Abstract:
A thermoplastic elastomeric composition is provided exhibiting reduced levels of hardness and enhanced levels of elongation. The composition contains a chlorinated polyolefin and graft copolymer having a rubber substrate present at a level of 65 to 90 percent by weight based on the total weight of the graft copolymer. Preferably the graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer and preferably the chlorinated polyolefin is a chlorinated polyethylene having a high molecular weight and a relatively low chlorine level. The composition is useful for making molded articles such as interior automotive components requiring high elongation and tear resistance, reduced hardness and often high strain recovery.

Description:
This is a continuation of application Ser. No. 08/530,547 filed on Sep. 19, 1995 now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to thermoplastic elastomer compositions, and more particularly relates to thermoplastic elastomers containing a chlorinated polyolefin and a graft copolymer. 
     2. Description of the Related Art 
     Graft copolymer/chlorinated polyethylene blends are generally known, see Grabowski et al., U.S. Pat. No. 3,494,982 issued Feb. 10, 1970, which is incorporated herein by reference. Such blends, however, have typically higher than desired levels of hardness and/or have had lower than desired levels of elongation. There is generally a need (such as for automotive interior parts) for thermoplastic elastomer compositions which exhibit the combined levels of low hardness, high elongation, high strain recovery and tear resistance. 
     Consequently, there is a need for graft copolymer/chlorinated polyolefin blends exhibiting low hardness, high elongation, high strain recovery, and tear resistance. 
     SUMMARY OF THE INVENTION 
     The present invention involves thermoplastic elastomer compositions comprising (a) a chlorinated polyolefin and (b) a graft copolymer comprising a rigid superstrate and a rubber substrate where in the rubber substrate is present at a level of from 65 to 90 percent by weight based on the total weight of the graft copolymer. Preferably the chlorinated polyolefin is a high molecular weight chlorinated polyolefin and preferably has a medium chlorine content, and preferably the graft copolymer has a vinyl aromatic-vinyl cyanide superstrate and a diene rubber substrate wherein the diene rubber substrate has a relatively large number average diameter particle size. The compositions exhibit relatively low levels of hardness and relatively higher levels of elongation. 
     DETAILED DESCRIPTION OF THE INVENTION 
     A thermoplastic elastomer composition is provided comprising (a) a chlorinated polyolefin and (b) a graft copolymer comprising (i) a rigid polymeric superstrate and (ii) a rubber substrate wherein the rubber substrate is a present at a level of from 65 to 90 percent by weight based on the total weight of the graft copolymer. Preferably, the chlorinated polyolefin is present at a level of 15 to 95 percent by weight based on the total weight of the composition, more preferably from 30 to 85 percent by weight thereof, and most preferably from 40 to 85 percent by weight thereof. Preferably the graft copolymer is present at a level of from 5 to 85 percent by weight based on the total weight of the composition, more preferably from 15 to 70 percent by weight thereof, and most preferably from 15 to 60 percent by weight thereof. 
     The chlorinated polyolefin contains chlorine at a level of from 20 to 55 percent by weight based on the total weight of the chlorinated polyolefin, more preferably from 25 to 45 percent by weight thereof, and more preferably from 33 to 40 percent by weight thereof. The chlorinated polyolefin preferably has a relatively low chlorine content to reduce the hardness of the final composition. The chlorinated polyolefin is preferably chlorinated polyolefin having a weight average molecular weight of between 30,000 and 1,500,000, more preferably between 50,000 and 500,000, and most preferably a relatively high molecular weight of between 100,000 and 300,000. The chlorinated polyolefin may be a chlorosulfonated polyolefin such as a chlorosulfonated polyethylene. 
     The graft copolymer is preferably a vinyl aromatic-vinyl cyanide-diene rubber graft copolymer comprising (i) a vinyl aromatic-vinyl cyanide and (ii) a diene rubber substrate. 
     Monovinylidene aromatic monomers (vinyl aromatic monomers) which may be employed include styrene, alpha-methyl styrene, halostyrenes i.e. dibromostyrene, mono or di alkyl, alkoxy or hydroxy substitute groups on the nuclear ring of the monovinylidene aromatic monomer i.e. vinyl toluene, vinylxylene, butylstyrene, para-hydroxystyrene or methoxystyrene or mixtures thereof. The monovinylidenearomatic monomers utilized are generically described by the following formula: ##STR1## wherein X is selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, and halogens. R is selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms and halogens such as bromine and chlorine. Examples of substituted vinylaromatic compounds include styrene, 4-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, α-methylstyrene, α-methyl vinyltoluene, α-chlorostyrene, α-bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, mixtures thereof and the like. The preferred monovinylidene aromatic monomers used are styrene and/or α-methylstyrene. 
     Comonomers which may be used with the monovinylidene aromatic monomer includes acrylonitrile, methacrylonitrile, C 1  to C 8  alkyl or aryl substituted acrylate, C 1  to C 8  alkyl, aryl or haloaryl substituted methacrylate, acrylic acid, methacrylic acid, itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl, aryl or haloaryl substituted maleimide, glycidyl (meth)acrylates, hydroxy alkyl (meth)acrylates or mixtures thereof. The acrylonitrile, substituted acrylonitrile, or acrylic acid esters are described generically by the following formula: ##STR2## wherein R 1  may be selected from the same group set out for R as previously defined and Y is selected from the group consisting of cyano and carbalkoxy groups wherein the alkoxy group of the carbalkoxy contains from one or about twelve carbon atoms. Examples of such monomers include acrylonitrile, ethacrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-bromoacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, propylacrylate, isopropyl acrylate and mixtures thereof. The preferred monomer is acrylonitrile and the preferred acrylic acid esters are ethyl acrylate and methyl methacrylate. It is also preferred that the acrylic acid esters, when included, are employed in combination with styrene or acrylonitrile. 
     The rubber modified graft copolymer comprises (i) the rubber substrate, and (ii) a rigid polymeric superstrate portion grafted to the rubber substrate. The rubber substrate is preferably present in the graft copolymer at a level of from 65 to 90 percent by weight based on the total weight of the graft copolymer, and more preferably from 65 to 80 percent by weight thereof, and the rigid superstrate is preferably present at a level of from 10 to 35 percent by weight based on the total weight of the graft copolymer, and more preferably from 20 to 35 percent by weight thereof. 
     Examples of rubbery polymers for the substrate include: conjugated dienes, copolymers of a diene with styrene, acrylonitrile, methacrylonitrile or C 1  to C 8  alkyl acrylate which contain at least 50% (preferably at least 65% by weight) conjugated dienes, polyisoprene or mixtures thereof; olefin rubbers i.e. ethylene propylene copolymer (EPR) or ethylene propylene non-conjugated diene (EPDM); silicone rubbers; or C 1  or C 8  alkyl acrylate homopolymers or copolymers with butadiene and/or styrene. The acrylic polymers and diene rubbers may also contain up to 5% of one or more polyfunctional crosslinking agents such as alkylenediol di(meth)acrylates, alkylenetriol tri(meth)acrylates, polyester di(meth)acrylates, divinylbenzene, trivinylbenzene, butadiene, isoprene and optionally graftable monomers such as, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl esters of citric acid or mixtures of these agents. 
     The diene rubbers may preferably be polybutadiene, polyisoprene and copolymers of butadiene with up to 35% by weight of comonomers such as styrene, acrylonitrile, methylmethacrylate or C 1  -C 8  -alkylacrylate which are produced by aqueous radical emulsion polymerization. The acrylate rubbers may be cross-linked, particulate emulsion copolymers substantially of C 1  -C 8  -alkylacrylate, in particular C 2  -C 6  -alkylacrylate, C 1  to C 18  alkyl methacrylates, optionally in mixture with up to 15% by weight of comonomers such as styrene, methylmethacrylate, butadiene, vinyl methyl ether or acrylonitrile and optionally up to 5% by weight of a polyfunctional crosslinking comonomer, e.g. divinylbenzene, glycol-bis-acrylates or methacrylates, bisacrylamides, phosphoric acid triallylester, citric acid triallylester, allylesters of acrylic acid or methacrylic acid, triallylcyanurate, triallylisocyanurate. Also suitable are mixtures of diene- and alkylacrylate rubbers and rubbers which have a so-called core/shell structure, e.g. a core of diene rubber and a sheath of acrylate or vice versa. 
     Specific conjugated diene monomers normally utilized in preparing the rubber substrate of the graft polymer are generically described by the following formula: ##STR3## wherein X 1  is selected from the group consisting of hydrogen, alkyl groups containing from one to five carbon atoms, chlorine or bromine. Examples of dienes that may be used are butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethylbutadiene, 2-ethyl-1,3-pentadiene 1,3- and 2,4-hexadienes, chloro and bromo substituted butadienes such as dichlorobutadiene, bromobutadiene, dibromobutadiene, mixtures thereof, and the like. A preferred conjugated diene is 1,3 butadiene. 
     The substrate polymer, as mentioned, is preferably a conjugated diene polymer such as polybutadiene, polyisoprene, or a copolymer, such as butadiene-styrene, butadiene-acrylonitrile, or the like. The rubbery polymeric substrate portion must exhibit a glass transition temperature (Tg) of less than about 0° C. 
     Mixtures of one or more rubbery polymers previously described for preparing the monovinylidene aromatic graft polymers, or mixtures of one or more rubber modified monovinylidene aromatic graft polymers disclosed herein may also be employed. Furthermore, the rubber may comprise either a block or random copolymer. The rubber particle size used in this invention as measured by simple light transmission methods or capillary hydrodynamic chromatography (CHDF) may be described as having an average particle size by weight of select one of the following: 0.05 to 1.2 microns, preferably 0.09 to 0.6 microns, for emulsion based polymerized rubber latices or 0.5 to 10 microns, preferably 0.6 to 1.5 microns, for mass polymerized rubber substrates which also have included grafted monomer occlusions. The rubber substrate is preferably a particulate, highly crosslinked diene or alkyl acrylate rubber, and preferably has a gel content greater than 70%. 
     Preferred graft superstrates include copolymers of styrene and acrylonitrile, copolymers of α-methylstyrene and acrylonitrile and methylmethacrylate polymers or copolymers with up to 50% by weight of C 1  -C 6  alkylacrylates, acrylonitrile or styrene or styrene and acrylonitrile. Specific examples of monovinylidene aromatic graft copolymers include but are not limited to the following: acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-butyl acrylate (ASA), methylmethacrylate-acrylonitrile-butadiene-styrene (MABS), acrylonitrile-ethylene-propylene-non-conjugated diene-styrene (AES). 
     The number average molecular weight of the grafted rigid superstrate of the monovinylidene aromatic resin is designed to be in the range of 20,000 to 350,000. The ratio of monovinylidene aromatic monomer to the second and optionally third monomer may range from 90/10 to 50/50 preferably 80/20 to 60/40. The third monomer may optional replace 0 to 50% of one or both of the first and second monomers. 
     These rubber modified monovinylidene aromatic graft polymers are preferably polymerized by emulsion processes well known in the art. Furthermore, these graft copolymers may be produced either by continuous, semibatch or batch processes. 
     Preferably the graft copolymer has a large particle size rubber to reduce the hardness of the final composition. Preferably the rubber substrate has a number average particle size diameter of between 0.05 and 1.2 microns, more preferably 0.08 and 0.6 and most preferably between 0.20 and 0.45 microns (2000 to 4500 Å). 
     The present composition exhibits reduced levels of hardness and enhanced levels of elongation. Preferably the composition has a shore hardness (Shore D and A) of less than 40 ShD, more preferably less than 90 ShA, and most preferably less than 80 ShA; and preferably has a elongation percent of at least 200%, more preferably at least 300% and most preferably at least 400% as measured by ASTM norm D638-89 at crosshead speed 20 inches/min. Preferably the composition has a tensile strength (psi) as measured by ASTM norm D638-89 of at least 200 psi, more preferably at least 250 psi. 
    
    
     EXAMPLES 
     CPE/ABS blends were prepared according to formulations set out in table 1. The compounding ingredients were mixed in laboratory high intensity mixer. Then the blends were milled on two roll mill for 3 minutes at 340° F. roll mill temperature. The 0.125 inch thick 6×6 inches plaques were pressed at 340° F., to cut out the testing specimens. 
     The blends were prepared using commercial chlorinated polyethylenes. Tyrin 3615 (36% chlorine), Tyrin 3623A (36% chlorine) produced by the Dow Chemical Company. ABS resins having 50, 70, 80% of polybutadiene rubber, and two ABS resins having 65% butadiene-styrene rubber were also used. The blends were stabilized using Mark 3101 octyl tin mercaptide stabilizer, DLTDP--dilauryl thiodipropionate from Witco Corporation and Irganox 1076 antioxidant produced by Ciba-Geigy. Oxidized polyethylene AC 316A produced by Allied Corp. was used as an external lubricant. 
     ABS1 is styrene-acrylonitrile graft onto polybutadiene crosslinked rubber substrate average particle size 0.3 microns having about 704 of the rubber. 
     ABS2 is styrene-acrylonitrile partly crosslinked graft onto 85% butadiene-154 styrene copolymer substrate average particle size about 0.085 microns having 65% of the rubber. 
     ABS3 is styrene-acrylonitrile copolymer graft onto polybutadiene crosslinked substrate 0.3 micron average particle size having 80% of the rubber. 
     ABS4 is styrene-acrylonitrile copolymer graft onto polybutadiene crosslinked substrate 0.3 micron average particle size having 50% of the rubber. 
     ABS5 is styrene-acrylonitrile graft onto polybutadiene crosslinked rubber substrate 0.3 micron average particle size having 50% of the rubber. Compared to ABS4 styrene to acrylonitrile ratio is significantly higher. 
     ABS6 is α-methyl styrene-styrene-acrylonitrile copolymer graft onto polybutadiene crosslinked rubber substrate 0.3 micron average particle size having 14% of the rubber. 
     ABS7 is styrene-acrylonitrile copolymer graft onto polybutadiene rubber substrate 0.3 micron average particle size having 29% of the rubber. 
     
                                           TABLE 1__________________________________________________________________________CPE/ABS Blends__________________________________________________________________________Ingredients/Blend#           A    1    2   3    4    5    6   7    8__________________________________________________________________________CPE1            100  75   50  40   30   20   75  50   50CPE2ABS1                 25   50  60   70   80ABS2                                         25  50ABS3                                                  50ABS4ABS5ABS6ABS7Tensile (PSI)Strength @ Yield           166  235  332 387  487  606  266 481  262Modulus @ 10% strain           45   112  256 352  471  630  160 494  121Modulus @ 50% strain           139  256  450 583  694  839  312 642  282Modulus @ 100% strain           164  302  536 701  816  972  346 707  356Modulus @ 200% strain           181  379  680 898  1033 1237 411 851  469Modulus @ 300% strain           211  473  840 1133 1304 1590 500 1033 591% Elongation    1514 1023 599 452  385  322  944 512  644Strain Recovery--% Difference           2.5  3.5  8.5 11.9 16.2 23.9 3.4 13.8 2.7After 100% Elongation--Holdfor 1 Min. and Recover for 48 Hrs.Strain Recovery--% Difference           3.4  7.2  18.3                         28.0 38.6 53.1 8.5 31.1 6.8After 200% Elongation--Holdfor 1 Min. and Recover for 48 Hrs.Hardness -- Shore D andShore A (Use &#34;A&#34; When&#34;D&#34; &lt;20 and Use &#34;D&#34;When &#34;A: &gt;90)&#34;A&#34;             57   66   74  77   83   87   68  81   68&#34;D&#34;             17   23   30  34   37   40   26  35   25Tear Strength   125  208  309 341  358  344  221 331  232lbs/in.__________________________________________________________________________  Ingredients/Blend#                  9    10   11   B    C    D    E__________________________________________________________________________  CPE1            30             50   50   50   50  CPE2                 30   20  ABS1                 70   80  ABS2            70  ABS3  ABS4                           50  ABS5                                50  ABS6                                     50  ABS7                                          50  Tensile (PSI)  Strenth @ Yield 780  527  642  907  634  1260 1201  Modulus @ 10% strain                  809  531  662  962  656  1314 1287  Modulus @ 50% strain                  894  743  838  1175 792  1627 1513  Modulus @ 100% strain                  971  860  960  1276 848  1839 1649  Modulus @ 200% strain                  1162 1076 1219 1633 979  2184 1850  Modulus @ 300% strain                  --   1349 1555 1939 1137 --   --  % Elongation    309  395  324  319  545  237  266  Strain Recovery--% Difference                  24.3 18.3 25.1 54.1 27.4 55.2 57.4  After 100% Elongation--Hold  for 1 Min. and Recover for 48 Hrs.  Strain Recovery--% Difference                  51.8 50.4 53.5 111  67.1 130  123  After 200% Elongation--Hold  for 1 Min. and Recover for 48 Hrs.  Hardness -- Shore D and  Shore A (Use &#34;A&#34; When  &#34;D&#34; &lt;20 and Use &#34;D&#34;  When &#34;A: &gt;90)  &#34;A&#34;             84   85   88   84   84   86   86  &#34;D&#34;             39   36   37   42   39   53   49  Tear Strength   351  369  370  511  475  662  595  lbs/in.__________________________________________________________________________