PL208723B1 - Polichlorovinyl composition with natural filler - Google Patents

Description

The subject of the invention is a polyvinylchloride thermoplastic composition containing a natural filler.

Thermoplastic compositions containing fillers in the form of comminuted natural polymers containing cellulose are known, as is shown, for example, in Natura Fibers, Biopolymers and Biocomposites, CRC Press, Taylor & Francis Group, Boca Raton, 2005. Of the natural polymers, cellulose ( 50% of all natural polymers) and lignin (95% used for energy purposes). Shredded renewable raw materials are used as fillers in the form of ground natural polymers. The most commonly used are perennial plant materials (trees), but also annual plant materials (cotton, jute, hemp, linen, sisal etc.) are used. It is also known to use ground wheat or rice straw. Apart from properties such as easy availability, low price, favorable mechanical properties, non-toxicity, biocompatibility, their unique property is renewable via biosynthesis, so their stocks are practically inexhaustible. Renewable raw materials containing cellulose also contain lignins, hence the fillers obtained after their grinding are called lignocellulosic fillers.

The literature data show that among all annual plant materials, rape straw has a chemical composition that is closest to that of wood (Table 1).

Ta b e l a 1

The chemical composition of various straws compared to coniferous wood

Component, wt.% * Cellulose Hemicellulose Lignins Mineral compounds Extractable substances Conifer** 54.09 23.40 30.15 0.24 1.47 Rapeseed straw ** 37.555 31.37 21.3 6.02 3.76 Wheat straw *** 39 36 10 6 3.6 Rice straw *** 33 26 7 13 4.2

* - relative to - dry weight material u ** - source: D. Dziurka, R. Mirski, J. Łęcka: Electronic Journal of Polish Agricultural

Universities, Wood Technology: 2005, Volume 8, Issue 3, 1 - 7 *** - Source: M. G. Jackson: Anim. Feed Sci. Technol: 2, 105, 1977

Research has shown that the burning of rapeseed straw is not very beneficial in terms of energy compared to other materials of plant origin (Table 2).

T a b e l a 2

Calorific values of different types of biomass *

Type of biomass Humidity biomass % Fresh calorific value MJ-kg ^-1 Dry calorific value MJ-kg ^-1 Wheat straw 15-20 12.9-14.1 17.3 Barley straw 15-22 12.0-13.9 16.1 Rapeseed straw 30-40 10.3-12.5 15.0 Corn straw 45-60 5.3-8.2 16.8 Wood dust 3.8-6.4 15.2-19.1 15.2-20.1 Scobs 39.1-47.3 5.3 19.3 Willow chips 40-55 8.7-11.6 16.5 Pellets 3.6-12 16.5-17.3 17.8-19.6 Straw briquettes 9.7 15.2 17.1 Wood briquettes 3.8-14.1 15.2-19.7 16.9-20.4

* I. Niedziółka, A. Zuchniarz, Energy analysis of selected types of biomass of plant origin, MOTROL, 2006, 8A, 232-237

PL 208 723 B1

With the increasing cultivation of rape - 1848.6 thousand. tonnes in 2007) -) (National Association of Rapeseed Producers) rapeseed straw becomes natural waste, with a composition similar to wood, the management of which in various areas has become a serious challenge.

The most commonly used lignocellulosic filler for polyvinyl chloride is wood dust and flour as well as natural fibers. The use of wood flour in the amount of 70 100 parts. wt. for 100 parts wt. PVC for the production of load-bearing, bottom layers of floor coverings is presented in the Polish patent description PL 195 047 (2000). In Chinese CN 1292398 (2000) and CN 1603088 (2004) plasticized PVC compositions with wood flour are used as non-flammable decorative wood products. The wood flour is used in an amount of 30-70 wt.%. Natural fibers (flax, hemp, sisal, jute) are also used as described in GB 1279497 (1972) for the use of jute fibers in PVC floor coverings or in Japanese JP 57108161 (1982). Ground wheat or rice straw is also used as filler, as disclosed in Chinese patents CN 1181875 (1998), CN 1629217 (2005) or CN 1830876 (2006).

The natural filler polyvinylchloride composition, containing primary or secondary polyvinyl chloride, natural filler and optionally auxiliaries, is characterized in that it contains ground, dried rapeseed straw in an amount of 5-60% by weight based on the polymer as the natural filler.

Preferably the composition according to the invention contains the filler in an amount of 8-50 wt. with respect to the polymer.

Preferably the composition according to the invention comprises a filler with a particle size in the range 0.25-5 mm.

The filler used in the composition according to the invention is obtained by grinding the dried rapeseed straw in a knife, hammer or other fluid with an interchangeable screen of various mesh sizes (range from 0.1-5 nm). In the mill, the straw is crushed with knives, hammers or friction discs to a size that allows the chopped straw particles to pass through the mesh of the mill screen.

The form of the filler for the composition according to the invention, obtained by grinding rapeseed straw, depending on the mesh size of the screen in the grinding mill, is shown in Figs. 1-3.

The composition according to the invention is obtained by obtaining a dry blend of plasticized PVC or by physically mixing plasticized PVC waste with a lignocellulosic filler obtained from rapeseed straw, and then granulating the composition on an extruder line with a single or twin screw extruder, or by rolling PVC with a filler a then granulation in a knife mill. The resulting compositions are further processed by standard methods such as injection or pressing. The composition can also be extruded directly from the dry blend or physical mixture onto profiles or pipes.

It was found that a polyvinylchloride thermoplastic composition in which the filler was ground rapeseed straw in an amount of 5 - 60 wt.%. It is characterized by mechanical properties similar to those of compositions in which flour and wood dust or mineral fillers are used as fillers. It was found that the residual rapeseed oil in the crushed rapeseed straw has a plasticizing effect on PVC. The composition has also been found to resist weathering and therefore not biodegradable.

The obtained compositions containing a filler from crushed rapeseed straw are characterized by very good mechanical properties. Young's modulus of elasticity is several times higher compared to the unmodified material (depending on the amount of filler). The stiffness of the composition increases, which is manifested by the doubled bending strength and the reduced deflection arrow. The breaking strength and the elongation at break decrease. The notched impact strength of the compositions obtained is also lowered. In terms of these properties, they are similar to PVC with wood flour or mineral fillers (chalk, talc).

Polyvinylchloride thermoplastic compositions with shredded rapeseed straw are not biodegradable under the influence of weather conditions. This is evidenced by a slight decrease in mechanical properties before and after aging as well as the lack of weight loss of the composition after aging.

Polyvinylchloride thermoplastic compositions are characterized by high stiffness and hardness with a simultaneously nice external surface and good, for selected applications.

Containers: disposable or reusable pots, buckets, containers, containers; wood-like profiles such as fence rails, base profiles, interior finishing elements in construction and automotive industry boards, also as interior finishing elements that sharply crack when struck, e.g. dashboards, seat covers, lockers, etc.

The use of crushed rapeseed straw as a filler for polyvinylchloride compositions allows for the disposal of rapeseed straw, which is difficult to manage in any other way. Rape crop waste, the production of which increases due to the production of biofuels, is becoming a cheaper and cheaper raw material. The composition of rapeseed straw is similar to that of wood, and the use of rapeseed straw as a PVC filler results in polyvinylchloride compositions with properties similar to those filled with wood flour.

The polyvinylchloride compositions according to the invention are shown in the examples.

P r x l a d I - V

Dry mixes, the so-called PVC dry blend with the recipes presented in Examples 1-5. The filler used was rape straw, dried and shredded in a knife mill with a 5 mm mesh screen, in the amount of 0-25 parts. wt. for 100 parts wt. PVC. Dry blends were rolled on a rolling mill with oil-heated rolls. The rolling process was carried out at the temperatures of 175-180 ° C. The skins obtained from the rolling mill were then pressed at a temperature of 175-180 ° C into tiles. Test pieces were cut from the plates. The fittings were tested for mechanical properties. The resulting compositions are characterized by the following properties:

Example number AND II III IV V PVC S-61 Part weight 100 100 100 100 100 OTGO ^{/ 1} Part weight 2.5 2.5 2.5 2.5 2.5 Ergoplast FDO ^{/ 2} Part weight 22.5 22.5 22.5 22.5 22.5 Stearin Part weight 0.4 0.4 0.4 0.4 0.4 Ergoplast ES ^{/ 3} Part weight 2.5 2.5 2.5 2.5 2.5 Ergowax GS ^{/ 4} Part weight 0.8 0.8 0.8 0.8 0.8 Wax A ^{/ 5} Part weight 0.4 0.4 0.4 0.4 0.4 Rapeseed straw max. 5 mm Part weight 0 13 21 26 32.5 Young's modulus in bending ^{/ 6} MPa 338.6 393 510 558 837 Bending stress ^{/ 6} MPa 5.28 5.60 8.57 10.67 12.32 Stress at break (paddle W1) ^{/ 7} MPa 22.54 10.24 10.87 10.48 8.22 Relative elongation at break (W1) ^{/ 7} % 274.9 35.96 29.42 25.15 13.43 Charpy notched impact strength ^{/ 8} kJ / m2 68.68 61.86 58.15 34.86 12.22

E xample d VI - X

Physical mixtures of PVC waste from the cable industry were made with the recipes presented in Examples VI - X. The filler was dried and shredded in a knife mill with a screen with a mesh of 0.75 mm (compositions VI - IX) or with a screen with a mesh of 0.25 mm ( composition X) rapeseed straw in the amount of 0-100 parts. wt. for 100 parts wt. PVC. The mixture of secondary polymer and filler was extruded on a granulation line with a T 45 single-screw extruder at a temperature of 165-180 ° C. The obtained granulate was injected onto the test pieces on an Arburg 420 M injection molding machine at a temperature of 165-190 ° C and an injection pressure of 60-80 MPa. The fittings were tested for mechanical properties. The resulting compositions are characterized by the following properties:

PL 208 723 B1

Example number VI VII VIII IX X PVC S-61 Part weight 100 100 100 100 100 Lead stabilizers Part weight 4 4 4 4 4 Ergoplast FDO ^{/ 1} Part weight 46 46 46 46 46 Stearin Part weight 0.4 0.4 0.4 0.4 0.4 Ergoplast ES ^{/ 4} Part weight 2.5 2.5 2.5 2.5 2.5 Ergowax GS ^{/ 5} Part weight 0.8 0.8 0.8 0.8 0.8 Wax A ^{/ 6} Part weight 0.4 0.4 0.4 0.4 0.4 Chalk Part weight twenty twenty twenty twenty twenty Rapeseed straw max. 0.75 mm Part weight 0 44 75 100 ^75/6 Young's modulus in bending ^{/ 6} MPa twenty 150 170 380 190 Bending stress ^{/ 6} MPa 1.0 3.6 3.7 6.0 3.9 Young's modulus in tension ^{/ 7} MPa 43 74 154 250 168 Stress at break ^{/ 7} MPa 33.9 10.16 10.64 11.67 11.15 Relative elongation at break ^{/ 7} % 164 59 29.6 12.8 30.1 Charpy notched impact strength ^{/ 8} kJ / m2 68.68 61.86 58.15 34.86 59.12

Example XI - XIII

Physical mixtures of PVC waste from the cable industry were made with the recipes presented in examples VI - X. The filler was wood flour intended for filling Lignocel C 120 plastics by the Manufactures of Fibers Rettenmaier. The mixture of secondary polymer and filler was extruded on a granulation line with a T 45 single-screw extruder at a temperature of 165-80 ° C. The obtained granulate was injected onto test specimens on an Arburg 420 M injection molding machine at a temperature of 165-190 ° C and an injection pressure of 60-80 MPa. The fittings were tested for mechanical properties. The resulting compositions are characterized by the following properties:

Example number VI XI XII XIII XIV PVC S-61 part weight 100 100 100 100 100 100 Lead stabilizers part weight 4 4 4 4 4 4 Ergoplast FDO ¹ part weight 46 46 46 46 46 46 Stearin part weight 0.4 0.4 0.4 0.4 0.4 0.4 Ereoplast ES ^{/ 4} part weight 2.5 2.5 2.5 2.5 2.5 2.5 Ergowax GS ^{/ 5} part weight 0.8 0.8 0.8 0.8 0.8 0.8 Wax A ^{/ 6} part weight 0.4 0.4 0.4 0.4 0.4 0.4 Chalk part weight twenty twenty twenty twenty twenty twenty LIGNOCEL C ^120/9 part weight 0 44 75 100 - - Pine flour part weight - - - - 75 100 Young's modulus in bending ^{/ 6} MPa twenty 160 180 410 360 440 Bending stress ^{/ 6} MPa 1.0 3.6 3.7 6.0 6.4 8.1 Young's modulus in tension ^{/ 7} MPa 43 84 162 301 340 420 Stress at break ^{/ 7} MPa 33.9 10.16 10.64 11.67 4.6 7.5 Relative elongation at break ^{/ 7} % 164 59 29.6 12.8 10.4 7.7 Charpy notched impact strength ^{/ 8} kJ / W 68.68 61.86 58.15 34.86 64.1 44.2

PL 208 723 B1

When comparing the mechanical properties of an unfilled polyvinylchloride composition (Example VI) with those filled with shredded rapeseed straw (Examples VII-IX) and filled with the same amounts of Lignocel C 120 (Examples XI-XV), it appears that the nature of the changes in properties for both fillers it is the same, but for wood flour (Lignocel and pine) the changes are slightly larger.

E xample XVI - XX

Dry mixes, the so-called PVC dry blend with the formulations shown in examples 11 to 15. The filler used was rape straw, dried and shredded in a knife mill with a 5 mm mesh screen, in the amount of 0-100 parts. wt. for 100 parts wt. PVC. Dry blends were rolled on a rolling mill with oil-heated rolls. The rolling process was carried out at the temperatures of 175-180 ° C. The skins obtained from the rolling mill were then pressed at the temperature of 175-180 ° C into plates. Test pieces were cut from the plates. The biodegradability of the compositions was assessed. The assessment of biodegradability was carried out by examining the effect of aging of the composition in three types of moist soil on the mechanical properties of the composition and the change in their mass, and the effect of accelerated aging in the Atlas UV 2000 chamber on the mechanical properties of composites. The moldings were tested before and after aging. The resulting compositions are characterized by the following properties:

Example number XVI XVII XVIII XIX XIX PVC S-61 part weight 100 100 100 100 100 OTGO ^{/ 1} part weight 2.5 2.5 2.5 2.5 2.5 Ergoplast FDO ^{/ 2} part weight 22.5 22.5 22.5 22.5 22.5 Stearin part weight 0.4 0.4 0.4 0.4 0.4 Ergoplast ES ^{/ 3} part weight 2.5 2.5 2.5 2.5 2.5 Ergowax GS ^{/ 4} part weight 0.8 0.8 0.8 0.8 0.8 Wax A ^{/ 5} part weight 0.4 0.4 0.4 0.4 0.4 Rapeseed straw max. 5 mm part weight 0 13 21 26 32.5 No aging Stress at break (W1) ^{/ 7} MPa 22.54 11.24 10.87 10.35 8.58 Relative elongation at break (W1) ^{/ 7} % 274.9 35.96 39.43 25.15 13.43 Mass change % 0 0 0 0 0 Aging in horticultural soil, ¹ Year Stress at break (W1) ^{/ 7} MPa 23.32 14.12 11.01 11.17 8.12 Relative elongation at break (W1) ^{/ 7} % 237 55.71 27.08 15.91 12.43 Mass change % -1.64 0.08 -0.52 -0.33 -0.66 Aging in forest soil, ¹ Year Stress at break (W1) ^{/ 7} MPa 21.9 11.91 12.38 9.61 9.98 Relative elongation at break (W1) ^{/ 7} % 212.7 29.58 35.46 9.95 13.36 Mass change % -1 -1.3 -1.62 -1.36 -1.83 Aging in compost, ¹ Year Stress at break (W1) ^{/ 7} MPa 22.91 11.17 10.97 10.63 9.84 Relative elongation at break (W1) ^{/ 7} % 237.5 23.69 20.62 19.5 12.62 Mass change % -0.9 0.08 -0.81 -0.42 -0.87 Aging in the Atlas UV 2000 chamber (168 hours) - cyclical irradiation and condensation of water every 6 hours Stress at break (W1) ^{/ 7} MPa 21.41 9.42 9.61 8.49 7.48 Relative elongation at break (W1) ^{/ 7} % 226.3 37.04 29.46 25.73 20.62

¹ Ergoterm OTGO organotin stabilizer

PL 208 723 B1 ² Ergoplast FDO - di (2-ethylhexyl) phthalate ³ Ergoplast ES - epoxidized soybean oil ⁴ Ergowax GS - glycerin monostearate ⁵ Wax A - paraffin wax ⁶ Rapeseed straw ground in a knife mill with a 0.25 mm mesh screen ⁷ PN-EN ISO 527 ⁸ PN-EN ISO 527 ⁹ Manufactures of Fibrrres Rettenmaier

Claims (3)

CLAIMS 1. Polyvinylchloride composition with a natural filler, containing primary or secondary polyvinyl chloride, a natural filler and optionally auxiliaries, characterized in that the natural filler comprises ground, dried rapeseed straw in an amount of 5-60% by weight with respect to the polymer. 2. A composition according to claim 1 The composition of claim 1, wherein the filler is 8-50% by weight based on the polymer. 3. A composition according to p. The method of claim 1, wherein the filler has a particle size in the range 0.25-5 mm.