Impact-resistant composition

 

(57) Abstract:

Use: in the manufacture of plastics. Essence: impact-resistant composition comprises a graft copolymer of polypropylene grafted with one or more vinyl monomer (10 - 88 wt.%), at least one rubber (2 to 40 wt.%) and polypropylene with a wide range of molecular weight (the rest up to 100%). The graft-copolymer is a polymer selected from the group comprising a homopolymer of polypropylene, a statistical copolymer of propylene with ethylene or an olefin C4- C10statistical trimer of propylene with ethylene and a-olefin, C4- C10statistical trimer of propylene with ethylene and a-olefin, C4- C10to which is grafted at least one vinyl monomer selected from the group comprising styrene, methyl methacrylate, a mixture of styrene and methylacrylate, a mixture of styrene and Acrylonitrile, a mixture of styrene, methyl methacrylate and Acrylonitrile. Polypropylene with a wide range of molecular weight is a homopolymer of propylene or polypropylene with a wide range of molecular weight-modified impact-resistant ethylene-propylene rubber. The rubber part of the composition, presented the s, selected from ethylene, propylene or butene and possibly diene with non-conjugate double bonds, one or more block copolymer monoalkyl aromatic hydrocarbon and a conjugated diene or a product of hydrogenation of the copolymer, the graft copolymer of propylene polymer grafted polymerized monomer or mixture of monomers that upon polymerization form a rubber polymer with a glass transition temperature below 20oWith mixtures of these compounds. The composition may further contain 10 to 100 wt.h. on 100 wt.h. the composition of the filler with a particle size of 0.5 to 4.0 μm, selected from the group comprising talc, calcium carbonate, silicate, a mixture of these fillers. 11 C.p. f-crystals, 16 PL.

The invention describes compositions comprising a graft copolymer, propylene polymer, a rubber component, the filled composition containing specified substance and the filler, in particular the composition of the graft copolymers modified with toughness, comprising the graft copolymer of propylene polymer, at least one propylene polymer with a wide range of molecular weights and at least one rubber component, and a composition containing the above components and order the ETUI polymer, represent an interesting class of polymeric hybrids possessing qualities as a graft-copolymer and the basic polymer, and not just some average properties characteristic components of these copolymers. Compared with physical mixtures of polymers, graft copolymers due to the chemical bonds between the molecule segments usually have a more subtle heterogeneous phase morphology in which the domain size of the dispersed phase is stable and can be much less. In addition, improves the adhesion between the phases. Physical mixtures of immiscible polymers, such as polypropylene and polystyrene, require the inclusion of agent compatibility /"part-time"/, for example, the corresponding block copolymer, which allows to mitigate the problems associated with high interfacial tension and poor adhesion between immiscible polymers in the mixture. Physical mixtures of polypropylene and polistirolo containing small amounts of styrene block-copolymer rubber as agent for ensuring the compatibility of the polymers in the mixture, described in U.S. patent N 4386187.

Structural plastics, based on the "chemical" mixture of the polymerized propylene and mo is the main propylene polymer, allows you to solve a number of problems in the art, since these plastics have a number of advantages due to the fact that the fine structure of the domain and good interphase adhesion between the propylene polymer and the polymerized monomer are provided with the chemical bonds in the graft-copolymer and does not depend on the actions of an external agent, i.e. the agent compatibility. However, to date the use of the graft copolymers was limited: they are used mainly as agents, ensuring the compatibility of immiscible polymer systems and as components of plastics based on resins.

In U.S. patent N 3314904 describes a method for "resinous plastic, including the production of grafted copolymer by inoculation of styrene on polyethylene or polypropylene, in particular the production of grafted copolymer of styrene, Acrylonitrile, and polyethylene or polypropylene, as well as mixing the grafted copolymer compatible with certain resins. The content of grafted styrene or styrene-Acrylonitrile in grattapaglia was 75-95%, preferably 85-95%, preferably 90-95%. Thus, the grafted copolymer is a main the flax is only a minor component, present in the dispersed phase. Therefore, this substance is dominated by the properties of the styrene or styrene-Acrylonitrile. In the manufacturing process of the grafted polyolefin copolymer is subjected to ionizing radiation is high-energy, and then interact irradiated polyolefin with styrene or styrene and Acrylonitrile.

However, in order to use grattafiori of the polymerized monomer/s/, grafted on the main chain of the propylene polymer, as an independent structural plastics, having the properties of propylene polymers (for example, excellent chemical resistance, good moisture resistance, etc.,), these graft copolymers should have such a heterogeneous morphology, in which the propylene polymer is a continuous phase. This means that the content of the polymerized monomer/s/ in the graft-copolymer should not exceed about 65 wt.%, but it should be high enough to increase the rigidity of the propylene polymer to the desired degree.

The advantages of the graft copolymers polymerized monomer/s/, grafted on the main chain of the propylene polymer, over physical mixtures of polymers based on how is possible to use, if it is better to balance the properties of the graft copolymers.

Attempts to improve this balance has led to the creation of a variety of compositions. For example, in U.S. patent N 4990558 described hard thermoplasty composition based grattapaglia, comprising: from 60 to 95 wt.% the graft-copolymer of styrene polymer grafted to the main chain of the propylene polymer; b) from 5 to 40 wt.% the rubber component includes /1/ 20 to 100 wt. % (i) at least one block copolymer monoalkyl aromatic hydrocarbons and dienes with conjugated double bonds (ii) at least one block copolymer, which is a product of hydrogenation of the copolymer (i) or (iii) a mixture of at least one of (i) at least one (ii); (2) from 0 to 80 wt.% rubber-based olefin copolymer, i.e., rubber-based copolymer of ethylene, propylene and diene monomer or static copolymer of ethylene with propylene. In U.S. patent N 4957974 described mixture having a high melting point and consisting of a polyolefin and a graft-copolymer comprising non-polar polyolefin and at least 80% of the monomer methacrylic ester, and from less than 20% acrylic or styrene monomer, and from 0.2 to 10% of all polymer. In U.S. patent N 07/860864, registered on March 31, 1992, described thermoplastische composition consisting of: propylene polymer grafted polymerized monomer/AMI/ hard polymer/s/, with Tcabove 80oC; b/ propylene polymer to which is grafted polymerized monomer/s/ soft polymer/s/, with Tcbelow are the 20oC, and optionally in at least one of the rubber modifier.

However, even after improved balance of properties remains a contradiction between material stiffness and impact strength. In other words, if you increase the force of impact is reduced modulus.

Closest to the technical essence is impact-resistant composition according to the U.S. patent N 4990558.

An object of the invention is to obtain compositions with modified impact strength, which would have the best balance between impact strength and rigidity and at the same time not too dropped their modulus.

It was found that in order to improve the balance between strength and stiffness in the compositions of the graft copolymers with a modified impact strength and not to reduce the module PLA is Ohm molecular masses. Thus obtained composition had improved balance between strength and stiffness without a significant reduction in modulus and maintaining the balance of other properties compared with the properties of the graft copolymers, individually or mixed with modified or unmodified rubber, as well as with conventional polypropylene.

The invention describes the composition of the graft copolymers with a modified impact strength, including /A/ 10 to 88 wt.% the graft-copolymer of propylene polymer to which is grafted one /or more/ vinyl monomer /B/ 2 to 40 wt.% at least one rubber component and (C) polypropylene with a wide range of molecular weight /the rest up to 100 wt.%).

The composition according to the invention may contain a filler, the composition has improved modulus, improved toughness specimen with notch /Izod/ and superior impact resistance of flat sample, and the composition includes the above composition with a filler, which can be used particles of mineral fillers, namely, talc powder, calcium carbonate and silicate fillers, as well as with the NAT calcium and calcium silicate give the plastics a certain degree of rigidity, this is usually achieved at the expense of the deterioration of impact strength and plastic elongation or ability to plastic deformation under tension. Compositions with fillers of the present invention contains from about 10 to 100 hours talc, calcium carbonate or silicate filler or mixtures thereof, having /when you wish/ shell of organic compounds per hundred parts of compositions, and in the specified filler, the average particle size is from 0.5 to 4.0 μm, by mixing the filler composition according to the invention are compositions with fillers having an improved balance of properties and improved impact strength and modulus. Data is hard and durable compositions with fillers can better be used as a material for the manufacture of casings for household appliances, parts for vehicles and for other purposes, i.e., where polymer materials are replaced or have to replace steel and aluminum.

Compositions or compositions with fillers, or composition of both types of the present invention can be used in the processes of injection molding, extrusion of profiled products or processes thermoforming melts or solid the research Institute of the parts in the present description is given in mass percent and mass parts.

The graft-copolymer of the component (A) is a material with the main chain of the propylene polymer to which is grafted one /or more/ vinyl monomer. Propylene polymer that forms the Foundation of the graft-copolymer, represents (i) a homopolymer of propylene, (ii) static copolymer of propylene and olefin selected from the group including ethylene and alpha-olefins, C4-C10provided that when the olefin is ethylene, the maximum content of polymerized ethylene is about 10%, preferably about 4%, and when the olefin is an alpha olefin C4-C10, the maximum content of polymerized material is about 20%, preferably about 16%, or (iii) statistical ternary copolymer of propylene and olefin selected from the group including ethylene and alpha-olefins, C4-C8provided that the maximum content of polymerized alpha-olefin C4-C8is about 20%, preferably about 16%, and when ethylene is one of the olefins, the maximum content of polymerized ethylene is about 5%, preferably about 4%, with a maximum content of co monomer 25%.

Alpha-olefin, 1-penten, 3-methyl-1-butene, 4-methyl-1-penten, 1-hexene, 3,4-dimethyl-1-butene, 1-hepten, 3-methyl-1-hexene, etc.

Statistical copolymers of polypropylene and ethylene-propylene are preferred major propylene polymers.

Suitable vinyl monomers which are grafted on the main chain of the propylene polymer include styrene, derivatives of styrene, methyl acrylate, acrylate, methacrylate, cyclohexylmethyl, fenilsalicilat, bezelmaterial, o-methoxyphenylacetate, Acrylonitrile, Methacrylonitrile, acrylic acid, methacrylic acid and mixtures of these substances.

Preference is given to styrene, methyl methacrylate, styrene/methyl methacrylate, styrene/Acrylonitrile and styrene/methyl methacrylate/Acrylonitrile.

From 10 to 90%, preferably from 10 to 75% compositions comprise graft copolymers of the component (A).

Component (C) is a propylene polymer with a wide range of molecular mass, with respect srednevekovoi molecular weight to srednekamennogo molecular weight of from 8 to 60, preferably from 12 to 40, with the fluidity of the melt from 0.5 to 50, preferably from 3 to 30, and the content is not soluble in xylene fractions at 25oC you what Ohm molecular masses may be a homopolymer of propylene or a propylene-rubber homopolymer of propylene with a modified toughness, moreover, the propylene homopolymer has a wide range of molecular masses.

The above propylene polymer with a wide range of molecular masses used in the present invention, can be prepared by sequential polymerization, carried out at least in two stages in the presence of a catalyst of Ziegler-Natta on the magnesium halide as a carrier, in the active form.

It is desirable that the catalyst contained as an essential element of a solid element of /a/ that includes a titanium compound with at least one titanium-halogen bond and connection, which is the electron donor, both compounds were present in the media, which is the halide in active form, and differ in that they are able to produce propylene polymers, which are insoluble in xylene at 25oC fraction is not less than 94%, preferably at least 96%, with sufficient sensitivity to molecular weight regulators, which gives you a propylene homopolymer having the fluidity of the melt is not more than 0.5 not less than 50 g/10 min.

Applied catalysts produced by the interaction of:

(a) above is juegos the electron donor.

The solid components of catalyst (a) having the above properties, are well known in the patent literature.

The most suitable are the solid components of catalyst used in the catalysts described in U.S. patent N 4339054 and Europatent N 45977. Other examples are found in U.S. patent N 4472524.

The solid components used in the above-mentioned catalysts include compound and a donor of electrons, compounds selected from ethers, ketones, lactones, compounds containing N atoms, P and/or S, and esters of mono - and dicarboxylic acids.

The most suitable are esters of phthalic acid, such as Diisobutyl, dioctyl and definiltely, and benzyl butylphthalate, esters of malonic acid, such as Diisobutyl and diethylmalonate, alkyl - and kilpivaara, alkyl-, cycloalkyl and animality, alkyl and arylcarbamoyl, such as Diisobutylene, ethylvinylbenzene and diphenylcarbonate, esters of succinic acid, such as mono - and diethylamine.

The preparation of the above catalysts produced using various methods.

For example, the magnesium halide /dry together under such conditions, when the magnesium halide is active. Milled product is then one or more times treated with TiCl4in excess of the concentration at temperatures from 80 to 135oC, and then washed several times with a hydrocarbon, such as hexane, to the complete disappearance of the chlorine ions.

According to another method, the anhydrous magnesium halide pre-activate one of the known methods, and then interact with TiCl4in excessive concentration, and the solution contains a compound which is a donor of electrons. In this case, as in the previous, the treatment is carried out at temperatures from 80 to 135oC. If desired, the processing of TiCl4repeat several times, and the solid product washed with hexane or other hydrocarbon solvent to remove all traces of unreacted TiCl4.

According to another method, the adduct MgCl2nROH (in particular) in the form of spherical particles), where typically n is from 1 to 3 and ROH is ethanol, butanol or Isobutanol, interact with TiCl4in excessive concentration, and the solution contains a compound which is a donor of electrons. The temperature is usually in the range from 80 to 120oC. Then the solid from the ka will not disappear all chlorine ions.

According to another method, the alcoholate and chloralkali magnesium /in particular, chloralkali prepared according to the method described in U.S. patent N 4220554/ interact with TiCl4in excessive concentration, and the solution contains a compound which is a donor of electrons, this interaction is carried out under the same conditions as in the above reactions.

In the solid component of catalyst /and/ compound of titanium, expressed as Ti, is usually present in the range from 0.5 to 10 wt.%. The number of connections, which is a donor of electrons, depends on the amount of solid component /internal donor/ and is usually from 5 to 20 mol.% from dihalogenide magnesium.

The titanium compounds which can be used to prepare solid catalyst component /a/ are the halides and halogen alcoholate. The preferred compound is titanium tetrachloride.

Satisfactory results can be obtained when using trihalogen of titanium compounds, in particular, TiCl3OR, where R is a phenyl radical.

The above reactions lead to the formation of magnesium halide in active form. In addition to these reactions in literatureto the original substances using compounds of magnesium, not being halides, such as carboxylates of magnesium /for example/.

Activated magnesium halides in the catalyst components and /a/ can be recognized due to the fact that in the x-ray spectrum of the catalyst component is no longer observed the reflection of the primary intensity, which is observed in the spectrum of the nonactivated magnesium chloride /having a surface area less than 3 m2/g/, instead, you receive the halo, and the maximum intensity is achieved in relation to the position of the main reflection intensity characteristic of the non-activated dihalogenide magnesium or due to the fact that the main reflection intensity has a width at half height of at least 30% greater than the width at half the height of the main reflection intensity, which appears in the spectrum of the nonactivated magnesium chloride.

The most active are those forms where the aforementioned halo appears on the x-ray spectrum of the component.

Among the magnesium halides preferred compounds are the chlorides. When applying the most active forms of magnesium chloride x-ray spectrum of the catalyst component shows a halo instead otragenie connection /b/ used as socialization, include Al-trialkyl compounds such as triethylaluminum, isobutylamine, tri-n-butylamine, and linear or cyclic Al-alkyl compounds containing two or more Al atoms attached through an O or N atoms or groups SO4and SO3.

Examples of such compounds are the following substances:

,

where

n is a number from 1 to 20;

Al - alkyl compound, usually used in such quantities that the ratio Al/Ti is in the range from 1 to 1000.

In addition to the solid catalyst component (a) and Al-alkyl compound (b), the catalysts contain the connection is//, which is the external electron donor, (i.e. electron donor added to the Al-alkyl compound). The specified connection, which is the external electron donor, which are selected from silanes, can give the catalyst above stereoregularity /defined high content of fractions, insoluble in xylene at 25oC, and the sensitivity to molecular weight regulators.

For this purpose, suitable silanes containing at least one cyclopentyloxy group associated with the silicon atom, and one or more group - OR, also associated with the silicon atom, and y-C18or aralkyl C7-C18. Preferably R represents methyl or ethyl. The most suitable is dicyclopentadienyliron (DCPMS). The above external donors are typically used in quantities of from 0.001 to 15 mol, preferably from 1 to 10 mol, depending on the molar concentration of the Al-alkyl compounds /b/.

Sequential polymerization is carried out in the presence of the above catalysts, and polymerization occurs at least in two stages, fraction (A) and (B) are prepared separately in the course of successive stages and each stage is carried out in the presence of polymer and catalyst coming from the previous stage.

The polymerization can be conducted intermittently or continuously in accordance with known technologies and in the liquid phase in the presence of an inert solvent or without him/ or in the gas phase or in the gas-liquid phase, preferably in the gas.

In reaction to the polymerization time and temperature are specifically mentioned, but it is preferable to conduct the polymerization at a temperature of from 20 to 100oC.

As stated above, the regulation of the molecular weight is carried out using known regulators, in particular STI preliminary polymerization/. The preliminary polymerization improves both the catalyst activity and the morphology of the polymer.

In the pre-polymerization catalyst must be in suspension in the solid hydrocarbon solvent (for example, hexane or heptane/, and the temperature of polymerization may be varied from ambient temperature to 60oC for a period of time sufficient for the formation of such a large number of polymer, which is greater than the mass of the solid component is 0.5 to 3 times. The preliminary polymerization can be carried out also in the liquid propylene at the above temperatures, the amount of the resulting polymer can reach up to 1000 g per 1 g of catalyst component.

Component (C) is present in an amount of from 90 to 10%, preferably from 20 to 75% of the total weight of the composition.

Rubber component (B) used in the composition of the present invention, can be either (i) one or more olefinic rubber series, containing two or more monomers selected from ethylene, propylene or butene, and optionally a diene with non-conjugate double bonds, (ii) one or more block copolymer monoalkyl aromatic uglevodorov ropranolol polymer, on which is grafted polymerized monomer or monomers which are polymerized in the form of form a rubber polymer(s) with Tgbelow are the 20oC, (iv) synthetic butyl rubber, (v) isoprene rubber, (vi) static copolymer of butadiene-styrene rubber or Acrylonitrile-butadiene rubber, or (vii) a mixture of these compounds.

As examples of suitable olefinic rubber series is lead (EPR) ethylene-propylene rubber with an ethylene content of 30 to 70%, the ethylene-butene-1-rubber with ethylene content of 30 to 70%, propylene-butene-1 rubber content of butene-1 from 30 to 70%, ternary ethylene-propylene rubber (non-conjugate diene copolymer) (EPDM) ethylene content of 30 to 70% and the content of the diene from 1 to 10%, the propylene-butene-1 heat polymer rubber with a propylene content of from 1 to 10% and a content of butene-1 from 30 to 70% or a propylene content of 30 to 70% and butene-1 from 1 to 10%.

Examples of dienes with non-conjugate double bonds can lead 1,4-hexadiene, tilidin-norborene and Dicyclopentadiene.

Ethylene-propylene rubber is the preferred olefinic rubber series.

The block copolymer monoalkyl aromatic diene with copv-A (or triple), radial type (A-B)nwhere n = 3-20, hydrogenation products of these compounds or a combination of these structural types, where block a is monoalkyl aromatic polymer, and B is a diene polymer with conjugated double bonds. Different classes of copolymers of this type are produced by the industry, They differ in structure, molecular weight, middle and end blocks against monoalkyl aromatic hydrocarbon to the rubber. In mixtures of two or more copolymers /one or more of which may be gidrirovanny/ hydrocarbons may be present in the same or different structural types. Typical monomers monoalkyl aromatic hydrocarbons are styrene, alkylthiol with substituted ring C1-4and linear or branched chain and vinyltoluene. Preferred is styrene. Suitable danami with paired double bond are butadiene and isoprene.

The average molecular weight of the block copolymer is typically in the range from about 45000 DL 260000 g/mol and mol are preferred. m 50,000 to 125,000 g/mol.

Propylene polymer grafted polymerized monomer /s/, the cat is the same propylene polymer, specified in the graft-copolymer of the component (A). As examples of the polymerized monomers can be butyl acrylate, hexyl acrylate, butyl acrylate/ butylmethacrylate, butyl acrylate/ethyl hexyl acrylate and hexyl acrylate/butylmethacrylate. Preferred are butyl acrylate and butyl acrylate-butylmethacrylate.

The rubber component is present in an amount of from 2 to 40%, preferably from 5 to 25%.

The graft-copolymer components (A) and (B) of this composition can be produced by one or several different ways. According to one of these methods on the propylene polymer to form active areas suitable for grafting carried out either in the presence of grafted monomer, or before processing this monomer. Place of vaccination can be created using processing peroxide go other chemical compounds, which are the initiators of free-radical polymerization, or by irradiation with ionizing radiation is high-energy. Free radicals formed in the polymer by chemical treatment or irradiation, to form active areas suitable for grafting on the polymer chain and serve as initiators of polymerization of the Dom.

The method of polymerization was initiated by using peroxide, involves the processing of propylene polymer at a temperature of from about 60 to 125oC, preferably from 80 to 120oC, and from 0.1 to 6, preferably from 0.2 to 0.3 pph initiator /mass parts per 100 wt. including propylene polymer/ possess period polurethane from about 1 DL 240 min, preferably from about 5 to 100 minutes, preferably from 10 to 40 minutes at the above temperature. Organic peroxides, especially those that give CNS radicals, form a preferred class of initiators of polymerization. These peroxides include allproxy, such as benzoyl and dibenzoylperoxide, dialkyl - and aralkylated, such as di-tert-butyl peroxide, documenr peroxide, cumenyl-butylperoxide, 1,1-di-tert-BUTYLPEROXY-3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di-tert-butylperoxide, and bis(alpha-tert-butyl-phenoxyisopropyl), peroxidase, such as tert-butyl peroxypivalate, tert-butylperbenzoate, 2,5-dimethyl-hexyl-2,5-di(peramental), tert-butyl-di-(perftest), tert-butyl peroxy-2-ethyl-hexanoate and 1,1-dimethyl-3-hydroxybutyrate-2-ethyl-hexanoate and percarbonate, such as di(2-ethylhexyl)peroxy-decarb the period of time which coincides with or follows the processing period the initiator /including cases where these periods partially overlap), the propylene polymer is treated grafted monomer/s/, the content of which is from 10 to 70 wt.% from the total mass of the propylene polymer and the grafted monomer/s/, and the rate of introduction of the additive does not exceed 4.5 pph /min, preferably around 4.0 pph/min, preferably below 3.0 pph/ min at any concentration of monomer. If the monomer is injected after the addition of the initiator, it is preferable that between the introduction of the initiator and the introduction of the monomer underwent a period of not more than 2.5 periods of polurethane initiator.

After vaccination, the unreacted monomer is removed from the obtained grafted propylene polymer, the entire unreacted polymerization initiator decomposes, and all the remaining free radicals inactivate preferably by heating usually at temperatures not lower than 110oC for at least 5 min, preferably at temperatures below 120oC for at least 20 minutes In the course of the process should be largely precluding oxidation.

In the present text the term "conditions, largely precluding oxidation of active oxygen /ie oxygen in the form in which it can react with the free radical polymer/ below 15%, preferably below 5%, preferably below about 1% by volume. The most preferred active oxygen concentration of 0.004% vol. or below. To create an atmosphere, largely precluding oxidation, can be used any gas or gas mixture, inert against free radicals propylene polymer, for example, nitrogen, argon, helium, or carbon dioxide.

In the method, involving the formation of active sites suitable for grafting by irradiation, the propylene polymer is irradiated at temperatures of from about 10 to 85oC ionizing radiation high energy, and the irradiated polymer is treated grafted monomer /s/ in the amount of from about 10 to 70 wt.% from the total mass of the propylene polymer and the grafted monomer /s/, the treatment is carried out at temperatures of from about 10 to 100oC, preferably from 10 to 70oC, preferably at 10-50oC for at least 3 minutes, preferably for at least 10 minutes, if the process is carried proporzioni, and preferably within 30-60 minutes, if the process is carried out continuously. After that, or ignoreme owashi monomer is removed from this material. Propylene polymer should be in the conditions, largely precluding oxidation, i.e., in the atmosphere of inert gas during the reaction, at least until the end of the deactivation of residual free radicals. Deactivation of free radicals preferably carried out with heating, for example, at temperatures not lower than the 11oC, preferably not lower than 120oC, usually for at least 20 minutes

Suitable forms of the grafted propylene polymer include powdered form, flaky, granular, spherical and cubic particles, etc. is Preferred propylene polymer in the form of spherical particles, where the volume fraction of pores is at least 0,07.

Most preferred for purposes of the present invention is a graphite-copolymer in the form of homogeneously grafted particles obtained from the particles of the propylene polymer with (a) volume fraction of pores equal to at least 0,07, where more than 40% of the pores have a diameter greater than 1 micron, (b) surface area of at least 0.1 m2g (in) srednevekovym diameter ranging from 0.4 to 7 mm, Such a polypropylene material is produced in industrial scale company "Himont Italia S. R. L".

Any organic compound applied as a coating on particles of the fillers in a quantity sufficient for the formation of a thin coating on all /virtually/surface area of the filler particles and reduces the adhesion of the particles with the polymer matrix to which the admixed particles of filler, among these organic compounds, which can be used for formation of the coating of the filler particles according to the invention, saturated and unsaturated fatty acids and their salts of the metals of groups 1A and 2A, containing from 10 to 32 carbon atoms in the alkyl or alkilinity radicals associated with radicals, carboxylic acid or salts of carboxylic acids. Typical fatty acids include lauric, myristic, palmitic, stearic, nondeciduous, gannaway, melissinos, hypogynous, oleic, linolenic or linoleic acid. Salts of such fatty acids include calcium, sodium and calcium salts.

In the composition of the invention may include other fillers and reinforcing substances, such as carbon and above in compositions with fillers according to the invention/, mica and glass, and the concentrations of these substances should not exceed about 80 wt. hours at 100 wt. h A + B + C.

The mixing or the addition of some components of the composition to another can be carried out in any conventional mixing machine such as an extruder or a mixer of "Banbury".

In more detail, the invention described in the examples below.

The physical properties mentioned in the tables of the substances was determined in the following ways:

The modulus: see S TM D-790 and D-618, procedure And /speed slider to 0.5 inch/min, the Central section of the T-shaped casting/.

Bending strength: see S TMW-638, procedure A (Central section of the T-shaped casting).

The Izod impact resistance of: see S TM D-256-87.

The rate of melt flow: see S TM D-1236, condition 1.

The porosity. Determined by the method of mercury porometry, according to which measure the amount of mercury absorbed by the particles, and the volume of the absorbed mercury corresponds to the pore volume.

The percentage of fractions, soluble in xylene at 25oC: is Determined by dissolving 2 g of polymer in 200 ml of xylene at 135oC, then the solution is cooled in a bath with a constant temperature t and calculate the amount (wt.%) the soluble fraction.

The distribution of molecular masses (srednevekovaja molecular weight/srednekislye): determined by the method of gel chromatography of waters 150-C ALC/GPC, in trichlorobenzene at 145oC using a differential detector refractive index.

Characteristic viscosity () : determined tetrahydronaphtalene at 135oC.

Propylene polymers with a wide range of molecular masses used in the following examples were prepared by the following method.

The preparation of the catalyst.

In a reactor equipped with a stirrer, under inert atmosphere, put 28.4 g MgCl249.5 g of anhydrous ethanol, 100 ml of paraffin oil ROL OB/30, 100 ml of silicone oil with a viscosity of 350, the contents of the reactor are heated to 120oC to dissolve the MgCl2. Then the hot reaction mixture is transferred to a reactor containing 150 ml of vaseline oil and 150 ml of silicone oil and equipped with a stirrer ULTRA TURRAX T-45". The temperature of the support at the level of the 120oC and stirred the mixture for 3 min at 3000 Rev/min the mixture is Then poured into a reactor equipped with a stirrer and containing 1,000 ml of anhydrous n-heptane and cooled to 0oC. the particles Obtained vosta what the alcohol content is reduced from 3 to 2.1 mol per 1 mol.

Then 25 g of the obtained adduct is transferred into a reactor equipped with a stirrer and containing 625 ml of TiCl4at 0oC under stirring, heating the mixture to 100oC for one hour. When the temperature reaches 40oC add diisobutylphthalate in such quantity to bring the molar ratio of magnesium to phthalate to 8.

The mixture is heated to 100oC for two hours under stirring, and then the solid particles are allowed to settle. Hot liquid decanted. Then add 550 ml of TiCl4and the mixture is heated to 120oC for one hour with stirring, after which the solid particles allow to settle. The liquid is decanted, and the solid is washed 6 times with 200 ml of n-hexane at 60oC, and then three times at ambient temperature.

The polymerization.

The polymerization is carried out in a continuous process in a series of reactors equipped with devices for rapid mixing of the product from the preceding reactor in the following.

Gas phase hydrogen and monomer undergoes continual review and served in such a way as to maintain the required concentration.

A mixture of triethylaluminum (TEAL) as the activator is a component of the catalyst, prepared as described above, in the container at 40oC for 15 min, and the molar ratio TEAL/Ti should be 80.

Then the catalyst is moved into the reactor containing liquid propylene in excessive concentration, and subjected to preliminary polymerization at 20oC for 1.5 to 2 minutes

Then the prepolymer then transferred to another reactor, where the polymerization in the gas phase before the formation of fractions (A).

The product obtained in the above reactor, served in the second reactor in the gas phase and the product of the second reactor is served in the third reactor in the gas phase before the formation of fraction (B).

Conditions for reactions during the preparation of propylene with a very wide range of molecular masses (VM W D-PP) and the physical properties of this substance, used in examples of the present invention, is presented in table B.

Examples 1 to 5 and comparative examples 1 and 2'.

The compositions of the present invention is manufactured by the method, which in General includes mixing in a drum mixer graft-copolymer of propylene polymer, polypropylene with a wide range of molecular weights, ethylene-propyleneamine links as shown in the table. 1, together with a stabilizing composition consisting of 0.5 C. D. calcium stearate, 0,075 C. D. stabilizer "JRGANOX 1010" and 0,075 pph stabilizer "SANDOSTA B P-EPQ" until a homogeneous mixture, after approximately 1 min of mixing. The mixture ekstragiruyut at 475oand 350 rpm with a speed of 32.5 lbs/HR 30 mm conical dvuhserijnom extruder with joint rotation and vacuum suction of the company, "Leistritz". The compound is supplied under pressure in the form of 1.5 ounces of 25-ton machines for casting under pressure of the type "BATTEN FEID when the temperature of the drum 475oF and the mold temperature is 135oF. the casting Process samples for tensile tests and plasticity involves the following stages: during the 10 with the compound pump in the form, within 20 the mixture is cooled and within 2 to open the form, with the maximum rate of discharge is set to 15, and the screw speed is set to 2.

In comparative examples 1 and 2 compositions were prepared from the ingredients listed in table. 1 according to the described method.

Notes to the table. 1.

1)The homopolymer polypropylene (spherical form, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93.8% of p is h active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethylhexanoate, 50% in white spirit/ temperature vaccinations 115oC, the feed speed of styrene and 1.0 pph/min, within 84 minutes (peroxide is served at the same time, 0,048 pph/min) 30 min, holding at 115oC, drying at 135oC for 180 min, produced by the method of separate continuous additive components.

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

3)Ethylene-propylene rubber with an ethylene content of 57% and a characteristic viscosity 3,37 DL/g firm Dutra".

4)Hydrogenated ternary copolymer of styrene/butadiene/ styrene with a styrene content of 29% and a content of the intermediate block tilebottom rubber 71%, company shell chemical company".

As shown in the table. 1, the compositions of the present invention containing PSRM and the graft-copolymer have improved impact strength as compared with comparative examples containing only PSRM or graft-copolymer.

Examples 6 to 9.

Compositions are given in table. 2, prehledovou rubber to gidrirovannogo block-copolymer monoalkyl aromatic diene with conjugated double bonds.

Notes to the table. 2.

1)A homopolymer of polypropylene /spherical shape, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93,8% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene, EXT. 84 pph, 2,0 pph active peroxide ("LUPERSOL PMS "tert-butyl-peroxide-2-ethyl-hexanoate, 50% in mineral spirit/ temperature vaccinations 115oC, the feed speed of styrene and 1.0 pph/min, within 84 min /peroxide is served at the same time, 0,048 pph /min, 30 min, holding at 115oC, drying at 135oC for 180 min, produced by the method of separate continuous additive components.

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye mol. mass 40.

3)Ethylene-propylene rubber with an ethylene content of 57% and a characteristic viscosity 3,37 DL/g firm Dutra".

4)Hydrogenated three-block copolymer (styrene/butadiene/styrene) styrene content of 29% and a content of the intermediate block ethylene-change relations ethylene-propylene rubber to the block copolymer KRATON" in the compositions of the present invention. The table shows that in this case, the compositions have improved impact strength with a slight decrease of the modulus or the modulus remains unchanged.

Examples 10 to 12 and comparative examples 3 to 5.

The compositions containing the ingredients listed in table. 3, were prepared according to the method described in examples 1 to 5 except that the composition was extrudible at 375 rpm and 35 pounds/hour and the temperature in the dryer was $ 450oF at the time when the composition was injected under pressure in the form of a 5 oz machines for casting under pressure of the type BATTENFELD, and temperature in the form of equal 135oF.

Notes to the table. 3.

1)A homopolymer of polypropylene /spherical shape, the fluidity of the melt 14,1, the porosity of 0.61 CC/g, the content of insoluble in xylene fractions 97% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene, EXT. 85 pph, 1,65 pph active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethyl-hexanoate, 50% in white spirit), the temperature of cultivating 120oC, the feed speed of styrene and 1.0 pph/min for 85 min (peroxide is served at the same time, 0,0388 pph/min), 30 min, holding at 120oC the century

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye mass 40.

3)A homopolymer of polypropylene, a spherical shape, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93,8% at room temperature, srednevekovaja/srednekislye molecular weight = 4,8.

4)Ethylene-propylene rubber with an ethylene content of 57%, the firm "Polysar Corporation.

5)Hydrogenated three-block copolymer (styrene/butadiene/styrene) styrene content of 29% and a content of ethylenebutylene in 71%.

As shown in the table.3, the composition of the invention containing polypropylene with a wide range of molecular masses, have high impact strength and rigidity as compared with the compositions shown in the comparative examples containing conventional polypropylene.

Examples 13-15 and comparative examples 6-10.

The compositions listed in table. 4 prepared by the method described in examples 10-12.

Notes to the table the holding insoluble in xylene fractions 97% at room temperature, srednevekovaja-srednekislye molecular weight = 4,8), grafted with styrene, EXT.85 pph, 1,65 pph active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethylhexanoate, 50% in white spirit), the temperature of cultivating 120oC, the feed speed of styrene and 1.0 C. D./min, within 85 min (peroxide is served at the same time, 0,0388 DM/min), 30 min exposure at 120oC, drying at 140oC for 180 min, produced by the method of separate continuous additive components.

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

3)A homopolymer of polypropylene, a spherical shape, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93,8% at room temperature, srednevekovaja/srednekislye molecular weight of 4.8.

4)Polypropylene homopolymer, the fluidity of the melt is 0.2, the content of insoluble in xylene fractions 96%, at room temperature, srednevekovaja/srednekislye molecular weight of 6.5, manufactured by a company "Chaumont" USA the fractions 96% at room temperature, srednevekovaja-srednekislye molecular weight of 6.5, manufactured by a company "Himont USA.

6)Ethylene-propylene rubber with an ethylene content of 57% of the company "Polysar Corporation.

7)Hydrogenated three-block copolymer (styrene/butadiene/styrene) styrene content of 29% and a content of ethylene-butenova rubber 71%, company shell chemical company".

In table. 4 shows that the composition of comparative examples 8-10, containing graft copolymer, conventional polypropylene, ethylene-propylene rubber and "KRATON", have high impact strength as compared with the compositions of comparative examples 6-7, which do not contain polypropylene, however, we have observed the decrease of the modulus. At the same time, the compositions of the present invention show a significant increase in strength at impact while maintaining the modulus.

Examples 16-19 and comparative example 11.

Compositions are given in table.5, were prepared according to the method described in the examples table.3, except that the melting temperature in the extrusion process was equal to 445oF, and the set of stabilizers contained a 0.25 pph DISTEARYL -3,3'-dithiophosphinate, 0,1 pph JRGANOX 1010" and 0.08 pph PEP-Q.oC, the feed speed of styrene and 1.0 pph/min, for 52 min (peroxide is served at the same time, 0,040 pph/min), 30 min of incubation at 120oC, drying at 140oC for 180 min, produced by the method of separate continuous additive components.

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

3)Ethylene-propylene rubber with an ethylene content of 57%, the firm "Polysar Corporation.

4)Hydrogenated ternary copolymer of styrene/butadiene/ styrene with a styrene content of 29% and a content ethylenebutylene rubber 71%, company shell chemical company

From table. 5 shows that can be used and a lower amount of the graft-copolymer, n is 20 to 23 and comparative examples 12-16.

Compositions are given in table. 6, were prepared according to the method used to prepare the compositions of table.3 except that in this case was used the other polypropylene with a wide range of molecular masses.

Notes to the table.6.

1)The homopolymer polypropylene (spherical form, the fluidity of the melt 14,1, the porosity of 0.61 CC/g, the content of insoluble in xylene fractions 97% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene, EXT.85 pph, 1,65 pph active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethylhexanoate, 50% in white spirit), the temperature of cultivating 120oC, the feed speed of styrene and 1.0 pph/min for 85 min (peroxide is served at the same time, 0,0388 pph/min), 30 min of incubation at 120oC, drying at 140oC for 180 min, produced by the method of separate continuous additive components.

2)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt 3.1 porosity of 0.13 CC/g, the content of insoluble in xylene fractions to 98.4% at room temperature, srednevekovaja/srednekislye molecular weight of 14.

3)25% manufactured by the firm "Himont, USA.

4)Ethylene-propylene rubber with an ethylene content of 57%, the firm "Polisar Corporal".

5)Hydrogenated three-block copolymer of styrene /butadiene/ styrene with a styrene content of 29% and a content of ethylene-butenova rubber 71%, company shell chemical company".

Compositions are given in table. 6 demonstrate that the compositions according to the invention have impact strength at lower temperatures than compositions containing polypropylene, grafted with styrene, or polypropylene with a wide range of molecular weights and rubber, this property has and ethylene-propylene rubber, polypropylene modified with toughness, taken separately.

Examples 24-27. The composition described in table. 7, were prepared according to the method used to prepare the compositions described in table. 1 except that in example 26 instead of the ethylene-propylene copolymer rubber was used heterophase polypropylene with a wide range of molecular masses, as in example 27 instead of the hydrogenated triple block copolymer of styrene/butadiene/styrene was used block copolymer of styrene/butadiene/styrene.

oC, the feed speed of styrene and 1.0 pph/min for 85 min (peroxide is served at the same time, 0,0194 pph/min), 30 min, holding at 120oC, drying at 140oC for 180 min, manufactured by the method of separate additive components.

2)Semiconductor homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt 32,1, the porosity of 0.11 CC/g, the content of insoluble in xylene fractions of 96.5% at room temperature, srednevekovaja/srednekislye molecular mass of 23.5.

3)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt 3.1 porosity of 0.13 CC/g, the content of insoluble in xylene fractions to 98.4% at room temperature, srednevekovaja/srednekislye molecular weight of 14.

4)Polypropylene homopolymer with a wide range of molecular masses of the spherical parliamentary, srednevekovaja/srednekislye molecular weight of 13.

5)Ethylene-propylene-rubber polypropylene homopolymer with a wide range of molecular masses and modified toughness with the content of the ethylene-propylene rubber 60%, the fluidity of the melt 10, C2/C3in the ethylene-propylene rubber 65/35, spherical shape.

6)The ethylene-propylene copolymer rubber having an ethylene content of 57%, the firm "Polisar Corporal".

7)Hydrogenated three-block copolymer (styrene/butadiene/styrene) styrene content of 29% and a content of ethylene-butenova rubber 71%, company shell chemical company".

8)Rubber, representing a three-block copolymer (styrene/butadiene/styrene) styrene content of 31% and a content of butadiene rubber 69%, company shell chemical company".

Examples 28-29. The compositions listed in table. 8, were prepared by the method, which were prepared with the compositions of table. 7 except that the graft copolymer, the rubber "KRATON G-1652", ethylene-propylene rubber "POLYSAR 30P", and a set of stabilizers were mixed in dry form and extrudible on the car LEISTRTTZ" at 375 rpm 35 lbs/HR and 445oF, and then granulated. the N. £ 35/h, 445oF. the Compound was heated in form 5 ounces machines for casting under pressure BATTENFELD when the temperature of the drum 450oF and the temperature in the form 135oF.

Note to the table. 8.

1)Cm. note 1 to table. 7.

2)A homopolymer of polypropylene /spherical shape, the fluidity of the melt 24,6, the porosity of 0.51 CC/g, the content of insoluble in xylene fractions 98% at room temperature, srednevekovaja/srednekislye molecular weight of 6.5) grafted with styrene, EXT. 85 pph, 1,65 pph active peroxide ("LUPERSOL PMS", tert-butyl peroxy-2-ethylhexanoate), temperature vaccinating 121oC, the feed rate of the styrene - 0,9 pph/min, for 94,4 min peroxide is served at the same time, a 0.035 pph/min, 30 min aging at 121oC, drying at 140oC for 180 min, produced by the method of separate continuous additive components.

3)Cm. note 2 to table. 7.

Examples 30-32. Compositions are given in table. 9, were prepared according to the method used to prepare the compositions shown in table. 3, except that instead of "POLYSAR 306P" and "KRATON G1652/ as the rubber component used graft-copolymer of butyl acrylate, grafted on to the basic price is the composition was extrudible at 475oF and 110 rpm in a cone-shaped dvuhserijnom extruder with protivovirusnym and vacuum suction firm "Haacke, the temperature of the drum forms of 1.5 ounces machines for casting under pressure "BATTENFELZ" was 450oF.

Note to the table. 9.

1)The homopolymer polypropylene (spherical form, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions of 93.3% at room temperature, srednevekovaja/srednekislye molecular mass of 4.8), grafted with styrene, 85 pph styrene 2,0 C. D. active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethylhexanoate, 50% in white spirit), the temperature of cultivating 121oC, the feed speed of styrene with 0.9 pph/min for 90 min, (peroxide is served at the same time, 0,0444 pph/min), 30 min aging at 121oC, drying at 135oC for 190 min, manufactured by the method of separate continuous add

2The homopolymer polypropylene (spherical form, the fluidity of the melt 4.8 porosity of 0.35 cubic cm g grafted butyl acrylate, 30.5% of butyl acrylate and 0.5 C. D. active peroxide ("LURERSOL 11" tert-butyl peroxypivalate, 75% in white spirit), the temperature of vaccinating 80oC, flow of butyl acrylate 44pph feed rate of butyl acrylate and 1.0 pph .Mina supplements peroxide and the polymerization of the monomer.

3Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

Examples 33-39. The compositions listed in table. 10, were prepared as compositions of GLA. 5, except that instead of polypropylene grafted with styrene, used propylene, grafted styrene/Acrylonitrile, and in examples 36-39 instead of the hydrogenated block copolymer of ethylene-propylene copolymer rubber used uterine mixture of hydrogenated blockcopolymer and polypropylene with a wide range of molecular masses, "KRATON G1652" /PSRM, as in examples 34-36 stabilizing kit included 0,07% "PEP-Q", 0,1% "JRGANOX 1010 and 0.5% of calcium stearate, and examples 33-35 stabilizing kit included 0,075 pph "PEP-Q", 0,075 pph JRGANOX 1010" and 0.5 pph calcium stearate.

Royal mixture "KRATON G1652" /PSRM were prepared in the following way: in the mixer of "BANBURY" 3 lbs loaded 50% "KPATON G" 50% PSRM and stabilizing the kit above. Using dvuhpaltsevoe mill and the mixture was pressed into a sheet and cut into strips. Bands were crushed in draw what obrusheniem / and extrudible at 175 rpm at a temperature of inclined drum in 475-575oF. the Product was granulated, and then introduced the other ingredients listed in table. 10, according to the method used for the compositions of table. 5.

Notes to the table. 10.

1A homopolymer of polypropylene /spherical shape, the fluidity of the melt 14,1, the porosity of 0.61 CC/g, the content of insoluble in xylene fractions 97% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene/Acrylonitrile /SAN/ (3:1 weight. ratio), EXT, 85 pph 1,07 active peroxide /"LUPERSOL PMS" tert-butyl-peroxypivalate 75% mineral spirit/ temperature vaccinating 90oC, feed rate CAH - 1 pph /min for 85 min /peroxide is served at the same time, 0,0126 pph min/ 30 min incubation at 90oC, drying at 140oC for 120 min, manufactured by the method of separate continuous additive components.

2Copolymer polypropylene (spherical form, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93,8% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene/Acrylonitrile (SAN) (the weight. ratio 3:1), EXT, 85 pph, 1,6 pph active peroxide ("LURERSOL 11" tert-butyl-peroxypivalate 75% mineral spirit, temperature/ min), keeping with the 90oC, drying at 140oC for 120 min, produced by the method of separated continuous additive components.

3)Copolymer polypropylene (spherical form, the fluidity of the melt 9,1, the density of 0.53, the content of insoluble in xylene fractions of 97.8%, srednevekovaja/srednekislye molecular weight 4,5), grafted methyl methacrylate/styrene weight. the ratio of 13:1), EXT. 70 pph (65 pph of methyl methacrylate, 5pph styrene), 1,26 C. D. active peroxide ("LUPERSO PMS" tert-butyl peroxy-2-ethylhexanoate, 50% in white spirit), the temperature of cultivating 115oC, the feed speed of MMA/SS to 1.0 pph /min for 70 min (peroxide is served at the same time, 0,018 pph/min), 30 min of incubation at 115oC, drying at 140oC for 120 min, produced by the method of separate continuous additive components.

4)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt 3.1 porosity of 0.13 CC/g, the content of insoluble in xylene fractions to 98.4% at room temperature srednevekovaja/srednekislye molecular weight of 14.

5)The ethylene-propylene copolymer rubber having an ethylene content of 57%, the firm "Polysar Corporation.

Examples 40-42. The compositions listed in table. 11 were prepared in the same way that the composition table. 3, except that instead of polypropylene grafted with styrene, used polypropylene, grafted styrene (methyl methacrylate) Acrylonitrile, polypropylene, grafted styrene-methacrylate or polypropylene, grafted with methyl methacrylate, and the extrusion of melt produced at a temperature of 445oF.

Notes to the table. 11.

1)The homopolymer polypropylene (spherical form, the fluidity of the melt 14,1, the porosity of 0.61 CC/g, the content of insoluble in xylene fractions 97% at room temperature srednevekovaja/srednekislye molecular weight 4,8), grafted styrene(methyl methacrylate)Acrylonitrile (PS/MMA/an) (the weight. ratio of 3.73:1:1), EXT. 70 pph (45,5 c.D. styrene, 12,3 pph MMA, 12,2 C. D. AHN), 1,1 pph active peroxide ("LUPERSOL 11" tert-butyl peroxy-pivalate, 75% in mineral spirit/ temperature vaccinating 90oC, feed rate PS/MMA/an to 1.0 pph /min for 70 min (peroxide is served at the same time, 0,0157 pph /min), 30 min of incubation at 90oC, drying at 140oC for 30 min produced by a method of joint continuous additive components.

oC, feed rate PS/MMA to 1.0 pph /min for 70 min (peroxide serves at the same time, 0,018 pph /min/ 30 min of incubation at 90oC, drying at 140oC for 120 min, made by a method of separated continuous supply of components.

3)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt 3,1, porosity of 0.13 CC/g, the content of insoluble in xylene fractions to 98.4% at room temperature, srednevekovaja/srednekislye molecular weight of 14.

4)Polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

5)Ethylene-propylene rubber with an ethylene content of 57%, the firm "Polysar Corporation".

the 29% and the content of the ethylene-butenova rubber 71%, manufactured by the shell chemical company, and polypropylene homopolymer with a wide range of molecular masses of the spherical shape, the fluidity of the melt is 3.5, the porosity of 0.12 CC/g, the content of insoluble in xylene fractions of 98.2% at room temperature, srednevekovaja/srednekislye molecular weight of 40.

Examples 43-44. These examples illustrate the preparation of compositions according to the invention containing fillers.

The ingredients listed in table. 12, are mixed in the mixer "HENSCHEI" until a homogeneous mixture/about 1 min. The resulting mixture compendious on dvuhserijnom the extruder of 30 mm joint rotation "LEiSTRiTZ, using batch flow when the rotation speed of 350 rpm, feed speed 30-35 lb/h and a temperature of 230oC (flat profile). After the extrusion, the product granularit in the usual way.

Comparative examples 17 to 21 were prepared in a similar way, except that in examples 20 and 21 were used granulated product "Pro-fax". Thus, these substances are already contained calcium stearate, stabilizer "JRGANOX 1010 and calcium carbonate "SUPERCOAT" in the quantities listed in the table. 12.

Compoundpisemnet products Danna 475oF and the temperature in the 100oF.

Notes to the table.12.

1)The homopolymer polypropylene (spherical form, the fluidity of the melt 9,1, the porosity of 0.53 CC/g, the content of insoluble in xylene fractions of 97.8% at room temperature, srednevekovaja/srednekislye molecular weight 4,5), grafted with styrene, EXT. 85 pph, 1,65 pph active peroxide ("LUPERSOL PMS" tert-butyl peroxy-2-ethyl-hexanol, 50% in white spirit), the temperature of cultivating 120oC, the feed speed of styrene and 1.0 pph/min for 85 min *peroxide is fed simultaneously 0,039 pph/min), 30 min kept at 120oC, dried at 140oC for 180 min, manufactured by the method of separate continuous supply of components.

2)see note2)to table.6.

3)see note 1)to table.1.

4)"Profax 73A6-2":20% CaCO3 "Supercoaf", containing as filler ethylene-propylene-rubber modified polypropylene with toughness, manufactured by the firm "Himont USA.

5)"Profax 73A6-4":40% CaCO3"Supercoat", containing as filler ethylene-propylene-rubber modified polypropylene with toughness, manufactured by the firm "Himont USA.

6)Naya table shows that composition with fillers according to the invention have improved impact strength and modulus and higher strength compared to the commercially available polypropylene modified with toughness, and also compared with polipropileno, grafted with styrene containing no polypropylene with a wide range of molecular masses.

Examples 45-49. For these examples use the ingredients listed in table. 13, which (without filler) is mixed in a large tilting mixer until a homogeneous mixture (approximately 10 min). Then the resulting mixture compendious 40 mm dvuhserijnom extruder with joint rotation "WERNER AND PFLEiDER ZSK" sequential feeding of the filler with the metering feed device when the rotation speed of 400 rpm and a feed rate of 200 lbs/HR and the temperature on the plane 260oC. After extrusion, the product granularit one of the usual ways.

Comparative example 22 based on the same method of preparation as the examples 45-49. Products "Profax" used in comparative examples 23 and 24, issued by the industry in granular form. Thus, these products are already compounding ptx2">

Compounded products obtained in these comparative examples, used for injection molding as well as the products listed in the table. 12. All impact toughness under plane deformation is performed on the plates 55 inches using the testbed RHEOMETPiCS RiT 8000" with the retaining plate 3 inches and standard deviation of diameter of 1/2 inch. The impact velocity of 2.2 m/s (5 miles/h).

Notes to table 13.

3)see note 1 to table. 12.

2)see note 2 to table. 6.

3)The homopolymer polypropylene (spherical form, the fluidity of the melt 5,8, porosity of 0.35 CC/g, the content of insoluble in xylene fractions 93,8% at room temperature, srednevekovaja/srednekislye molecular weight 4,8), grafted with styrene, EXT. 85 pph, 1,51 pph active peroxide ("SUPERSOL PMS" tert-butyl peroxy-2-ethylhexanoate 50% in white spirit/ temperature vaccinating 123oC, the feed speed of styrene and 1.0 pph /min for 85 min (peroxide is served at the same time, being 0.036 pph /min, 30 min conditioning at 128oC, drying at 135oC for 208 min, manufactured by the method of separate continuous supply of components).

4)Protax 73A6-2: 20% CaCO3 "Supercoat" with filler in the form of aumont", USA.

5)Profax 73A6-4: 40% CaCO3 "Supercoat" with filler in the form of ethylene-propylene rubber modified polypropylene with toughness, manufactured by a company /"Himont USA.

6)see note 4 to the table.1.

7)see note 4 to the table.3.

The above data show that compositions with fillers of the present invention have better impact strength and modulus, and high strength in comparison with polypropylene modified with toughness, manufactured, and also compared with polypropylene, grafted with styrene, but without polypropylene with a wide range of molecular masses. In addition, compositions with fillers of the present invention demonstrate excellent ability to withstand biaxial shock at low temperatures.

Examples 50-51. In these examples, the ingredients listed in table 14 were prepared, compoundable was granulated in the same manner as in examples 43 and 44 in the table. 12.

Notes to the table. 14.

1)see note 1 to table.12.

2)see note 2 to table.6.

3)see note 4 to the table.1.

1. Impact-resistant composition comprising a graft copolymer of polypropylene grafted with one or more vinyl monomer and at least one rubber, characterized in that it further comprises at least one polypropylene with a wide range of molecular weight, in the following ratio, wt.%:

The graft-copolymer - 10 - 88

Rubber - 2 - 40

Polypropylene with a wide range of molecular weight - Rest

2. The composition according to p. 1, characterized in that the graft-copolymer is a polypropylene selected from the group comprising a homopolymer of propylene, a statistical copolymer of propylene with ethylene or an olefin WITH4-C10statistical trimer of propylene with ethylene and-olefin WITH4-C10to which is grafted at least one vinyl monomer selected from the group of clucouriarelo and Acrylonitrile.

3. The composition according to p. 1, characterized in that the polypropylene with a wide range of molecular weight is a homopolymer of propylene or polypropylene with a wide range of molecular weight-modified impact-resistant ethylene-propylene rubber.

4. The composition according to p. 1, characterized in that the rubber is a compound selected from the group comprising olefinic rubber, consisting of two or more monomers selected from ethylene, propylene or butene, and possibly diene with non-conjugate double bonds, one or more block copolymer monoalkyl aromatic hydrocarbon and a conjugated diene or the products of hydrogenation of the copolymer, the graft-copolymer polypropylene, grafted polymerized monomer or mixture of monomers that upon polymerization form a rubber polymer with a glass transition temperature below 20oWith mixtures of these compounds.

5. The composition according to p. 1, characterized in that it contains a graft-copolymer polypropylene, which is grafted styrene, a mixture of styrene and methyl methacrylate or a mixture of styrene and Acrylonitrile, polypropylene with a wide range of molecular weight as the mixture of olefinic rubber and blockcopolymer manouche is 5, characterized in that the olefinic rubber is an ethylene-propylene rubber.

7. The composition according to p. 1, characterized in that it contains a graft-copolymer of polypropylene grafted with styrene, polypropylene with a wide range of molecular weight as the mixture of olefinic rubber and hydrogenation product of blockcopolymer monoalkyl aromatic hydrocarbon and a diene with paired double bonds.

8. The composition according to p. 7, characterized in that the olefinic rubber is an ethylene-propylene rubber.

9. The composition according to p. 1, characterized in that it contains a graft-copolymer with grafted with styrene, polypropylene with a wide range of molecular weight and graft-copolymer of polypropylene grafted with a monomer or mixture of monomers that upon polymerization form koutsokoumnis polymers with a glass transition temperature below 20oC.

10. The composition according to p. 9, characterized in that the rubber is a graft copolymer of polypropylene grafted with butyl acrylate, a mixture of butyl acrylate and butyl methacrylate or a mixture of butyl acrylate and ethylhexyl acrylate.

11. The composition according to p. 10, characterized in that the rubber is a graft-sprinklers which contains additional 10 - 100 wt.h. on 100 wt.h. the composition of the filler with a particle size of 0.5 to 4.0 μm, selected from the group comprising talc, calcium carbonate, silicate, a mixture of these fillers.

 

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