Binding agents for polyolefins filled with natural fibres and compositions thereof
SUBSTANCE: described is a composition for obtaining a binding agent for soaking cellulose fibres. The composition contains polyolefin resin which reacts with 1.6-4.0% maleic anhydride. The composition has less than 1500 ppm free maleic anhydride. The resin has melt flow index at 190°C and 2.16 kg ranging from approximately 0.1 to 500 g/10 min. The composition has yellowing index of 20-70. The polyolefin is polyethylene. Described also is a cellulose composite containing 10-90% cellulose fibre; a first polyolefin resin having melt flow index from 0.1 to 100 g/10 min; 0.1-10 wt % composition for obtaining the binding agent. The maleic anhydride is grafted on the polyethylene.
EFFECT: high binding efficiency of the binder.
12 cl, 8 tbl, 20 ex
The authors claim the benefit under section 35, United States Code, § 119, of provisional patent application number 60/779396, filed March 3, 2006, entitled "cross-Linking agents for filled with natural fibers of polyolefins".
The level of technology
The technical field to which the invention relates
The invention relates to polyolefin composites containing natural fibers. More specifically, the present invention relates to filled with natural fibres, polyolefin composites with high strength that can be achieved by incorporating polyolefin binder agents with low levels of functionalization.
Description of the prior art
A well-known problem in the formation of composite materials produced from plastics and natural fibers, is the incompatibility of fiber with plastic. Natural fibers are hydrophilic, with plenty of free polar hydroxyl groups on the surface. Plastics are hydrophobic. For this reason, plastics do not moisten easily the surface of natural fibers and does not stick to them. This fact causes loss of strength and increased absorption of water in the obtained composite material.
This problem can be overcome by adding binding agents compositename material. A binding agent, assumed to operate through the interaction of reactive anhydride or acid residue with a hydroxyl group on the surface of the fiber with the formation of ester bonds. Hydrophobic polymer chains extend outward from the surface of the fibers, however, they can interact with the polymeric matrix. The specific nature of the interaction will depend on the choice of coupling agent and the polymer and the degree of crystallinity of the polymer. Binder, generally serves as a transitional bridge, which improves adhesion of the plastic and the surface of the natural fibers. It is well known that binding agents improve performance filled with natural fibers of polyolefins. Impact strength, bending strength and tear, as well as the temperature of thermal bending increases. Plastic creep, the linear coefficient of thermal expansion (LCTE) and water absorption are reduced.
The polyolefin containing a polar or reactive groups suitable for use as binding agents, can be obtained by grafting polar monomers, such as maleic anhydride to polyolefin. Various technologies vaccinations, well-known specialists in this field include the inoculation of the solution is the use of peroxide initiation, shot in the solid phase using peroxide or radiation initiation, and reactive extrusion in a twin screw extruder, usually with the use of peroxide initiation. Alternatively, the polyolefin containing a polar or reactive groups suitable for use as binding agents, can be obtained by copolymerization of at least one olefinic monomer, at least one polar monomer, for example, maleic anhydride.
Preparation of composites containing thermoplastic matrix materials of the resin having dispersed in organic reinforcing fillers such as cellulosic or lignocellulosic fibers, is known in this field. The improvement of the mechanical properties of such composites by processing such fibers with a binder agent before putting them in thermoplastic matrix materials of the resin is also known in this field. The following article are some of the many that refer to known technology.
P. Jacoby et al., "Wood Filled High Crystalline Propylene," Wood-Plastic Conference sponsored by Plastics Technology, Baltimore, Md., December 5-6, 2000;
M. Wolcott et al., "Coupling Agent/Lubricant Interactions in Commercial Wood Plastic Formulations," 6th International Conference on Wood fiber-Plastic Composites, Madison, Wis., May 15-16, 2001;
W. Sigworth, "The Use of Functionalized Polyolefins in Environmentaly Friendly Plastic Composites," GPEC 2002, February 13-14, 2002, Detroit, Mich.;
J. and Wefer, W. Sigworth, "The Use of Functionalized Coupling Agents in Wood-Filled Polyolefins," Wood-Plastic Composites, A Sustainable Future Conference, May 14-16, 2002, Vienna, Austria;
R. Heath, "The Use of Additives to Enhance the Properties and Processing of Wood Polymer Composites," Progress in Wood fibre - Plastic Composites Conference 2002, May 23-24, 2002, Toronto, Canada; and
W. Sigworth, "Additives for Wood Fiber Polyolefins: Coupling Agents," Progress in Woodfibre - Plastic Composites Conference 2002, May 23-24, 2002, Toronto, Canada.
In addition, Kokta, B.V. et al., 28(3) Polym.-Plast. Technol. Eng. 247-59 (1989) studied the mechanical properties of polypropylene with sawdust. Wood chips pretreated with polymethylenepolyphenylisocyanate and Milanovich binding agents before adding them to the polymer.
Raj, R.G. et al., 29(4) Polym.-Plast. Technol. ENG. 339-53 (1990) filled high-density polyethylene in three different cellulose fibers, which are pre-treated using a silane/polyisocyanate coupling agent to improve adhesion between fibers and polymer matrix.
Matuana, L.M. et al., ANTEC 3:3313-18 (1998) studied the influence of surface acid-base properties of plasticized PVC and cellulose fibers on the mechanical properties of the composite plastic/cellulose. They modify the surface of the fibers by means of γ-aminopropyltriethoxysilane, dichloromethylsilane, phthalic anhydride and melirovanie polypropylene.
U.S. patent No. 4717742 describes composites based resins, ar is new with silanes, grafted on organic fillers, which, as indicated, have superior wear resistance, even at sub-zero temperatures or at high temperatures, improved physical properties and can be obtained by using a method in which the organic filler to be grafted with silane coupling agent in the matrix melirovanie polymer.
U.S. patent No. 4820749 describes a composite material based on a polymer or copolymer of a substance, which may be a thermoplastic or thermoset material or rubber, and organic material, which is a cellulose or starch. Cellulosic material is grafted with cilleruelo agent. The methods of preparation of this composite are also described.
U.S. patent No. 6265037 describes an improved structural element of the composite containing the structural element of a complex type, made of a composite material containing polypropylene polymer and wood fiber. The material, as indicated, is suitable for use in conventional structural applications.
U.S. patent No. 6300415 describes the polypropylene composition to obtain various molded products, which, as indicated, are excellent for formemost, the shrinkage in the mold during molding, rigidity, flexibility, UDA is prochnosti, in particular, low-temperature impact resistance, transparency, gloss, resistance to whitening under the action of stresses and their balance; various molded products having the above properties; propylene composition, which is suitable for the foundations of the polypropylene resin composition; and a method of production thereof. Propylene composition comprises a propylene homopolymer and propylene-ethylene copolymer.
The aim of the present invention is to increase the efficiency of binding of the binding agents. Increasing the efficiency of binding reduces the amount of binding agent and costs, at the same time, making it possible to obtain the same or better binding.
Functionalityand polyolefins, which are characterized as high content of maleic anhydride and a high molecular weight, are more effective in improving the properties of mechanical strength, resistance to plastic creep and resistance to water uptake in filled natural fibers of polyolefin composites than the more common polyolefins, which have a lower degree of functionality and/or molecular weight. In addition, using the present invention, the efficiency of binding of polyolefins, functionalityof the data maleic anhydride, in the pulp and polyolefin composite can be increased at lower levels of functionality of maleic anhydride by adjusting the reaction conditions during the functionalization reaction.
The present invention preferably represents a binding agent, which is produced from a polyolefin composition and which is intended for wetting the cellulose fibers. The binding agent preferably contains a polyolefin resin having a melt flow index at 190°C and 2.16 kg of from about 0.1 to 500 g/10 min polyolefin resin preferably is combined with the 1.6-4.0 wt.% maleic anhydride, and the composition preferably has less than 1500 parts per million (h/mn) of free maleic anhydride. The binding agent preferably has an index of yellowing from 20 to 70.
Cellulose composite is preferably derived from a coupling agent by combining a bonding agent and cellulose fibers and at least one thermoplastic polymer. Cellulose composite preferably contains 10-90% cellulose fiber, the first polyolefin resin having a melt flow index from 0.1 to 100 g/10 min, and 0.1-10 wt.% a bonding agent.
The composite of the present invention is suitable for use for decks of ships, under deck beams, fencing systems, car parts and when such is eneny, where additional structural strength. The present invention also provides for the composites with improved wear resistance due to the lower water absorption and higher resistance to plastic creep.
Description of the preferred embodiments
It is often desirable to increase the strength properties of the filled natural fibers of polyolefin composites, such as wood-polyolefin composites for structural and automotive applications. It is known that melirovanie polyolefins improve the dispersion of the fibers in polyolefins and increase the interfacial adhesion between the fibers and the resin. These improvements lead to an increase in strength properties.
Binding agents typically increase the cost of raw materials for pulp and thermoplastic composites, because they are more expensive than the material of the particles of cellulose and thermoplastic resin. For this reason, it is desirable to improve the efficiency of binding of these binding agents. The efficiency of binding can be defined as the improvement of the properties provided by adding a specified amount of binding agent in comparison with the same drug that does not contain a coupling agent. The following example is set out here, to demonstrate the principle of increasing the efficiency of the binding.
If adding 2% coupling agent A increases bending strength by 20% compared with the control connection without a bonding agent, while 2% coupling agent B increases the bending strength by 50%, then the binding agent B should be considered as more effective at binding than binder A. Another way to see the increase in efficiency is that you may need a low level of binding agent B to obtain the same improvement of the properties, as obtained using 2% of a bonding agent A. For this reason, binder B must be less expensive in use than a binder, considering that both materials have a similar price. Typically, it is assumed that the increase in the level of functionality of the binder is greater than 4% increases the efficiency of the binding.
The present invention preferably represents a binding agent, which is produced from a polyolefin composition and which is intended for wetting the cellulose fibers. The binding agent preferably contains a polyolefin resin having a melt flow index at 190°C and 2.16 kg of from about 0.5 to 100 g/10 min, more preferably from about 5 to 50 g/10 min, and most of predpochtitel is but 10-30 g/10 min polyolefin resin preferably is combined with the 1.6-4.0 wt.% maleic anhydride, and more preferably from 1.6 to 3.0 wt.% maleic anhydride, and most preferably from 2.0 to 3.0 wt.% maleic anhydride. The composition preferably has less than 1500 hours/million of free maleic anhydride, more preferably less than 600 hours/million of free maleic anhydride, and most preferably, less than 200 hours/million of free maleic anhydride. The binding agent preferably has an index of yellowing from 20 to 70, more preferably from 20 to 55, and most preferably, from 20 to 40.
More preferably, the binder contains a polyolefin resin having a melt flow index at 190°C and 2.16 kg of from about 5 to 50 g/10 min polyolefin resin preferably is combined with the 1.6-3.0 wt.% maleic anhydride. The composition preferably has less than 600 hours/million of free maleic anhydride. The binding agent preferably has an index of yellowing from 20 to 55.
Most preferably, the binder contains a polyolefin resin, preferably, the homopolymers and copolymers of high density polyethylene having a melt flow index at 190°C and 2.16 kg of about 10-30 g/10 min polyolefin resin preferably is combined with 2.0 to 3.0 wt.% maleic anhydride. The composition preferably has less che is 200 hours/million of free maleic anhydride. The binding agent preferably has an index of yellowing from 20 to 40.
Desirable values of melt flow index for binder agent, functionalized with maleic anhydride ranges from 0.1 to 500 g/10 min, more preferably about 0.5-100 g/10 min, and most preferably ranges from 2 to 50 g/10 minutes
Cellulose composite is preferably derived from a coupling agent by combining a bonding agent and cellulose fibers and at least one thermoplastic polymer. Cellulose composite contains 10-90 wt.% cellulose fibers, the first polyolefin resin having a melt flow index from 0.1 to 100 g/10 min, and 0.1-10 wt.% a bonding agent. More preferably, the cellulose composite contains 20-80 wt.% cellulose fibers, the first polyolefin resin having a melt flow index of 0.3 to 20 g/10 min, and 0.5-3.0 wt.% a bonding agent.
Most preferably, the cellulose composite is obtained from a bonding agent by combining a bonding agent and cellulose fibers selected from the group comprising wood chips, wood fibers or combinations thereof, and at least one thermoplastic polymer, preferably, homopolymers and copolymers of polyethylene of high density. Cellulose composite contains 40-65 wt.% cellulose fiber, p is pout polyolefin resin, having a melt flow index of 0.3 to 5 g/10 min, and 0.5-2.0 wt.% a bonding agent.
The term "natural fibers" refers to fibers obtained directly or indirectly from a source in nature. Included in this term, but not limited to, are sawdust, wood fiber and fiber crops, such as wheat straw, alfalfa, wheat bran, cotton, corn stalks, corn cobs, rice hulls, rice onions, walnut shells, sugar cane, bamboo, palm fiber, hemp, flax, Bombay hemp, plant fiber, vegetable fiber, viscose, herbs, boiled wood fiber, rice, rice fiber, cane, fiber rush, fibers, bast, jute, jute fiber, flax fiber, hemp, fibre hemp, flax yarn, fiber flax yarn, Chinese nettle fibers Chinese nettle, leaf cuttings, Manila hemp, fiber, Manila hemp, sisal, sisal fiber, cellulose, cotton fiber, fiber, herbs, oats, chopped oat straw, barley, chopped barley straw, seed embryo in the form of flour and powdered form, tubers, potatoes, roots, tapioca, tapioca root, cassava root cassava, manioc, cassava root, sweet potatoes, arrowroot, core, stems, peels, shells, fruits, sago, again COI is Lithuania paper fiber, recycled boxes, fiber recycled boxes, recycled newspaper, recycled fiber Newspapers, recycled sheets printed on computer text, recycled fiber sheets printed on computer text, the waste from grinding, fiber, solid wood, fiber soft wood, newsprint, magazines, books, cardboard, chopped wheat straw, bamboo fiber, the sludge from the clarifier, tube, and the like, and combinations thereof. Preferably, the cellulose material from the material of the particles is selected from the group consisting of wood fibers, sawdust, and combinations thereof. Wood fiber, from the point of view of their ampleness and facilities, can be obtained either from soft wood, either from softwood or hardwood lumber, commonly known as deciduous trees deciduous trees.
The polyolefins used in the present invention, as a rule, are polymerized from ethylene, copolymers of ethylene and other alpha-olefins such as propylene, butene, hexene and octene, copolymers of polyethylene and vinyl acetate, and combinations thereof. Preferably, when using ethylene, it may constitute, for example, high density polyethylene (HDPE), low density polyethylene (LDPE), or linear polyethylene is low density (LLDPE), and combinations thereof. More preferably, the polyolefins are homopolymers of high density polyethylene and copolymers of ethylene high density with butene, hexene, octene, and combinations thereof.
Functionalized polyolefin, which is preferably a functionalized polyethylene or polypropylene is a polymer which contains reactive groups that can interact with functional groups on the surface of natural fibers. Such polymers are modified with reactive groups comprising at least one polar monomer selected from the group consisting of anhydrides, ethylene-unsaturated carboxylic acid or ethylene-unsaturated carboxylic acid. Can be used also, mixtures of acids and anhydrides and derivatives thereof. Examples of acids include maleic acid, fumaric acid, taconova acid, crotonic acid, acrylic acid, methacrylic acid, maleic anhydride, itacademy anhydride and substituted maleic anhydrides. Maleic anhydride is preferred. Derivatives which can be used include salts, amides, imides and esters. Their examples include glycidylmethacrylate, mono - and diatrypaceae and acrylamide. Essentially, any OLE the new reactive residue, who can provide reactive functional group in the modified polyolefin polymer, may be suitable for use in the present invention.
Functionalityand polyolefins as binding agents receive by way of melt-called reactive extrusion. This mechanism is well established and is described DeRoover et al., Journal of Polymer Science, Part A: Polymer. Functionalized monomer and free radical initiator added to the twin screw extruder and subjected to exposure to elevated temperature. In this way the hydrogen atom is removed from the polymer chain by using an initiator. The functional monomer and then reacting to the center of the free radical, obtained by the formation of functional center on the polymer chain. As more high-molecular polymer chains are statistically more likely to interact with free radicals, the narrowing of the distribution of molecular masses of the polymer represents the characteristic of the method of the reaction extrusion.
Although it is not intended to limit the scope of the present invention, functional polyolefins as a binding agent according to the present invention can be obtained by methods from solution or in the solid phase. Such methods are well known experts who am in this field and are described, for example, in U.S. patent No. 3414551 and 5079302, to G. Ruggeri et al., 19 European Polymer Journal 863 (1983), and Y. Minoura et al., 13 Journal of Applied Polymer Science 1625 (1969), the contents of each of which is included here by reference. These methods contribute to the reaction of functional monomers with the centers of free radicals on the polymer before the polymer can be subjected to open circuit. Then the end result is a functional monomers along the polymer chain instead they were present only at the ends. In addition, the narrowing of the distribution of molecular masses of the polymer is observed in the ways of the reaction extrusion, has no place in the functionalization methods from solution or in the solid phase.
Optionally, the composites of the present invention can contain other additives. These supplements can be a lubricant which does not affect adversely on the binding agent.
Inorganic materials of the particles can be included for the implementation of the lubricant and to improve the mechanical properties. Examples include talc, calcium carbonate, clay, mica, pumice and other materials.
The composition may contain at least one additional component. Examples of additional suitable components include, but are not limited to, an antioxidant, in panjwayi agent, dye, pigment, agent for cross-linking, inhibitor, and/or a reaction accelerator. Can be used, at least one additional conventional additive, such as agents to improve the compatibility-enhancing agents, agents to facilitate demolding, sealing materials, humectants, plasticizers, sealing materials, thickening agents, diluting agents, binders, and/or any other commercially available or conventional components.
Antioxidants added to prevent degradation of the polymer during processing. An example is a Naugard B25 from Chemtura Corporation (a mixture of Tris(2,4-di-tert-butylphenyl)phosphite and tetracycline(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane). Foaming agent added to reduce the density of the cellulosic-thermoplastic composite by foaming. Examples of foaming agents include Celogen TSH from Chemtura Corporation (toluensulfonate), Celogen AZ (azodicarbonamide), Celogen OT (p-p'-oxybis(benzosulfimide)), Celogen RA (p-toluensulfonate), Opex 80 (dinitrosopentamethylenetetramine) and Expandex 5-PT (5-phenyltetrazol).
Coloring agents are pigments or dyes. Dyes are common organic compounds that are soluble in plastics, forming neutral mole is ularly solution. They give a vivid intense color and are transparent. Pigments are generally insoluble in the plastic. Color is obtained by dispersing fine particles (in the range of from about 0.01 to about 1 μm) in thermoplastic. They give a matte or at least some translucency in cellulosic-thermoplastic composite. The pigments can be an organic or inorganic compounds and are available in a variety of forms, including dry powder, non-ferrous concentrates, liquids and granules of resin with pre-cooked preparation for painting. The most common inorganic pigments include oxides, sulfides, chromates, and other systems based on heavy metals such as cadmium, zinc, titanium, lead, molybdenum, iron, combinations thereof, and others. Ultramarines are usually complexes of sulfide-silicate containing sodium and aluminum. Often the pigments contain a mixture of two, three or more iron oxides, barium, titanium, antimony, Nickel, chromium, lead, and other, relationships. Titanium dioxide is a widely used and well-known bright white thermally stable inorganic pigment. Other known organic pigments include azo - or diazo-pigments, pyrazolone the haunted pigments, permanent red 2B, Nickel azo yellow, molten red and pigment red.
Agent for cross-linking may optionally be added to reinforce the links between the cellulose material of the particles, as described above, in the final homogeneous product. Agent for the cross-linkage connects through the side of hydroxyl groups on the cellulose molecular chains. Agent for cross-linking should be the characteristics of the formation of strong bonds at relatively low temperatures. Examples of agents for cross-linking, which can be used include polyurethanes, such as isocyanates, phenolic resins, unsaturated polyesters and epoxy resins, and a combination thereof. Phenolic resin can be any single-stage or two-stage resin, preferably with a low content of hexane.
Inhibitors can be added to slow down the reaction rate of cross-linking. Examples of known inhibitors include organic acids such as citric acid.
The reaction accelerators may be added to increase the reaction rate of cross-linking. Examples of reaction accelerators include amine catalysts such as Dabco BDO (Air Products), and DEH40 (Dow Chemical).
The number of different components of the composition may be regulated by the experts in this area and, depending on the particular materials used and the intended use of the material.
Composition malaimbandy polyolefins, preferably polyethylene compositions of the present invention, preferably get through a well-known way of reaction extrusion. The preferred extruder is a twin screw extruder with a same rotating direction of the screw, provided with a device for entering, for the introduction of polyethylene granules at a constant speed in the open input orifice areas for discharge for measuring molten maleic anhydride and a liquid peroxide, vacuum system to remove neproreagirovavshikh maleic anhydride and decomposition products of the peroxide and output Villeroy and granulation system to collect the final product.
The temperature of the cylinder of the extruder, the number of RPM of the screw and configuration augers are designed to implement the required functions of the method: (1) melting of polyethylene, (2) mixing of injected maleic anhydride, (3) mixing the pressurized peroxide, (4) retention of materials during the grafting reaction, (5) removal of unreacted decomposition products of maleic anhydride and peroxide in the vacuum zone, and (6) the introduction of grafted devolatilising product through the die plate and in the granulation system. These technologies are well known to specialists in the field of the reaction melirovanie polyolefins.
Binding agents of the present invention and comparative used in this study are listed in table 1. Raw materials and other specific parameters of the method used in the present invention, are given in Table 2. The design of the screws used to obtain these samples are those which could be developed by a person skilled in the art based on the requirements described above.
Functionalityand polyolefins as a binding agent within the present invention, and outside of this framework, are synthesized. Data characterization for these binding agents are given in Tables 1 and 2.
The content of maleic anhydride in a binder agents determined by dissolving them in boiling toluene and titration to the end point of bromthymol blue using standard 0,03N methanolic solution of KOH. KOH titration standardise using benzoic acid. Determine the number of milliequivalents KOH titration, is required to neutralize one hundred grams of the binder agent. The percentage of maleic anhydride in a binder agent then calculates, assuming that one mole of KOH to neutralize one mole of maleic anhydride. This involves the provision is confirmed by titration undiluted maleic anhydride under the same conditions, used to study binding agents.
The melt flow index of the binder agent determined using a Tinius Olsen Extrusion Plastometer Model MP600, following the procedures described in ASTM D1238.
The levels of free maleic anhydride is measured by extracting the crushed sample binder agent in acetone for 40 minutes at room temperature. Then the extracts in acetone titrated with standardized methanolic solution of potassium hydroxide to an endpoint bromtoluola blue. Free maleic anhydride, the amount of maleic anhydride in acetone extracts, and then calculated using the same assumptions as used to determine the percentage of maleic anhydride associated with a bonding agent.
The yellowing index is measured at the reflection in accordance with ASTM E-313 using spectrocolorimeter Datacolor SF600 or similar tool with molded dies bonding agent.
Die get by pressing pellets binder agent in plate press at 400°F for 30 seconds at a pressure of 30 tons.
Wood-PE products derived using either oak sawdust, 40 mesh, or pine sawdust, 40 mesh. Wood is dried in a convection oven at 121°C for 24 hours. Get the contents wet the STI is less than 1%. Thermoplastic resin is either recycled resin containing at least 80% LLDPE and 20% of other polyolefin resins, or partially melted flakes of high density polyethylene BP Solvay (now INEOS) B54-60 (melt flow index of 0.5 g/10 min). Antioxidant Naugard B-25, a lubricating agent Lubrazinc W (zinc stearate), Kemamide EBS (ethylene bis-stearamide) and Kemamide W-20 (ethylene bis-oleamide) all use, as they are obtained. Talc Silverline 403 from Luzenac America is used, how it was obtained.
Obtained by injection molding the samples in Tables 3-6 are mixed in a laboratory pan mixer Brabender heated to 170°C. the Powdered ingredients are pre-mixed by shaking in a plastic bag. The resulting mixture is introduced into the mixer for three times, approximately one minute after the previous injection. After all the ingredients and add melted obtained molten mass is stirred for 10 minutes at 100 rpm Mixed sample is placed in trecastell form 5'×4,5'×1/8" and pressed for three minutes at a pressure of 40 tons and at 177°C in an automated tiled media type Tetrahedron.
Extruded samples in Tables 7 and 8 is obtained using twin screw Brabender Intelli-Torque Plasti-Corder with the configuration of rotating in different directions conical screw #403 and the drive unit Brabender 7150. Those who of temperature zones set as follows: Zone 1 (150°C), Zone 2 (160°C), Zone 3 (160°C), Zone 4 (filler) (150°C). Filler produces a continuous flat analyzed sample is 1.0 inch wide and 0,080 inch thick. Data is recorded by using a Brabender Measuring Extruder Basic Program with Multiple Evaluation, Version 3,2,1. Compounded drugs are injected into the extruder from a device with a measuring volume of K-Tron K2VT20. Samples ekstragiruyut at 60 Rev/min
The test procedure of ASTM D790 used to generate data on the bending strength and modulus of bending. The absorption of water is determined by immersing strips of extrudate 1.0 inch to 2.0 inches in tap water at room temperature and measure the increase in mass. Obtained by molding the samples (1/8") is immersed for 30 days, while the extruded samples (0,07") immersed within 24 hours.
Investigational drugs are presented in Tables 3, 5 and 7. Output data and survey data are presented in Tables 4, 6 and 8. Digital codes represent the samples of the present invention, while the letter codes note the comparative samples.
Characterization of the binding agents
|Example||Type||% (wt.) Maleic anhydride||MFI at 190°C, 2,16 kg||Free MA, h/million||The yellowing index|
|A comparative||HDPE grafted MA||1,5||4||115||the 15.6|
|Comparative B||copolymer E-MA||6,8||30||Not defined||Not defined|
|1||HDPE grafted MA||2,2||2,1||Not defined||31|
|2||HDPE grafted MA||1,6||2,6||41||27|
|3||HDPE grafted MA||2,1||1,9||Not defined||37|
|4||HDPE grafted MA||2,6||0,7||Not defined||55|
|5||HDPE grafted MA||1,8||2,4||135||38|
|6||HDPE grafted MA||1,7||5,0||22||14,5|
|7||HDPE grafted MA||2,0||2,7||There is practically no||27|
Conditions vaccinations used to obtain binding agents
|Example||Resin type||Source materials MA, lb/hour for 1000 pounds of resin per hour||Source materials peroxide, lb/HR for resin/hour||The temperature of the cylinder, °C||The speed of the screw of the extruder rpm|
|A comparative||HDPE (20 MFI)||15,3||0,585||177-204||500|
|2||HDPE (20 MFI)||20,0||0,585||177-204||500|
|3||HDPE (20 MFI)||22,5||0,504||177-204||500|
|4||HDPE (20 MFI)||35,0||0,504||177-204||500|
|6||HDPE (MFI 51)||20||0,513||17-191||600|
|7||HDPE (MFI 51)||24,9||0,673||177-191||600|
The drugs obtained by the injection molding of examples LLDPE
|Oak sawdust (40)||50||50||50||50||50||50||50|
|Oak sawdust (40)||50||50||50|
|Recycled LLDPE||to 49.9||49,4||49,4|
Properties of samples obtained by injection molding
|Flexural strength (MPa)||22,9||22,8||of 21.9||23,1||22,5||a 21.5||22,0|
|Bending modulus (MPa)||1078||1089||1049||1153||1156||993||1109|
|Water absorption - 30-day,%||the 3.8||a 3.9||a 3.9||a 3.9||4,3||4,3||4,2|
|Flexural strength (MPa)||13,7||19,4||21,3|
|Bending modulus (MPa)||986||1125||1121|
|Water absorption - 30-day,%||6,4||4,3||4,1|
Preparations for HDPE samples obtained by injection molding
|Examples of the present invention:||8||9||10||11||12||13||14||15||16|
|Pine sawdust (40)||50||50||50||50||50||50||50||50||50|
|HDPE (partially molten)||49,4||48,9||49,4||48,9||47,9||49,4||48,9||47,9|
|Pine sawdust (40)||50||50||50||50||50||50||50|
|HDPE (partially molten)||to 49.9||49,4||48,9||47,9||49,4||48,9||47,9|
Properties of HDPE samples obtained by injection molding
|Examples of the present invention:||8||9||10||11||12||13||14||15||16|
|Flexural strength (MPa)||41,6||45,1||44,9||36,6||39,8||47,9||37,3||42,0||45,0|
|Bending modulus (MPa)||2443||2478||2373||2447||2327||2460||2677||2349||2511|
|Water absorption - 30-day,%||3,6||3,5||3,4||3,4||3,0||3,0||3,5||2,9||3,0|
|Flexural strength (MPa)||22,4||35,3||39,7||43,2||34,2||33,5||of 31.4|
|Bending modulus (MPa)||2211||2688||2260||2646||2511||2400||2079|
|Water absorption - 30-day,%||11,5||4,0||3,6||3,3||4,2||3,7||3,7|
Preparations for extruded examples HDPE
|Examples of the present invention:||17||18||19||20|
|HDPE B54-60 FLK (0,5) MFI)||35,4||34,9||34,4||33,9|
|The zinc stearate||2,0|
|HDPE B54-60 FLK (0,5) MFI)||35,9||35,9||35,4||34,9||34,4||33,9|
Properties of Extruded examples of HDPE
|Examples of the present invention:||rpm||17||18||19||20|
|Output (ft/min)||60||2,24||of 2.26||2,25||of 2.26|
|Flexural strength (MPa)||60||30,1||33,5||38,9||45,9|
|Bending modulus (MPa)||60||2954||3519||3632||3958|
|Water absorption, 24 hrs (%)||60||8,0||6,9||5,6||5,2|
|Flexural strength (MPa)||60||27,4||30,5||29,0||30,1||31,2||30,6|
|Bending modulus (MPa)||60||3031||3299||3076||3214||3288||3422|
|Water absorption, 24 hrs (%)||60||9,6||8,3||8,5||7,9||6,8||7,6|
You can easily see that functionalityand polyolefins as a binding agent according to the present invention provide superior mechanical properties compared to previously known binding agents with similar flow velocity of the melt.
Whereas many alterations and modifications which may be the floor of the ENES without deviating from the principles of this invention, reference should be made to the accompanying claims, to understand the limits of what is protected as the present invention.
1. Composition to obtain a bonding agent for wetting the cellulose fibers, comprising: a polyolefin resin, which interacts with 1,6-4,0% maleic anhydride, the composition has less than 1500 hours/million of free maleic anhydride;
where this resin has a melt flow index at 190°C. and 2.16 kg of from about 0.1 to 500 g/10 min; and
where this composition has an index of yellowing from 20 to 70.
2. The composition according to claim 1,
where specified maleic anhydride is 1.6 to 3.0% of the specified composition, the composition has less than 600 hours/million of free maleic anhydride;
where this resin has a melt flow index at 190°C. and 2.16 kg of from about 0.5 to 100 g/10 min; and
where this composition has an index of yellowing from 20 to 55.
3. The composition according to claim 2,
where specified maleic anhydride is 2.0 to 3.0% of the specified composition, the composition has less than 200 hours/million of free maleic anhydride;
where this resin has a melt flow index at 190°C. and 2.16 kg of from about 2 to 50 g/10 min; and
where this composition has an index of yellowing from 20 to 40.
4. The composition according to claim 1, where the specified polyolefin is in etilen.
5. The composition according to claim 4, where the specified polyethylene is a polyethylene selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, copolymers with other alpha-olefins, and combinations thereof.
6. The composition according to claim 5, where the specified polyethylene is a Homo - and copolymers, high density polyethylene.
7. The composition according to claim 1 where the cellulose fibers are selected from the group consisting of wood fibers, sawdust, and combinations thereof.
8. Cellulose composite containing from 10 to 90% cellulosic fibers;
the first polyolefin resin having a melt flow index from 0.1 to 100 g/10 min;
0.1 to 10 wt.% a bonding agent, the specified binding agent contains the second polyolefin resin having a melt flow index at 190°C. and 2.16 kg of from about 0.1 to 500 g/10 min; which vzaimodeistvie from 1.6 to 4.0 wt.% maleic anhydride, with specified bonding agent has less than 1500 hours/million of free maleic anhydride; and where the specified binding agent has an index of yellowing from 20 to 70.
9. Cellulosic composite of claim 8, where this first polyolefin resin is a polyethylene, which is a polyethylene selected from the group consisting of high density polyethylene, low density polyethylene,linear low density polyethylene, copolymers with other alpha-olefins, and combinations thereof.
10. The cellulose composite according to claim 9, where the specified maleic anhydride is grafted polyethylene as specified polyethylene is a polyethylene selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, copolymers with other alpha-olefins, and combinations thereof.
11. Cellulosic composite of claim 8, where this first polyolefin resin has a melt flow index of 0.3 to 20, the specified cellulose fiber is 20-80% of the specified composite, and the specified binding agent is 0.5-3% from the specified composite.
12. The cellulose composite according to claim 11, where this first polyolefin resin is a Homo - and copolymers, HDPE (high density polyethylene)having a melt flow index of 0.3 to 5 specified cellulose fiber is 40-65% of the specified composite, and the specified binding agent is 0.5-2% of the specified composite.
FIELD: process engineering.
SUBSTANCE: invention relates to pulp of organic stuff particles for production of ligno-carbohydrate plastic. Said pulp comprises minced particles of conifer needle, coniferous branch bast peeling, timber and wastes of Siberian pine cones in various versions. Said pulp features improved extraction of active natural substances from said components to produced binder.
EFFECT: pulp of organic stuff particles for production of ligno-carbohydrate plastic at reduced temperature of thermal compaction.
11 cl, 11 tbl
SUBSTANCE: polyvinyl chloride-based wood-polymer composition for profiled-trim moulding articles contains polyvinyl chloride, wood flour, a complex stabiliser, an acrylic modifier, polyethylene wax and a metal-containing lubricant. The metal-containing lubricant used in the composition is obtained by reacting higher monocarboxylic acids with glycerin at 130-230°C at molar ratio 1:(1-2) in the presence of oxides of divalent metals Ca, Zn, Mg or their two-component mixtures in weight ratio 0.25-1.0:0.5-1.0 in amount of 0.5-2.0 wt % of the overall reaction mass, where the higher monocarboxylic acids used are VIK, oleic and stearic acid. The composition also uses polyethylene wax with melting point not higher than 100°C. The complex stabiliser used is selected from: BAEROPAN R 9003 (produced by Baerlocher GmbH, Germany) or Naftosafe PEK 922 B (produced by Chemson, Austria). The acrylic modifier used is impact-resistant modifiers selected from: MB-87, DURASTRENGTH D320, DURASTRENGTH D300S (produced by Arkema, France), Metablen P-5500S (produced by Dangdong), Paraloid BTA 736H-S OS (produced by Rohm & Haac), Kane ACE F50 (produced by Kalek), Lariks on TU 2216-235-05757533-2000.
EFFECT: high quality of profiled-trim moulding articles, which is expressed by improved operational and technological parameters, specifically melt flow index, thermal stability, impact viscosity, low water absorption and environmental safety of the composition.
2 cl, 1 tbl
SUBSTANCE: product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can contain 20-80 wt % thermoplastic, 30-70 wt % binder or natural adhesive. The hybrid resin is obtained via water-emulsion polymerisation of an acrylate monomer - butylacrylate, methyl methacrylate or butylacrylate, on an alkyde resin based on fatty acids in the presence of a radical initiator at 30-100°C. Fatty acids are selected from tall oil, suberin fatty acids, cutin fatty acids, vegetable oils and mixtures thereof. The composite product is obtained by mixing acrylate hybrid and natural material or combination thereof. Further, the product is moulded and hardened under heat at 120-200°C until a composite product of the given type is obtained.
EFFECT: invention enables to obtain composite plates with improved properties, good biodegradability and low toxicity; such properties of the plates are achieved by using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.
22 cl, 1 tbl, 1 dwg, 9 ex
SUBSTANCE: moulding composition contains an aggregate made from carbon-containing crushed plant and/or synthetic fibre material, binder made from inorganic polymers and a target additive. The inorganic polymers used in the composition are metal phosphates with aluminium, chromium, boron and magnesium cations and anions РО4 --- or metal silicates with sodium, potassium and lithium cations and with anions SiO3 --, pre-modified with solutions of organic bases with an amide bond and/or oxides or trihydrates of aluminium oxide or mixtures thereof. The target additive is a water repellent or hardener or surfactant. The aggregate, working solution of the binder and target additive are prepared first. The aggregate is treated with the working solution, dried and moulded into briquettes.
EFFECT: ecologically clean, non-toxic, non-combustible slab materials which are resistant to aggressive media are obtained.
41 cl, 3 tbl
SUBSTANCE: composition contains the following, wt %: 0.05-6.9 (a) bisamide of saturated fatty acid with the structure: , where R1 and R2 are saturated hydrocarbyl groups with C11-C35; 0.14-7.6 (b) bisamide of unsaturated fatty acid with the structure: , where R3 and R4 are unsaturated hydrocarbyl groups with C11-C35; (c) dispersed cellulose material such as wood flour; (d) thermoplastic resin - flakes fractionated from molten high-density polyethylene (HDPE); (e) a finishing agent for finishing the cellulose material (c) with thermoplastic resin (d). The composition also contains an optional (f) inorganic dispersed material selected from pumice and talc and (g) a lubricant, separately or in a combination, selected from zinc stearate, sodium stearate, potassium stearate, paraffin wax or polyethylene wax.
EFFECT: invention enables to obtain composites with improved operational properties, ultimate bending strength and resistance to water absorption.
11 cl, 10 tbl, 31 ex
SUBSTANCE: invention relates to composite products, particularly a composite panel containing hybrid resins based on natural acids, as well as a method of producing a composite product. The product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can optionally contain 20-80 thermoplastics, 30-70 binder or natural adhesive. The hybrid resin is obtained via condensation of a mixture of natural C12-C20 fatty acids modified with maleic acid or anhydride, and an alkyde resin based on fatty acids of tall oil, suberin fatty acids, cutin fatty acids, plant oil or mixtures thereof. Properties of the panel are achieved using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.
EFFECT: invention enables to obtain composite panels with improved properties, specifically good biodegradability and low toxicity.
17 cl, 1 tbl, 27 ex
SUBSTANCE: wood-polymer composition for articles contains polyvinyl chloride, wood flour, calcium-zinc complex stabiliser and the composition can additionally contain a metal-containing lubricant obtained via reaction of higher monocarboxylic acids with glycerine at 130-230°C in molar ratio 1:(1-2) in the presence of oxides of divalent metals Ca, Zn, Mg or other two-component mixtures in weight ratio 0.25-1.0:0.5-1.0 and polyethylene wax.
EFFECT: high quality of ready articles owing to improved technological parameters of the compositions, thermal stability, melt fluidity, water absorption and environmental safety.
2 cl, 1 tbl
FIELD: wood industry.
SUBSTANCE: invention may be used to extract, recycle and process wood wastes in process of fibreboards production. The method includes supplying waste waters downstream pouring-forming machine into an accumulating-balancing reservoir, its pumping along a bypass pipeline into a disperser with simultaneous air supply from atmosphere into the bypass pipeline, formation of air and water mixture passing through the disperser, supply of air and water mixture into a dynamic absorber to create floating complexes, their supply into a receiving chamber of a flotation plant, separation into foam sent to the pouring-forming machine and treated water supplied to the accumulator. The system for method realisation comprises an accumulating-balancing reservoir for collection of waste waters, a bypass pipeline and a disperser to create air and water mixture, a dynamic absorber to form floating complexes, a floatation plant with a receiving chamber, a foam-producing mechanism and a foam-collecting pocket to separate caught fibre in the form of foam and an accumulator of treated water.
EFFECT: inventions ensure simple and cheap technology for extraction, recycling and processing of internal fibreboard production wastes with the possibility of secondary wood fibre catching and return directly into the process cycle without its additional treatment.
2 cl, 1 dwg, 2 tbl, 1 ex
SUBSTANCE: method involves plastification with extrusion of dispersion components, and specifically cellulose filler and thermoplastic polymer matrix. The thermoplastic polymer matrix consists of high-density polyethylene, a compatibiliser in form of graft polyolefin and a lubricant. The lubricant used is pre-ozonised polyethylene homologues in form of super-molecular polyethylene, low-density linear polyethylene and ethylene vinylacetate in ratio of 1:3:5. The graft polyolefin used in the compatibiliser is high-density polyethylene to whose molecular structure glycidyl methacrylate is grafted. Use of such a compatibiliser increases energy compatibility of dispersion components used in preparing a cellulose-containing polymer super-concentrate. The composite material contains a polymer and a super-concentrate with 30-70 wt % content of the super-concentrate.
EFFECT: composite materials based on the obtained cellulose-containing polymer super-concentrate have good physical and mechanical characteristics, namely strength and water resistance.
6 cl, 1 tbl, 3 ex
FIELD: process engineering.
SUBSTANCE: invention relates to method of fuel production. Fuel is produced in mixing lignin with metallurgy wastes. Note here that lignin moisture content may vary. Chips of steel and foundry iron parts and scale are used as metallurgy wastes. Said mix comprises lignin in amount of 70-90 wt % and scale in amount of 10-30 wt %.
EFFECT: universal high-energy fuel.
SUBSTANCE: composition contains the following, %: (A) 9.9-99.8 polycarbonate resin based on bisphenol A; (B) 0.1-90 polyethylene terephthalate, and (C) 0.1-30 grafted rubber, as well as 0.1 pts.wt heat stabiliser, 1 pts.wt dye and 0.7 pts.wt UV absorber. The grafted rubber consists of 30-80% substrate and 70-20% solid graft phase. The graft phase is obtained through copolymerisation of a monomer from a first group consisting of styrene, α-methylstyrene, styrene which is halogenated in the ring and styrene which is alkylated in the ring, and a monomer from a second group containing (meth)acrylonitrile and maleic anhydride, with the weight ratio of said monomers ranging from 90:10 to approximately 50:50. The substrate contains the following, %: (C1) 1-50 core of cross-linked polymerised vinyl monomer and (C2) 50-99 shell of cross-linked polymerised acrylate with glass transition point lower than 0°C.
EFFECT: invention enables to obtain articles characterised by intense lustre, high impact strength and absence of tiger stripes.
8 cl, 1 tbl, 4 ex
SUBSTANCE: invention relates to binder for co-extrusion based on a mixture of co-grafted polyolefins, as well as a multilayer structure containing the binder. The binder contains a mixture of at least homo- or copolymer of ethylene (A1), having density 0.940-0.980 g/cm3, and at least one copolymer of propylene (B) containing at least 51 wt % propylene. (Co)polymers of the said mixture are co-grafted with a functional monomer selected from carboxylic acids and their derivatives. The degree of graft polymerisation of the extrusion binder is more than 0.05 wt % and less than 0.5 wt % of the total weight of the said binder. The mixture is possibly diluted in at least a homo- or copolymer of ungrafted ethylene (A2). Said binder has density of 0.940-0.980 g/cm3.
EFFECT: disclosed binder has sufficient fluidity, high resistance to peeling of layers at temperature higher than 80°C, and is meant for use in a multilayer structure for protecting metal surfaces and for making packaging, rigid hollow housings, particularly bubbles or bottles, or flexible reservoirs, as well as multilayer films.
13 cl, 2 tbl, 4 ex
FIELD: technological processes.
SUBSTANCE: present invention relates to the technology of modifiers production on the basis of nuclear-shell type particles used for production of molding such as films, pipes, mirror housings etc. from poly(meth)acrylates. The nuclear-shell type particle consists of a nucleus, the first shell and, if required, the second shell that on every single case consist of alkylmetacrylate and styrene recurring units with minimum glass-transition temperature of 30°C. The said particles are produced by multistage emulsion polymerisation.
EFFECT: invention ensures implementation of the process with minimum labour costs and small investments for commercial deployment.
15 cl, 2 tbl
FIELD: organic chemistry, polymers.
SUBSTANCE: invention relates to polymers additives for lubricant oils improving viscosity index and representing dispersers. Disperser-additive improving viscosity index is prepared by a method involving grafting in solution on hydrocarbon polymer prepared from at least one (C2-C28)-polymerizing hydrocarbon wherein abovementioned polymer has an average molecular mass value in the range from about 5000 Da to about 500000Da, compounds of ethylene-unsaturated type comprising from 3 to 10 carbon atoms and at least one group of carboxylic acid or anhydride group, or nitrogen-containing monomer of ethylene-unsaturated type comprising from 6 to 30 carbon atoms and from 1 to 4 nitrogen atoms and with using free-radical initiator wherein the process is carried out in the presence of ester as oil corresponding to the formula: wherein R1, R2, R3, R4, R5 and R6 are chosen independently from the group consisting of hydrogen atom, -COOR7, -COOR8, -COOR9, -COOR10, -COOR11 and -COOR12 under condition that 5 radicals (not above) among R1, R2, R3, R4, R5 and R6 represent hydrogen atom, and R7, R8, R9, R10, R11 and R12 are chosen independently from the group consisting of alkyl and alkyl esters. Disperser-additive improved viscosity index of lubricant oils and elicits dispersing capacity providing suspending sediment that can form in the process of exploitation or using lubricant and prevents carbon formation in engines. Method shows the improved qualities in grafting in solution of unsaturated fragments on hydrocarbon polymer by carrying out the grafting reaction in solution medium containing at least one aromatic ester.
EFFECT: improved preparing method, valuable technical properties of additive.
20 cl, 4 tbl, 4 ex
FIELD: polymer production.
SUBSTANCE: in the first step of two-step polymer-polyol preparation, polyether, notably Laprol 5003 or Laprol 5003/Laprol 3003 mixture, is combined with polymer selected from group, including polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene plastic, and mixtures thereof, at temperature 100°C. In the second step, at 90°C and pressure 0.2 MPa, monomer selected from group including acrylonitrile, styrene, acrylate, vinylidene chloride, and mixtures thereof is added before addition of catalyst. Resulting mixture is stirred at 100-110°C and pressure 0.25 MPa.
EFFECT: enabled preparation of stable dispersion, reduced process cycle time, and lowered power consumption.
2 cl, 2 tbl, 5 ex
FIELD: polymers, in particular composition for molded articles useful in building materials.
SUBSTANCE: claimed composition contains (A) 100 mass pts of vinyl chloride-based resin; (B) from 1 to 30 mass pts of graft copolymer obtained by graft polymerization; (C) from 0.1 to 5 mass pts of methylmethacrylate-based polymer obtained by two-step method in presence of polymer, wherein 0.1 g of said polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.7 or more and contains 0-50 mass % of methylmethacrylate repeated units, and 0.1 g of in two step obtained polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.5 or more; and (D) from 1 to 20 mass pts of calcium carbonate.
EFFECT: articles with high processibility, whether resistance, impact resistance and luster.
5 cl, 19 ex, 3 tbl
FIELD: polymer materials.
SUBSTANCE: composition comprises polyolefin A, containing anhydride function and having viscosity at least 20 g/10 min measured at 190°C and loading 2,16 kg, and epoxy function-containing product B destined for cross-linking polyolefin A. Relative proportions of A and B are such that for each epoxy function there are from 0.1 to 1.5 anhydride functions. Composition can be used in slush molding process, in thermal molding of sheets, or in on-rod casting process.
EFFECT: increased flowability resistance and wear resistance.
6 cl, 1 tbl, 6 ex
SUBSTANCE: material contains high-density polyethylene M 273-83, low-density linear polyethylene M.PE 2 NT 05-5 and low-density polyethylene ML 5313-003, calcium stearate, talc with particle size of up to 20 mcm and stabilisers such as Richnox 1010 and Richnox 168. The combination of components in defined ratios enables the polymer composite material to retain its mechanical, thermophysical, chemical and electrical insulation properties for a long period of time at operating temperature ranging from -30°C to + 90°C.
EFFECT: preserving properties of the material.
1 tbl, 3 ex