Abstract:
A composition of matter including a polymeric material which is either a plastic having carbon to carbon linkages or a binary blend of the plastic and starch, in which the plastic is at least 25% by weight of the binary blend; and an organic peracid compound dispersed in the polymeric material, the quantity of the peracid compound being 0.1 to 10% by weight of the polymeric material.

Description:
FIELD OF THE INVENTION 
     The present invention relates to plastic compositions and, in particular, to those which are degradable. 
     BACKGROUND OF THE INVENTION 
     Starch-containing biodegradable plastics have been widely commercialized in environmental applications because of their low prices. U.S. Pat. Nos. 4,016,117, 4,207,221 and 4,125,495, as well as British Patent 1,487,050, disclose the technologies of preparing starch-containing biodegradable plastics. 
     More specifically, U.S. Pat. Nos. 4,016,117 and 4,207,221 teach the addition of low molecular weight compounds, such as unsaturated fatty acids/fatty acid esters and unsaturated wax, to plastic-starch blends. The unsaturated double bonds in the additives can react with transition metal salts in soil and water to initiate auto-oxidation, thereby improving degradability of the plastic-starch blends. However, this approach has a major drawback, i.e., the low molecular weight additives worsens the mechanical properties of the blends. 
     U.S. Pat. No. 4,125,495 and British Patent 1,487,050, on the other hand, utilize a silane coupling agent or isocyanate as graft-modifier to the starch surface to improve the compatibility of starch and plastics. The mechanical properties of the plastic-starch blends is thus improved. However, modified starch is quite expensive. Furthermore, the biodegradation rates of such blend systems are rather low. Consequently, addition of low molecular weight unsaturated fatty acids/fatty acid esters or unsaturated wax to plastic-starch blends remains in large part the method of choice. 
     Whether the plastic portion of the starch-containing biodegradable plastics can really degrade is an unsettled issue. The plastic ingredient of conventional starch-containing degradable plastics is supposed to degrade via an auto-oxidation mechanism. However, as a matter of fact, the degradation is too slow to be observed. Some researchers have asserted that the plastic ingredient does not degrade by auto-oxidation and therefore the starch-containing biodegradable plastics are at best destructible, rather than degradable. 
     In the present invention, the degradability of a plastic is improved by adding thereto a reactive functional compatibilizer, instead of low molecular weight unsaturated fatty acids/fatty acid esters or unsaturated wax. As a result, the mechanical properties only slightly deteriorate, if at all. 
     SUMMARY OF THE INVENTION 
     The main object of the present invention is to provide an organic peracid compound as an additive to increase both the biodegradation and photodegradation rates of plastics without considerably impairing its mechanical properties. 
     Accordingly, this present invention relates to a composition of matter which includes: (1) a polymeric material which is either a plastic having carbon to carbon linkages or a binary blend of the plastic and starch, in which the plastic is at least 25% (e.g., 25-99%) by weight of the blend; and (2) an organic peracid compound which is dispersed in, and is 0.1 to 10% by weight of, the polymeric material. Preferably, the binary blend includes the plastic at 50-99% by weight of the blend and the peracid compound is 0.5 to 10% by weight of the polymeric material. 
     A plastic having carbon to carbon linkages refers to a synthetic organic polymer/copolymer with chemical bonds between carbons or a blend of two or more of such polymers/copolymers. Typical examples of such a polymer/copolymer include, but are not limited to, polyethylene, polypropylene, poly(1-butene), poly(4-methyl-1-pentene), ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers and their salts, polystyrene, rubber-modified polystyrene, styrene-butadiene copolymers, styrene-isoprene copolymers, polyvinyl chloride, poly(vinylidene chloride), polyvinyl fluoride, poly(vinylidene fluoride), polyoxymethylene, poly(ethylene oxide), poly(propylene oxide), polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, poly(-methyl acrylate), poly(ethyl acrylate), poly(caprolactam), poly(hexamethyleneadipamide), poly(ethylene terephthalate), vinyl chloride-vinyl acetate copolymers, cellulose acetate, cellulose propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, acrylonitrile polymers and copolymers, and methacrylonitrile polymers and copolymers. Preferred polymers include organic hydrocarbon polymers such as polyethylene, polyvinyl chloride, and polystyrene. 
     An organic peracid compound is an organic compound which contains one or more peroxy-carboxyl group (i.e., --COOOH). 
     In the above-described composition of this invention, it is preferred that the peracid compound contain a functional group which can react with a hydroxyl group of starch. Examples of such functional groups include, but are not limited to, a carboxyl group, an aldehyde group, and a cyanate group. 
     It is also preferred that the peracid compound contain either an aliphatic group with a carbon to carbon double bond or an aromatic group. What is meant by an aromatic group is a substituted or unsubstituted benzoid hydrocarbon group (e.g., benzene, naphthalene, anthracene, diphenyl, and fluorene) or a substituted or unsubstituted heterocyclic hydrocarbon group with aromatic properties (e.g., pyridine, furan, thiophen, and pyrrole). 
     Other features and advantages of the present invention will be apparent from the following description of the preferred embodiments, and also from the appending claims. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Polymeric compositions containing hydroxyl groups or carboxyl groups have been found to possess a higher biodegradation rate. The present invention teaches addition of an organic peracid compound to a plastic or a plastic-starch blend to provide functional groups in order to accelerate the photodegradation/biodegradation of the plastic or plastic-starch blend. 
     For illustrative purposes only, we provide below a formula which covers some preferred peracid compounds which can be used in preparing a polymeric composition of this invention: ##STR1## in which R is an aliphatic hydrocarbon moiety containing 1-18 carbons (e.g., --CH═CH-- or --CH 2  --CH 2  --CH═CH--CH 2  --CH 2  --) or an aromatic hydrocarbon moiety containing 6-18 carbons (e.g., an o- or a p- phenylene group); and Y is a functional group capable of reacting with hydroxyl groups (e.g., --COOH or --CHO). 
     In a starch-containing polymeric composition of this invention, introduction of functional group Y can reinforce the weak plastic/starch interface since that functionality is capable of reacting with a hydroxyl group of the starch to form chemical bonding. Consequently, the mechanical properties of the polymeric composition are superior to those of the conventional starch-containing plastics, which, as discussed above, include low molecular weight unsaturated fatty acids/fatty acid esters or unsaturated wax. 
     Note that addition of too much peracid will worsen the processability and mechanical properties of the plastic-peracid or plastic-starch-peracid blends. Thus, the amount of peracid added should be carefully controlled so as to increase the degradation rate without substantially impairing the processability and mechanical properties of the blends. 
     According to the present invention, peracid and plastic and/or starch are blended at high temperature. The peracid and oxygen from the air will oxidize the plastic to form ketone groups. As well known in the art, plastic materials containing ketone groups will undergo photodegradation via Norrish type I and Norrish type II reaction mechanisms. If the peracid compound contains an aliphatic group with an unsaturated carbon-carbon double bond, the effect of auto-oxidation will be further reinforced since the double bond can react with metal salts in soil or water to initiate auto-oxidation reaction. 
     Furthermore, after blending under high temperature some peracid will be converted to carboxylic acid, which is capable of catalyzing the hydrolysis of starch. As a result, the starch is inverted to reducing sugar and becomes more digestible to microorganisms, thereby accelerating the degradation of the starch-containing plastics. 
     Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. The specific embodiments described in Examples I-V below are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. 
     In the following examples, the compounding temperatures of various plastics were as follows: polystyrene or PS (PG-383 from Chi Mei Industrial Co., Ltd., Taiwan) at 154° C., polyvinyl chloride or PVC (S-65 from Formosa Plastics Corp., Taiwan) at 150° C., polyethylene or PE (NA207-66 from USI Far East Corp., Taiwan) at 140° C. 
     Corn starch (granular size: 15 μm; fat content: max. 0.4%; and capillary viscosity, Std. II, 5% d.s., at 80° C.: 40˜50 sec.) was purchased from Swiss Starch Corporation Taiwan Ltd., Taiwan. COOH·CH═CH·COOOH (hereinafter &#34;aliphatic peracid&#34;) and ##STR2## (hereinafter &#34;aromatic peracid&#34;), the two peracids used in the following examples, were synthesized according to the methods described in R. H. White and W. D. Emmons, Tetrahedron. 17:31, (1962); and E. E. Royals and L. L. Harrell, Jr., J. Am. Chem. Soc. 77:3405 (1955), both of which are hereby incorporated by reference. Compounding was performed in two roll mills for 10 minutes. Tensile strength was tested according to the ASTM D638 standard method. Specimens of PS and PVC were type V dumbbell-shaped with a thickness of 1.5 mm. Specimens of PE were type IV dumbbell-shaped with a thickness of 60 μm. 5 to 7 samples were routinely tested for each tensile strength experiment. Biodegradability was tested according to the ASTM G21-70 standard method. Table 1 shows how the observed growth of fungus on specimens was rated. A higher rating reflects greater biodegradability. 
     
                       TABLE 1______________________________________Observed Growth of Fungus on Specimens                      Rating______________________________________           0%             0below          10%             1          10˜30%    2          30˜60%    3above          60%             4______________________________________ 
    
     The tensile strengths and the ratings of fungus growth of various PS-starch blends with different ratios (which are not within the scope of this invention) are shown in Table 2. 
     
                       TABLE 2______________________________________    Experiment Number    (1)   (2)     (3)    (4)   (5)   (6)______________________________________Ingredient(gram)PS         100     90      80   70    50    25Starch     --      10      20   30    50    75Tensile Strength      554     466     414  368   300   231(Kg/cm.sup.2)Rating of Fungus       0       1       1    1     1     4Growth (10 days)Rating of Fungus       0       1       1    1     2     4Growth (21 days)______________________________________ 
    
     As shown in Table 2, the starch content in plastic-starch blends should be higher than 50% in order to achieve acceptable biodegradability. On the other hand, gradual increase of the starch content resulted in deterioration of the mechanical properties of plastic-starch blends. 
    
    
     EXAMPLE I 
     Various polymeric compositions containing aliphatic peracid or unsaturated fatty acid/oil as shown in Table 3 were prepared in a manner described above. PS was used as the plastic component of plastic-starch blends. The content of peracid (as well as unsaturated fatty acid/oil) is expressed herein as % by weight of the polymeric material in which it was dispersed, or parts per hundred resin (&#34;phr&#34;). For example, 0.18 phr peracid means that 0.18 g of that peracid was added to 100 g of a plastic-starch blend or a plastic. 
     
                                           TABLE 3__________________________________________________________________________     Experiment Number     Contrast     (7) (8)  (9) (10)                      (11) (12)                               (13)__________________________________________________________________________Ingredient(gram)PS        90  90   90  90  90   90  90Starch    10  10   10  10  10   10  10Aliphatic peracid     0.18         0.59 1.18                  1.77                      2.95 --  --Sunflower oil     --  --   --  --  --   1.5 3Linolenic acid     --  --   --  --  --   0.2 0.5Tensile Strength     387 420  442 385 360  355 322(Kg/cm.sup.2)Rating of Fungus     1   2    3   3   3    --  --Growth (10 days)Rating of Fungus     1   3    4   4   4    1   3Growth (21 days)__________________________________________________________________________ 
    
     Three conclusions can be reached from the experimental results shown in Table 3: 
     1. The biodegradability of a plastic-starch blend was enhanced considerably by increasing the content of aliphatic peracid. 
     2. The tensile strength of a plastic-starch blend could be improved by increasing the content of aliphatic peracid when the content of aliphatic peracid was lower than 1.18 phr. 
     3. Blends containing aliphatic peracid had better tensile strength and biodegradability than conventional starch-containing plastics containing low molecular weight unsaturated fatty acid and fatty acid ester. Compare results from Experiments (8), (9), (10) or (11) with (12) or (13). 
     EXAMPLE II 
     Various plastic-starch blends with or without aliphatic peracid as shown in Table 4 were prepared in a manner described above. PVC or PE was used instead of PS (as in Example I) as the plastic component of plastic-starch blends. 
     
                       TABLE 4______________________________________      Experiment Number      (14)   (15)     (16)     (17)______________________________________Ingredient(gram)PVC          90       90       --     --PE           --       --       90     90Starch       10       10       10     10Aliphatic peracid        --       1.18     --     1.18Tensile Strength        526      508      152    150(Kg/cm.sup.2)Rating of Fungus        2        3        1      2Growth (10 days)Rating of Fungus        2        4        1      3Growth (21 days)______________________________________ 
    
     The results clearly show that aliphatic peracid could also increase the biodegradability of both PVC-starch blends and PE-starch blends. 
     EXAMPLE III 
     Various starch-free plastic-aliphatic peracid binary blends as shown in Table 5 were prepared in a manner described above. PS or PVC was used as the plastic component of plastic-starch blends. Results in Table 5 show that PS and PVC did not exhibit any biodegradability [Experiments (1) and (23)], while addition of aliphatic peracid invariably enhanced the biodegradability of both PS and PVC [Experiments (18), (19), (20), (21), (22) and (24)]. 
     
                                           TABLE 5__________________________________________________________________________    Experiment Number    (1)       (18)           (19)               (20)                   (21)                       (22)                           (23)                              (24)__________________________________________________________________________Ingredient(gram)PS       100       100 100 100 100 100 -- --PVC      -- --  --  --  --  --  100                              100Aliphatic peracid    -- 0.18           0.59               1.18                   1.77                       2.95                           -- 1.18Rating of Fungus     0 0   0   1   0   1   0  0Growth (10 days)Rating of Fungus     0 1   1   1   1   1   0  1Growth (21 days)__________________________________________________________________________ 
    
     The photodegradability of the plastic-peracid binary blends were also tested according to the ASTM G26-84 standard method. A Corning 7740 glass filter with a thickness of 1.5 mm was used, with an Xenon-Arc lamp being the light source. 
     The results shown in Table 6 below indicate that addition of aliphatic peracid enhanced the photo-degradability of PS and PVC plastics. More specifically, as the content of the peracid was increased, so was the photo-degradability of the composite plastics. 
     
                                           TABLE 6__________________________________________________________________________    Experiment Number    (25)        (26)            (27)                (28)                    (29)                        (30)                            (31)                                (32)__________________________________________________________________________Ingredient(gram)PS       100 100 100 100 100 100 --  --PVC      --  --  --  --  --  --  100 100Aliphatic    --  0.18            0.59                1.18                    1.77                        2.95                            --  1.18peracidTensile  Before exposureStrength 554 488 451 461 476 459 670 665Kg/cm.sup.2)    Exposure for 300 hours    464 467 325 416 402 246 659 444    Exposure for 600 hours    460 406 321 270 250 154 419 223The ratio    0.83        0.83            0.71                0.59                    0.53                        0.34                            0.64                                0.34of tensilestrengthafter 600hoursexposure totheoriginaltensilestrengthbeforeexposure__________________________________________________________________________ 
    
     EXAMPLE IV 
     A PS-starch blend and a PS-starch-aliphatic peracid blend as shown in Table 7 were prepared in a manner described above. The concentrations of reducing sugar of both blends were measured after they had been dipped in a buffer solution (3.297 g Na 2  HPO 4  ·7H 2  O and 12.103 g NaH 2  PO 4  ·H 2  O in 1,000 ml) for 7 days. 
     
                       TABLE 7______________________________________           Experiment Number           (33)   (34)______________________________________Ingredient(gram)PS                90       90Starch            10       10Aliphatic peracid --       0.89Reducing sugar    0.009    0.029concentration afterthe blends are dippedin buffer solutionfor 7 days (%)______________________________________ 
    
     Comparison of the results from Experiments (33) (34) shows that addition of aliphatic peracid increased the concentration of reducing sugar which was a product from the hydrolysis of starch. As discussed above, presence of reducing sugar in a polymeric composition will accelerate its degradation, since reducing sugar is more digestible to microorganisms than starch. 
     EXAMPLE V 
     Various polymeric compositions containing aromatic peracid as shown in Table 8 were prepared in a manner described above. PS or PVC was used as the plastic component of various blends. 
     
                       TABLE 8______________________________________    Experiment Number    (1)  (35)    (2)    (36)  (14)  (37)______________________________________Ingredient(gram)PS         100    100     90   90    --    --PVC        --     --      --   --    90    90Starch     --     --      10   10    10    10Aromatic peracid      --     1.63    --   1.63  --    1.63Tensile Strength      554    490     466  427   526   515(Kg/cm.sup.2)Rating of Fungus       0     1        1   1      2    3Growth (10 days)Rating of Fungus       0     1        1   2      2    4Growth (21 days)______________________________________ 
    
     The results shown in Table 8 indicate that aromatic peracid, like aliphatic peracid, also improved the biodegradability of both plastic-starch blends [Experiments (36) and (37)] and PS itself [Experiment (35)]. 
     As exhibited by the above illustrative examples, peracid is capable of increasing the biodegradability and photodegradability of both plastics and plastic-starch blends. Since the plastic portion of plastic-starch-peracid blends and plastic-peracid blends degrade, the polymeric compositions of the present invention can degrade completely. In addition, the mechanical properties of the starch-containing plastics which contain peracid are superior to those of the conventional starch-containing plastics which comprise of low molecular weight unsaturated fatty acids/fatty acid esters or unsaturated wax. 
     OTHER EMBODIMENTS 
     The above examples merely illustrate the preferred embodiments of the present invention. Many variations thereon may be made without departing from the spirit of the disclosed invention, as will be evident to those skilled in the art, and such variations are intended to come within the scope of what is claimed. Other embodiments are also within the appending claims.