DE4408855A1 - Solid or foamed plastic using biomass as filler - Google Patents

Abstract

Fibre-reinforced solid or foamed plastics compsns. comprise, by wt. (A) 100 pts. plastics matrix; (B) 0.05-80 (esp. 5-35) pts. filler/reinforcement comprising a biomass capable of also acting as a blowing agent and comprising tropical grasses, esp. rapid growth, lignifying materials such as bamboo fibres etc., and opt. (c) 0.1-50 (pref. 1-40) pts. known inorganic filler/reinforcement; (D) 0.1-35 (pref. 1-15) pts. polymeric impact modifier e.g. ABS or other known styrene copolymer; (E) 0.05-15(pref. 0.5-6) pts. known stabiliser; (F) 0.05-20 (pref. 0.5-10) pts. known lubricant, (G) 0.01-6 (pref.0.1-3) pts. known silane coupling agents; and (H) 0.01-5 (pref. 0.1-2) pts. known pigments. Pref. the matrix (A) (opt. of recycled or scrap) material is of polyurethane (elastomer), polyolefin, PVC, SBR etc.. Filler/reinforcement (B) is a biomass multi-component, heterogeneous, colloidal material capable of generating CO2 etc. as agent and contg. mainly cellulose, hemicellulose and lignin as main components together with (in)organic impurities such as silicification cpds.. The bamboo fibres are e.g. 3-20 mu thick and of length from below 100 to above 1000 mu . Coupling agent (G) is beta (3,4-epoxy-cyclohexyl)-ethyltrimethoxysilane for use with phenolic resins, PVC, polycarbonate, polystyrene, ABS, SAN, polypropylene etc..

Description

The present invention relates to the field of filled or reinforced Plastics, especially the composition of its internal structure filled / reinforced, compact to cellular plastic material and Art and how it is used, including those that can be made from this material Products.

For the purposes of this invention, plastic is a macromolecular substance Compounds or masses, which in turn consist of such macromolecular Connections exist, understood.

It is generally known that plastics in the pure as well as in the filled or reinforced condition, then with the application or Appropriate additives are used.

As one of the first additional or reinforcing materials, papers and Textile components, based on their origin, organic materials. There this applies equally to wood flour and these additional components to Matrix material is generally recognized knowledge, it does not require any supporting evidence. The use of these types of materials eliminated the Date of emergence of the first deficiency prevailing plastics insufficient strength of the actual plastic during use. At the time of the prior art, only these known appeared organic materials as suitable. In the pursuit of plastic and  general technology development, to create materials that on the one hand usually contain more valuable matrix material economically, on the other hand mechanical, physical, chemical and thermal Properties of the products as optimal as possible for the respective application are known to have been adapted, inorganic additional components, especially for extremely high strength requirements, but also organic Additional components such. B. on the basis of synthetic polymeric fiber materials built into the plastic matrix. As one of the numerous representatives of with inorganic fillers and additives provided PVC's, with only the only provided indicative term "reinforcing fibers" is DE 39 27 777 to name. Furthermore, DE 41 16 025 describes the use of a mixture Made of inorganic and organic material, in the form of recycled filled and / or unfilled thermosets, as fillers for thermoplastics suggested. DE 36 14 533 describes the reinforcement of a thermoplastic, including the reinforcement of a polyolefin, by means of inorganic fibers, such as. B. glass fibers, rock wool fibers, Asbestos fibers but also organic fibers based on synthetic origin from Z. B. polyolefins, styrene and vinyl chloride polymers and organic fibers as natural products, such as. B. wool fibers, silk fibers, Cotton fibers, hemp fibers or jute fibers in the embodiment of physical reinforcements.

Likewise, the state forms of plastic products are compact as well zellig already well-known ideas. For making cellular State forms in all their varieties with thermoplastic as well as thermosetting Plastics are special blowing agents, so far also based on used environmentally harmful CFC and CFC products, known. The DE 31 29 032 describes the production of a polyester resin foam organic fibers of a non-advanced type and inorganic fibers especially glass fibers. The plastic foam is after the receive the aforementioned DE in that the still uncrosslinked polymer liquid by mechanically introducing a gas, by adding a chemical as Foaming agent or blowing agent or by processing in one Foaming device, for example in a mixer or a Turbine, mechanically foamed, filled in a mold and under Reacts to heat, thus maintaining its shape.

All previously known technical solutions, the named, as well as the much larger part of the undisclosed solutions of the prior art, are affected by the shortcomings described below. A part of  Reinforcing fibers themselves, as well as incorporation into or processing these fibers with plastics are expensive, sometimes time consuming and complicated to handle, e.g. B. reinforcement with carbon fibers or Whyskern. The application of these fibers mentioned above, but also the widespread glass fiber reinforcement, irretrievably consume natural Resources. For certain applications, those with the aforementioned appear Reinforcement materials achievable qualities and property values, especially the physico-mechanical, unnecessarily or unadjusted high. Sometimes it is appropriate to use organic fibers of synthetic origin Use reinforcement. But this fiber group also consumed irretrievable natural resources are usually involved in their manufacture harmful impacts on people and the environment and likewise costly and time-consuming, mostly also energy-intensive in the raw material and fiber manufacturing. If certain property values, the aforementioned fibers effect as reinforcing material, not necessarily used to the limit have to be, but property values in the lower / lower level it may be sufficient to meet the required utility value organic fibers of natural origin also appear appropriate Use reinforcement. These natural fibers, such as. B. hemp, Jute, cotton, flax (see e.g. flax - a renewable one Reinforcing fiber for plastics?, Th. Fölster and W. Michaeli, plastics 83, 1993, 9, Carl Hanser Verlag Munich), wood or wool do not consume irreversible natural resources, but are constantly growing. But you stand naturally only available to a limited extent as they are usable require relatively long regrowth periods or longer vegetation periods. For high volumes, therefore, large acreage would have to be in each required climatic areas of the earth are available. It would also result through then monocultural management of the available land societal as well as climatic and ecological negative effects. Plants growing somewhat faster, from which reinforcing fibers are obtained could be, for example, grasses and reeds. These are fibrous materials however of such poor quality, especially in strength behavior and in their thermal resilience, which is determined by plastics processing is that they have practically no meaning as a reinforcing material.

The invention is based on the object and the objective of To create inexpensive plastic for preliminary, intermediate and end products, which in Interaction with its reinforcing material is reasonably high strength  and stability properties, optionally having a cellular structure, its reinforcement material itself high inherent strength and the Plastic processing has adapted thermal stability, quickly, in the sense rapidly growing / renewable, as a natural product, therefore none Natural resources are consumed irretrievably. The filling or Reinforcing material is intended to be used in an economically efficient manner guarantee and biodegradable or recyclable be a more economically efficient disposal without burdening the Ensure the environment.

Furthermore, the invention is based on the aim and the object, preferred Uses of the products created in this way, if possible as mass products, to propose.

According to the invention, this objective and task is solved in that a According to this invention and defined plastic mass, each 100 parts by weight (parts by weight) of plastic as a matrix material 0.05 to 80 parts by weight, preferably 0.5 to 60 parts by weight, in particular 5 to 35 Parts by weight of filling and / or reinforcing material by means of a biomass, the also has a blowing agent-like effect from the group of tropical Grasses, especially the fast-growing, woody sweet grasses, preferably bamboo fiber, bamboo needle and / or bamboo splinter material in Form of a heterogeneous and colloidal multicomponent system with the main components Cellulose, hemicellulose and lignin as well as small amounts of organic and inorganic accompanying substances, such as. B. and especially remarkable Ver pebble components.

In the following of this invention this is for the sake of simplicity Multi-material system summarized as "fibrous components" or "bamboo fibers" represented (defined) and understood.

Each of these 100 parts by weight of plastic matrix material contains the solution according to the invention summarily or in the respective plastic adapted selection further 0.1 to 50 parts by weight, preferably 1 up to 40 parts by weight of an inorganic filler / reinforcing material, 0.1 to 35 parts by weight, preferably 1 to 15 parts by weight, impact modifier as high molecular plastic, such as. B. Acrylonitrile-butadiene-styrene polymers (ABS) or other styrene copolymers, 0.05 to 15 parts by weight, preferably 0.5 to 6 parts by weight, stabilizer of known type, 0.05 to 25 parts by weight, preferably 0.5 to 10 parts by weight, lubricant of a known type, 0.01 to 6 parts by weight, preferably 0.1 to 3 parts by weight, of silane coupling agent  known type and / or 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight Color pigments. The bamboo material to be used as reinforcement material has a low density, high tensile strength, significantly high elongation Tensile load and high flexural strength, which makes it very strong similar materials and these property values particularly advantageous to the plastic thus reinforced.

As preferred embodiments, instead of a pure, uncut plastic matrix material, e.g. B. an LD PE, a plastic Waste (plastic mixture) from several primary plastics as Matrix material or a plastic mixture of primary plastic or Primary plastics with plastic recycling material (secondary material) use advantageously. The exclusive use of plastic Recycled material provided as a matrix material. In the embodiments, in which matrix-material mixtures are used, it can be special be advantageous to use up to 50 parts by weight of polyolefins. Under the LD PE provides the polyolefins as packaging material, e.g. B. for foils, Bottles, containers make up the bulk of the plastics recycling economy. On Because of the relatively poor mechanical properties of LD PE, e.g. B. of E-modulus, the tensile strength, is achieved with the use of this Recyclates in conjunction with a large quantity of high inherent strength and toughness as well as relatively low density in the amount of about 0.82 g / cm³ bamboo fiber reinforcement material are noticeable Relief for the recycling economy, connected with the provision suitable plastic semi-finished products or -Finished parts to be expected. Defects and disadvantages, for example in comparatively high processing costs due to complex Processing processes in the recycling industry exist to be single-variety Provide material or consist of that mostly not pure recycling plastics comparatively low mechanical Resilience can be achieved by using this higher strength Bamboo fiber reinforcement material in plastic recyclates advantageous fixed way. The recycling economy is worth mentioning Share of recovery may count. In addition to the reinforcing effects of Bamboo fiber, which when using the fiber parts from the woody Bamboo plants, to be expected, were other beneficial effects determined inventive. First, the availability of at any time, thus almost climatically and regardless of vegetation periods, large Quantities are referenced, as this type of sweet grass is a rapidly growing,  no natural resources irretrievably, constantly represents a natural product at hand. By means of suitable preparation and Separation technology can be the strength, elasticity and toughness as well relatively low density about 0.82 g / cm³ possessing fiber shares for the Provide reinforcement of plastics. The thermal resistance up to approx. 110 ° C and above that the beginning decomposition from approx. 120 ° C of the bamboo fiber and their composition or peculiarities lie in areas whereby the State of the art so far no technical solution for the application of this Offers fiber with or in the plastic material. When choosing more suitable Plastic processing parameters can be a partial thermal degradation of the Fiber, the CO, CO₂ gas, water and water vapor separations in plastic has to be brought about in a targeted manner, especially by the high O₂ content, since this multi-component system has a very large specific surface with moisture and air connections, favors, creating a Blowing agent effect of the bamboo fiber achievable and thus a cellular material is effected. In particular, the cellulose content of the bamboo fiber exploited. This cellulose has a crystalline structure and exercises one Dual function, on the one hand as a nucleating agent and germ cell for the CO, CO₂ and H₂O gases, on the other hand as a propellant gas dispenser, which makes a special fine-pored, high-quality foam is created. The blowing agent-like effect of Bamboo fiber can also be further controlled by adjustable Moisture content of the fiber used for plastics processing, expand. By means of these processes to be controlled in plastics processing reinforced compact and cellular plastics can thus be a portion of bamboo fibers that have not yet decomposed and have a reinforcing effect, without Use a conventional blowing agent. In this respect, this is Solution also a contribution to the replacement of environmentally harmful blowing agents, such as. B. CFCs, in the production of foamy / cellular moldings through targeted Development of environmentally friendly blowing agents in the product. The woody, firm, depending on The type of bamboo used can also be highly elastic and tough bamboo fiber as long fibers in the area larger than 1000 µm, in medium fiber lengths of 100 up to 1000 µm or as short fibers in the area under 100 µm in length with fiber thicknesses between about 3 and 20 microns can be used and effects like a Embodiment below shows high quality mechanical, in particular also elastic properties of the reinforced compact plastic, which makes it a good construction material. The property-improving effect, especially in the impact resistance, is achieved by a small fraction, less than 5 µm, of the bamboo fiber.  

This portion provides seeds for the formation of spherical crystal structures ready and forms by a high number of the initial germs fine-spherical structure in semi-crystalline plastics. Experience with it especially the recycled plastics reinforced with bamboo fibers are not insignificant material and material technical upgrading, in particular because of the mechanical properties of the composite targeted selection of varieties from approx. 90 different types of bamboo and the targeted selection of fiber pretreatment for the selected one The type of bamboo (variety) can be specifically adapted to the intended application can. A not insignificant positive effect of the bamboo fiber reinforcement is that in the thermal disposal of plastic products, the would be particularly suitable for this, such as. B. polyolefins Reinforcement material leaves hardly any residues because it is environmentally friendly Decomposition products such as CO, CO₂, water can be broken down.

According to further preferred embodiments, a silane coupling agent is matched to the plastic matrix, used in the plastic composite, whereby the silicification contained in bamboo fibers in the form of considerable Silicate deposits for bridging with the silane coupling agents and Water or moisture contained in the bamboo fiber over the hydrolyzable groups on the one hand and the organofunctional groups on the other hand, be used consciously. This makes significant qualitative Improvements in the mechanical behavior of the invention fiber-reinforced, compact to cellular plastics.

Another preferred embodiment consists in the use of elastics as Matrix material. The material is largely preserved elasticity increases in wear resistance, coefficient of static friction, to achieve the pressure and tensile strength or targeted settings these values are possible for the required technical applications.

Another preferred embodiment is the use of plastic foams previously known type provided as a matrix material. When foaming out In the liquid phase, the bamboo fibers become with / in the foaming mass turbulently moved and randomly distributed in the foamed geometry, so that itself in the plastic foam precast due to adhering to the bladder surfaces Bamboo fibers one of the bamboo fiber length and the bamboo fiber volume fraction forms certain spatial grids.

The use of bamboo tangled fiber mats creates very thin shapes achieved, the small masses due to the low density of the bamboo fiber have as a consequence. Strength behavior is thus analogous to that of reinforcement  expected with glass fiber mats. Compared to the glass fiber reinforcement is with higher elasticity, due to the higher bamboo fiber elasticity. Health effects in fiber production and processing are compared to the production and processing of mineral fibers hardly to be expected.

Uses according to the invention of these bamboo fiber-reinforced or with Bamboo fiber processable products can be determined as follows.

Advantageous use as preliminary and intermediate products in plastic Processing methods and as an end product in the form of semi-finished products, such as Pipes, strips, plates, profiles, in the form of technical molded parts and as Shaped parts for consumer and / or consumer / consumer goods, these Products with low weight and high strength are created. This is because especially in the low density of approx. 0.82 g / cm³ of firm, elastic and tough reinforcement bamboo fiber.

The wood-like surface is particularly advantageous Products using PVC-h as matrix material.

The following exemplary embodiments are intended to explain the invention in more detail.

Embodiment 1 (soft PVC)

• - 100 parts by weight of PVC-S with a K value of 68,
• - 50 parts by weight of the multi-component system described,
• 4 parts by weight of modified 3-base lead sulfate,
• - 1 part by weight of lead stearate,
• 0.5 part by weight of carbon black,
• - 50 parts by weight of plasticizer in the form of a di (2-ethylhexyl) phthalate.

Example 2 (PVC hard):

About the described multi-material system with an average fiber length of 160 µm and approx. 0.5% residual moisture (approx. 2% residual moisture in one version) Example 2.1. with 10 parts by weight of bamboo fibers with otherwise the same stock divide as under 2. and about 3% residual moisture in one embodiment 2.2. with 10 parts by weight of bamboo fibers with otherwise the same components as under 2. as well as with an average fiber length of 800 µm and a residual moisture of about 3% in one embodiment 2.3. with 30 parts by weight of bamboo fibers with otherwise the same components as under 2.) were added and mixed With:

• - 60 parts by weight of PVC-S with a K value of 68,  
• - 8 parts by weight of an impact modifier based on chlorinated PE with a chlorine content of 40%,
• 5 parts by weight of a calcium carbonate,
• 5 parts by weight of titanium dioxide,
• - 4 parts by weight of a stabilizer-lubricant compound with a high Barium-cadmium content,
• 4 parts by weight of a 2 basic lead phosphate,
• - 3 parts by weight of a processing aid based on Polymethacrylate,
• - 7 parts by weight of a polymer plasticizer based on epoxidized Soybean oil,
• - 4 parts by weight of a lubricant, composed of Hydrocarbon wax, PE wax, Ca stearate and stearic acid and processed into tubes in an extruder.

The quality test is carried out according to DIN 53 760. The impact bending test Strength was achieved on test specimens from this tube in accordance with DIN 53 453. The test the tensile and compressive strength deviated from DIN 53 392 and DIN 53 454 carried out. The test was carried out across the pipe cross-section.

Embodiment 3 (PP)

• - 100 parts by weight of PP powder or regrind,
• - 3 parts by weight of white oil, hydrocarbon,
• - 0.4 parts by weight of 2,2-thio-bis / 4-methyl-6-tert-butyl-phenol as a powder with a melting point at 83 ° C, thermal stabilizer,
• 1.5 parts by weight of gamma-methacryloxypropyltrimethoxysilane, Silane coupling agent,
• - 30 parts by weight multi-component system of the type described.
  Application: sheets, profiles.

Embodiment 4 (PE) Variations in parts by weight of the multi-component system described in injection molding Shares of the multicomponent system

• - LD PE, A 17 powder + 0 parts by weight: Var. 1
• - LD PE, A 17 powder + 10 parts by weight: Var. 2nd
• - LD PE, A 17 powder + 20 parts by weight: Var. 3rd
• - LD PE, A 17 powder + 30 parts by weight: Var. 4th

The test results from the tensile test according to DIN 53 455 and the bending test according to DIN 53 452 are shown in FIGS. 1 and 2.

Claims (13)

1. Fiber-reinforced, compact to cellular plastic, which is defined in the sense of this invention as a substance made of macromolecular compounds or masses, which in turn consist of such macromolecular compounds, consisting of the plastic matrix, filler / reinforcing materials of organic, natural origin and Additives of a known type, characterized in that they contain fiber-reinforced, compact to cellular plastic

• - 100 parts by weight (parts by weight) of plastic as a matrix material, as well as summary or optional
• - 0.05 to 80 parts by weight, preferably 0.5 to 60 parts by weight, in particular 5 to 35 parts by weight of filler / reinforcing material by means of a biomass, optionally also as a blowing agent, from the group of tropical grasses , especially the fast-growing, woody sweet grasses, preferably bamboo fiber, bamboo needle and / or bamboo splinter material,
• 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, of an inorganic filling / reinforcing material of a known type,
• - 0.1 to 35 parts by weight, preferably 1 to 15 parts by weight of impact-resistant fashion in the form of high-molecular plastic, such as. B. acrylonitrile-butadiene-styrene polymers (ABS) or other styrene copolymers of a known type,
• 0.05 to 15 parts by weight, preferably 0.5 to 6 parts by weight, stabilizer of a known type,
• 0.05 to 20 parts by weight, preferably 0.5 to 10 parts by weight, lubricant of a known type,
• - 0.01 to 6 parts by weight, preferably 0.1 to 3 parts by weight, silane coupling agent of a known type and / or
• 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, of color pigments of a known type.

2. Fiber-reinforced, compact to cellular plastic according to claim 1, characterized in that as the matrix material of the plastic as the primary material of a kind, as Primary material mixture, as a mixture of primary material and plastic Recycling material, as a plastic recycling material mixture, as one Plastic foam or as an elast, in particular a polyurethane elastomer, is inserted. 3. fiber-reinforced, compact to cellular plastic according to claim 2, characterized in that Polyvinyl chloride as primary material and / or recycling material with up to 80 parts by weight of polyolefin is used as the matrix material. 4. fiber-reinforced, compact to cellular plastic according to claim 2, characterized in that a mixture of primary material and / or recycled material with up to 95 parts by weight of polyolefin is used as the matrix material. 5. fiber-reinforced, compact to cellular plastic according to claim 2, characterized in that mixed recycling material with at least 50 parts by weight of polyolefin Share from waste management collections, e.g. B. the dual system Germany, is used as a matrix material. 6. Fiber-reinforced, compact to cellular plastic according to claim 1, characterized in that the filling / reinforcing material by means of a biomass, if necessary also as a blowing agent, from the group of tropical grasses, in particular the fast-growing, woody sweet grasses, preferably bamboo fiber, Bamboo needle and / or bamboo splinter material in the form of a heterogeneous and colloidal multicomponent system with the main components cellulose, Hemi cellulose and lignin as well as small amounts of organic and inorganic Accompanying substances, such as B. and in particular considerable silicification stock parts, exists and this multi-material system is summarized as "fibrous Components "or" bamboo fibers ", as far as defined.   7. fiber-reinforced, compact to cellular plastic according to claim 6, characterized in that the multicomponent system only consists of individual components or components combinations of the multi-substance system exists. 8. fiber-reinforced, compact to cellular plastic according to claim 6, characterized in that the bamboo fibers used as long fibers in lengths of more than 1000 µm, as medium fibers in lengths from 100 µm to 1000 µm, as short fibers in Lengths below 100 µm and fiber thicknesses from 3 to 20 µm, as well as a splitter in the the multi-material system forming the filling / reinforcing material is contained. 9. fiber-reinforced, compact to cellular plastic according to claim 6, characterized in that as silicification components in the filling / reinforcing material Multicomponent system silicate deposits are present. 10. Fiber-reinforced, compact to cellular plastic according to claim 1, characterized in that as a silane coupling agent, preferably vinyl triethoxysilane for art material matrix materials UP resins, PP, PE and SBR is used. 11. Fiber-reinforced, compact to cellular plastic according to claim 1, characterized in that preferably as a silane coupling agent Beta (3,4-epoxycyclohexyl) ethyl trimethoxysilane for the plastic matrix Materials UP resins, EP resins, PVC, PC, PS, ABS, SAN, PP, PE and PUR is inserted. 12. Fiber-reinforced, compact to cellular plastic according to claim 1, characterized in that the molding of the bamboo fibers with fiber lengths in the mm and cm range in the plastic matrix as an admixture of loose fibers to casting resins, as a mess fiber mat impregnated or as a knitted fabric made of predominantly long fibers be poured in.   13. Use of the fiber-reinforced, compact to cellular plastic one or more of claims 1 to 12 characterized in that the use is intended in injection molding, extrusion, intrusion or Casting process, if necessary using the cold and hot mix technology and that the use is also intended as a preliminary, Intermediate and as end products, as semi-finished products, such as. B. pipes, strips, Sheets, profiles as well as technical molded parts as well as molded parts for Consumer and / or consumer / consumer goods.