that in nylon blends containin~ polyolefins and block copolym2rs, when one or both of the polyolefin or block copolymers are functlonalized, the balance of ultimate and low strain properties are significantly improved.
Examples 20 and 21 show that similar improved properties are obtained when the elastomer is maleic anhydride functionalized olefin copolym~r.
Examples 22-24 show that improved properties can be also obtained by blending with a modified mixture of polyolefin and elastomer which has been prepared by simultaneously subjecting both components to a functionalization reaction.
Claims (29)
1. Impact resistant polymeric compositions comprising (a) from 1 to 95 per cent by weight of a polyamide having a number average molecular weight of at least 5000;
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1 to 50 per cent by weight of an elastomer, calculated on the total of (a), (b) and (c), said total being 100 per cent.
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1 to 50 per cent by weight of an elastomer, calculated on the total of (a), (b) and (c), said total being 100 per cent.
2. The composition of claim 1 wherein the elastomer is a selectively hydrogenated block copolymer.
3. The composition of claim 1 wherein the elastomer is an olefin copolymer.
4. The composition of claim 1 wherein the elastomer is EPDM.
5. The composition of claim 1 wherein the elastomer is an acrylic containing polymer.
6. The composition of claim 2 wherein the block copolymer is of the formula Bn(AB)oAp where n - 0 or 1, o - 1 to 100 and p - 0 or 1, to which has been grafted an acid compound or its derivative wherein, (1) each A is predominantly a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of 2,000 to 115,000;
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
(4) the unsaturation of the block B is less than 10% of the original unsaturation.
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
(4) the unsaturation of the block B is less than 10% of the original unsaturation.
7. The composition of claim 6 wherein the block copolymer is a selectively hydrogenated block copolymer having at least 1 B mid block and at least two A end blocks wherein, (1) each A is predominantly a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of 2,000 to 115,000;
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
(4) the unsaturation of the block B is less than 10% of the original unsaturation;
(5) the unsaturation of the A blocks is above 50% of the original unsaturation.
(2) each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having an average molecular weight of 20,000 to 450,000;
(3) the blocks A constituting 5-95 weight per cent of the copolymer;
(4) the unsaturation of the block B is less than 10% of the original unsaturation;
(5) the unsaturation of the A blocks is above 50% of the original unsaturation.
8. The composition of claim 6 wherein the block copolymer is a styrene-butadiene-styrene block copolymer.
9. The composition of claim 6 wherein prior to hydrogenation, the polymeric blocks A are polymer blocks of a monoalkenyl aromatic hydrocarbon.
10. The composition of claim 6 wherein the unsaturation of block B
is reduced to less than 5% of its original value and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its original value.
is reduced to less than 5% of its original value and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its original value.
11. The composition of claim 6 wherein A is a polymerized styrene block having an average molecular weight of between 4,000 and 60,000.
12. The composition of claim 6 wherein B is a polymerized butadiene block having an average molecular weight of between 35,000 and 150,000, 35%-50% of the condensed butadiene units having 1,2-configuration.
13. The composition of claim 6 wherein the unsaturation of block B
has been reduced by hydrogenation to less than 10% of its original value.
has been reduced by hydrogenation to less than 10% of its original value.
14. The composition according to claim 6 wherein an average of less than about 10% of the monoalkenyl aromatic hydrocarbon units are hydrogenated.
15. The composition according to claim 6 wherein an average of more than about 25% of the monoalkenyl aromatic hydrocarbon units are hydrogenated.
16. The composition of claim 1 wherein the polyolefin is func-tionalized with maleic acid or derivatives thereof.
17. The composition of claim 1 wherein the functionalized polyolefin is functionalized polypropylene.
18. The composition of claim 1 wherein the functionalized polyolefin is functionalized polybutylene.
19. The composition of claim 1 wherein the functionalized polyolefin is functionalized high density polyethylene.
20. The composition of claim 1 wherein the functionalized polyolefin is functionalized low density polyethylene.
21. The composition of claim l wherein the polyamide is present at between 10 and 70 per cent by weight.
22. The composition of claim 1 wherein the polyamide is present at between 15 and 45 per cent by weight.
23. me composition of claim 1 wherein the polyamide is nylon 66.
24. A composition of claim 1 wherein the polyamide resin is selected from the group consisting of polyhexamethylene adipamide, polyhexamethylene sebacamide, polycaprolactam, polyhexamethylene isophthalamide, polyhexamethylene tere-co-isophthalamide and mixtures and copolymers of the above.
25. The composition of claim 1 wherein the elastomer is present at between 15 and 35 per cent by weight.
26. The composition of claim 1 wherein the elastomer is present at between 10 and 25 per cent by weight.
27. The composition of claim 1 wherein the functionalized polyolefin is present between 10 and 70 per cent by weight.
28. The composition of claim 1 wherein the functionalized polyolefin is present between 15 and 45 per cent by weight.
29. A process for the preparation of a composition as claimed in claim 1 which process comprises melt-blending (a) from 1 to 95 per cent by weight of a polyamide having a number average molecular weight of at least 5000;
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1 to 50 per cent by weight of an elastomer, calculated on the total of (a), (b) and (c), said total being 100 per cent.
(b) from 1 to 95 per cent by weight of a functionalized polyolefin;
and (c) from 1 to 50 per cent by weight of an elastomer, calculated on the total of (a), (b) and (c), said total being 100 per cent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91155786A | 1986-09-25 | 1986-09-25 | |
| US911,557 | 1986-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1322797C true CA1322797C (en) | 1993-10-05 |
Family
ID=25430462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545946A Expired - Fee Related CA1322797C (en) | 1986-09-25 | 1987-09-02 | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1322797C (en) |
-
1987
- 1987-09-02 CA CA000545946A patent/CA1322797C/en not_active Expired - Fee Related
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU602725B2 (en) | Impact resistant polymeric compositions and process for the preparation thereof | |
| US5006601A (en) | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers | |
| US4795782A (en) | Impact resistant blends of thermoplastic polyamides, functionalized polyolefins and functionalized elastomers | |
| AU659724B2 (en) | Engineering resin-propylene polymer graft composition | |
| EP0216347B1 (en) | A modified block copolymer composition | |
| US5506299A (en) | High impact resistant blends of thermoplastic polyamides and modified block copolymers | |
| US6008297A (en) | Polyamide resin composition and process for producing the same | |
| US5525668A (en) | Polyamide thermoplastic elastomer obtained by blending | |
| EP0595886A1 (en) | Graft polymers for use in engineering thermoplastic blends | |
| CA1326093C (en) | Modified polyolefin resin | |
| US4757112A (en) | Single step bulk process for high impact polyamide masterbatches, products thereof and blends with polyamides | |
| JPS6344784B2 (en) | ||
| WO2004048466A1 (en) | Compatibilizing agent for engineering thermoplastic/polyolefin blend | |
| JPH06192502A (en) | Thermosetting resin composition | |
| CA1322797C (en) | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereof | |
| WO1998054262A1 (en) | Toughened polyketone composition | |
| CA1322798C (en) | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereof | |
| JP2529807B2 (en) | Good flow high impact polyolefin composition | |
| AU626799B2 (en) | Polyesters having improved impact strength | |
| CA1339040C (en) | Grafted block copolymers and process for the preparation thereof | |
| US5218044A (en) | Blends of modified radial polymers and engineering thermoplastic polymers | |
| JP2513951B2 (en) | Polyolefin composition with excellent impact resistance | |
| JPS58198501A (en) | Production of crosslinked modified polyolefin | |
| DE3610596A1 (en) | THERMOPLASTIC POLYMER BLENDS | |
| JPS6375047A (en) | Thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |