Composition containing a polymer of unsaturated hydrocarbons, a starch derivative and an ethylene butylacrylate copolymer

Abstract: This invention provides a composition, containing a polymer of unsaturated hydrocarbon, a C₁₋₄ alkyl- or hydroxyalkylether of starch for improving the biodegradability, a compatibilizing agent comprising an ethylene-butylacrylate copolymer having grafted thereon an unsaturated acid and a polyhydric aliphatic alcohol having 2-10 carbon atoms and 2-6 hydroxyl groups as a dispersant/plasticizer for the starch ether.

Description: This invention relates to a composition, containing a polymer of unsaturated hydrocarbon, a C 1-4 alkyl- or hydroxyalkylether of starch for improving the biodegradability and an acrylate polymer as compatibilizing agent and a polyhydric aliphatic alcohol having 2-10 carbonatoms and 2-6 hydroxyl groups as a dispersant/plasticizer/lubricant for the starch ether. A similar composition is described in Dutch patent application 9001826, which is not a prior publication, and the corresponding European application 91201981.7; the compatibilizing agent is a vinyl or acrylate polymer. Dutch patent application 8902321 discloses a composition which contains a polymer of unsaturated hydrocarbon, a C 1-4 alkyl or hydroxyalkyl starch ether and a vinyl or acryl polymer; preferably a higher carboxylic acid, such a stearic acid, oleic acid or di-oleic acid, is added as a plasticizer or lubricant. The compositions according to Dutch patent application 9001826, which contain an alcohol, constitute an improvement over the compositions according to Dutch patent application 8902321 which contain a carboxylic acid; the alcohol has a better dispersing action than the carboxylic acid and provides better properties in terms of strength, elasticity and film forming. This invention provides a further improvement over the compositions according to Dutch patent application 9001826 in terms of the elongation at break, while the tensile strength remains practically the same. According to the invention an ethylene butylacrylate copolymer containing 12-25% of butylacrylate and having grafted thereon 0.1-20% by weight of unsaturated acid, based on the total sum of ethylene, butylacrylate and unsaturated acid. The use of this compatibilizing agent yields the above mentioned improvement over the compositions according to Dutch patent application 9001826. In the structure of the above figure 1, representing the compatibilizing agent used according to this invention, the grafting of the acid only takes place at the C-atoms marked* because only these sites are active enough for said grafting. When grafting the ethylene-butylacrylate copolymer, the starting materials are, in addition to the copolymer, 0.1-20% of unsaturated acid or anhydride 0.01-0.5% of radical former, which are mixed at a temperature at which the mixture is in molten state. The radical former decomposes and produces the radicals which cause the grafting. Examples of the acids and anhydrides are acrylic acid, methacrylic acid, maleic acid, fumaric acid and maleic anhydride. Examples of the radical formers are organic peroxides, peresters, percarbonates or radical former of another type. Specific examples of common radical formers are dicumyl peroxide, cumyl tert.butyl peroxide and di-tert.butyl peroxide. The temperature can be varied between 100 and 300°C. For more detailed information reference is made to EP 0 225 067 and US 4.877.685. Preferably the amount of unsaturated acid is 0.3-1.5% and more preferably 0.6-1.2%, and the amount of butylacrylate is preferably 14-21%. A product containing the above preferred amounts and fumaric acid as the unsaturated acid, is sold by Neste under the name NCPE 0414; a product containing the same preferred amounts and maleic acid as said unsaturated acid, is available under the name NCPE 0424. As in Dutch patent applications 8902321 and 9001826, the polymers of unsaturated hydrocarbons to be used are in the first place polyolefins, such as the different kinds of polyethylene and polypropylene, and furthermore polystyrene, as well as copolymers of these unsaturated hydrocarbons; in particular ethylene polymers are used. As in Dutch patent applications 8902321 and 9001826, the degree of substitution of the etherified starch should be at least 0.25 and is preferably 0.4-1.0. The preferred starch ethers are hydroxypropyl ethers, obtained by condensation of starch with propylene oxide; this condensation is preferably carried out using alkaline catalysis, in particular with NaOH, whereby a statistic distribution of the products occurs. Examples of the polyhydric alcohol used in this invention, are ethylene glycol, propylene glycol, glycerine, butylene glycol, diethylene glycol, pentaerythritol, dipentaerythritol, sorbitol en combinations thereof. These alcohols are used in amounts which cause to swell or partially dissolve the starch ether and they should not be used in such a large amount that a complete dissolution is achieved. For example the preferred hydroxypropyl starch dissolves in ethylene glycol in an amount of 30% at 75°C and in propylene glycol in an amount of 40%; in glycerol this compound dissolves in an amount of 10% at 100°C. Preferably 20-70% by weight of polymer of unsaturated hydrocarbon, 20-80% by weight of starch ether, 11-19% by weight of compatibilizing copolymer and 2-8% by weight of polyhydric alcohol is used in the composition of this invention. Because processing the mixture always involves a heating step, the polyhydric alcohol can completely develop its swelling or partially dissolving action. Although the invention is not dependant on or restricted by theoretical considerations, it is believed that the hydrogen bondings of the starch are disrupted by the etherification, whereafter the polyhydric alcohol causes a further disentanglement of the starch molecules, so that the starch particles are present independently of each other and can be substantially completely molecularly dispersed. The composition of this invention is excellently suitable for the manufacture of films, but also of three-dimensional objects. Furthermore, starch ethers and the polyhydric alcohol used are cheap materials, cheaper than the hydrocarbon polymer. A perfect composition containing 50% of starch ether can be obtained easily and also higher percentages of starch ether are suitable. Of course the optimal percentage of starch ether will also depend on the use of the composition. The following non-limiting example illustrates this invention. Example The mixtures indicated below where extruded at 180°C. The hydroxypropyl starch (HPS) had a degree of substitution of 0.5. The polyethylene was linear low density polyethylene (LLDPE) which is sold by Neste under the name NCPE 8020. Compositions 4 and 5, which contained a copolymer of ethylene and acrylic acid (EAA) as a compatibilizing agent, served as comperative compositions. The EAA copolymer is sold by Exxon under the name EXXON Escomer 526 and contains 18% of acrylic acid. Each of the mixtures was extruded at 180°C. The extruded materials were made into films by extrusion-blowing at 180°C. The films were examined for tensile strength and elongation at break. Composition-parts of weight 1 2 3 4 5 LLDPE (NCPE 8020) 30 37.5 50 30 50 HPS 50 42.5 30 50 30 NCPE 0414 or NCPE 0424 15 15 15 - - EAA - - - 15 15 Glycol 5 5 5 5 5 Tensile strength MPa/mm 2 Elongation at break % Foil of composition 1 21.1 300 Foil of composition 2 23.8 465 Foil of composition 3 25.0 620 Foil of composition 4 (Comparative) 12.3 330 Foil of composition 5 (Comparative) 14.6 640 LLDPE 100% 29.5 760 As appears from the above results, compositions 1 and 3 gave better results in terms of the tensile strength than the directly comparable compositions 4 and 5, respectively, which did not contain the acrylate of this invention but another acrylate, while composition 2, in which the amounts of LLDPE and HPS where in between the amounts of these ingredients in compositions 1 and 3, gave an intermediate result. Thus, it can be seen that the present compositions provide a better tensile strength than the compositions of European patent application 91201981.7, while the elongation at break is substantially of the same order of magnitude.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, GR, IT, LI, LU, MC, NL, PT, SE A composition, containing a polymer of unsaturated hydrocarbon, a C 1-4 alkyl or hydroxyalkyl ether of starch, an acrylate polymer as a compatibilizing agent and a polyhydric aliphatic alcohol having 2-10 carbon atoms and 2-6 hydroxyl groups as a dispersant/plasticizer for the starch ether, characterized in that said compatibilizing agent is an ethylene-butylacrylate copolymer, containing 12-25% of butylacrylate and having grafted thereon 0.1-20% by weight of unsaturated acid based on the total sum of ethylene-butylacrylate copolymer and unsaturated acid. A composition according to claim 1, characterized in that the unsaturated acid is fumaric acid. A composition according to claim 1, characterized in that said unsaturated acid is maleic acid. A composition according to claim 2 or claim 3, characterized in that the amount of fumaric acid or maleic acid is 0.3-1.5%, more preferably 0.6-1.2%, and the amount of butylacrylate in the copolymer is 12-25%, more preferably 14-21%. A composition according to claims 1-4, characterized in that it contains an ethylene polymer as said hydrocarbon polymer. A composition according to claims 1-5, characterized in that the polyhydric alcohol is ethylene glycol, glycerin, propylene glycol, pentaerythritol or sorbitol. A composition according to claims 1-6, characterized in that the composition contains at least 20% by weight of polymer of unsaturated hydrocarbon, at least 20% by weight of starch ether, 11-19% by weight of compatibilizing agent and 2-8% by weight of polyhydric alcohol. A process for preparing a composition according to one or more of the foregoing claims, characterized in that the starch ether and the polyhydric alcohol are extruded together and thereafter the so obtained homogeneous material is admixed with the other components and this mixture is extruded. Articles, manufactured with the use of a composition according to claims 1-7 or with the use of the process according to claim 8, respectively. Claims for the following Contracting State : ES A process for preparing a composition, containing a polymer of unsaturated hydrocarbon, a C 1-4 alkyl or hydroxyalkyl ether of starch, an acrylate polymer as a compatibilizing agent and a polyhydric aliphatic alcohol having 2-10 carbon atoms and 2-6 hydroxyl groups as a dispersant/plasticizer for the starch ether, the process comprising preparing a mixture of the components, characterized in that said compatibilizing agent is an ethylene-butylacrylate copolymer, containing 12-25% of butylacrylate and having grafted thereon 0.1-20% by weight of unsaturated acid based on the total sum of ethylene-butylacrylate copolymer and unsaturated acid. A process according to claim 1, characterized in that the unsaturated acid is fumaric acid. A process according to claim 1, characterized in that said unsaturated acid is maleic acid. A process according to claim 2 or claim 3, characterized in that the amount of fumaric acid or maleic acid is 0.3-1.5%, more preferably 0.6-1.2%, and the amount of butylacrylate in the copolymer is 12-25%, more preferably 14-21%. A process according to claims 1-4, characterized by using an ethylene polymer as said hydrocarbon polymer. A process according to claims 1-5, characterized by using as said polyhydric alcohol ethylene glycol, glycerin, propylene glycol, pentaerythritol or sorbitol. A process according to claims 1-6, characterized by preparing a composition containing at least 20% by weight of polymer of unsaturated hydrocarbon, at least 20% by weight of starch ether, 11-19% by weight of compatibilizing agent and 2-8% by weight of polyhydric alcohol. A process according to claims 1-7, characterized in that the starch ether and the polyhydric alcohol are extruded together and thereafter the so obtained homogeneous material is admixed with the other components and this mixture is extruded. Articles, manufactured with the use of the process according to claims 1-8.

Inventors: BUSSINK JAN PROF DRS, DELRUE RITA MARIA ING, GERMAN ANTON LEENDERT PROF DR, MEIJER HENRICUS EDUARD HUBERTU, VIRTANEN KARI, ZIJDERVELD ANTONIUS HENDRIK DR, BUSSINK, JAN, PROF. DRS., DELRUE, RITA MARIA, ING., GERMAN, ANTON LEENDERT, PROF. DR. IR., MEIJER, HENRICUS EDUARD HUBERTUS, PROF. DR. IR., VIRTANEN, KARI, ZIJDERVELD, ANTONIUS HENDRIK, DRS.
Applicants: CARGILL BV, NESTE OY, CARGILL B.V.
Application year: 1992
Main classification: C08L3
IPC codes: C08L51, C08L3, C08K5, C08L23