Poly Alpha-1,3-Glucan Compounds

Abstract

A poly alpha-1,3-glucan compound comprising: a) poly alpha-1,3-glucan, and b) a functionalized polyolefin; wherein said poly alpha-1,3-glucan compound comprises from 0.5 to 70 weight percent of poly alpha-1,3-glucan, based on the total weight of poly alpha-1,3-glucan (a) and functionalized polyolefin (b) in the poly alpha-1,3-glucan compound and wherein said functionalized polyolefin is grafted onto the poly alpha-1,3-glucan. These poly alpha-1,3-glucan compounds have many uses including films for packaging applications and as elastomers for automotive applications.

Claims

1. A poly alpha-1,3-glucan compound comprising: a) poly alpha-1,3-glucan, and b) a functionalized polyolefin; wherein said poly alpha-1,3-glucan compound comprises from 0.5 to 70 weight percent of poly alpha-1,3-glucan, based on the total weight of poly alpha-1,3-glucan (a) and functionalized polyolefin (b) in the poly alpha-1,3-glucan compound and wherein said functionalized polyolefin is grafted onto the poly alpha-1,3-glucan.

2. The poly alpha-1,3-glucan compound of claim 1, wherein the functionalized polyolefin is selected from the group consisting of maleic anhydride grafted ethylene/-olefin copolymers, maleic anhydride grafted ethylene-propylene-diene (EPDM) polymers, glycidyl grafted ethylene/-olefin copolymers, ethylene (meth)acrylate copolymers, ionomers, alkyl acrylate copolymers, ethylene copolymers of the formula E/X/Y, and combinations of these.

3. The poly alpha-1,3-glucan compound of claim 1 comprising 5 to 60 weight percent of poly alpha-1,3-glucan.

4. The poly alpha-1,3-glucan compound of claim 1 in the form of a film, pellet, or strand.

5. A poly alpha-1,3-glucan compound prepared by the process of grafting a functionalized polyolefin onto poly alpha-1,3-glucan, said poly alpha-1,3-glucan compound comprising before grafting: a) poly alpha-1,3-glucan, and b) a functionalized polyolefin; wherein said poly alpha-1,3-glucan compound comprises from 1 to 70 weight percent of poly alpha-1,3-glucan, based on the total weight of poly alpha-1,3-glucan (a) and functionalized polyolefin (b) in the poly alpha-1,3-glucan compound.

6. A polymer composition comprising from 1 to 70 weight percent of the poly alpha-1,3-glucan compound of claim 1.

7. The polymer composition of claim 6 comprising from 5 to 60 weight percent of the poly alpha-1,3-glucan compound of claim 1.

8. The polymer composition of claim 6 wherein the polymer composition comprises a polymer selected from the group consisting of polyamides, polyesters, and polyolefins.

9. The polymer composition of claim 8 wherein the polymer is a polyamide.

Description

EXAMPLES

[0058] The disclosure is further defined in the following Examples. It should be understood that these Examples, while indicating certain preferred aspects of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions.

[0059] The exemplary articles are identified by E in the tables below are intended only to further illuminate and not to limit the scope of compounds, processes, and articles described and recited herein. Comparative examples are identified in the tables below by C.

Materials

[0060] In the compounds, processes, and articles exemplified in the tables below, the following materials were used. All percent values are by weight unless indicated otherwise.

Poly alpha-1,3-glucan was enzymatically produced from sucrose using one or more glucosyltransferase (gtf) enzymes following the procedure of example 6 of U.S. Pat. No. 9,080,195 using a gtfJ enzyme.
Functionalized Polyolefin: An ethylene -olefin copolymer grafted with 1.8 wt % maleic anhydride available from E.I. DuPont de Nemours and Company, Wilmington, Del., USA as TRX301E.
Polyamide: polyamide 612 available as Zytel 151 from E.I. DuPont de Nemours and Company, Wilmington, Del., USA.

Process for Making Poly Alpha-1,3-Glucan Compounds

[0061] The poly alpha-1,3-glucan compounds used in the examples below were prepared by reactive extrusion using a twin-screw extruder. The extruder temperature was set at 190 C. for each heating zone and the poly alpha-1,3-glucan and functionalized polyolefin were fed into the extruder in the desired weight ratios with a residence time in the extruder of about 1 to 2 minutes with any gases generated vented through the vacuum port. The resulting poly alpha-1,3-glucan compound was extruded through an exit die, cooled in a water bath, and pelletized to provide the desired poly alpha-1,3-glucan compound.

Process for Making Polyamide Compositions

[0062] For the examples, the polyamide resin and poly alpha-1,3-glucan compound, are compounded together using a twin-screw extruder. The mixture is then injection molded into ASTM D638 Type I tensile bars. The molded tensile bars were tested for mechanical properties and the results shown in Tables 1 and 2.

[0063] For the comparative examples, polyamide resin, and when present, poly alpha-1,3-glucan and functionalized polyolefin, were compounded together using a twin-screw extruder. The mixture is then injection molded into ASTM D638 Type I tensile bars. The molded tensile bars were tested for mechanical properties and the results shown in Tables 1 to 3.

Test Methods

[0064] Tensile properties, including tensile strength (TS), elongation at break (EB) and tensile modulus (TM) of thermoplastic polymer compositions were measured according to ASTM methods. C1 and E1 to E4 in table 1 were tested according to ASTM D1708 (Micro Tensile) and tested at 23 C. using an Instron Universal tester model 4202 at a crosshead speed of 50.8 mm/min (2 inches/min).

[0065] The examples and comparative examples in tables 2-4 were measured per ASTM D638 at 23 C. with Type I bars using an Instron Universal tester model 4202 at a crosshead speed of 50.8 mm/min (2 inches/min). The numerical values listed in the tables are averages of five test samples.

[0066] Table 1 shows various physical properties of poly alpha-1,3-glucan compounds disclosed herein in which the amount of poly alpha-1,3-glucan which is reacted with the functionalized polyolefin ranges from 20 to 65 weight percent based on the sum of the total amounts of poly alpha-1,3-glucan and functionalized polyolefin in the poly alpha-1,3-glucan compounds.

TABLE-US-00001 TABLE 1 Ingredient C1 E1 E2 E3 E4 Functionalized 100 80 60 50 35 Polyolefin Glucan 0 20 40 50 65 Physical Properties Elongation at break 890 855 587 300 120 (%) Stress at 100% strain 2.2 3.1 4.9 6.7 8.4 (MPa) Stress at 200% strain 2.9 4.6 7.4 9.8 (MPa) Stress at 300% strain 3.6 6.3 10 12.1 (MPa) Tensile Modulus 4.7 7.7 14.7 21 46 (MPa) Storage Modulus 12536 16508 31545 31846 23964 at 50 C. (MPa) Storage Modulus 333 390 1062 1217 1989 at 0 C. (MPa) Storage Modulus 201 177 636 592 975 at 23 C. (MPa) Storage Modulus 52 108 312 404 309 at 50 C. (MPa) Storage Modulus 32 70 165 259 173 at 100 C. (MPa) Shore A Hardness 72 77 83 88 94 (MPa)

[0067] Table 1 shows that by covalently grafting a functionalized polyolefin onto poly alpha-1,3-glucan, the stress at a given strain, storage modulus, and tensile modulus all increase relative to the functionalized polyolefin which has not been grafted onto poly alpha-1,3-glucan.

[0068] Table 2 shows the effect of using poly alpha-1,3-glucan as an individual component in a polyamide resin. Table 3 shows the effect of using poly alpha-1,3-glucan and a functionalized polyolefin as individual components in a polyamide resin.

[0069] For table 4, poly alpha-1,3-glucan compound E4 was blended with a polyamide resin for all the examples in the table.

TABLE-US-00002 TABLE 2 Ingredient C2 C3 C4 C5 C6 Polyamide 100 95 90 80 70 Glucan 0 5 10 20 30 Physical Properties Strain at break (%) 17 2.2 2 2 1.8 Izod Impact Strength 3.7 2.6 2 1.6 1 (KJ/m.sup.2)

[0070] The results in table 2 show the strain at break and Izod impact strength of a polyamide comprising poly alpha-1,3-glucan. Table 2 clearly shows that the presence of poly alpha-1,3-glucan in the polyamide (C3 to C6) decreases both strain at break and Izod impact strength values compared to the polyamide resin alone (C2).

TABLE-US-00003 TABLE 3 Ingredient C2 C7 C8 C9 C10 Polyamide 100 92.5 85 70 55 Functionalized 0 2.5 5 10 15 Polyolefin Glucan 0 5 10 20 30 Physical Properties Strain at break (%) 17 2.4 11.3 5.1 8 Izod Impact Strength 3.7 1.6 3.2 3.4 5.7 (KJ/m.sup.2)

[0071] The results in table 3 show the strain at break and Izod impact strength of a polyamide comprising both poly alpha-1,3-glucan and a functionalized polyolefin in a 2:1 weight ratio respectively, which have been added as separate and individual components into the compositions of table 3. Table 3 shows that the presence of poly alpha-1,3-glucan and a functionalized polyolefin in the polyamide (C7 to C10) decreases both strain at break and Izod impact strength values compared to the polyamide resin alone (C2) except at very high levels of both poly alpha-1,3-glucan and a functionalized polyolefin (C10).

TABLE-US-00004 TABLE 4 Ingredient C2 E5 E6 E7 E8 Polyamide 100 92.31 84.62 69.23 53.85 Poly alpha-1,3- 0 7.69 15.38 30.77 46.15 glucan compound Physical Properties Strain at break (%) 17 15.2 16.1 15.6 15.8 Izod impact strength 3.7 3.8 4.3 6.4 8.3 (KJ/m.sup.2)

[0072] Table 4 shows the strain at break and Izod impact strength of a polyamide composition comprising a poly alpha-1,3-glucan compound disclosed herein. Table 4 shows the presence of a poly alpha-1,3-glucan compound in a polyamide composition (E5 to E8) improves Izod impact strength compared to a polyamide composition which only comprises a polyamide resin (C2) without a significant decrease in strain at break.