Composition based polyolefin and a molded product made from the composition

 

(57) Abstract:

Describes a new composition for the manufacture of products with a shiny surface containing at least one polyolefin and one silicone, characterized in that the polyolefin has a molecular weight distribution corresponding to the ratio of Mw/Mnequal to from 5 to 12, and a silicone having a viscosity of from 500 to 300000000 cSt, is in the amount of 0.08 to 10 wt.%. Also described molded product made of this composition for food packaging. The technical result - the creation of a new composition having good properties for application and allowing to produce brilliant products. 2 c. and 5 C.p. f-crystals.

The invention relates to compositions based on polyolefin, in particular to such compositions which, in addition, includes silicone. It also relates to articles molded from this composition.

It is well known that in order to facilitate the application of polyolefins, such as polypropylene or polyethylene, there include one or more additives, such as fluorinated polymer such as polyvinylidene fluoride) or silicone. In fact, in the European patent 0158140 has already been suggested getting captured is nymi mechanical and optical properties.

It is now established that some of these known compositions do not allow to produce products that have a shiny surface.

The invention avoids this drawback by using a new composition having good properties for application and allowing to produce brilliant products. In particular, according to the present invention features a composition used for the manufacture of food packaging.

Therefore, the present invention relates to compositions comprising at least one polyolefin and at least one silicone and polyolefin has a molecular weight distribution corresponding to the ratio of Mw/Mnthe maximum is 12.

The ratio of Mw/Mnrefers to the ratio between srednevekovoi molecular weight (Mw) polyolefin and srednetsenovoj molecular weight (Mn) polyolefin.

The ratio of Mw/Mnis measured by spatial exclusion chromatography implemented in 1,2,4-trichlorobenzene at 135oC chromatograph company BOTEPC type 150C.

The composition according to the invention contains on the edge of the mi methods. Examples used according to the invention polyolefins are polymers of olefins containing up to 20 C-atoms, preferably 2 to 12 C-atoms, in the molecule, such as ethylene, propylene, 1-butene, 1-penten, 3-methyl-1-butene, 1-hexene, 3 - and 4-methyl-1-pentene, 1-octene, 3-ethyl-1-butene, 1-hepten, 3,4-dimethyl-1-hexene, 4-butyl-1-octene, 5-ethyl-1-mission and 3,3-dimethyl-1-butene. The preferred polyolefins are polyethylene and polypropylene. Needless to say that the composition according to the invention may include multiple homopolymers.

The polyolefin compositions according to the invention may also be a copolymer of olefin such as specified above, at least one olefinonesaturat the co monomer. Examples olefineverbund of comonomers used in polyolefins according to the invention are substituted or unsubstituted olefins containing up to 8 C-atoms, such as 1-butene, 1-penten, 3-methyl-1-butene, 1-hexane, 3 - and 4-methyl-1-pentene and 1-octene, and diolefin containing 4 to 18 C-atoms. Especially recommended are the copolymers of ethylene and/or propylene. The comonomers of ethylene is most often chosen from propylene, 1-butene, 1-hexene and 1-octene. Preferred is I, can contain multiple copolymers, such as those listed above.

Particularly preferred polyolefins are Homo - and copolymers of ethylene.

The composition according to the invention may also include one or more homopolymers and one or more copolymers, such as described above.

Polyolefins, leading to satisfactory results are those that have a standard density at least equal 0,920 g/cm3preferably 0.930 g/cm3most common are the values below or equal to 0,970 g/cm3for example 0,965 g/cm3. Especially recommended values 0,920 - 0,970 g/cm3. Preferred standard densities are 0,935 - 0,955 g/cm3.

Polyolefins are typically flow index, measured at 190oC under a load of 2.16 kg according to the standard ACTMD 1238 /1986/ at least 0.05 g/10 min, in particular at least 0.1 g/10 min, with the most preferred value at least equal to 0.2 g/10 min. flow Index is typically less than 10 g/10 min, mostly it is at most 5 g/10 min, and the recommended value of at most 1 g/10 MIA narrow molecular weight distribution polyolefin, determined by the ratio of Mw/Mnbelow or equal to 12, preferably 10, the ratio of Mw/Mnusually higher than or equal to 3, with the usual amount at least equal to 5. The ratios of Mw/Mnabout 8 good fit.

The composition according to the invention includes, in addition, silicone. Used silicone can have, for example, macromolecules, formed by units of General formula

< / BR>
in which R' and R" each represent a hydrocarbon group which may be linear or cyclic, saturated or unsaturated, aromatic or aliphatic, unsubstituted or partially or fully substituted and which, if necessary, may include another element, such as oxygen or nitrogen. Especially recommended hydrocarbon groups are aliphatic, linear saturated alkyl groups. As example can be mentioned: methyl, n-propyl, isopropyl, N-butyl, tert-butyl, pentyl and hexyl. Macromolecules, of course, can consist of several different parts. Typical examples of the silicone, leading to satisfactory results are polydimethylsiloxane and silicones, which correspond to the following formula:

< / BR>
< / BR>
in which R1, R2, R3, R4, R5, R6, R7, R8and R9each represent an alkyl radical,

R is a hydrocarbon radical containing at least one apachegroup or tertiary amino group,

"x" 1 and y" 1.

The values "x" and "y" depend on the viscosity of the silicone. Usually "x" and "y" do not exceed 200.

Preferably use silicones, such as defined above, in which the group R1, R2, R3, R4, R5, R6, R7, R8and R9denote alkyl radicals containing up to 6 C-atoms. Especially preferred derivatives of polydimethylsiloxane in which the group R1, R2, R3, R4, R5, R6, R7, R8and R9represent a methyl group.

The silicone in the composition according to the invention can be obtained, for example, according to the method described in European patent 0158140.

Preferred are silicones, which have a viscosity at least equal to 500 cSt, in features 1000 cSt, with the most preferred value at least equal to 30,000 cSt, but recomende 500-10000000 cSt. Particularly satisfactory results are obtained when using silicones with a viscosity 1000-2000000 cSt. Under viscosity understand the kinematic viscosity, measured at 25oC.

In the composition according to the invention, the optimum amount of silicone mixed with the polyolefin, depends on the viscosity of the silicone and the required degree of gloss. In fact, the minimum required number of low-viscosity silicone to get shiny surfaces, while maintaining a fully good properties in use, above the number required in the case of very viscous silicones. The weight amount of silicone is usually higher than or equal to 0.08 wt.% based on the weight of polyolefin, in particular at least equal to 0.2 wt.% based on the weight of the polyolefin, it is usually lower than or equal to 20%, preferably 10% by weight of the polyolefin. Especially recommended values of 0.08 - 10 wt.%. The most preferred values, the maximum is equal to 2% by weight of the polyolefin, for example 1%.

The composition according to the invention may include individual silicone or mixture of silicones.

In addition to the polyolefin and silicone composition according to the invention can also contain conventional additives, such as stabilizers (EmOC is the cue dyes (such such as titanium oxide or iron oxide) or antistatics. The content of these various additives are usually below 10 weight. parts per 100 weight. parts of polyolefin.

Preparation of compositions according to the invention can be accomplished by any known means of technology. A particularly simple method involves mixing in a dry state in the desired quantities of the various components, for example in a mechanical mixer.

It is also possible to prepare initially a primary mixture, called uterine mixture containing a proportion of polyolefin, silicone, and, if necessary, additives such as those mentioned above, and this Royal blend enriched with silicone. The content of silicone in this masterbatches is usually 0.05 to 50 wt.%, preferably 0.5 to 40 wt.%, mostly 1 to 30 wt.% in the calculation of the mixture. Particularly preferred mixtures containing 2 to 25 wt.% the silicone. This uterine mixture is then mixed with the rest of the shares of the polyolefin during the manufacture of the molded product to obtain a composition according to the invention.

If necessary, you can heat the silicone to mix it in a liquid state with the polyolefin, which is usually in powder form.

The ratio between realizowane.

The composition according to the invention is suitable for the manufacture of products from plastics using in any classical way, and mainly the way of extrusion, extrusion with subsequent blowing, extrusion and subsequent thermoforming and injection. It is suitable for the manufacture of molded products, the surface of which has a superior Shine, such as films, sheets, plates, tubes, bags, packages or tube. Taking into account its non-toxic properties, the composition according to the invention are particularly well suited for the manufacture of molded articles intended for packaging of beverages and foods, such as vessels, films and sheets.

The present invention also relates to articles molded from the composition according to the invention, in particular to the products obtained by extrusion, extrusion with subsequent blowing, extrusion and subsequent thermoforming or injection, such as products used as food packaging.

An unexpected advantage of the molded products according to the invention is their shiny surface. In addition, molded articles according to the invention have a smooth surface, devoid of the antibody to illustrate the invention. In these examples, the prepared composition based on polyethylene according to the invention, of which then produce the bottles. The meaning of the symbols used in these examples, the units in which are expressed the above values, and ways of measuring these values is explained below. Mw/Mn= the ratio between srednevekovoi molecular weight (Mw) polyethylene and srednetsenovoj molecular weight (Mn) polyethylene, as measured by spatial exclusion chromatography implemented in 1,2,4-trichlorobenzene at 135oC chromatograph firm WOUTERSE type 150 C.

SPP = standard density polyethylene, expressed in g/cm3and measured according to the standard ISO 1183 /1987/.

IL = melt index of the polyethylene, expressed in g/10 min measured at 190oC under a load of 2.16 kg according to the standard ACTMD 1238 /1986/.

Example 1 (according to the invention).

In a rotary mixer for about 7 minutes and at a speed of 720 rpm./min at room temperature to prepare the uterine mixture containing:

94,87 weight. % polyethylene (containing 0.6 wt.% butene) having a ratio of Mw/Mn= 10,4, SPP = 0,952 g/cm3and IL = 0.6 g/10 min,

5 wt.% silicone BAYS IL ON ,

0,04 IP(2,4-di - tert-butyl)-pentaerythritol-diphosphite],

0.05 wt.% stabilizer (hydrocalc).

Uterine mixture then granularit in the extruder at 190oC. the Thus obtained pellets in a rotary mixer for about 7 minutes and at a speed of 420 rpm at room temperature is mixed with the above-mentioned polyethylene with obtaining a composition containing 0.1 wt.% silicone, and with the above-mentioned stabilizers, taken in such quantities that their concentrations were, respectively, 0.04 wt.%, 0.04 wt.% and 0.05 wt.%. Then by extrusion with subsequent blown produce bottles with a capacity of 1 L. the resulting vials have a shiny surface.

Example 2 (according to the invention).

Repeat the operation of example 1 with polyethylene (containing 0.6 wt.% butene), with Mw/Mn= 6,8, SPP = 0,936 g/cm3and IL = 0.6 g/10 min.

Received the bottles have a shiny surface.

1. The composition for manufacturing products with a shiny surface containing at least one polyolefin and one silicone, characterized in that the polyolefin has a molecular weight distribution corresponding to the ratio of MW/Mnequal to from 5 to 12, and a silicone having a viscosity of from 500 to 300000000 cSt, nahodil ethylene copolymer.

3. Composition under item 1 or 2, characterized in that the polyolefin has a density standard, 0,920 - 0,970 g/cm3.

4. Composition according to any one of paragraphs.1 to 3, characterized in that the silicone meets the General formula:

< / BR>
where R1, R2, R3, R4, R5, R6, R7, R8and R9each denote an alkyl radical;

R is a hydrocarbon radical containing at least one apachegroup or tertiary amino group;

x 1 and y 1.

5. The composition according to p. 4, characterized in that the alkyl groups of R1, R2, R3, R4, R5, R6, R7, R8and R9represent a methyl group.

6. Molded product with a shiny surface, designed for packaging of food products, characterized in that it is made from the composition according to one of paragraphs.1 - 5.

7. The moldings on p. 6, characterized in that it is obtained by extrusion, extrusion with subsequent blowing, extrusion and subsequent thermoforming or injection.

 

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FIELD: polymer materials.

SUBSTANCE: invention relates to stabilizer mixture used for stabilizing polyolefin against destruction initiated by visible light, heat, or oxidation and to thus stabilized polyolefin. Stabilizer mixture comprises spatially hindered amine compound and polymer containing polar residues, weight ratio of the two compounds being between 20:1 and 1:20, respectively, provided that (i) polymer cannot be the same compound as hindered amine compound and does not contain groups of formula (1) or (II): . Where G represents hydrogen atom or methyl and G1 and G2, independently of each other, each represents hydrogen atom or methyl or they together form =O; and (ii) polymer cannot contain acidic hydrogen atom.

EFFECT: considerable increased efficiency of stabilizer composition.

22 cl, 4 tbl, 4 ex

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