COMPOSITES AND USES THEREOF

Abstract

The technology disclosed herein concerns a methodology for modifying properties of raw materials, offer final composites with preselected and unique mechanical properties.

Claims

1-74. (canceled)

75. A composition comprising A) poly(vinyl alcohol) (PVOH) in an amount ranging between 30 and 99 wt %; B) at least one crosslinking compound being present in an amount ranging between 0.1 and 20 wt %; C) at least one additional bioplastic in an amount ranging between 0.1 and 50 wt %; and D) optionally at least one additive in an amount ranging between 0.1 and 20 wt %.

76. The composition according to claim 75, wherein the at least one crosslinking compound is selected from polymers, copolymers and nonpolymeric materials, each having a functionality capable of associating to PVOH.

77. The composition according to claim 76, wherein the at least one crosslinking compound is a polymer or an oligomer having a functionality selected from alcohols, epoxides, anhydrides, carboxylic acids, amines, amides, glycidyl functionalities, aldehyde functionalities or esters.

78. The composition according to claim 76, wherein the polymer is a polyacid optionally being poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMAA).

79. The composition according to claim 75, wherein the at least one crosslinking compound is a polymer having carboxylic acid functionalities, the polymer being optionally selected from poly(ethylene-co-acrylic acid) (PE-co-AA), poly(ethylene-co-methacrylic acid) (PE-co-MAA), poly(lactide-block-acrylic acid) (PLA-block-AA), PVOH with carboxylic groups and carboxymethyl cellulose (CMC).

80. The composition according to claim 79, wherein the polymer is poly(ethylene-co-acrylic acid).

81. The composition according to claim 75, wherein the at least one additional bioplastic is selected from aliphatic or aromatic polyesters, co-polyesters and polyesteramides.

82. The composition according to claim 75, wherein the at least one additional bioplastic is selected from poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polycaprolactone (PCL), poly(lactic acid) (PLA), cellulose and cellulose derivatives, starch, thermoplastic starch (TPS), chitosan and polyhydroxyalkanoates (PHAs).

83. The composition according to claim 82, wherein the at least one additional bioplastic is TPS.

84. The composition according to claim 75, wherein the at least one additive is selected from inorganic additives, fillers, reinforcing agents, processing aids, slip agents, light stabilizers, UV absorbers, flame retardants, antimicrobial, antiviral agents, blowing agents, nucleating agents, antioxidants, antiblocking agents and antistatic agents.

85. The composition according to claim 75, wherein the amount of the PVOH, at least one crosslinking compound and at least one additional bioplastic being selected to modulate water degradation of a composite formed of said composition, wherein water degradation is arrested or slowed down or delayed with a decrease in the amount of said at least one additional bioplastic relative to the amount of said at least one crosslinking material, and wherein the at least one additional bioplastic is optionally PEO.

86. The composition according to claim 75, wherein the PVOH is present in an amount between 73-96.5, 68.5-89.8, 77.5-96.3, 67.5-91.5, 72-95, 71-85, 81-90, 68-81, 75-84, 60-78, 91.5-99.3, 87.5-98.7, 94.6-82.5, 87-93.3, 83-98.7, 78.5-94.3, 79.5-93.8, 68-93.5, 81.5-93.7, 73.5-93.3, 82-98.6 or between 77.5-98.2 wt %; and the at least one crosslinking compound is present in an amount of 0.1-1.5, 1.5-2.5, 1-2.5, 1.5-4, 1, 1.5-2, 1.5-2, 5, 0.1-0.5, 0.5-2, 0.1-0.5 or between 1-2 wt %; and/or the at least one bioplastic in an amount between 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or between 0.1-1 wt %, and wherein the composition optionally comprises at least one additive.

87. The composition according to claim 75, comprising PVOH, PAA and PEO, respectively, in an amount selected from: 73-96.5 wt %, 0.1-1.5 wt % and 1.5-10 wt %; 68.5-89.8 wt %, 0.1-1.5 wt % and 5-10 wt %; 77.5-96.3 wt %, 1.5-2.5 wt % and 1.5-5 wt %; 67.5-91.5 wt %, 1-2.5 wt % and 1.5-5 wt %; 72-95 wt %, 1.5-4 wt % and 1.5-4 wt %; 71-85 wt %, 1 wt % and 5 wt %; 81-90 wt %, 1.5-2 wt % and 2 wt %; 68-81 wt %, 1.5-2 wt % and 5 wt %; 75-84 wt %, 5 wt % and 5 wt %; 60-78 wt %, 5 wt % and 10 wt %; 91.5-99.3 wt %, 0.1-0.5 wt % and 0-1 wt %; 87.5-98.7 wt %, 0.1-0.5 wt % and 1-5 wt %; 94.6-82.5 wt %, 0.1-0.5 wt % and 5-10 wt %; 87-93.3 wt %, 0.5-2 wt % and 0-1 wt %; 83-98.7 wt %, 0.5-2 wt % and 1-5 wt %; 78.5-94.3 wt %, 0.5-2 wt % and 5-10 wt %; 79.5-93.8 wt %, 0.1-0.5 wt % and 5-10 wt %; and further optionally comprises PCL in an amount ranging between 1-5 wt %; 68-93.5 wt %, 0.1-0.5 wt % and 1-5 wt %; and further optionally comprises PCL in an amount ranging between 5-10 wt % 81.5-93.7 wt %, 0.1-1.5 wt % and 0-1 wt %; and further optionally comprises PCL in an amount ranging between 5-10 wt %; 73.5-93.3 wt %, 0.5-1.5 wt % and 5-10 wt %; and further optionally comprises PCL in an amount ranging between 1-5 wt %; 82-98.6 wt %, 1-2 wt % and 0.1-1 wt %; and further optionally comprises PCL in an amount ranging between 1-5 wt %; or 77.5-98.2 wt %, 0.5-1.5 wt % and 0.1-1 wt %; and further optionally comprises PCL in an amount ranging between 5-10 wt %.

88. A process for modifying at least one property of a solid composite material formed of a composition according to claim 75, the process comprising treating a composition comprising an amount of PAA and an amount of PEO with a composition comprising an amount of PVOH and optionally at least one additive, wherein the amount of PAA, the amount of PEO and optionally the amount of PVOH is selected to modify the at least one property, under conditions permitting compounding of the PAA, PEO and PVOH, and optionally at least one additive, into the solid composite having the at least one property.

89. The process according to claim 88, wherein the at least one property is water degradation.

90. A process for modulating water degradation profile of a solid composite material formed of a composition according to claim 75, the process comprising treating a composition comprising an amount of PAA and an amount of PVOH and optionally at least one additive with an effective amount of PEO, the effective amount being selected to increase or decrease water degradation of said solid composite, wherein the process is carried out under conditions permitting compounding of the PAA, PEO and PVOH, and optionally at least one additive, into the solid composite having the water degradation profile.

91. A process for setting a water-degradation onset of a solid composite comprising PVOH, the process comprising: in preparing a composition comprising PVOH, at least one crosslinking material and at least one additional bioplastic, selecting an amount of the at least one crosslinking material and an amount of the at least one additional bioplastic which, in combination, hastens or delays water-degradation of the solid composite, and thermally treating said composition to form into the solid composite.

92. A polymeric composite being formed of a composition according to claim 75.

93. The composite according to claim 92, in a form of material granules or in a form of a master batch.

94. An object comprising a composite according to claim 92.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0246] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0247] FIG. 1 is a schematic representation of embodiments of the invention demonstrating the ability to modulate properties of a composite material.

[0248] FIG. 2 demonstrates effect of PAA on PVOH dissolution.

[0249] FIG. 3 demonstrates effect of PEO on PVOH dissolution.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

[0250] PAA and ground thermoplastic PVOH were mixed at a 1:99 ratio and extruded using an L/D 40 twin-screw co-rotating extruder at 50 rpm and 190-210° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer.

Example 2

[0251] PAA, HPMC and ground thermoplastic PVOH were mixed at a 1:10:89 ratio and extruded using an L/D 40 twin-screw co-rotating extruder at 50 rpm and 190-210° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer.

Example 3

[0252] PEO and PAA were mixed together at a 8:2 ratio and extruded using an L/D 40 twin-screw co-rotating extruder at 150 rpm and 80° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer. The resulting PEO/PAA pellets were further mixed with PVOH at a 2:98 ratio and extruded using an L/D 40 twin-screw co-rotating extruder equipped with a devolatizing system at 50 rpm and 190-210° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer.

Example 4

[0253] PEO and PAA were mixed together at a 8:2 ratio and extruded using an L/D 40 twin-screw co-rotating extruder at 150 rpm and 80° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer. The resulting PEO/PAA pellets were further mixed with PCL and PVOH at a 2:5:93 ratio and extruded using an L/D 40 twin-screw co-rotating extruder equipped with a devolatizing system at 50 rpm and 190-210° C. through a round die 3 mm in diameter, and the emerging polymer strand was passed through an air cooling system and a pelletizer.

[0254] FIG. 2 demonstrates the effect of PAA on PVOH dissolution: Compounds with 0%, 0.5%, 1%, 1.5% and 2% PAA in PVOH were produced by reactive extrusion. A sample was then pressed to 200 microns from each compound and dissolution was studied at room temperature under agitation. The time of initial deformation (D), tearing of the film (T), breaking into particles in water (P) and solubility (S) is recorded. In general, as PAA concentration increases in the compound, deformation, tearing, breaking into particles and solubility are delayed.

[0255] FIG. 3 demonstrates the effect of PEO on PVOH dissolution: Compounds with 0%, 1%, 5% and 10% PEO in PVOH at a constant concentration of PAA (0.5%) were produced by reactive extrusion. A sample was then pressed to 200 microns from each compound and dissolution was studied at room temperature under agitation. The time of initial deformation (D), tearing of the film (T), breaking into particles in water (P) and solubility (S) is recorded. In general, as PEO concentration increases in the compound, deformation, tearing, breaking into particles and solubility are accelerated.

[0256] In addition to dissolution kinetics, some more physico-mechanical parameters for the compounds were characterized (data not shown). The polymer pellets were processed into 100 μm films at 200° C. films a cast extruder. The cast films were conditioned in accordance with ASTM E171/71M-11 (Reapproved in 2015). Standard Practice for Conditioning and Testing Flexible Barrier Packaging at 23±2° C. and 50±5% RH for 48 hours. The tests were performed under the same temperature/humidity conditions as mentioned. Tensile properties of the films were determined according to ASTM D882-18 Standard Test Method for Tensile Properties of Thin Plastic Sheeting. For that purpose, 25.4 mm wide and 250 mm length strip specimens were cut out from the films using a Dual Blade Share Cutter in accordance with procedure B specified in ASTM D6287-17 Standard Practice for Cutting Film and Sheeting Tests Specimens. Five specimens for each film were tested. A Tensile Testing Machine LLOYD INSTRUMENTS (UK) LRX 5K with a 500 N load cell and line grips as per ASTM D882 was used in the tests. The initial distance between the grips was 100 mm. All specimens were tested along the films Machine Direction (MD) with a grips separation rate of 500 mm/min. According to these measurements, increasing PAA content in the compounds has increased the tensile strength, stress at break and Young's modulus, while the elongation at break was decreased.

[0257] The exemplary composite comprising 1% PAA have demonstrated higher tensile strength, stress at break and Young's modulus than the composite comprising 0.5% PAA, and the elongation at break of the composite comprising 1% PAA was lower than that of the composite comprising 0.5% PAA.

[0258] Another exemplary composite comprising 1% PAA have demonstrated lower tensile strength, stress at break and Young's modulus than the composite comprising 1.5% PAA, and the elongation at break of the composite comprising 1% PAA was higher than that of the composite comprising 1.5% PAA.

[0259] Another exemplary composite comprising 0.5% PAA have demonstrated higher tensile strength, stress at break and Young's modulus than the composite that did not contain PAA, and the elongation at break of the composite comprising 0.5% PAA was lower than that of the composite that did not contain PAA.