Free flowing powder composition, its preparation, homogeneous layer, derived from it, the carpet, conveyor belt and sealant for bottle caps

 

(57) Abstract:

Free flowing powder composition with a particle size of 800 μm or less, containing block copolymers containing at least one poly(monovinylacetylene hydrocarbon) block at least one block of hydrogenated or negidrirovannogo poly(conjugated diene), plasticizing oil, resin, compatible with the block poly(monovinylacetylene hydrocarbon), and optimouse tool. Free flowing powder composition contains (a) 100 wt.h. blockcopolymer containing monovinylacetylene hydrocarbon in the range from 10 to 60 wt.% calculated on the total weight of blockcopolymer: 30-200 wt.h. plasticizing oil; 5-200 wt.h. resins compatible with the block poly(monovinylacetylene hydrocarbon) and 0.1-10 wt.% from the total mass of the composition outrivaled means consisting of a fine powder, the average particle size is in the range from 1 nm to 100 μm. The technical result is to obtain such a stable free flowing powder composition comprising an elastomeric polymer and plasticizing oil, which can be stored without problems, getting free fluid composition, which can respectively use abode flowing powder composition, which is easy to carry out and which is efficient from an economic point of view. 6 C. and 8 C.p. f-crystals.

The present invention will otnositsa to a free flowing powder composition, its preparation, homogeneous layer, derived from it, the carpet, the conveyor belt and hermetico for caps of the bottles.

Currently, rubber latexes are widely used, for example, in the carpet industry as the basis for carpets, as well as in the paper and cardboard industry for coating. However, the use of such rubber latexes, i.e. dispersion of thermoplastic rubber in an organic solvent is undesirable from the point of view of environmental pollution due to the evaporation of organic solvent and due to the impossibility of re-forming latexes. Thus, there is a need in the relevant materials to replace rubber latexes, which are not harmful to the environment.

In U.S. patent N 4163031 disclosed powder composition suitable for coating, which comprises a mixture of from 25-90 wt.% selectively hydrogenated blockcopolymer and 75-10 leaky cable wt.% one or more aromaticheskiye. Block copolymers contain monovinyl arene end blocks and at least one middle block (blocks) of the partially hydrogenated conjugated diene and has a content moulinrouge arena 5-50 wt.%. The powder composition may further include up to 8 wt. % silicon-containing adhesion promoter. In U.S. patent N 4163031 also disclosed is a method of obtaining such a powder composition, which consists in the successive stages of mixing in the molten state components with subsequent cooling, granulating composition and grinding, for example by cryogenic grinding of granules to the desired size.

In U.S. patent N 4325770 disclosed is a method of obtaining products, coated with adhesive, effective under pressure, in which thermoplastic elastomer and resin, increase stickiness, separately pulverized into a powder, the resulting powder is mixed in dry form at room temperature. The mixture of powders is applied in dry form on the surface of the base and then the base covered with the powder, is heated to melt together powder particles and a homogeneous coating. Finally, the coating is cooled to room temperature.

Applied thermopla what about the diene). This block copolymers milled at a temperature below -20oC, preferably below -50oC.

Famous free flowing powder composition with a particle size of 800 μm or less, containing block copolymers containing at least one poly(monovinylacetylene hydrocarbon) block at least one block of hydrogenated or negidrirovannogo poly(conjugated diene), plasticizing oil, resin, compatible with the block poly(monovinylacetylene hydrocarbon) and optimouse tool /3985702/.

None of the known powders do not contain any oil as plasticizer, thus the coatings obtained from these powders are fairly rigid, which makes them unsuitable for such applications that require a flexible and elastic coatings or layers, for example, for the base of carpets, conveyor belts, sealants for bottle caps, coverings for the lower part of the body of the car and the basis for rubberized textile fabrics, paper or cardboard. Up to the present time believed that oil as a plasticizer may not be part of a freely flowing powder composition containing elastomeric block copolymers, because the oil can you is that the storage of powder, already containing oil, is virtually impossible. Thus, the known method is the preparation of a free flowing powder blockcopolymer, possibly together with some other non-adhesive components, and additives oil only during powder handling to avoid problems of agglomeration during storage. Also, for reasons of problems coagulation exclude the simultaneous grinding of elastomeric polymers, on the one hand, and plasticizing oils and/or resins that increase stickiness, on the other hand. This is shown in U.S. patent N 4325770 in which block copolymers and resin that increases the stickiness, crushed separately before mixing them in a dry form. Thus, it is desirable, from the standpoint of processing and expense, to obtain a stable and free flowing powder composition comprising an elastomeric polymer and a plasticizing oil that can be stored.

The aim of the present invention to provide such a stable free flowing powder composition comprising an elastomeric polymer and plasticizing oil, which can be stored without problems. Also the aim of the present invention to provide a freely flowing composition, which can respectively plaetse development of a method for producing stable, free flowing powder composition, which is easy to carry out and which is efficient from an economic point of view. The aim of the present invention to provide a homogeneous layer of the free flowing powder composition, which can be applied accordingly as the basis of the carpet.

Thus, the present invention relates to free flowing powder composition with a particle size of 800 μm or less, containing:

(a) 100 wt. parts of blockcopolymers containing monovinylacetylene hydrocarbon in the range of 10-60 wt.% calculated on the total weight of blockcopolymer;

(b) 30-200 wt. parts plasticizing oil;

(C) 5-200 wt. resin parts that are compatible with the block poly(monovinylacetylene hydrocarbon); and

(d) 0.1 to 10 wt. % of the total weight of the composition outrivaled means consisting of a fine powder, the average particle size is in the range from 1 nm to 100 μm.

The expression "free flowing powder composition," as it is used everywhere in this description, means the powder, the particles of which consist of a composition containing at least components (a) to(g), as defined above, and do not attach to each other.

In principle, as blockcopolymer you can use any block copolymers containing at least one block of poly(moulinrouge aromatic hydrocarbon) and at least one block of hydrogenated or dehydrogenation poly(with Arnim impact and resistance to oxidation, the preferred selectively hydrogenated block copolymers. This is desirable when, for example, provides for processing of the finished product by heating for secondary use. On the other hand, dehydrogenation the copolymers may be preferred for less demanding applications.

Block copolymers may be linear, radial or star-shaped structure. One preferred type of blockcopolymer is a linear block copolymers containing two terminal block poly(moulinrouge aromatic hydrocarbon) and one middle block poly(conjugated diene). Another preferred type of blockcopolymer is a radical block copolymers of the General formula:

(AB)n(B)m>X

where: A - block poly(monomineralic aromatics), B - block poly(conjugated diene), X is the remainder of the binder, and n and m are integers from 0 to 30. In addition to the main monomer of the polymer blocks A and B may contain small amounts, i.e. up to 20% by weight, but preferably less than 10 wt.% one or more other monomers that can be copolymerizable with the main monomer. Other relevant types of copolymers are those kotadia as monomineralic aromatic hydrocarbon, and conjugated diene, and the content of one of these monomers is increased gradually in one direction. It is also possible to use mixtures of different block copolymers, for example, a mixture of copolymers AB/ABA with values A and B, defined above. For all types of copolymers preferably as a block of poly(moulinrouge aromatic hydrocarbon) was a polystyrene block, and the block poly(conjugated diene) was polybutadiene or branch, Rubezhnoe, Ukraine bloc.

The apparent molecular mass of blockcopolymer, i.e. molecular weight, determined by chromatography on a permeable gel using methods of calibration polystyrene may vary in a wide interval in the range from 25,000 to 1,000,000, preferably 50000-500000. In the case of copolymers branched chain or a star structure, the apparent molecular mass can exceed 1000000.

In General, the copolymers can be obtained by any known polymerization method, for example, by the methods disclosed in U.S. patents NN 3322856, 3231635, 4077893, 4219627 and 4391949.

Examples of commercially available block copolymers that can be used in the powder composition in solarola - butadiene-styrene) and CARIFLEX-1107-TR (linear block copolymers of styrene-isoprene-styrene). CARIFLEX is a trademark. An example of a suitable blockcopolymer styrene-isoprene with many branches is the block copolymers KRATON D-1320X (KRATON is a trademark). Examples of commercially available selectively hydrogenated block copolymers are KRATON G-1650, 1651 and 1652 (all of them are linear copolymers of styrene-ethylene/butylene-styrene). As plasticizing oils can be used mineral oil as naphthenic and paraffinic oils, or polibutilenovye polymers with low molecular weight. Examples of appropriate plasticizers are SHELLFLEX 371 and 451, CATENEX 956 and TUFFLO 6204 (naphthenic oil), TUFFLO 6056 (paraffin oil) and polybutylene HYVIS 200, NAPVIS 30, NAPVIS D-10 and EZL 675. SHELLFLEX, CATENEX, TUFFLO, HYVIS, NAPVIS - brand. Also very useful products are products on the basis of poly-olefin, for example, ETHILFLO (ETHYLFLO - trade mark), as well as other commercially available plasticizers, e.g., REGALREZ 1018 (trade mark), ONDINA 68 (trade mark) and V OIL-7047 (trade mark). The plasticizer is used preferably in an amount of from 50 to 200 phr, and preferably 100 to 150 phr. The abbreviation "phr" means wt.part./100 wt. frequent. rubber, i.e. blockcopolymer.

The plasticizing oil is required to obtain a powder, Koti smooth surface.

As the resin that is compatible with poly(monovinyl aromatic hydrocarbon) is usually referred to as a resin that is compatible with the terminal block, it is possible to use any resin known as suitable for this purpose. Particularly suitable resins that are compatible with terminal blocks include a resin with a low molecular weight, mainly those derived from alpha-methylsterol. An example of such a resin that is missing is KRISTALEX 3115 (original KRISTALEX F-120; KRISTALEX - brand). Other examples include Kumanovo-indene resins, phenolaldehyde and aromatic resins in General or light or shatter-resistant resin PS(TPS 476 ex BASF). The resin that is compatible with the terminal blocks, the use of 50-200 wt. frequent. /100 wt.frequent. blockcopolymer, preferably in an amount of about 70-120 wt.part./100 wt.frequent. blockcopolymer.

Optimouse tool is a very fine powder, i.e. a powder which has an average particle size in the range between 1 nm and 100 μm, preferably 5 nm and 10 μm. In principle, you can apply any powder fine grinding, but it is preferable to use a powder of silicon dioxide or calcium carbonate. Examples are available in progestin 12 nm), SUPERNAT, DUROSIL, DUREX, ULTRASIL, DURCAL 5 (average particle size = 6 μm) and MILLICARB (average particle size = 3 μm) are examples of commercially available powders of calcium carbonate. Optimouse tool used in an amount of 0.1-10% by weight, preferably 1-5 wt.% on the basis of the total weight of the composition.

In addition to the described components of the free flowing powder composition in accordance with the present invention may optionally include up to 500 wt. often., preferably 50-300 wt.often., and best of 100-250 wt.frequent. filler/100 wt.frequent. blockcopolymer. As filler, you can use any filling material, known in the art. Appropriate fillers include calcium carbonate, aluminum silicate, clay, talc, silica, etc. are Also very useful are secondarily crushed polymer waste, for example, vulcanized rubber powder, recycled polyurethane or carpets. As a material particularly suitable filler are calcium carbonate, aluminum oxide (alumina), magnesium hydroxide, barium sulfate and silicon dioxide. Of these the most preferred are calcium carbonate and silicon dioxide.

Svobodoval. The presence of blowing agent in ready free flowing powder compositions may be desirable if the powder composition should be applied as the basis of the carpet. If the base of the carpet should be soft and flexible than is commonly practiced in the manufacture of carpets, then apply the foam or porous basis for carpet. To obtain such a foamed or porous carpeted framework requires the presence of a blowing agent in the composition for the base of the carpet. Typically, the blowing agent decomposes above a certain temperature, it releases a gas, such as nitrogen, which causes an increase in the reaction mass. The temperature at which the blowing agent begins to decompose, will be referred to as the activation temperature. In General, the known gas-forming means are, for example, compounds based azodicarbonamide and diphenyloxide-4,4'-disulfohydrazide. The last commercially available under the trademark GENITRON OB (GENITRON is a trade mark), and connection-based azodicarbonamide are available under the trademark GENITRON EPE, EPA, EPB. If at all it is present, the gas-forming agent may be present in free-flowing powder compositions in number In addition to the described components may also be present other known ingredients, for example, antioxidants, stabilizers, ultraviolet radiation, additives reduce friction additives that increase the resistance, etc. Such ingredients are only present in small amounts, i.e. up to 2 wt.% based on the total weight of the composition. In this connection it should be noted that some of the above inorganic fillers may also have properties to improve the fire resistance and hence they may be present in quantities greater than 2 wt.%.

The present invention also relates to a method of obtaining a free flowing powder composition, as described, and in the process:

mixed in the molten state, all the components present in freely flowing powder compositions, except outrivaled funds or outrivaled funds in a mixture with a blowing agent, followed by cooling;

granularit or receive in the form of balls composition formed at the previous stage;

cryogenic milled granules or beads formed at the previous stage; and

mix dry optimouse tool or optimouse tool in a mixture with a blowing agent with the powder form is Lonnie composition, containing copolymers moulinrouge aromatic hydrocarbon and a conjugated diene, as well as components that soften block copolymers, for example, plasticizing oils and resins that improve the adhesiveness. In General believed that because of the presence of oil, the powder particles are unstable and have a tendency to grip each other, making it difficult to obtain a stable free flowing powder compositions that can be stored for an extended period of time. It has been unexpectedly discovered that it is possible to obtain a stable free flowing powder composition containing block copolymers and oil. To obtain such a stable powder it is important that after cryogenic grinding was added optimouse tool. Without connection with any theory we believe that the very small particles outrivaled means are attached to the surface of the powder particles formed by cryogenic grinding, thus preventing the powder particles adhere to each other.

Cryogenic grinding of pellets or balls of the previous step can be performed by known methods cryogenic grinding, in which the cooling medium is often used liquid and the or freon as a cooling medium.

Free flowing powder in accordance with the present invention can be applied to form a homogeneous layer having a smooth surface. To obtain such a layer, you must first apply a dry free flowing powder on an appropriate basis as a layer. Upon exposure to heat, the powder particles are melted and formed a homogeneous layer. If you want foamed layer, it is necessary blowing agent. As already noted, the blowing agent decomposes above its activation temperature. Because the components of the powder composition are first mixed in the molten state, i.e. at elevated temperature, which is above the melting temperature components of gas-forming means adds only in the form of powder after cryogenic grinding and just mixed in dry form with the powder formed in the cryogenic grinding. Otherwise it will decompose during the stage of mixing in molten form. Thus, if in the final powder is present blowing agent, and this powder is heated to a sufficiently high temperature, the powder particles are melted, and at the same time wspanialy the tool is not used. If the blowing agent is present in the powder composition, it is possible to obtain a homogeneous layer having a low density, for example, 0.5 g/cm3. It is very low for compositions containing elastomeric copolymers and oil. Thus, the present invention also encompasses a homogeneous layers, obtained by fusion described freely flowing threshold composition. Preferably, the melting freely flowing powder composition is achieved by heating the layer composition. The preferred method of heating is the impact on the unmelted powder composition to infrared radiation. However, it is possible to apply other methods of heating, for example, flame spraying or contacting hot products with powder to melt the powder particles on the surface of the product. In the latter method of heating will be very useful ways of molding with the use of fluidized bed, forming filled with slow rotation of the form.

It is clear that the carpet, which consists of a homogeneous layer formed from a freely flowing powder compositions, and other molded articles containing a layer of molten freely flowing the diamonds of the present invention.

The invention will be illustrated in the following examples.

Example 1.

Composition consisting of:

100 frequent. by weight (wt.part./100 wt.frequent. blockcopolymer) KRATON - 1652;

140 frequent. by weight of oil (PRIMOL 352);

100 frequent. mass KRISTALEX 3115;

200 wt.frequent. filler of calcium carbonate (DURCAL 5);

1 wt.frequent. antioxidant (IRGANOX 1010) and

1 wt. frequent. additives, reducing friction (KEMAMIDE E) was prepared by mixing the dry components and then extruding the mixture in a twin-screw extruder at a temperature of between 140 and 190oC. the Composition was cooled and then it was granulated. DURCAL, IRGANOX, KEMAMIDE - brand.

Then granulated cryogenic composition was ground in an impact mill fine grind ALPINE 160 UPZ. First granules made fragile by placing them in a bath of liquid nitrogen and then they had passed through the mill, which was cooled to - 95oC. the obtained powder was 98.2 wt.% which had a particle size of less than 500 microns, and to 88.7 wt.% had a size of less than 315 μm (determined by the screen method, with the use of an air jet, ALPINE 200 LS). After drying powder for 60 minutes without heating in polymer dryer RETSCH received a fine powder grinding.

ZAT is the first free flowing powder was stable and showed no adhesion of the powder particles even after storing it within 8 weeks.

Free flowing composition was molded to obtain a sheet and heated in an oven under vacuum at a temperature of 180oC for 10 minutes to education related sheets with smooth surfaces.

From these sheets cut out circles for the measurement of mechanical properties. The ultimate tensile strength and elongation at break were determined in accordance with ASTM D412. The speed of the RAM was 500 mm/min

The results:

Ultimate tensile strength: 1.8 MPa

Elongation at break: 240%

Stress at elongation at 100%: 1.2 MPa

Hardness shore A (0 sec): 53,5

Hardness shore A (23 sec): 49,5

Example 2.

Prepared as described in example 1, free flowing composition comprising:

100 wt. frequent. KRATON - 1652;

140 wt. frequent. paraffin oil (CATENEX 956);

100 wt.frequent. KRISTALEX 3115;

200 wt.frequent. filler of calcium carbonate;

11 wt.frequent. outrivaled funds (AEROSIL 200);

1 wt.frequent. antioxidant (IRGANOX 1010) and

1 wt.frequent. additives, reducing friction (KEMAMIDE).

Free flowing powder was stable and showed no melting of the powder particles even after storage for 8 weeks.

With the e approximately 45 seconds by infrared heating. After cooling, the obtained flexible framework carpet with a smooth surface, which showed good consolidation of the pile loops.

Example 3.

Free flowing composition comprising:

100 wt.frequent. CARIFLEX TR 1102;

140 wt.frequent. paraffin oil (CATENEX 956);

100 wt.frequent. CRISTALEX 3115;

200 wt.frequent. filler of calcium carbonate;

11 wt.frequent. outrivaled funds (AEROSIL 200);

1 wt.frequent. antioxidant (IRGANOX 1010) and

1 wt.frequent. additives, reducing friction (KEMAMIDE E) was prepared in the same manner as in example 1 except that, together with outrivals means added 11 wt.frequent. blowing agents (GENITRON EPE).

Free flowing powder was stable and showed no melting of the powder particles even after storage for 8 weeks.

The dry powder was molded layer 1200 g/m2and was heated at a temperature of 190-200oC for 5 minutes in the oven. The result was a well-linked and foamed microequity sheet having a density of 0.5 g/cm2.

Example 4.

Free flowing composition comprising:

100 wt.frequent. CARIFLEX TR-4271;

5 wt.frequent. high impact polystyrene (TPS 476);

30 wt.frequent. paraffin Mas TINUVIN P;

1 wt.frequent. additives, reducing friction (KEMAMIDE);

11 wt. frequent. outrivaled funds (AEROSIL 200), prepared as described in example 1. Free flowing powder was applied on a polyester (or polyamide) fabric was heated and fused in a furnace at a temperature of 160oC and for 5 minutes.

1. Free flowing powder composition with a particle size of 800 μm or less, containing block copolymers containing at least one poly(monovinylacetylene hydrocarbon) block, at least one block of hydrogenated or negidrirovannogo poly(conjugated diene), plasticizing oil, resin, compatible with the block poly(monovinylacetylene hydrocarbon), and optimouse means, characterized in that the free flowing powder composition comprises 100 wt.h. blockcopolymer containing monovinylacetylene hydrocarbon in the range from 10 to 60 wt.% calculated on the total weight of blockcopolymer; 30 to 200 wt.h. plasticizing oil, 50 to 200 wt. including resin, compatible with the block poly(monovinylacetylene hydrocarbon), and 0.1 - 10 wt.% from the total mass of the composition outrivaled means consisting of a fine powder, the average particle size is in the range from 1 nm to 100 μm.

2. the th block copolymers, consisting of two end blocks of poly(monovinylacetylene hydrocarbon) and one middle block poly(conjugated diene).

3. Free flowing powder composition under item 1 or 2, characterized in that the plasticizing oil is present in amounts of 100 to 150 wt.h.

4. Free flowing powder composition according to any one of paragraphs.1 to 3, characterized in that the resin that is compatible with the block poly(monomineralic aromatic hydrocarbon), is present in the amount of 70 to 120 wt.h.

5. Free flowing powder composition according to any one of paragraphs.1 to 4, characterized in that outrivals tool is present in quantities of 1 to 5 wt.% based on the total weight of the composition.

6. Free flowing powder composition according to any one of paragraphs.1 to 5, characterized in that it additionally contains up to 500 wt.h. the filler.

7. Free flowing powder composition according to any one of paragraphs.1 - 6, characterized in that it additionally contains up to 3 wt.% blowing agents based on the total weight of the composition.

8. A method of obtaining a free flowing powder composition according to any one of paragraphs. 1 to 7, characterized in that the mixing in the molten state, all the components are present in free acocella, with further cooling, granularit or receive in the form of balls composition formed at the previous stage, cryogenic milled granules or beads formed at the previous stage, and mixed in dry form optimouse tool or optimouse tool in a mixture with a blowing agent powder generated at the previous stage.

9. Homogeneous layer obtained by melting a freely flowing powder composition according to any one of paragraphs.1 - 7.

10. Homogeneous layer under item 9, characterized in that the melting freely flowing powder compositions reach by heating the layer composition.

11. Homogeneous layer on p. 10, characterized in that the heating is performed by the impact on the unmelted powder composition to infrared radiation.

12. Carpet, characterized in that the core consists of homogeneous layer according to any one of paragraphs.9 - 11.

13. Conveyor belt, characterized in that it contains a homogeneous layer according to any one of paragraphs.9 - 11.

14. Sealant for caps of bottles, characterized in that it contains a homogeneous layer according to any one of paragraphs.9 - 11.

 

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