Thermoplastic and elastomeric formulations on basis of compound ethers of starchy material and methods of synthesis thereof
SUBSTANCE: invention relates to an elastomeric composition with a biodegradability degree below 50%, preferably below 30%, which comprises at least 0.5% and at most 99.95 wt % acetate of a starchy material, having a degree of substitution (DS) between 2.5 and 3 and, at least, 0.05 wt % and at most 99.5 wt % of a polymer other than starch, where the polymer is selected from a group comprising natural rubber and its derivatives, polyisobutylenes, polyisoprenes, styrene-butadiene copolymers (SBR), butadiene-acrylonitrile copolymers, hydrogenated butadiene-acrylonitrile copolymers, acrylonitrile-styrene-acrylate copolymers (ASA), ethylene-methyl acrylate copolymers (EAM), thermoplastic polyurethanes (TPU) in the form of simple ethers or in the form of a compound ether-simple ether, polyethylene or polypropylene, functionalised with halogenated silane, units of acrylic or maleic anhydride, ethylene-diene monomer rubber (EDM) and ethylene-propylene-diene monomer rubber (EPDM), thermoplastic elastomers, derived from polyolefines (TPO), styrene-butylene-styrene copolymers (SBS) and styrene-ethylene-butylene-styrene copolymers (SEBS), functionalised with units of maleic anhydride, and other blends of the above polymers. The composition may be used as a masterbatch or a matrix of the masterbatch, a plastic raw material, a compound for plastic or elastomeric articles, an adhesive, especially of a hot-melt type, or a matrix for the formulation of an adhesive, in particular of a hot-melt type, as a gum base or a matrix of the gum base, in particular for chewing gum, resin, co-resin or nanofiller for rubber, elastomers, bitumens, printing ink, varnish, paint, paper and cardboard, woven and non-woven products or thermosetting resins. It may also be used for the production of parts of equipment for the transport industry, in particular the automotive, aeronautical, railroad or ship building industry, for the electrical appliance, electronic appliance or electrical household appliance industries or for the sports and leisure industry.
EFFECT: compositions with low or very low biodegradability, long term high stability in water.
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The present invention relates to new thermoplastic or elastomeric compositions based on esters of starchy material with a high degree of substitution (Sz) esters and polymers other than starch.
The expression "thermoplastic or elastomeric composition" in the present invention, it should be understood that a reversible manner softened under the action of heat and hardens when cooled (thermoplastic) and/or returns more or less rapidly to its original shape and its initial dimensions after application of the elongation under load (elastomeric). She has at least one glass transition temperature (Tg), below which all or part of the amorphous fraction compositions are brittle glassy state and above which the composition can undergo reversible plastic deformation. The glass transition temperature or at least one of glass transition temperatures of thermoplastic or elastomeric composition of the present invention is preferably from -120°C to +150°C.
The claimed composition may, in particular, be a thermoplastic, in other words, can demonstrate the ability to take the form of using the methods traditionally used in the technology of plastics, such as extrusion, injection molding, molding, wydown� molding and calendering. Its viscosity, measured at a temperature of from 100°C to 200°C, is generally from 10 to 106PA·C. thermoplastic composition may contain, in combination, at least one ester of starchy material, at least one polymer other than starch selected from the group of thermoplastic or thermosetting polymers, such as, for example, polyolefins, polyvinyl, polystyrenes, acrylic and methacrylic polymers, polyamides, polycarbonates, linear polyesters, cellulose polymers, fluoropolymers, polysulfones, phenolic plastics, aminoplasts, crosslinked polyesters, polyurethanes, polyepoxide, silicones, alkyds and polyimides.
The composition of the present invention may also be elastomeric, in other words, it can show high ability to stretch and elastic recovery, like natural or synthetic rubbers. Elastomeric properties of the composition can be obtained or adjusted by cross-linking or vulcanization to a greater or lesser extent, after shaping in a viscous flow condition. Also the expression "elastomeric composition" in this invention mean any composition type "thermoplastic elastomer", having both elastomeric and thermoplastic properties due to structure�round the block polymer type with a "soft" segments (the glass transition temperature below ambient temperature) and hard segments (glass transition temperature above ambient temperature).
This type of composition can contain, in particular, in combination, at least one ester of starchy material, at least one polymer other than starch selected from the group of natural or modified rubbers, elastomers based on polystyrene, polyesters elastomers, elastomers based on polypropylene, silicone elastomers or rubbers and polyurethane elastomers.
Preferably, thermoplastic or elastomeric composition according to the present invention is a "hot melt" composition, in other words, it can be shaped without the use of high shear forces, in other words, by using a simple fill or simple extrusion of the molten material. Its viscosity, measured at a temperature of from 100°C to 200°C, is generally from 10 to 103PA·s.
Thermoplastic or elastomeric composition according to the present invention has characteristics:
(a) a low degree of Biodegradability, in other words, less than 50%, preferably less than 30%; and
- at least 0.5% and not more than 99.95 wt.% ester of starchy material having a degree of substitution (Sz) esters of 1.6 to 3; and
at least, of 0.05 wt.% and not over 99.5 wt.% the polymer other than starch,
moreover, these interest ODS�neighing given relative to the total weight of the composition.
According to the first embodiment of the composition according to the present invention is also characterized in that:
- the ester of starchy material as such has a degree of Biodegradability of less than 50%, preferably less than 30%; and/or
the polymer other than starch, as such, has a degree of Biodegradability of less than 50%, preferably less than 30%.
According to one particularly preferred embodiment of the composition according to the present invention is characterized in that the ester of starchy material, and a polymer other than starch has a degree of Biodegradability of less than 50%, preferably less than 30%.
The expression "degree of Biodegradability" in the understanding of this invention it should be understood the degree of aerobic biodegradation by determining the oxygen demand in a closed respirometer according to international standard ISO 14851:1999.
A specific procedure for the determination of this degree of Biodegradability are described below.
Measurement of the degree of Biodegradability according to the ISO 14851
The measurement is performed in accordance with the international standard ISO 14851 (first edition 1999-05-15), entitled "Plastic. Determination of the ability to complete aerobic biodegradation in the aquatic environment. Method by measuring the oxygen demand in a closed respirometer", while it is �:
- determine the degree (or level) biodegradation by comparing the biological oxygen demand (BOD) with theoretical oxygen demand (ThOD) and expressing it as a percentage (according to the principle mentioned in paragraph 4 of this standard);
- the calculation of ThOD according to Annex A of the standard;
- the use of conditions, reagents, apparatus and test procedures according to paragraphs 5, 6, 7 and 8 of the standard, respectively;
- calculating, expressing and validating the results in accordance with paragraphs 9 and 10 of the standard.
In this case, used, inter alia, the following:
the inoculum was in the form of activated sludge;
- a standard test environment;
- test conditions in the dark at 25°C with an accuracy of ±1°;
the microcrystalline cellulose powder as a reference material. According to one embodiment, the composition according to the present invention has a degree of Biodegradability according to the above definition, which is extremely low, namely less than 20%, in particular less than 15%, or less than 10% or even 5%.
According to another embodiment, the composition according to the present invention has a degree of Biodegradability, which remains low, but which lies in the higher ranges than the above values, namely, �degree of Biodegradability, at least 20% and less than 30%, in particular from 20 to 28%.
In modern conditions of climate disruption due to the greenhouse effect and global warming, the trend towards higher prices for fossil raw materials, particularly oil, from which the plastic condition of public consciousness in the search for sustainable development, products that are more natural, cleaner, healthier and more economical, and changes in systems of regulation and taxation is necessary to have available a new composition derived from renewable resources that are appropriate, in particular for the production of plastics and elastomers and are very competitive, designed from the outset so that to have little or no adverse impact on the environment, and technically as efficient as the polymers obtained from raw materials of fossil origin.
Starch is a raw material that has the advantages that is renewable and available in large quantities at a price that is cost-effective compared to oil and gas, which are used as raw material for modern plastics.
Krahm�l to the present time has already been used in the production of plastics, in particular, due to the fact that it is a biodegradable product.
The first compositions based on starch were developed approximately thirty years ago. Starches are then used in the form of mechanical mixtures with synthetic polymers, such as polyethylene, as filler, in granular and unmodified native state, in other words, in a state in which it exists in nature.
Consequently, the starch used in the production of biodegradable products, but in the state, which is essentially amorphous and thermoplastic. This degraded condition with low crystallinity or lack of crystallinity is obtained by plasticizing granular native starch by adding a suitable plasticizer in an amount of usually 15 to 25% compared to granular starch and the application of mechanical and thermal energy.
However, the mechanical properties of thermoplastic starches, although they may, to some extent, be adjusted by choice of starch, plasticizer and the amount of use of the latter, are generally quite mediocre, as the material, thus obtained, are always extremely high viscosity, even at high temperature (from 120°C to 170°C), and very brittle, CL�SCOM fragile very solid and not very film-forming at a low temperature, i.e., below the transition temperature.
Consequently, there were numerous scientific studies aimed at the development of biodegradable or water-soluble compositions exhibiting better mechanical properties by physical mixing of these thermoplastic starches or biodegradable polymers of petroleum origin (polycaprolactone or PCL, aromatic complex sobolifera or RAT, aliphatic polyesters, or PBS) or water-soluble polymers (polyvinyl alcohol or PVOH), or with complex polyesters of renewable origin, such as polylactate (PLA), a microbial polyhydroxyalkanoates (PHA), or cellulose derivatives.
Water resistance of these biodegradable compositions or even water-soluble compositions, as a rule, is weak and insufficient to maintain the possibility of production of products and any products with a long or medium term operation, such as auto parts. In addition, physico-chemical stability of these compositions in this case is also a factor that severely limits potential applications.
After studying the problem in detail, the Applicant has unexpectedly discovered that it is possible to obtain t�moplastics or elastomeric compositions with low or very low Biodegradability, but also with great stability in the water for a certain period of time, which can be used in the production of products with a long life-time operation or which must be stable in aqueous or biological media, with the use of esters of starchy material having a high to very high degree of substitution (Sz) esters, even by combining them with polymers that are known to be vysokoposeschaemym.
The present invention provides an effective solution to the aforementioned problems by proposing new compositions based on the ester of starchy material, which have improved properties compared with compositions of the prior art.
Regardless of the option discussed above, thermoplastic or elastomeric composition according to the present invention preferably includes an ester of starchy material having a high or very high NW. NW may, in particular, to range from 1.8 to 3, preferably from 2.0 to 2.9 and more preferably from 2.5 to 2.9, while the Northwest from 2.6 to 2.8 is optimal for the application.
Irrespective of the option of thermoplastic or elastomeric composition according to the present invention preferably includes:
from 5 to 99 wt.% ester of krahm�sinuous material, as described above; and
from 1 to 95 wt.% the polymer other than starch,
moreover, these percentages are given relative to the total weight of the composition.
According to another embodiment, thermoplastic or elastomeric composition according to the present invention preferably includes:
- from 10 to 70 wt.%, preferably from 10 to 60 wt.% ester of starchy material and
- from 30 to 90 wt.%, preferably from 40 to 90 wt.% the polymer other than starch,
moreover, these percentages are given relative to the total weight of the composition.
Content in the composition of the ester of starchy material can mainly be from 10 to 55%.
The content in the composition of the polymer other than starch may mainly be from 45 to 90%, in particular from 45 to 85%.
According to another embodiment, the ester of starchy material is the primary or even the predominant component of the composition of the present invention, and the composition may in this case, in particular, differ in that it comprises from 50 to 99 wt.%, preferably from 51 to 98 wt.% the specified ester.
Along with this, the polymer other than starch (or "non-starchy polymer"), which in this case is either the main component or the predominant component of the composition according to the present and�finding, moreover, the composition may in this case, in particular, differ in that it comprises from 1 to 49 wt.%, preferably from 2 to 40 wt.% and even more preferably from 2 to 35 wt.% the specified polymer.
According to another embodiment, the ester of starchy material is not the predominant component and usually is not the main component of the composition of the present invention, and the composition may in this case, in particular, differ in that it includes no more than the 49.5% and in particular from 5 to 49%, preferably from 7 to 49 wt.% and even more preferably from 10 to 49 wt.% the specified ester.
Along with this, the polymer other than starch may in this case be the main component or even the predominant component of the composition of the present invention, and the composition may then, in particular, differ in that it comprises at least 40% and up to 95 wt.% the specified polymer and, in particular, from 50 to 95 wt.%, preferably from 51 to 93 wt.% and even more preferably from 51 to 90 wt.% the specified polymer.
Irrespective of the above options ester of starchy material with NW from 1.6 to 3 may be present in the compositions of the present invention in any form, in particular, in a dispersed state in the form of fibers of micron or nanometer size, or other �particles in the non-starchy polymer or thermoplastic or elastomeric, continuous, discontinuous or co-continuous phase, which is combined with non-starchy polymer to a greater or lesser extent.
Moreover, non-starchy polymer may also be present in compositions of the present invention in any form, in particular, in a dispersed state in the form of fibers in the ester of starchy material or a thermoplastic or elastomeric, continuous, discontinuous or co-continuous phase, which is combined with the ester of starchy material to a greater or lesser extent.
As far as known to the Applicant, the use of esters of starchy material, in particular, with high or very high NW, recommended only for:
the production of thermoplastic compositions, which, as indicated, are biodegradable, which, moreover, contain or do not contain at least one non-starch polymer, which, as we know, is itself biodegradable or water-soluble, such as, for example (a), modified cellulose, b) proteins, C) biodegradable polyesters, especially hydroxycarbonate type, as described in patents US 5462983, WO 95/04108, EP 1054599 or EP 1142911, or polyalkylacrylate, as described in patents US 5936014 or WO 98/07782, and g) water-soluble polymers, such as those described in patents EP 638609, US 5936014, US 2002/0032254 or WO 00/7338; or
- production of elastomeric compositions that can be used as Gumienny for chewing gum without (a) any non-starchy polymer, or a thermoplastic or an elastomer, and b) any plasticizer ester of starchy material, as described, for example, in patents US 3666492, US 4035572 or US 4041179.
In the context of this invention the term "starchy material" should be understood as any oligomer or polymer of D-glucose elementary stages, linked together via alpha-1,4 linkages and not necessarily for other communications, alpha-1,6 and alpha-1,2, alpha-1,3 or links of another type.
This starchy material can occur from any type of starch and, in particular, be selected from starches cereal plants such as wheat, corn, oats, triticale, sorghum or rice; tubers starches, such as potatoes or cassava; starches of legumes, such as peas, soybeans or beans, amylose-rich starches or, conversely, rich in amylopectin (waxy) starches derived from these plants, or any mixtures of these starches.
According to the present invention, this starchy material may preferably have a molecular weight from 103up to 108g/mol, better still from 5,103up to 107g/mol and even better still from 104to 10 g/mol.>
According to the first variant implementation of the starchy material may be obtained by esterification, to a high degree, granulated, optionally hydrolyzed and/or modified starch.
In this document the term "granular starch" is understood to native starch or a starch that has been modified physically, chemically or enzymatically and which is retained inside the starch granules, semi-crystalline structure, similar to that which exists in the starch grains that are present naturally in the spare tissues and organs of higher plants, particularly in seeds of cereals or of leguminous plants, tubers, roots, bulbs, stems and fruits. This is a semi-crystalline state is essentially due to the amylopectin macromolecules, one of the two main components of starch. In the native state, starch grains have a degree of crystallinity ranging from 15 to 45% and which essentially depends on the vegetable origin of the starch and from treatment, to which it is optionally subjected to.
Starch in granules, placed in polarized light, showing the characteristic black cross, called the Maltese cross, typical for this condition.
According to one in�to approach the ester of starchy material derived from granular starch, hydrolyzed acidic, oxidative or enzymatic means. Such starches are usually called fluidized starches, oxidized starches or white dextrins.
According to another embodiment, it can be obtained by esterification of starch, which essentially retained the granular structure of native starch, but was modified physico-chemically, for example, weakly esterified and/or subject to obtaining a simple ether starches, in particular, that are modified by acetylation, hydroxypropylamino, cationization, cross-linking, fosfatazy or succinylcholine, or starches treated in an aqueous medium at low temperature (processing "annealing").
The ester of starchy material may preferably be obtained by esterification of hydrolyzed, oxidized or modified granular starch, in particular corn, wheat, potatoes or peas.
According to a second embodiment of the starchy material is selected to obtain a composition of the present invention, is obtained by esterification, to a higher grade, granular starch, i.e. starch that does not contain starch grains, which exhibit, under the microscope and in polarized light, �Altayskiy cross. In this case it would be water-soluble organomodified starch or starch, which may also be of any vegetable origin, rich in amylose starch, or, conversely, rich in amylopectin (like wax) starch.
According to the first embodiment of the ester of starchy material with NW from 1.6 to 3 is an ester of water-soluble granular starch. In the understanding of this invention, the term "soluble starch" is understood any starchy material having, at 20°C and under mechanical stirring for 24 hours, the fraction that is soluble in demineralised water at least equal to 5 wt.%.
Water-soluble starch may preferably be selected from the pre-castelsangiovanni starches, extruded starches, spray-dried starches, dextrins, maltodextrins, functionalized starches or any mixtures of these products, optionally plasticized.
Pre-clijstersrauncy, extruded or spray-dried starches can be obtained by hydrothermal treatment gelatinization of native starches or modified starches, in particular, by cooking steamed, cooking burner, cooking on a drum, cooking in musiln�th/extruder systems and then drying, for example, in a drying oven, hot air in a fluidized bed, on a rotating drum, using spray drying, extrusion, deposition by nerastvorim, or lyophilization of starchy solution or suspension. We can mention, as an example, products that are manufactured and sold by the Applicant under the trade name PREGEFLO®.
Dextrins can be produced from native or modified starches by dextrinization in a relatively anhydrous acid medium. They may, in particular, to be soluble white dextrin or be yellow dextrin. We can mention, as an example, products STABILYS®And 053 or TACKIDEX®With 072, manufactured and sold by the Applicant.
Maltodextrins can be obtained by acidic, oxidative or enzymatic hydrolysis of starches in an aqueous medium. They may, in particular, to show the dextrose equivalent (DE) of 0.5 to 40, preferably from 0.5 to 20 and better still from 0.5 to 12. Such maltodextrins, for example, manufactured and sold by the Applicant under the trade name GLUCIDEX®.
Functionalized starches can be obtained in particular by acetylation in aqueous phase with acetic anhydride, mixed anhydrides, hydroxypropylamino, cationization, unionization, fosfatazy or succinimido�of. These functionalized starches can exhibit a degree of substitution of from 0.01 to 2.7 and even better from 0.05 to 1.
Water-soluble starch preferably is a water-soluble corn, wheat, potato or pea starch or water-soluble derivative.
According to the second embodiment esterified starchy material with NW from 1.6 to 3 is an ester of organomodified starch, preferably starch solvent-borne, which can have any vegetable origin. In the understanding of this invention the expression "organomodified starch" should be understood as any starchy component that is different from granular starch or soluble starch according to the definitions presented above. Preferably this organomodified starch is actually amorphous, in other words, shows the degree of crystallinity of starch is less than 5%, typically less than 1% and, in particular, the zero degree of crystallinity of starch. He is also preferably "solvent-borne", in other words, exhibits, at 20°C, a fraction at least equal to 5 wt.%, which is soluble in a solvent selected from ethanol, ethyl acetate, propyl acetate, butyl acetate, diethylmalonate, propylenecarbonate, dimethylglutaric�the one triethylcitrate, dibasic esters, dimethyl sulfoxide (DMSO), dimethylselenide, glyceryltrinitrate, isosorbidinitrate, isosorbidinitrate complex and methyl esters of vegetable oils. Of course, solvent-borne starch can be completely soluble in one or more of the solvents indicated above.
Organomodified starch can be obtained from native or modified starches, such as presented above, using the esterification reaction or the reaction for producing ethers to a high enough level to maintain its essentially amorphous and to ensure its insolubility in water and preferably a solubility in one of the above organic solvents.
Organomodified starch can be obtained, in particular, by conducting the graft copolymerization oligomers of caprolactone or lactitol by hydroxypropylamino and cross-linking, by cationization and cross-linking, by unionization, fosfatazy or succinylcholine and cross-linking, by sililirovanie or by telomerization with butadiene. These organomodified, preferably solvent-borne starches can exhibit a degree of substitution (Sz) from 0.01 to 2.7, preferably from 0.05 to 2.0 and in particular from 0.1 �about 1,5.
Organomodified starch preferably is an organomodified corn, wheat, potato or pea starch or organomodified derived.
Esterifying agent used to obtain the ester of starchy material may be an organic acid anhydride, organic acid, a mixed anhydride, an organic acid chloride, or any mixture of these products. This agent for esterification may be selected from saturated or unsaturated acids having from 2 to 24 carbon atoms, and, in particular, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptane acid, pelargonii acid, octanoic acid, decanoas acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, anhydrides of these acids, mixed anhydrides of these acids, and any mixtures of these products.
The ester of starchy material with a degree of substitution (Sz) from 1.6 to 3.0, preferably from 1.8 to 3.0, more preferably from 2.0 to 2.9, in particular, from 2.5 to 2.9 and optimally 2.6 to 2.8, preferably is an ester of water-soluble organomodified starch or starch, preferably CL�iny ester pre-castelsilano starch, extruded starch, spray-dried starch, dextrin, maltodextrin, functionalized starch, starch solvent-borne or any mixture of these products, optionally plasticized.
Preferably the specified ester of starchy material has a chain containing from 2 to 22 carbon atoms, and a is acetate, propionate, butyrate, valerate, hexanoate, octanoate, decanoate, Euratom, palmitate, oleate or stearate, starch, dextrin or maltodextrin, pure or as a mixture. Preferably it is an acetate of starchy material. A composition according to the present invention includes, in particular, as the ester of starchy material is an ester with a NW within any one of the previously mentioned ranges, preferably acetate type, water-soluble or organomodified starch, particularly preferably pre-castelsilano, extruded or spray-dried starch, dextrin, maltodextrin, functionalized starch or starch solvent-borne.
Most preferably the ester of starchy material is a water-soluble acetate or organomodified starch, acetate of dextrin or acetate malto�of extrema.
The ester of starchy material may be mixed in any proportions with optionally hydrolyzed and/or modified granular starch with water-soluble starch or organomodified starch, as defined above.
Regarding the conditions of esterification specialist in the art will be able without difficulty to turn for information regarding used esterifying agent, to the methods and conditions described in the literature, in particular, in patents US 3795670, EP 603837, US 5667803, WO 97/03120, WO 98/29455, WO 98/98/29456 and US 2008/0146792.
Esterification can be carried out, in particular by acetylation in the phase solvent, in the environment of organic acids, in the presence of an anhydride or mixed anhydride of this organic acid and an acid catalyst.
Esterified starchy material can contain other groups, integrated by carrying out the graft copolymerization, for example, oligomers of caprolactone or lactitol or built by hydroxypropylamino, cross-linking, cationization, unionization, succinylcholine, sililirovanie or telomerization.
Thermoplastic or elastomeric composition according to the present invention also contains at least one polymer other than starch (also called "non-starchy polymer")./p>
Non-starchy polymer may be of any chemical nature. It can be thermoplastic or thermosetting polymers or thermoplastic elastomers. It preferably includes a functional group containing active hydrogen and/or functional groups which give, in particular, by hydrolysis, such functional groups containing active hydrogen.
It may be a polymer of natural origin or synthetic polymer obtained from monomers of fossil origin and/or monomers derived from renewable natural resources.
Polymers of natural origin can be obtained directly by extraction from plants or animal tissues. They are preferably modified or functionalized, in particular selected from the protein polymers, cellulosic or lignocellulosic nature, chitosan and natural rubber. They can also be polymers obtained by extraction from microbial cells, such as polyhydroxyalkanoates (PHA).
Such a polymer of natural origin can also be selected from flour or proteins that are preferably modified; cellulose, which are unmodified or modified, in particular by carboxymethyl�tion, amoxilonline, hydroxypropylamino, cationization, acetylation or alkylation; hemicelluloses; lignin; modified or unmodified Gurovich gums; Chudinov and chitosans; natural gums and resins such as natural rubbers (NR) and their derivatives, rosin, shellac, terpene resin and bitumen; polysaccharides extracted from algae, such as alginates and carrageenans; polysaccharides of bacterial origin, such as xanthane or gallante; ligno-cellulosic fibers such as flax, hemp or coconut fibers or fibers of natural origin.
Non-starchy polymer may be synthetic and obtained in particular by polymerization, polycondensation or paliperidonesee.
Particularly preferably, when the non-starchy polymer itself has a degree of Biodegradability of less than 50%, preferably less than 30%. Therefore, in the case where it is used as the only non-starchy polymer, this polymer is preferably selected from polymers non biodegradable polyesters, such as polictically (e.g., polylactic acid (PLA), polyglycol acid (PGA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (GAP), polyhydroxyvalerate (PHV), polyhydroxybutyrate-polyhydroxyvalerate copolym�ry (PHBV) or polycaprolactone (PCL)), polyetherimide (for example, the biodegradable polyetherimide (WAC)) or aromatic or aliphatic difficult sobolifera (e.g. poliatilenaksida (PBS) and butylenediamine-terephthalate copolymers (RAT)), other than polyalkyleneglycol (e.g. polietilensorbit (RES) and polypropenkarbonat (RRS)) and non water-soluble polymers such as polyvinyl alcohols, ethylene/vinyl alcohols, proteins, cellulose and their derivatives.
It can be selected in particular from thermoplastic polymers such as polyolefins, in particular polyethylene, polypropylene, polyisobutylene and copolymers, vinyl polymers, styrene polymers or styrene copolymers (Acrylonitrile-butadiene-styrene (ABS), styrene-Acrylonitrile (SAN), methyl methacrylate-butadiene-styrene (MBS)), acrylic or methacrylic polymers, polyoxethylene, Polyacetal, polyamides, polycarbonates having a degree of Biodegradability of less than 50%, preferably less than 30%, the polyesters having a degree of Biodegradability of less than 50%, preferably less than 30%, such as Pets (PET), amorphous Pets (PETG), fluoropolymers, polysulfones, polyphenylenesulfide (or Polyphenylene sulfides), polyurethanes, polyepoxide, silicones, alkyds and polyimides, functionalized variants, and any mixtures of the aforementioned �of polimerov.
May be mentioned as non-starch thermoplastic polymers which can be particularly preferably used in the present invention, Pets (PET), amorphous Pets (PETG), or functionalized defunctionalization polyethylene (PE) and polypropylene (PP), polyacrylonitrile (PAN), polyethersulfone, polymetylmetacrylate (PMMA), polyamides, in particular polyamide PA-6, PA-6,6, PA-6,10 and PA-6,12, polyacrylates, polyvinyl acetate, polyurethanes, polyoxymethylenes (RUM) and any mixtures of these polymers.
The polymer other than starch, preferably can be selected from elastomeric polymers such as synthetic rubbers (SR), such as butyl rubbers (in particular, halogenated butyl rubbers, such as bromatologia and hloretilova rubbers); polyacrylate rubber (ACM); nitrile rubbers (in particular, carboxylated nitrile rubbers); polybutadiene (BR) and polyisoprene; mixed elastomers based on butadiene, isoprene and/or styrene, in particular, on the basis of styrene and butadiene (SBS or SBR), on the basis of styrene and isoprene (SIS), on the basis of styrene and polyolefin; thermoplastic elastomers (TPE) in the form of multiblock copolymers consisting of hard blocks, in particular, styrene, urethane or polyamide and soft blocks, to a pri�STI, type of polyether, polyester, polybutadiene, polyethylene, polyisoprene, or polybutylene (e.g., TPS, TPU or REVA); elastomers based on ethylene (ethylenically or EAM), or on the basis of polypropylene (ethylene-propylene-diene monomer or EPDM), or based on ethylene and propylene (EPM); semi-crystalline elastomers based on polyolefins; silicone rubbers, such as methylsilicone (in particular, phenyl, vinyl and Versiliana) and polysiloxane (polydimethylsiloxane); physical mixtures or alloys between thermoplastic polymers and elastomers, such as polypropylene (PP) or polyvinyl chloride (PVC), which is dispersed elastomers, which are uncured, partially or fully vulcanized vulcanized like rubber (PP/NR, PP/NBR-VD, PVC/NBR and TRO) or EPDM (PP/EPDM-VD).
Particularly preferably, the elastomeric non-starchy polymer has a glass transition temperature (Tg) -5 to -120°C, preferably from -10 to -105°C and more preferably -20 to -80°C.
As elastomeric non-starchy polymer, the following may be particularly recommended, in particular, natural rubbers and their derivatives, polyisobutylene, polyisoprene, butadiene-styrene copolymers (SBR), optionally hydrogenated butadiene-Acrylonitrile copolymers (NBR and H-NBR), acrylic�nitrile-styrene-acrylate copolymers (ASA), ethylene-methylacrylate copolymers (EAM), thermoplastic polyurethanes (TPU) type of simple ether type or ester-Prosti ether, polyethylene or polypropylene, functionalized, for example, halogenated silane, with the help of elementary stages, acrylic or maleic anhydride, EDM and EPDM, thermoplastic elastomers derived from polyolefins (TPO), styrene-butylene-styrene copolymers (SBS) and styrene-ethylene-butylene-styrene copolymers (SEBS), functionalized, for example, by means of elementary parts of maleic anhydride, and any mixtures of these polymers.
Preferably all or part of thermoplastic or elastomeric non-starchy polymer synthesized from monomers derived from rapidly renewable natural resources such as plants, microorganisms or gases, in particular from sugars, glycerol, oils or their derivatives, such as monofunctional, bifunctional or polyfunctional alcohols or acids. A portion of the non-starchy polymer may, in particular, can be synthesized from monomers of biological origin, such as bioethanol, bioecological, bioproperties, the 1,3-PROPANEDIOL biological origin, bipotential, lactic acid, succinic acid of biological origin, glycerol, isosorbide, sorbitol, �agarose, diols derived from plant or animal oils, and resin acids extracted from pine trees, as well as their derivatives.
A portion of the non-starchy polymer is particularly preferably may be polyethylene, obtained from bioethanol, PVC, obtained from bio-ethanol, polypropylene, obtained from bioproperties, complex polyesters PLA or PBS type on the basis of lactic acid of biological origin or on the basis of succinic acid of biological origin and complex polyesters RAT type-based butanediol biological origin or on the basis of succinic acid of biological origin and complex polyesters of the type SORONA® - based 1,3-PROPANEDIOL biological origin, polycarbonates comprising isosorbide, polyethylene glycols on the basis of bio-ethylene glycol, polyamides based on castor oil or plant-based diols and polyurethanes on the basis of, for example, vegetable diols polyols or vegetable, which are short or long, such as glycerol, isosorbide, sorbitol or sucrose, and/or on the basis of fatty acids, which are gidroksietilirovanny.
In any case, and as has already been clarified, particularly preferably, when the non-starchy polymer itself has a degree of Biodegradability of less than 50%, the preferred�about less than 30%.
According to another preferred embodiment of the non-starchy polymer has a low solubility in water, namely, less than 10% (less than 10% of material soluble in water at 20°C) and, in particular, less than 5%. It is preferably insoluble in water (less than 0.1% of material soluble in water at 20°C).
According to another embodiment, the non-starchy polymer has a weighted mean molecular weight of from 8500 to 10,000,000 daltons, in particular from 15,000 to 1,000,000 daltons.
In addition, non-starchy polymer preferably consists of carbon of renewable origin in the meaning of standard ASTM D6852 and preferably is nonbiodegradable or unsuitable to biochemical decay in the meaning of standards EN 13432, ASTM D6400 and ASTM 6868.
The inclusion of non-starch polymer in the ester of starchy material in the composition of the present invention may preferably be carried out using hot plastifitsirovanie at a temperature of from 35 to 300°C, in particular from 60 to 200°C and better still from 100 to 180°C. This incorporation can be carried out using a thermomechanical mixing portions or continuously and, in particular, in the production line. In this case, the mixing time may be short, from a few seconds to a few minutes.
According to a preferred embodiment, thermoplastic or elastomeric composition of the present and�finding may be plasticized and include a plasticizer.
The expression "plasticizer" or "plasticizing agent" refers to any molecule with a low molecular weight, in other words, preferably having a molecular weight less than 5000, which, when included in the composition of the present invention, in particular by means of thermomechanical treatment at a temperature of generally at least equal to 35°C, preferably from 35°C to 300°C, in particular from 60°C to 260°C and better still from 65°C to 200°C, leads to lower glass-transition temperature of the composition of the present invention or the glass transition temperature of the ester of starchy material and/or change their crystallinity.
When the term "plasticized" is used in this invention in respect of "starchy material", it necessarily implies the presence of a plasticizing agent. Esterified starch material may contain a certain amount of one or more compounds present in the list of plasticizing agents below that, in particular, can include water.
A plasticizing agent may, in particular, be selected from water, esters and ethers of diols, triolo and polyols, which are glycerin, polyglycerol, isosorbide, sorbitan, sorbitol, mannitol and hydrogenated glucose syrups, esters organic�of such acids, urea and any mixtures of these products. A plasticizing agent may, in particular, be chosen from methyl, ethyl or fatty esters of organic or inorganic acids, such as lactic, citric, succinic, adipic, sabotinova, phthalic, glutaric, or phosphoric acid or acetic or fatty esters of monoalcohols, diols, triolo or polyols such as ethanol, diethylene glycol, glycerol or sorbitol. As an example we can mention, in particular, glycerol diacetate (diacetin), glycerol triacetate (triacetin), isosorbide diacetate, dioctanoyl isosorbide, dioleate isosorbide, dilaurate isosorbide, esters of dicarboxylic acids or dibasic esters (DBE) and any mixtures of these products. A plasticizing agent may also be epoxidized vegetable oil, a glycol, or a derivative, such as a complex polyester of ethylene glycol.
The plasticizer may also be selected from the above-mentioned products, connected together by a linking agent such as epichlorohydrin or isocyanate.
According to another embodiment, the plasticizing agent is characterized by its solubility parameter (which is called the Hildebrand solubility), which actually represents a force of attraction that exists between molecules of a specified plasticizer and �what any polymer (starchy or non-starchy nature), the presence in the composition of the present invention, and more specifically the variability in energy density of cohesion of the plasticizer, i.e. the energy required to vaporize. The units of the solubility parameter is then expressed at 25°C and in (j·cm-3)0,5or (MPa)1/2(where 1 (j·cm-3)0,5=1 (MPa)1/2).
A plasticizing agent which is optionally used, may preferably have a solubility parameter of 15 to 28 (j·cm-3)0,5preferably from 17 to 25 (j·cm-3)0,5and more preferably from 18 to 22 (j·cm-3)0,5. This can be, for example, glyceryltrinitrate (triacetin), the solubility parameter of Hildebrand which is calculated from its latent heat of evaporation (85,74 kJ/mol) or from its boiling point (259°C), is 21 (j·cm-3)0,5.
According to another embodiment, the plasticizer used, if necessary, preferably has a molecular weight of less than 1500, in particular less than 500. Plasticizing agent preferably has a molecular weight of more than 18, in other words, it preferably does not include water. Optimum plasticizing agent has a molecular weight of from 150 to 450.
A plasticizing agent such as, for example, triacetin (molecular weight 218) may preferably have along with this:
- in molecular�with from 150 to 450; and
the Hildebrand solubility from 18 to 22 (j·cm-3)0,5.
If starchy composition comprises a plasticizing agent specified plasticizing agent preferably is present in an amount of from 1 to 150 parts by dry weight, preferably in an amount of from 10 to 120 parts by dry weight and in particular in an amount of from 25 to 120 parts by dry weight, per 100 parts by dry weight of ester of starchy material.
According to one preferred embodiment of the if the composition of the present invention contains a plasticizing agent, in particular, the plasticizing agent is the ester of starchy material, said composition comprises from 2 to 40 wt.%, preferably from 4 to 35 wt.% and, in particular, from 5 to 30 wt.% specified a plasticizing agent.
Especially preferably, thermoplastic or elastomeric composition according to the present invention may differ in that it includes:
- from 10 to 60 wt.% ester of starchy material;
- from 40 to 85 wt.% the polymer other than starch; and
- from 5 to 30 wt.% a plasticizing agent.
Not required, but preferred the inclusion of the plasticizer may be carried out at cold, for example, by mixing at room temperature with a complex ester of starchy material or not�orestano while obtaining a thermoplastic or elastomeric composition of the present invention, in other words, in the hot mode, at a temperature preferably from 60 to 200°C, more preferably from 100 to 180°C, in individual portions, for example, by plastilinovaya/mixing, or continuously, for example, by means of extrusion. The duration of this mixing can vary in the range from several seconds to several hours depending on the method of mixing.
According to another embodiment, the composition according to the present invention is characterized in that the starchy material used to obtain the ester contained in the composition has a degree of crystallinity less than 15%, preferably less than 5% and more preferably less than 1%. This degree of crystallinity of starchy material may in particular be measured using the technique of x-ray diffraction, as described in the patent US 5362777 (column 9, lines 8 to 24).
The composition of the present invention may optionally include a binder.
The term "binder" used in the present invention should be understood any organic molecule containing at least two free or latent functional groups able to react with molecules containing functional group containing active hydrogen, such as, for example, such ester groups starchy mate�ial or plasticizer. This binder can be added to the composition in order to provide attachment by covalent linkages of at least one part of plasticizer added to the complex ester of starchy material and/or added to the non-starchy polymer. A binder may optionally be added as a crosslinking or vulcanizing agent.
This binder in this case we can choose, for example, from compounds containing at least two identical or different, free or latent functional group selected from functional groups of isocyanate, carbamylcholine, aldehyde, epoxide, halo, protonic acid, acid anhydride, allhelgona, oxychloride, trimetaphosphate or alkoxysilane and combinations thereof.
The binder preferably you can choose from the following connections:
- diisocyanates, preferably methylenedianiline (MDI), colorvision (TDI), naphthalenedisulfonate (NDI), hexamethylenediisocyanate (HMDI) and liaindizecign (LDI);
- dicarbonitrile, preferably 1,1'-carbonyl-bisoprololum;
- glyoxaline, dialdehyde starches and TEMRO-oxidized starches;
- compounds containing an epoxy functional group and a halogen functional group, predpochtitel�but the epichlorohydrin;
- organic dibasic acid, preferably succinic acid, adipic acid, glutaric acid, oxalic acid, malonic acid or maleic acid and the corresponding anhydrides;
- oxychloride, preferably phosphorus oxychloride;
- trimetaphosphate, preferably trimetaphosphate sodium;
the alkoxysilanes, preferably tetraethoxysilane; and
- any mixture of these compounds.
In one preferred embodiment of the present invention the binder is a diisocyanate, in particular, methylenedianiline (MDI).
In the case where the composition contains a binder, the binder is preferably present in an amount of from 0.1 to 15 parts by dry weight, preferably in quantities of from 0.2 to 9 parts by dry weight and in particular in an amount of from 0.5 to 5 parts by dry weight, per 100 parts by dry weight of ester of starchy material.
The composition of the present invention may further comprise an agent that improves the compatibility for compatibility between the ester of starchy material and non-starchy polymer. This can be, for example, polymers or other surface-active substances with a low molecular weight or polymeric surfactants, sod�ramie, at least one relatively hydrophilic portion and at least one relatively hydrophobic portion. We can mention, in particular, proteins, block copolymers and synthetic polymers, functionalized by carrying out the graft copolymerization of maleic anhydride, etc.
The composition of the present invention may include other additional products.
We can mention, in particular, the possible addition of fillers, fibers or additives that are listed, in particular, below, which can be included in thermoplastic or elastomeric composition of the present invention. It can be products aimed at further improvement of its physico-chemical properties, in particular, its technological properties and its strength, or its mechanical, thermal, conductive, adhesive or organoleptic properties.
Additional product can be an agent that improves or adjusts mechanical or thermal properties, selected from inorganic materials, salts and organic substances. Additional products can be a nucleating such as talc, agents that improve the impact strength or the resistance to scratching, such as calcium silicate, agents, regulating shrinkage, such as magnesium silicate, agents which trap or deactivate items�t water acids, catalysts, metals, oxygen, infrared radiation or UV radiation, hydrophobic agents such as oils and fats, antivalentine and flame-retardants, such as halogenated derivatives, anti-smoke agents or inorganic or organic reinforcing fillers, such as calcium carbonate, talc, vegetable fibres, especially coconut, sisal, cotton, hemp, and flax fiber, fiberglass or Kevlar fiber.
Additional product may also be an agent that improves or adjusts the conductive or insulating properties in relation to electricity or heat or tightness, for example, in respect of air, water, gases, solvents, fatty substances, gasoline, smells or fragrances, selected in particular from inorganic materials, salts and organic substances, in particular, agents that conduct or dissipate heat, such as metal powders and graphite.
Additional product may also be an agent which improves the organoleptic properties, in particular:
aromatic properties (fragrances or agents, masking the smell);
- optical properties (bishopshostel, whiteners such as titanium dioxide, dyes, pigments, dye amplifiers, substances that make the material opaque, matte �Genty, such as calcium carbonate, thermochromic agents, phosphorescent and fluorescent agents, metallizers agents or agents to simulate marble and protivoprilipajushchie agents);
sound properties (barium sulfate) and barites), and
- tactile properties (fatty substances).
Additional product may also be an agent that improves or adjusts adhesive properties, in particular, adhesion properties in relation to cellulosic materials such as paper or wood, metal materials such as aluminum and steel, glass or ceramic materials, textile materials and inorganic materials, such as, in particular, pine resin, rosin, copolymers of ethylene/vinyl alcohol, fatty amines, lubricants, grease, mold, antistatic agents and mould release.
Additional product can be an agent that improves the strength of the material or agent for regulation of its (bio)degradability, selected in particular from waterproofing or granulating agents such as oils and greases, corrosion inhibitors, preservatives, such as, in particular, organic acids, particularly acetic acid or lactic acid, antimicrobial agents such as Ag, cu, and Zn, decomposition catalysts, such as oxo catalysts, and enzymes, such as amylase.
Additional product can�t be nanosized product which makes possible a significant reduction in sensitivity to water and steam end of the obtained thermoplastic or elastomeric compositions in comparison with compositions comprising starch, are known in the art. Nanoscale product can also be added to improve the processing properties and the properties of the molding compositions according to the present invention, but also its mechanical, thermal, conductive, adhesive or organoleptic properties. Preferably nanoscale product consists of particles having at least one size from 0.5 to 200 nanometers, preferably from 0.5 to 100 nanometers and even more preferably from 1 to 50 nanometers. This size may, in particular, to be from 5 to 50 nanometers.
Nanoscale product can be of any chemical nature and, if necessary, may be deposited on or attached to the substrate. It can be selected from natural or synthetic lamellar clay, organic, inorganic or mixed nanotubes, organic, inorganic or mixed nanocrystals and nanocristalline, organic, inorganic or mixed nanogramme and nanospheres, in a separate form, in the form of clusters or agglomerates, and any mixtures of these nanoscale products. As plate glino�reservoirs, also called silicates/phyllosilicates of calcium and/or sodium, can we name products known under the names of montmorillonite, bentonite, saponite, hydrotalcite, hectorite, forgetit, attapulgite, beidellite, nontronite, vermiculite, halloysite, stevensite, manasseite, pyroaurite, serenit, static, Barberton, takovite, desotelle, motokariya, honest, Montcaret, verlanget and mica. Such alumina plate are publicly available on sale, for example, from Rockwood under the trade names Nanosil and Cloisite. You can also mention the hydrotalcite, such as products Pural from Sasol.
Nanotubes that can be used in the context of the present invention have a tubular structure with a diameter on the order of a few tens of nanometers to several tens nanometers. Some of these products are already commercially available, such as carbon nanotubes, for example, from Arkema under the trade names Graphistrength and Nanostrength and Nanocyi under trade names Nanocyi, Plasticyi, Epocyi, Aquacyi and Thermocyl. Such nanotubes may also be cellulose nanofibrils with a diameter of approximately 30 nanometers, a length of a few microns, which consist of natural fibers of wood pulp and can be obtained by isolation and purification, based on the latest.
Nanocrystals or nanocrystallite �predpochtitelno can be obtained by crystallization, in thermoplastic or elastomeric composition as such or outside materials in a very diluted solvent environment, and implement the new system in the specified solvent which is part of a composition in accordance with the present invention. We can mention nanometals, such as iron or silver nanoparticles, which are used as the reducing or antimicrobial agents, and oxide nanocrystals, known as agents for improving the resistance to scratching. Mention should also be made of synthetic nanoscale talc, which can be obtained, for example, by crystallization from aqueous solution. You can also mention, in fact, amylose/lipid complexes with structures of type Vh (stearic), V, V, Isopropanol or Anatola, with the width or length of 1 to 10 microns, with a thickness of approximately ten nanometers. They may also be complexes with cyclodextrins, with similar characteristics. Finally, they can be a polyolefin nucleating able to crystallize in the form of nanoscale particles, such as derivatives of sorbitol, for example, dibenzylidene (DBS) and its specific alkylated derivatives.
Nanoscale product that can be used may be represented in the form of separate hour�CI type nanogramme or nanospheres, in other words, in the form of pseudosphere with a radius of from 1 to 500 nanometers, in some form, in the form of clusters or agglomerates. We can mention, in particular, the types of carbon black conventionally used as fillers for elastomers and rubbers. These species include soot primary particles, the size of which can range from about 8 nanometers (furnace carbon black) to approximately 300 nanometers (thermal carbon black), and generally, to exercise the standard abilities of malopolske from 40 to 180 cm per 100 grams for the specific surface area STSA of from 5 to 160 meters per gram. Such types of carbon black are sold, in particular, Cabot, Evonik, Sid Richardson, Columbian and Continental Carbon.
Mention should also be made hydrophilic or hydrophobic, and precipitated or pyrogenic silicas, such as those used as agents, providing fluidity, for powders or fillers in the "green" tires. Such silicas, in particular, in the form of powders or dispersions in water, ethylene glycol or acrylate resins or epoxy type sold Grace, Rhodia, Evonik, PPG and Nanoresins AG.
You can also mention neosartorya calcium carbonates or metal oxides (titanium dioxide, zinc oxide, cerium oxide, silver oxide, iron oxide, magnesium oxide, aluminum oxide, etc.), which are nanoscale, for example, by burning, such as the products sold� Evonik under TORGOVLI names or Aeroxide Aerodisp, or through exposure to acids, such as the products sold by Sasol under the trade names Disperal or Dispal.
In conclusion may be mentioned proteins, precipitated or coagulated in the form of nano-sized granules. In conclusion may be mentioned polysaccharides, such as starches, placed in nanospheres form, such as nanoparticles of crosslinked starch with size from 50 to 150 nanometers, which are sold Ecosynthetix under Torgoviy name Ecosphere, or nanoparticles of starch acetate Cohpol C6N100 from VTT, or even the nano-grains synthesized directly in nanoscale condition, for example, granules of politicalpolitical from Topchim.
Performed when necessary the inclusion of any additional product can be carried out by physical mixing, at cold or at low temperature, but preferably by plastilinovaya in hot mode at a temperature greater than the glass transition temperature of the composition. This temperature plastilinovaya is preferably from 60 to 200°C, better still from 100 to 180°C. This incorporation can be carried out by thermomechanical mixing, portions or continuously and, in particular, in the production line. In this case, the mixing time may be short, from a few seconds to a few minutes.
A composition according to the present invention preferably prowl�em complex viscosity, measured on the rheometer Physica MCR 501 or equivalent type, from 10 to 106PA·s, for temperatures from 100 to 200°C. for the purpose of processing by injection molding, for example, its viscosity at these temperatures is preferably at the bottom of the range specified above, and the composition is then preferably is a hot melt composition in the meaning as specified above.
Thermoplastic or elastomeric composition of the present invention additionally exhibit the advantage that are virtually or completely insoluble in water, that it is difficult hydrate and that retain good physical integrity after immersion in water, saline solution, oxidizing, acidic or alkaline solutions or more complex aquatic environment, such as a biological environment, such as saliva, sweat and digestive juices. Unlike thermoplastic compositions with high contents of starch prior art composition according to the present invention preferably demonstrates a stress/deformation that are characteristic of the plastic material, not fragile material type.
Its mechanical properties in tension may primarily be evaluated according to the following Protocol.
Measurement of mechanical properties
Mechanical�technical characteristics tensile various compositions was determined according to the standard NFT51-034 (Determination of tensile properties), using the test bench Lloyd Instruments LR5K, the pulling speed of 50 mm/min 300 mm/min and standardized test samples of H2 type.
Note the elongation at break and the corresponding maximum tensile strength for each of the compounds of the curves of stress-strain (stress = f(elongation)) obtained at a pulling speed of 50 or 300 mm/min.
Elongation at break measured for the compositions of the present invention for the rate of pulling of 50 mm/min, is usually from 10% to 1000%. It is usually more than 20%, more preferably 40%, even better more than 60%. This elongation may preferably be at least equal to 70%, in particular at least equal to 80%. It is noteworthy that it may even reach or exceed 100% or even 200% or even much more (from 300% to 900%, or even 1000%). According to one preferred embodiment of this elongation at break at least equal to 70% and less than 500% and, in particular, from 80% to 480%.
The maximum tensile strength of the compositions of the present invention, also measured at a pulling speed of 50 mm/min, is, as a rule, from 4 MPa to 50 MPa. She is usually more than 4mpa, preferably greater than 5 MPa, even better than 6 MPa. It is noteworthy that it may even reach or exceed 7 MPa, or 10 MPa, and�and even much more (from 15 MPa to 50 MPa). According to one preferred embodiment of this maximum tensile strength at least equal to 7 MPa and less than 50 MPa, and in particular from 10 MPa to 45 MPa.
The composition of the present invention may additionally exhibit the advantage that it consists of, essentially, renewable raw materials, and that it is able to show, after controlling the composition, the following properties are used in various applications in the plastics industry or other fields:
acceptable thermal plasticity, acceptable melt viscosity and an acceptable glass transition temperature within normal ranges, known for standard polymers (Tg of -120°C to +150°C), allowing the implementation of processing through existing industrial installations, which are traditionally used for standard synthetic polymers;
- sufficient Miscibility with a wide variety of polymers fossil or renewable origin based on the market or in development;
- satisfactory physical and chemical stability conditions;
- low sensitivity to water and steam;
- mechanical strength, which is very noticeably improved compared to thermoplastic starch compositions known level�technology I (elasticity, elongation at break, maximum tensile strength);
- good barrier effect against water, water vapor, oxygen, carbon dioxide, UV radiation, fatty substances, odors, gasoline and fuels;
- opacity, translucency or transparency, which can be adjusted according to the applications;
- good suitability for printing and the ability to be painted, especially inks and paints in the aqueous phase;
- adjustable shrinkage in size;
- Vysokomolekulyarnye stability within a certain time;
- adjustable Biodegradability and suitability for biochemical decomposition; and
- good recyclability.
Another object of the present invention is a method for producing a thermoplastic or elastomeric composition, as previously described in all its variants, where said method comprises the following steps:
(i) selecting at least one ester of starchy material with NW from 1.6 to 3, preferably from 1.8 to 3 and more preferably from 2.0 to 2.9;
(ii) selecting at least one polymer other than starch; and (iii) the receipt, preferably by thermomechanical mixing, hot-swappable, thermoplastic or elastomeric composition.
Thermoplastic or elastomeric, composite� of the present invention can be used as such or as a mixture with synthetic polymers, artificial polymers or polymers of natural origin. It may also include polymers that are known to be biodegradable or suitable for biochemical decay in the meaning of standards EN 13432, ASTM D4600 and ASTM 6868, or materials that comply with these standards, such as PLA, PCL, PBS, RAT and RNA.
The composition of the present invention can mainly be nonbiodegradable (degree of Biodegradability of less than 5%, preferably close to 0%) and/or preferably to the biochemical breakdown in the understanding of the EN or ASTM standards mentioned above. You can adjust the lifetime and stability of the compositions of the present invention with the regulation, in particular, its affinity to water so that it was suitable for the intended uses of the material and for ways to reuse/recycling provided at the end of life.
Thermoplastic or elastomeric composition according to the present invention preferably contains at least 15%, preferably at least 30%, in particular at least 50%, better still at least 70% or even more than 80% of carbon of renewable origin in the understanding ASTM D6852 standard in relation to all the carbon present in the composition. This carbon renewable�about the origin is essentially, that is the ester of starchy material, necessarily present in the compositions according to the present invention, but preferably may also be, by appropriate choice of component composition, which is used if necessary, a plasticizer, or any other component of the composition in the case where they originate from renewable natural resources, such as those preferably defined above.
In particular, may provide for the application of compositions of the present invention as films, gaskets or barrier products with regard to oxygen, carbon dioxide, odors, fuels and/or fatty substances alone or in multilayer structures obtained by co-extrusion, in particular, to the field of packaging for food products.
They can also be used to increase the hydrophilic nature, the ability to conductivity and permeability for water and/or steam or resistance to organic solvents and/or fuels, synthetic polymers in the context of, for example, manufacturing a printable electronic labels, films or membranes, of textile materials, containers, or tanks, or extra improved adhesive properties of the hot-melt interocclusal films or sealing films on hydrophilic substrates, such as wood, glass or leather.
It should be noted that the relatively hydrophilic nature of thermoplastic or elastomeric composition of the present invention significantly reduces the risks of bioaccumulation in fatty tissues of living organisms and, consequently, also in the food chain.
Said composition can be in powder, granular or bead form. It can be uterine mixture or matrix masterbatches are provided for cultivation in the matrix of biological origin or non-biological origin.
It can also be the raw material for plastics or compound that can be used directly by the hardware manufacturer or firm plastic processing in order to obtain a plastic or elastomeric products.
It is, as such, may also be an adhesive, especially hot-melt type, or matrix for the preparation of the adhesive, in particular hot-melt type.
It may be part of or the entire gum base or matrix of Gumienny, in particular, for chewing gum or resin, the additional resin or nanosatellites, in particular, those which are of biological origin that can be used in industry, in particular, in the production of rubbers and elastomers, incl�tea bus, road asphalt or other bitumen, in the manufacture of printing inks, manufacture of paints, manufacture of paints, manufacture of paper and paperboard and manufacture of woven and non-woven products.
One object of the present invention is the use of the compositions according to the present invention, in particular, the elastomeric compositions, to obtain Gumienny for chewing gum.
Another object of the present invention, the gum base for chewing gum, which contains the composition according to the present invention, preferably in an amount of from 5 to 50%, preferably from 10 to 45% and in particular from 10 to 40%.
Another object of the present invention is the use of the compositions according to the present invention, in particular, the elastomeric compositions, to produce parts or components for the transport industry, in particular, automotive, aviation, railway, and shipbuilding industries, for the production of electrical appliances, electronic devices or electrical appliances or for sports and leisure.
This can be, for example, tires or frames for tires, belts, cables, pipes, gaskets and molded parts, teats, gloves, shoes soles or coated fabrics.
In conclusion, the composition of the present invention, if necessary, can be�ü used to produce thermosetting resins (Duroplast) by extensive irreversible cross-linking, the resin thus finally lose all thermoplastic or elastomeric nature.
The present invention also relates to plastic, elastomeric material and adhesive material comprising a composition of the present invention or a finished or semi-finished product obtained from it.
Example 1. Obtaining compositions of the present invention
For this example, use:
as the ester of starchy material acetate of potato starch with NW esters 2.7 and called hereafter "the ASSET I";
- as the plasticizer of this ester of starchy material, a liquid composition of glyceryltrinitrate (triacetin);
as the polymer other than starch, a thermoplastic polymer, in this case, PLA (polylactic acid);
- as another polymer other than starch, the elastomeric polymer is a polyester TPU (thermoplastic polyurethane) type, sold a Noveon under the trade name ESTANE® 58887;
- as another polymer other than starch, low density polyethylene (LDPE);
- as another polymer other than starch, polyethylene grafted maleic anhydride, sold Polyram under Torgoviy name BONDYRAM® 4001;
- as a binder �etilendiamindisuktsinatov (MDI), sold by Huntsman under the trade name Suprasec 1400.
First, in several stages receive a composition containing by weight:
- 30% of the ester ACET 1 starchy material;
- 20% of triacetin and
- 50% PLA.
During the first stage, 60 parts of the ester ACET 1 and 40% parts of triacetin mixed in a mixer of the Hobart type for 5 minutes. After crushing the obtained mixture is injected through the main feeding hole, single screw extruder of the type NAACE having a diameter (D) of 19 mm and a length of 25 D, according to the following temperature profile, respectively, for 4 barrels: 40°C, 140°C, 130°C and 110°C, With a rotation speed of 80 rpm.
Rod plasticized ester ASET 1 starchy material is then granulated.
Further, also in the mixer of the Hobart type and within 5 minutes, these granules are plasticized ester ASET 1 ("ASET 1 P1) was mixed with PLA in a weight ratio of 50/50.
Further, also through the main feeding hole obtained ASET 1 pl/PLA mixture was injected into the single screw extruder NAACE described above, according to the following temperature profile, respectively, for 4 barrels: 40°C, 140°C, 130°C and 110°C at a rotation speed of 40 rpm.
It turns out that this compound corresponds to that expected from a conventional thermoplastic material, which you can enter, test and convert to obsip�inatom equipment for conversion, such as an extruder.
The obtained extruded composition (here forth "somr I") is in the shape of a bar of cream color, which is continuous, can extend under its own weight and which seems visually homogeneous. To the touch he shows good elasticity, but has a rather slow elastic response type unsewn rubber.
The composition has the following mechanical characteristics in tension, measured in accordance with the Protocol described previously in the section "Measurement of mechanical properties at a rate of pulling of 50 mm/min:
- elongation at break: 23%;
- the maximum tensile strength: 16 MPa.
Furthermore, the composition has a degree of Biodegradability, measured in accordance with the Protocol described previously in the section "measurement of the degree of Biodegradability according to the ISO 14851", the mean value is very low, namely, less than 15%, whereas under the same conditions microcrystalline cellulose has a degree of Biodegradability, close to 90%.
PLA, PHA or other polymers, classified as biodegradable, while processing them themselves under the same conditions, have the values of the degree of Biodegradability, which are, as a rule, more than 50%.
Composition somr 1 described above, in accordance with the present invention, are then used� in extruded compositions ("somr 2", "Somr 3" and "somr 4"), in accordance with the present invention, and these compositions respectively contain by weight:
- Somr 2: 100 pieces somr 1+2 parts binder (MDI);
- Somr 3: 50 piece somr 1+50 parts of polyester ESTANE TPU®58887+2% MDI and
- Somr 4: 50 somr parts 1+45 parts of low density polyethylene (LDPE)+5% RE, grafted maleic anhydride, BONDYRAM®4001.
They have, under the same measuring conditions as were used for the composition somr 1, the mechanical characteristics listed in the table below, using as control compositions, compositions consisting only of LDPE or only from Acrylonitrile-butadiene-styrene copolymer ("ABS").
|Composition||Elongation at break||The maximum tensile strength|
|Somr 2||130%||18 MPa|
|Somr 6||207%||17 MPa|
|Somr 4||112%||8 MPa|
|LDPE (control�)||250%||8 MPa|
|ABS (control)||40%||32 MPa|
These results show overall that the mechanical characteristics tensile composition somr 1 of the present invention can be considerably improved by adding small amounts of binder ("somr 2") and/or by mixing with polymers, respectively polyether TPU ("somr 3") or polyolefin ("somr 4") type.
The applicant is more generally observed, notably:
- although the composition somr 3 of the present invention contain a very high proportion of somr 1, it had thermal and mechanical properties that were comparable with those of commercial "developed" thermoplastic elastomers such as TPU elastomers or ABS type;
songs somr 2 and somr 4 of the present invention, which have a very high content of somr 1, had, in spite of the relative decrease in the elongation, characteristics similar to commercial polymers, known as "polymers of consumption" LDPE type.
Example 2. Application of elastomeric compositions of the present invention upon receipt of chewing gum
In the context of this example appreciate the opportunity approx�application of the compositions of the present invention to, at least partial substitution of Gumienny based on a synthetic polymer used to produce chewing gum.
2.1: Raw materials
As the main raw materials for this example, use:
as esters of starchy material, respectively:
- acetate maltodextrin derived from waxy corn starch (maltodextrin GLUCIDEX® (8) sold by the Applicant), wherein said acetate is NW of esters of around 2.7 (referred to hereinafter as the "ASSET 2");
- acetate fluidized corn starch, in this case starch CLEARGUM® MB-80 sold by the Applicant, wherein said acetate is NW esters of about 2.5 (referred to hereinafter as the "ASSET 3");
- acetate of potato starch (so equal to 0,45), then inoculated with Epsilon-caprolactone, obtained the ester of starchy material has a General NW esters of about 2.6 (referred to hereinafter as the "ASSET 4"); and
- acetate of potato starch with NW esters of about 2.6, wherein said acetate is moreover hydroxypropionate with MS (molar degree of substitution) of about 0.4 (referred to hereinafter as the "ASSET 5");
- as the plasticizer of these esters of starchy material triacetin (denoted hereinafter as "PLAS 1"); and
- as a synthetic elastomeric polymer composition (gum base) that contains, in General, about 52 wt.% mixture of polymers other than starch, wherein the mixture comprises poly (vinyl acetate) (PVAc), esters of rosin, butadiene/styrene copolymers and polyisobutylene, the remainder to 100% consists primarily of calcium carbonate, paraffin wax and emulsifier. Polyisobutylene and butadiene/styrene elastomers comprise about one third, in other words, 14% 52% polymers Gumienny.
2.2: Plasticizing esters of starchy material
In the Z-kneader vane Ktistner heated to 110°C, each of the esters of starchy material ACET 2 to ASET 5 is heated with the plasticizer PLAST 1 in the following respective weight proportions:
- 70% ASET 2+30% PLAST 1,
- 60% ASET 3+40% PLAST 1,
- 60% ASET 4+40% PLAST 1,
- 60% ASET 5+40% PLAST 1.
After plastilinovaya for 50 minutes to see the following:
- very good homogeneity of the mixtures on the basis of esters ASSET 2 and ASSET 5,
- lower the homogeneity of the mixtures on the basis of ester ASSETS (the presence of several former spots after plastifitsirovanie) and ester ASET 4 (presence gelatinizing particles after plastilinovaya),
- good elasticity of mixtures, especially those based on the ester ACET 4.
2.3: VC�Uchenie plasticized ester of starchy material in the gum base
In the same kneader as that described above, 70 wt.% elastomer composition (Gumienny), as previously described, is mixed, also at 110°C and within 30 minutes, with 30 wt.%, accordingly, each of plasticized ester of starchy material derived in section 2.2, hereinafter designated respectively as ASET 2 P1, 3 ASET P1, ASET 4 P1 and ASET 5 P1.
It is observed that all four plasticized ester of starchy mixtures material/Gumienny are homogeneous, which illustrates the good compatibility between the synthetic polymer material that forms the gum base, and each of the previously acetates plasticized starchy material ACET 2 P1 - ASET 5 P1.
2.4: Getting chewing gum out of Gumienny. combined or not combined with a plasticized ester of starchy material
Composition of chewing gum get according to the recipe below.
2.4.1: the Recipe
|The gum base, combined or not, with a plasticized ester of starchy material||35,0|
|The sorbitol powder NEOSORB® P650||42,45|
|Powder xylitol XYLISORB® P90||5,0|
|Syrup of maltitol LYCASIN® 80/55||10,0|
|Powdered mint flavour SILESIA||0,2|
|Liquid mint flavour SILESIA||1,5|
Introducing the gum base, combined or not with a plasticized ester of starchy material in a Z-blade kneader IKA (IKA VISC MKD 0,6 - MESSKNETER H60), preheated to 50°C. Add half of powdered sorbitol. Knead for 2 minutes.
- Add syrup of maltitol, knead for 2 minutes.
- Add mannitol and powdered xylitol, knead for 2 minutes.
- Add the other half of powdered sorbitol and glycerol, knead for 2 minutes.
- Add powdered flavoring, menthol and aspartame, knead for 1 minute.
- Add liquid flavoring, kneading for 1 minute.
- Empty plasticizer, RA�to roll the mixture into a strip, having a thickness of 5 mm, and cut it into "tiles" that have a length of 30 mm and a width of 18 mm.
2.4.3 Tested components "gummiente"
Experiencing various components of Gumienny" GUM I - 5 GUM (the number in the formulation of chewing gum: 35% - see above), composed, respectively, of:
- GUM of 1: 100 wt.% Gumienny = CONTROL
- GUM 2: 70 wt.% Gumienny +30 wt.% plasticized acetate of starchy material ACET 2 pl;
- GUM 3: 70% of Gumienny/30% ASET 3 pl;
- GUM 4: 70% of Gumienny/30% ASET 4 pl and
- GUM 5: 70% of Gumienny/30% ASET 5 pl.
2.4.4 Measurement of the hardness of the tiles
The hardness, expressed in Newtons, of the received tiles are measured using the instrument INSTRON 4500 (measuring cell: 100 Newton; a cylindrical punch with a diameter of 3.9 mm; travel speed: 50 mm/min). Tile is measured either directly after receiving them (DO) and at different temperatures (45°C, 35°C or 20°C) or using respectively 1, 8 and 15 days of storage in aluminum packaging, which itself is placed in a climate chamber (temperature: 20°C; relative humidity (RH): 50%).
The results, expressed in Newtons, are presented in the table below:
|The gum base||D0 - 45°C||D0 - 35°C||D0 - 20°C||D8 - 20°C 50% RH||D15 - 20°C 50% RH|
|GUM 1= CONTROL||3,0||7,2||Of 17.8||25,9||25,7||27,7|
|GUM 2||2,4||4,5||10,9||16,6||20,5||A 20.7|
Typically, the chewing gum, in which 30% of Gumienny substituted plasticized ester of starchy material:
are � "Helion Ukraine" completely homogeneous, except that the obtained gum base GUM 4, for which there is a residual presence of a few scattered particles of plasticized ester of starchy material ACET 4 P1; and
- are less solid and less solid than the control. Chewing gum, in which the texture according to the measurement INSTRON is the closest to the control are made with gum base GUM 2 containing 30% plasticized ester of starchy material ACET 2 P1, namely, 30% acetate GLUCIDEX®2, plasticized triacetin.
Organoleptic tests showed that, overall, the texture and taste of these chewing gums are perfectly acceptable, and chewing gum prepared from Gumienny GUM 2 also prove during such tests that are closest to the control chewing gum in which the gum base is not combined with a complex ester of starchy material.
The results of this example 2 as a whole show that esters of starchy material, such as plasticized products, ASSET 2, ASSET 3 ASSET 4 ASSET 5, can be used in the preparation of chewing gums as at least a partial, but significant replacement (from a few % to at least 30 wt.%) for obsidian�Gumienny synthetic nature.
Example 3. A composition of the present invention on the basis of plasticized ester of starchy material and a polymer-based ester TPU type
For this example, use:
- as a plasticized ester of starchy material acetate maltodextrin ASET 2 as described in example 2;
- as the plasticizer benzyl alcohol in an amount of 15 parts by weight per 100 parts by weight of the specified ester;
as the polymer other than starch, a polymer of ester TPU type sold a Noveon under the trade name ESTANE® 58447;
as the binder methylenedianiline (MDI) sold by Huntsman under the trade name Suprasec 1400.
If the General conditions of example 1 afforded the composition according to the present invention (hereinafter, "somr 5") containing:
50 parts of the polymer ESTANE®58447;
- 50 parts by weight of plasticized ester ACET 2 and
- 1 part by weight of MDI.
This composition somr 5 has the following mechanical characteristics in tension, measured in accordance with the Protocol described above in "Measurement of mechanical properties at a rate of pulling of 50 mm/min:
- elongation at break: 80%;
- the maximum tensile strength: 14 MPa.
Com�azizia somr 5, although it has a high relative content of the ester of starchy material, exhibits characteristics similar to certain indicators of the polymer type "high impact polystyrene" or type "EVA for agricultural films".
1. The elastomeric composition, characterized in that:
a) she has a degree of Biodegradability according to the ISO 14851 less than 50%, preferably less than 30%; and
b) it contains:
- at least 0.5% and not more than 99.95 wt.%, preferably from 1 to 99 wt.% acetate starchy material having a degree of substitution (Sz) from 2.5 to 3, and
at least, of 0.05 wt.% and not over 99.5 wt.%, preferably from 1 to 95 wt.% the polymer other than starch, and the specified polymer selected from the group consisting of natural rubbers and their derivatives, polyisobutylene, polyisoprene, butadiene-styrene copolymers (SBR), butadiene-Acrylonitrile copolymers, hydrogenated butadiene-Acrylonitrile copolymers, Acrylonitrile-styrene-acrylate copolymers (ASA), ethylene/methylacrylate copolymer (EAM), thermoplastic polyurethanes (TPU) type of simple ether type or ester-ether, polyethylene or polypropylenes functionalized halogenated silane, elementary links of acrylic or maleic anhydride, varieties of rubbers on the basis of copolym�RA ethylene-diene monomer (EDM) and rubber-based copolymer of ethylene-propylene-diene monomer (EPDM), thermoplastic elastomers derived from polyolefins (TPO), styrene-butylene-styrene copolymers (SBS) and styrene-ethylene-butylene-styrene copolymers (SEBS), functionalized elementary units of maleic anhydride, and any mixtures of these polymers.
2. A composition according to claim 1, characterized in that the acetate of starchy material as such has a degree of Biodegradability according to the ISO 14851 less than 50%, preferably less than 30%.
3. A composition according to claim 1, characterized in that the polymer other than starch itself has a degree of Biodegradability according to the ISO 14851 less than 50%, preferably less than 30%.
4. A composition according to claim 1, characterized in that NW acetate starchy material is from 2.6 to 2.8.
5. A composition according to claim 1, characterized in that the polymer other than starch has a solubility in water at 20°C less than 10%.
6. A composition according to claim 1, characterized in that it includes:
- from 10 to 70 wt.%, preferably from 10 to 60 wt.% acetate starchy material; and
- from 30 to 90 wt.%, preferably from 40 to 90 wt.% the polymer other than starch.
7. A composition according to claim 1, characterized in that it includes:
- from 51 to 99 wt.%, preferably from 51 to 98 wt.% acetate starchy material; and
from 1 to 49 wt.%, preferably from 2 to 40 wt.% and even more preferably from 2 to 35 in�S.% polymer, different from starch.
8. A composition according to claim 1, characterized in that it includes:
- from 5 to 49 wt.%, preferably from 7 to 49 wt.% and even more preferably from 10 to 49 wt.% acetate starchy material, and
- from 51 to 95 wt.%, preferably from 51 to 93 wt.% and even more preferably from 51 to 90 wt.% the polymer other than starch.
9. A composition according to claim 1, characterized in that the acetate of starchy material is an acetate granular, preferably hydrolyzed, oxidized or modified starch.
10. A composition according to claim 1, characterized in that the acetate of starchy material is a water-soluble acetate starch or organomodified starch, preferably acetate pre-castelsilano starch, extruded starch, spray-dried starch, dextrin, maltodextrin, functionalized starch, starch solvent-borne or any mixture of these products, which are plasticized.
11. A composition according to claim 1, characterized in that the acetate of starchy material is a water-soluble acetate or organomodified starch, acetate of dextrin or acetate maltodextrin.
12. A composition according to claim 1, characterized in that it contains plastification, which preferably is present in an amount of from 1 to 150 parts by dry weight, preferably in an amount of from 10 to 120 parts by dry weight and in particular in an amount of from 25 to 120 parts by dry weight per 100 parts by dry weight of acetate of starchy material.
13. A composition according to claim 1, characterized in that it includes:
- from 10 to 60 wt.% acetate starchy material;
- from 40 to 85 wt.% the polymer other than starch; and
- from 5 to 30 wt.% a plasticizing agent.
14. A composition according to claim 1, characterized in that it has:
- elongation at break at least equal to 70% and less than 500%; and
- tensile strength at least equal to 7 MPa and less than 50 MPa.
15. A composition according to claim 1, characterized in that it contains at least 15%, preferably at least 30% of carbon of renewable origin according to ASTM D6852, expressed relative to all the carbon present in said composition.
16. The gum base for chewing gum containing a composition according to any one of claims. 1-15.
17. The gum base according to claim 16, characterized in that it contains from 5 to 50%, preferably from 10 to 45% and in particular from 10 to 40% of a composition according to any one of claims. 1-15.
18. Use of the composition according to any one of claims. 1-15 as masterbatches, matrix, master batch, raw material for plastics, with�unity for plastic or elastomeric articles adhesive, in particular hot-melt type, the matrix for the preparation of the adhesive, in particular hot-melt type, as a component of Gumienny or matrix Gumienny, in particular, chewing gum, resin, the additional resin or nanosatellites for rubbers, elastomers, asphalts, inks, varnishes, paper, cardboard, woven and non-woven products or to obtain thermosetting resins.
19. Use of the composition according to any one of claims. 1-15 to obtain Gumienny for chewing gum.
20. Use of the composition according to any one of claims. 1-15 to obtain parts or components for the transport industry, in particular, automotive, aviation, railway, and shipbuilding industries, for the production of electrical appliances, electronic devices or electrical appliances or for the sports industry and leisure.
SUBSTANCE: invention relates to foam polyisocyanurate composition, which can be applied in production of heat-insulating materials and building panels. Foam polycyanurate composition includes polyisocyanate compound, first polyetherpolyol based on ester, including residue of orthophthalic acid, second polyetherpolyol based on ester, including residue of terephthalic acid, at least one polyetherpolyol based on ether, which is characterised by functionality, constituting at least 3, and hydroxyl number, which changes in the range from 200 to 850 mg KOH/g. Composition also includes physical foaming agent and water in quantity from 0.2 to 3 wt % counted per the total quantity of components in reaction mixture, where isocyanate index constitutes from 250 to 500. Also described is product, which contains claimed composition, and method of panel obtaining, which has facing and block from foam polyisocyanurate.
EFFECT: stability of geometrical dimensions in all directions, small degree of shrinkage, increase of strength limit of foam material, as well as absence of waved pattern formation on the product surface.
7 cl, 2 tbl, 5 ex
SUBSTANCE: compound casting method for electrical goods includes mixing of components with receipt of the compound and casting of the electrical goods with the compound. At that before casting an electrical good is heated at temperature of 50-55°C and residual pressure of 10-15 mm hg at least during 3 hours. The compound is received by mixing of predried components in the following ratio, g: styrene - 50, castor oil - 38, product 102T - 12, benzoyl peroxide paste - 1. The paste made by mixing of predried benzoyl peroxide with dibutyl phthalate is used as the benzoyl peroxide paste. At that before casting the compound is vacuumised additionally at temperature of 15-35°C and residual pressure of 10-15 mm hg at least during 3-5 minutes. The pretreated electrical goods and compound are heated in the same furnace at temperature of 70°C during 1 hour. Then the heated electrical goods are casted step by step with the hot compound by the free casting method initially to ѕ of the electrical good height or volume with further vacuum degassing of the casted electrical goods at temperature of 15-35°C and residual pressure of 10-15 mm hg during 15-20 minutes with further casting of the electrical good with the same compound up to the required level. The multistage polymerisation of the compound is carried out. At that the casted electrical goods are held in the furnace heated up to 70°C during 4 hours at first, then they are casted with the same compound and its polymerisation takes place again at temperature of 70°C during 4 hours.
EFFECT: non-availability of defects in the form of cracks and air bubbles in the compound mass thus ensuring high quality of the casted electrical goods, and namely increasing their electric strength and reducing quantity of wastes.
SUBSTANCE: invention relates to chemistry, particularly quick-setting polyurethane compositions and can be used in construction to seal joints between enclosing structures of buildings and control joints of concrete floors, slits and cracks. The urethane putty contains a component A as the basic paste, which contains a hydroxyl-containing polyether with molecular weight 3600, silicon dioxide, diethylene glycol, a cationic catalyst, a plasticiser containing dibutylphthalate and chloroparaffin, filler, and a component B as the putty hardener, which is obtained by reacting the hydroxyl-containing polyether - laprol 3603-2-12 with toluylene diisocyanate and further contains a stabiliser, wherein before application, components A and B are mixed with each other in ratio 9:1 pts.wt, respectively.
EFFECT: broader processing capability of urethane putty in construction of buildings.
SUBSTANCE: invention relates to chemistry, particularly polyetherurethane compositions based on polyethers and can be successfully used to insulate inner surfaces of drill pipes from asphalt-gum, paraffin and salt deposits during oil and gas extraction. The polyetherurethane is obtained by mixing a hydroxyl-containing fatty-aromatic polyether with terminal hydroxyl groups and molecular weight of 1002, modified by vinyl links with a polyfunctional isocyanate and an additional cross-linking component - bis-monotetrapropanol-2-urea, obtained through direct oxypropylation of carbamide, with the following ratio of components, pts.wt: fatty-aromatic modified polyether 100, bifunctional polyisocyanate 22-25 and bis-monotetrapropanol-2-urea 2.5-3.0.
EFFECT: low level of toxicity, high hydrolytic stability and shorter time for coating.
2 cl, 2 ex
SUBSTANCE: invention relates to the chemistry of foamed polyurethanes, particularly a polyurethane system for making elastic articles, preferably for medical purposes, for example, orthopaedic articles, technical parameters of which have improved sanitary properties which meet their operating requirements. The present invention can also be used to make polyurethane bandages. The polyurethane system for making articles with improved sanitary properties contains compositions based on a polyol compound A, an isocyanate compound B and a mineral agent C, which is dispersed in polyol compound A. The isocyanate compound B used is prepolymers of methylene diphenyl diisocyanates MDI. The mineral agent C used is a mixture of bentonite nanopowders which are intercalated with silver ions Ag+ and cerium ions Ce3+.
EFFECT: improved sanitary properties of the obtained elastic articles, with regard to both inhibiting growth of microorganisms and reducing gas release of volatile toxic organic compounds.
9 cl, 2 dwg, 5 ex
SUBSTANCE: invention relates to a sealing compound containing polythioether, where the sealing compound (a) essentially does not contain volatile organic compounds; (b) can be applied via pulverisation and (c) is fuel-resistant, where the polythioether contains polythioether-polyurethane and/or -polythiourethane with functional isocyanate groups and polythioether with functional amino/hydroxy groups. Described also is a multi-component sealing compound containing (a) a first component which contains polythioether-polyurethane and/or -polythiourethane with isocyanate functional groups, and (b) a second component containing polythioether with terminal amino/hydroxy groups. The invention also describes an aerospace vehicle having a hole which is at least partly sealed by said sealing compounds, and the hole itself, which is at least partly sealed by said sealing compounds.
EFFECT: obtaining sealing compounds which essentially do not contain volatile organic compounds, which are fuel-resistant, can be applied via pulverisation and harden fast in ambient conditions, and have good elasticity at low temperature.
20 cl, 4 ex, 1 tbl
SUBSTANCE: polyurethane composition contains the following in pts. wt: 100 - polyether having molecular weight of 1000-2000; 150-350 2,3-toluene diisocyanate, 1-95 amine hardener, 10-35 plasticiser, 1-20 fluorooligomeric alcohol with molecular weight of 1000-5000 and 5-100 polyol with molecular weight of 1200-3500. Content of NCO- groups in the composition equals 4.09-6.5%.
EFFECT: elastomers obtained from said composition have high durability, good strength properties and high frost resistance, which enables use of articles made from the said composition under heavy loads, in conditions with large differential temperature and in aggressive media.
8 cl, 1 tbl
FIELD: chemistry of polymers, covers.
SUBSTANCE: invention relates to compositions of film-forming polyurethane compositions. Invention describes a composition for covers comprising the following components, mas. p. p.: polyoxypropylenetriol of molecular mass 3000-5000 Da, 80-95; 4,4'-diphenylmethanediisocyanate-base polyisocyanate, 100-200; ethyl acetate, 35-40; butyl acetate, 30-40; toluene,20-35; concentrated hydrochloric acid, 0.05-0.1, and ethylene glycol, 5-20. Invention provides enhancing adhesion to metal by 2-2.5-fold (up to 8.2 MPa) and enhancing cover hardness by 1.5-1.6-fold (up to 0.85 a. u. by method M-3). Invention can be used in preparing a protective cover for wood, concrete, glass, metal.
EFFECT: improved and valuable technical properties of composition.
1 tbl, 29 ex
FIELD: petrochemical processes.
SUBSTANCE: invention relates to a method for production of bitumen-polyurethane compositions designed mainly for manufacturing road, protective, insulation, and anticorrosive coatings. Modification of bitumen comprises interaction of bitumen bulk with prepolymer preliminarily prepared from components containing polyol and isocyanate groups, interaction being carried out at 60-140°C for 0.25-1 h, said components with polyol groups being polyethers and groups of polyuoxypropylene glycols and polyethylene(butylene) glycol adipates with functionality at least 2, whereas components with isocyanate groups are 2,4-tolylene diisocyanate, provided that molar ratio OH/NCO is 1:2 and amount of prepolymer corresponds to 1-10 wt % of the weight of bitumen.
EFFECT: achieved production of material with lowered brittleness temperature and water absorption, raised softening temperature, increased adhesion and elongation strength, and enhanced corrosion resistance.
2 tbl, 28 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to polyurethane foams and urethane rubbers, in particular to compositions for manufacturing cushioning polyurethane foams containing: at least one polyetherpolyol having average molecular mass between 10 and 20 thousands; aromatic polyisocyanate; tackiness-enhancing resin; surfactant; and optionally plasticizer in amount between 0.1 and 10 wt parts per 100 wt parts polyetherpolyol. Such polyurethane foams are non-soft cushioning polyurethane materials showing low elasticity and having a wide application area. Urethane rubbers obtained from at least two polyetherpolyols, tackiness-enhancing polymeric resin, aromatic polyisocyanate, and at least one catalyst also show low-elasticity properties and can be employed to manufacture of medicinal and orthopedic articles. A method for manufacturing such rubbers is proposed.
EFFECT: increased assortment of useful polyurethane foams.
4 cl, 8 tbl
FIELD: pulp-and-paper industry, in particular, additive for pulp.
SUBSTANCE: product contains first polysaccharide having at least one first cationic substituent comprising aromatic group, and second polysaccharide having at least one second cationic substituent free of aromatic group. Method for producing of paper from water suspension containing cellulose fibers and, optionally, fillers involves adding cationized polysaccharide product to water suspension; forming and dehydrating water suspension on fabric, said cationized polysaccharide product being produced by providing reaction between first polysaccharide with at least one first aromatic agent, and second polysaccharide with at least one second agent free of aromatic group; mixing resultant polysaccharides.
EFFECT: improved dehydration and retention capacity through utilization of cationized polysaccharide product.
25 cl, 11 tbl, 10 ex
SUBSTANCE: group of inventions relates to polyethylene compositions for films or cast products. Composition has melt fluidity index at 5 kg/190°C (MI5 kg) from 0.25 to 3 g/10 min, Mz higher than 2000000 g/mol and lower than 370000 g/mol and Hostalen index (HI) value from 0.18 to 18. When melt fluidity index at 5 kg/190°C (MI5 kg) is higher than 1.9 g/10 min, Hostalen index (HI) value is higher than 1.
EFFECT: polyethylene composition in accordance with invention, possessing specified molecular-weight distribution and long-chained branched structure, possesses improved technological properties, and obtained films have higher mechanical impact strength with film thickness being 10 mcm than at 20 mcm, in accordance with measurement of dart drop impact (DDI).
9 cl, 4 tbl, 8 ex, 1 dwg
SUBSTANCE: sealing mastic contains, wt %: chlorobutyl rubber - 3.6-4.2, ether of glycerol tall oil rosin - 1.0-1.5, high pressure polyethylene in the form of a film - 0.3-0.4, zinc borate - 4.0-4.6, magnesium hydroxide - 6.0-7.0, aluminium hydroxide - 22.0-12.0, trichloropropylphosphate - 2.5-3.0, a barite concentrate - 48.0-51.0, chloroparaffin CP-470 - 1.8-2.0, PN-6sh oil - 7.0-8.0.
EFFECT: invention makes it possible to increase soundproofing, vibration damping, adhesion properties and ecological safety.
SUBSTANCE: non-drying rubber mixture contains, wt %: butyl-rubber regenerate from waste diaphragm chambers - 17.0-31.0, ether of glycerol tall oil rosin - 0.5-1.0, PN-6sh oil - 20.0-25.0, chalk - 10.0-45.0, high-pressure polyethylene in the form of a film - 0.5-1.3, waste fibres of cotton ginneries - 0.7-1.0, alumosilicate microspheres - 4.0-25.0, talc - 4.0-11.0.
EFFECT: invention makes it possible to increase the damping properties, adhesion to metal and frost resistance of the composition.
SUBSTANCE: invention relates to polymer composition for manufacturing sealing and electroinsulating materials for production of connection cable envelope. Composition contains low-pressure polyethylene, lubricant buxol as plasticiser and filling agent representing titanium oxide.
EFFECT: composition is characterised by high thermodynamic compatibility of components, which makes it possible to obtain material with high mechanical characteristics and optimal combination of electro- and hydroinsulating properties.
SUBSTANCE: invention relates to polyethylene composition, intended for obtaining slow-burning construction materials of general technical and engineering-technical purpose. Composition contains high-density polyethylene and filling agent with particle size 0.145-0.315 mm in quantity 30-50 wt. p. per 100 wt. p. of polyethylene. Filling agent represents mixture of crushed basalt and crushed basalt wool.
EFFECT: obtained compositions possess increased output of coke residue at 600°C, Vicat softening temperature, temperature of destruction starting, toughness, bending strength, as well as high weight loss during combustion.
1 tbl, 5 ex
SUBSTANCE: invention relates to an antifrictional polymer composition based on ultra-high-molecular-weight polyethylene, particularly for making friction bearings in mobile friction assemblies of machines and mechanisms. The composition contains ultra-high-molecular-weight polyethylene and an inorganic modifier, wherein the inorganic modifier used is thermally expanded graphite in amount of 2 wt %.
EFFECT: composition has improved deformation-strength properties, wear resistance and bearing capacity.
SUBSTANCE: invention relates to a bimodal polyethylene high-density composition for obtaining products by pressure moulding, in particular caps and plugging means. The composition includes bimodal high-density polyethylene, a composition of an inorganic alpha-nucleating agent, a composition of a friction-reducing agent, representing amide of primary fatty acid, and a composition with one or more additives, selected from antioxidants, acid acceptors, pigments and UV-stabilisers. The application of bimodal polyethylene in a combination with the inorganic alpha-nucleating agent, in particular, with talc and behenamide, as the friction-reducing agent, makes it possible to obtain the moulding composition with an unexpected and synergic impact on crystallisation temperature, and the composition friction coefficient.
EFFECT: composition by the invention demonstrates higher crystallisation temperature and lower friction coefficient.
14 cl, 5 tbl
SUBSTANCE: invention deals with ultrahigh molecular weight polyethylene (UHMWPE), modified with nanosized particles of tantalum pentoxide. It is applied for the obtaining polycomposite materials, which can be applied in microelectronics, medicine and other fields. It is obtained by the addition of benzyl alcohol to a UHMWPE benzene solution. The formed reaction mixture is mixed at a rate of 400-500 rev/min in boiling for 5-6 hours. Then, it is filtered, washed with benzene, the solvent is distilled. After that, a benzene solution of tantalum pentachloride is added to the reaction mass in a quantity corresponding to the molar ratio of tantalum pentachloride to benzene alcohol, equal to 1:5-5.3. Then the obtained reaction mass is mixed at the same rate in boiling for 3-4 hours, cooled and the target product is separated by filtering, extraction with chloroform and vacuum distillation of the solvent.
EFFECT: extension of application fields of materials with higher physical-mechanical properties.
3 dwg, 2 tbl, 2 ex
FIELD: process engineering.
SUBSTANCE: invention relates to production of articles of granulated polymer materials. Die is filled with polymer granules over 1 mm in size. Cold moulding and blank forming are performed at pressure not destructing the granule structure with subsequent sintering and cooling down. Note here that granulated material sintering temperature makes 0.58-0.80 of the polymer flow point. At making of articles from the mix of granules of at least two polymers with different flow points the sintering temperature makes 0.58-0.80 of that of easily melted polymer.
EFFECT: lower material and power input.
4 cl, 2 dwg
SUBSTANCE: invention relates to a PVC-free floor or wall covering comprising at least one layer of a thermoplastic composition. The composition contains a polymer matrix comprising at least two polymers and at least 100 pts.wt of least one filler per 100 pts.wt of the polymer(s). Said matrix contains 10-40 pts.wt of a polymer with carboxylic acid anhydride groups in amount of 0.5-3.1 wt %, and the other polymer of the matrix is selected from a group comprising EVA, EMA, EBA, EEA, EPM, EPDM, VLDPE, LLDPE, POE, POP and mixtures thereof, and has melt flow index between 0.6 and 3 g/10 min at 190°C and mass of 2.16 kg. The total amount of combined polymers in the composition is 100 pts.wt.
EFFECT: floor or wall covering obtained according to the invention preferably in form of rolls or tiles has improved residual indentation properties and is also suitable for recycling.
14 cl, 7 dwg, 9 tbl