Polyolefin compositions having good bleaching resistance

FIELD: chemistry.

SUBSTANCE: composition contains crystalline propyelen polymer, elastomeric copolymer of ethylene and propylene and polyethylene. When combined with components with certain values of polydispersity index and characteristic viscosity in given ratios, the composition exhibits high hardness, impact resistance and resistance to bleaching under loading. The composition has flexural modulus higher than 1300 MPa, resistance to bleaching during impact corresponding to diametre of the bleaching area not greater than 1.7 cm, caused by a die falling from a height of 76 cm and diametre of the bleaching area not greater than 1.2 cm, caused by a die falling from a height of 20 cm, and Izod impact resistance at 23°C greater than 14 kJ/m2 and at least equal to 6.5 kJ/m2 at -20°C.

EFFECT: composition has good balance of mechanical properties, is suitable for making articles through pressure casting, such as casings of batteries and consumer goods, and during hot shaping processes.

2 cl, 4 tbl, 3 ex

 

The present invention relates to polyolefin compositions having a good balance of mechanical properties, and to a method for producing these compositions. In particular, the compositions exhibit good stiffness, impact resistance and resistance to whitening under load (usually drums).

Polyolefin compositions in accordance with the present invention find application in products obtained by injection molding, such as the casings of the batteries and consumer goods, and thermoforming processes.

As you know, lack of isotactic polypropylene, although he has an exceptional combination of excellent properties, is the lack of resistance at relatively low temperatures.

In accordance with the information of the prior art, it is possible to eliminate the above drawback and to keep the resistance to whitening noticeable effect on other properties of the polymer, adding properly rubbers and polyethylene to polypropylene.

European patent application 86300 belongs to the so-called “shock compositions based on polypropylene and discloses block copolymers of polypropylene having improved impact resistance and high rigidity.

U.S. patent 4521566 discloses compositions based on polypropylene comprising cu is starecheski polymer of propylene, amorphous copolymer fraction, and a crystalline copolymer fraction of ethylene and propylene. Disclosed compositions exhibit high stiffness and good impact resistance. However, as illustrated in the examples, these compositions have the drawback consisting in the fact that they have low impact resistance at ambient temperatures, when the composition is sufficiently hard; increase the impact of conjugate reduction of rigidity.

In U.S. patent 4734459 disclosed compositions based on polypropylene has good resistance to whitening. In accordance with the instructions in this document of the prior art, it is possible to improve the resistance to whitening when replacing rubber copolymer of ethylene and propylene in the copolymer rubber of ethylene and butene-1.

Now unexpectedly found that it is possible to obtain a composition based on polypropylene, endowed with high impact resistance even at low temperatures and good resistance to bleaching, despite the fact that they exhibit a sufficiently high rigidity.

This balance of properties is achieved by obtaining a composition based on polypropylene with a specific polymer components, exhibiting specific properties, and in specific proportions.

Thus, embodied the giving of the present invention is a composition based on polypropylene, includes (mass percentage):

a) 65-77%, preferably 70 to 77% of a crystalline propylene polymer having an amount of the isotactic pentad (mmmm), measured by means of the13C-NMR of fraction insoluble in xylene at 25°C., higher than a 97.5 molar % and the index polydispersity in the range from 5 to 10;

b) from 8 to less than 13%, preferably from 9 to 12% of an elastomeric copolymer of ethylene and propylene, the copolymer has a number of structural units derived from ethylene in the range from 30 to 70%, preferably from 35 to 60%, and is partially soluble in xylene at ambient temperature; and the polymer fraction soluble in xylene at ambient temperature, has a value of the characteristic viscosity in the range from 2 to 4 DL/g; and

C) 10-23%, preferably from 10 to 20% of polyethylene having a value of the characteristic viscosity in the range from 1.5 to 4 DL/g, and optionally containing structural units derived from propylene in amounts lower than 10%.

The term “copolymer”as used herein, refers to polymers with two different structural units, and polymers with more than two different structural units, such as ternary copolymers (terpolymers), in the chain.

In a typical case, the composition of meatatarian amount of the component (b) and component (a) in the amount at least 18 wt.%, preferably higher than 25 wt.%, and General content copolymerizing ethylene, at least 12 wt.%, preferably equal to or greater than 18 wt.%, more preferably at least 20 wt.%.

The composition typically has a speed value of the melt flow in the range of from 0.50 to 10 g/10 min, preferably from 0.10 to 5 g/10 min, more preferably from 1.3 to 4 g/10 minutes

The composition typically has a number of polyethylene (C)equal to or greater than the amount of elastomeric copolymer (b), preferably the mass ratio between the polyethylene (C) and the copolymer (b) is, at least, 1,4.

Typically, the composition of the present invention showing the value of the modulus in bending of at least 1300 MPa, preferably higher than 1350 MPa, such as from 1400 to 1600 MPa, the values of resistance to bleaching at a load corresponding to the diameter of the whitened area not more than 1.7 cm, caused by the falling of a punch from a height of 76 cm, and the diameter of the whitened area of no more than 1.2 cm, caused by the falling of a punch from a height of 20 cm, the value of impact resistance Izod at 23°C for more than 14 kJ/m2preferably more than 30 kJ/m2and at -20°C for at least 5 kJ/m2preferably more than 6.5 kJ/m2more preferably 7.5 kJ/m2or higher.

The crystalline polymer of propylene (a) you who eraut from homopolymer propylene and copolymers of propylene, containing not more than 3 wt.% ethylene or4-C10α-olefin or a combination of both. Especially preferred is a homopolymer of propylene.

Usually crystalline propylene polymer (a) shows the molecular weight distribution expressed by the ratio of mass-average molecular weight and srednekamennogo molecular weight, i.emeasured using GPC, equal to or greater than than 7.5, in particular from 8 to 20. The rate of flow of the melt of the crystalline propylene polymer (a) typically has a value in the interval from 1 to 60 g/10 minutes

Usually crystalline propylene polymer (a) shows the z value of the ratio of the average molecular weight to srednekamennogo molecular weight, i.emeasured by the GPC method, of at least a 3.5, preferably 4, more preferably 5, for example, from 9 to 10.

Elastomeric copolymer of ethylene and propylene (b) may optionally include a diene. When it is, the diene is usually present in amounts in the range from 0.5 to 10 wt.% in relation to the weight of the copolymer (b). The diene may be conjugated or not, and selects, for example, from butadiene, 1,4-hexadiene, 1,5-hexadiene and ethylidenenorbornene.

The copolymer (b) is characterized by the fraction insoluble in xylene at temperatures of the environment, which is usually present in amounts less than 45 wt.%, preferably equal to or lower than 25 wt.%. The polymeric fraction of the copolymer (b)which is insoluble in xylene-rich ethylene; the amount of ethylene is usually higher than 55 wt.%.

The polyethylene (C) is a crystalline or semi-crystalline and is selected from homopolymer of ethylene or copolymer of ethylene and propylene having an average content of co monomer in amounts lower than 10 wt.%. The values of the characteristic viscosity of the copolymer (C) are preferably within the range from 2.0 to 3.5 DL/g

The composition of the present invention receive through process of sequential copolymerization.

Thus, the present invention is additionally directed to a method of obtaining a polyolefin compositions, as mentioned above, and the method includes at least three successive stages of polymerization, with each subsequent polymerization is carried out in the presence of the polymeric material directly formed in the preceding reaction polymerization, which spend at least one-stage polymerization of propylene to obtain a crystalline polymer (a), then stage copolymerization of mixtures of ethylene with propylene (and optionally a diene) to obtain the elastomeric polymer (b) is, finally, conduct phase polymerization of ethylene to obtain polyethylene (C). Stage polymerization can be carried out in the presence of a stereospecific catalyst of Ziegler-Natta.

In accordance with the preferred embodiment all stage polymerization is carried out in the presence of a catalyst comprising a compound trialkylamine, optional electron donor, and a solid catalyst component comprising a halide or halogenoalkanes Ti and electron-donating compound deposited on anhydrous magnesium chloride. Catalysts having the above characteristics, are well known in the patent literature; particularly useful are the catalysts described in USP 4399054 and EP-A-45977. Other examples can be found in USP 4472524.

Preferably the catalyst for polymerization is a catalyst of Ziegler-Natta comprising a solid catalytic component containing:

a) Mg, Ti and halogen and an electron donor (internal donor),

b) connection alkylamine and optional (but preferred)

C) one or more electron-donor compounds (external donor).

The internal donor is preferably selected from esters of mono - and dicarboxylic organic acids, such as benzoate, maleate, phthalates and some succinate. They are described, for example, in PA is anti USA 4522930, European patent 45977 and international patent applications WO 00/63261 and WO 01/57099. Particularly suitable are the esters of phthalic acid, esters of succinic acid. Preferred are alkylphenate, such as Diisobutyl, dioctyl and definiltely and benzylbutylphthalate.

As succinate preferably selected from succinates formula (I)below:

in which the radicals R1and R2the same or different from each other, are1-C20-linear or branched alkyl, alkenylamine, cycloalkenyl, aryl, arylalkyl or alcylaryl groups, optionally containing heteroatoms; the radicals R3to R6the same or different from each other, are hydrogen or C1-C20- linear or branched alkyl, alkenylamine, cycloalkenyl, aryl, arylalkyl or alcylaryl groups, optionally containing heteroatoms, and the radicals R3for R6are attached to the same carbon atom, may be joined together with formation of a cycle; with the proviso that when R3-R5are both hydrogen, R6is a radical selected from branched primary, secondary or tertiary alkyl groups, clearcoling, aryl, arylalkyl or alcylaryl groups having from 3 to 20 carbon atoms;

or formula (II)below:

in which the radicals R1and R2the same or different from each other, are1-C20-linear or branched alkyl, alkenylamine, cycloalkenyl, aryl, arylalkyl or alcylaryl groups, optionally containing heteroatoms, and the radicals R3is a linear alkyl group having at least four carbon atoms, optionally containing heteroatoms.

Al-alkyl compounds used as socialization include trialkyl Al, such as triethyl Al, triisobutyl Al, tri-n-butyl Al, and linear or cyclic Al-alkyl compounds containing two or more Al atoms linked to each other through atoms O or N or groups SO4or SO3. Al-alkyl compound, typically applied in an amount such that the ratio Al/Ti was from 1 to 1000.

The external donor (C) may be the same type or it can differ from succinate formula (I) or (II). Suitable connections external electron donor include silicon compounds, ethers, esters, such as phthalates, benzoate, succinate, also having a structure different from that with the joining of the formula (I) or (II), amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine, ketones and complex 1,3-esters of General formula (III):

in which RIand RIIare the same or different and represent radicals With1-C18alkyl, C3-C18cycloalkyl or7-C18aryl; RIIIand RIVare the same or different and represent radicals With1-C4alkyl or complex 1,3-diesters in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6 or 7 carbon atoms and containing two or three bonds.

Ethers of this type are described in published European patent applications 361493 and 728769.

Preferred electron-donor compounds that can be used as external donors include aromatic silicon compound containing at least one bond of Si-OR, where R is a hydrocarbon radical. Especially preferred class of compounds of external donors is a class of silicon compounds of the formula Ra7Rb8Si(OR9)cwhere a and b are integers from 0 to 2, p is an integer from 1 to 3 and the sum (a+b+C) is 4; R7, R8and R9represent carbohydrate is adnie group 1-C18optional containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, C is 2, at least one of R7and R8selected from branched alkyl, alkenyl, alkilinity, cycloalkyl or aryl groups with 3-10 carbon atoms, optionally containing heteroatoms, and R9represents a C1-C10alkyl group, especially methyl. Examples of such preferred silicon compounds are cyclohexyltrichlorosilane, t-butyldimethylsilyl, t-hexyltrimethoxysilane, cyclohexanedimethanol, 3,3,3-cryptochrome-2-typeparameters, diphenylmethylsilane, methyl-t-butyldimethylsilyl, dicyclopentadienyliron, 2-ethylpiperidine-2-t-butyldimethylsilyl, (1,1,1-Cryptor-2-propyl)metaldimension and (1,1,1-Cryptor-2-propyl)-2-ethylpiperidine. In addition, are also preferred compounds of silicon, in which a is 0, C is 3, R8represents a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R9is stands. Particularly preferred specific examples of silicon compounds are (tert-butyl)2Si(OCH3)2(cyclohexylmethyl)Si(OCH3)2, (phenyl)2 Si(OCH3)2and (cyclopentyl)2Si(OCH3)2.

Preferably electron-donating compound (C) is used in such amount to provide a molar ratio between alyuminiiorganicheskikh connection and the specified electron-donating compound (C) from 0.1 to 500, more preferably from 1 to 300 and in particular from 3 to 100.

As explained above, the solid catalytic component includes, in addition to the above-mentioned electron donor, Ti, Mg and halogen. In particular, the catalytic component includes a compound of titanium with at least a link Ti-halogen, and the above-mentioned electron-donating compounds deposited on the Mg halide. The magnesium halide preferably represents MgCl2in the active form, which is widely known from the patent literature as a substrate for catalysts of the Ziegler-Natta. Patents USP 4298718 and USP 4495338 first described the use of such compounds in catalysis Ziegler-Natta. Of these patents, it is known that dihalogenide magnesium in the active form, used as a substrate or a part of a substrate in components of catalysts for the polymerization of olefins, different x-ray spectra in which the most intense diffraction line which appears in the spectrum of active halide, mensalao intensity and is replaced by halo, the maximum intensity of which is shifted towards lower angles relative to the intensity of the more intense lines.

The preferred titanium compounds are TiCl4and TiCl3; moreover, you can also use Ti-galogenangidridy formula Ti(OR)n-yXywhere n denotes the valence of titanium, y is a number from 1 to n, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.

Preparation of solid catalyst component can be carried out in accordance with several methods that are well known and described in the technique.

In accordance with the preferred method of the solid catalytic component can be obtained by the interaction of the titanium compounds of formula Ti(OR)n-yXywhere n denotes the valence of titanium, y is a number from 1 to n, preferably TiCl4with a magnesium chloride deriving from an adduct of formula MgCl2·d, where p is a number between 0.1 to 6, preferably from 2 to 3.5, and R represents a hydrocarbon radical having 1-18 carbon atoms. The adduct can appropriately be obtained in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon, not mixed with the adduct, operating under conditions of agitation at a temperature of melting of the adduct (100-13°C). Then the emulsion is rapidly cooled, thereby causing the solidification of the adduct in form of spherical particles.

Examples of spherical adducts obtained in accordance with the method described in USP 4399054 and USP 4469648. Thus obtained adduct can directly interact with the connection Ti or it can be first subjected to a controlled heat dealcoholization (80-130°C.)to obtain an adduct in which the number of moles of alcohol, as a rule, is lower than 3, preferably between 0.1 and 2.5. Interaction with connection Ti can be performed in suspendirovanie adduct (dealcoholizing or as such) in cold TiCl4(usually 0°C); the mixture is heated up to 80-130°C and maintained at this temperature for 0.5-2 hours. Processing TiCl4carry out one or more times. During processing TiCl4you can add electron-donating compound(connections).

No matter which method of obtaining a finite amount of electron-donor compounds (compounds) is preferably such that the molar ratio with respect to TiCl2ranged from 0.01 to 1, more preferably from 0.05 to 0.5.

These catalyst components and catalysts are described in WO 00/63261 and WO 01/57099.

The catalysts can be pre-entered in contact with the sky the larger quantities of olefins (terpolymerization), maintaining the catalyst in suspension in a hydrocarbon solvent and conducting the polymerization at temperatures from ambient temperature up to 60°C, thereby obtaining the polymer in an amount of from 0.5 to 3 times by weight of the catalyst. The operation may also occur in the liquid monomer to produce in this case, the polymer in amount in 1000 times greater mass of the catalyst.

When applying the above-mentioned catalysts for polyolefin compositions obtained in the form of spheroidal particles, and the particles have an average diameter from about 250 to 7000 μm, the fluidity of less than 30 seconds and bulk density (compacted) of more than 0.4 g/ml

Stage polymerization can occur in the liquid phase, gas phase or in the gas-liquid phase. Preferably the polymerization of the crystalline polymer (C) is carried out in liquid monomer (for example, using liquid propylene as diluent), while stage copolymerization of elastomeric copolymer (b) and polyethylene (C) is carried out in the gas phase. Alternatively, all three stages of polymerization can be conducted in the gas phase.

Temperature interaction on stage polymerization to obtain a crystalline polymer (a) and upon receiving the elastomeric copolymer (b) and polyethylene (C) may be the same or different and costal the em preferably from 40 to 100°C.; more preferably, the temperature of the interaction varies in the range from 50 to 80°C upon receipt of the polymer (a) and from 70 to 100°C. to obtain a polymer components (b) and (C).

Pressure stage polymerization to obtain the polymer (a), if it is carried out in liquid monomer, is the pressure, which competes with the vapor pressure of the liquid propylene at the applicable operating temperature, and it can be modified by the vapor pressure of the small quantity of inert diluent used to load the catalytic mixture, the excess pressure optional monomers and hydrogen, used as molecular weight regulator.

Pressure polymerization preferably ranges from 33 to 43 bar, if the stage is carried out in the liquid phase, and from 5 to 30 bar, if the stage is carried out in the gas phase. The time (duration of treatment) relative to the two stages depends on the desired ratio between the polymers (a)and (b), and (C) and may typically vary in the range from 15 minutes to 8 hours. You can apply conventional molecular weight regulators, known in the art, such as transfer agents circuit (for example, hydrogen or ZnEt2).

You can add conventional additives, fillers and pigments commonly used in olefin polymers, such as nuclearmoose agents (Genty the formation of crystallization centers), additional oils, mineral fillers and other organic and inorganic pigments. In particular, the addition of inorganic fillers such as talc, calcium carbonate, and mineral fillers, also causes improvement in certain mechanical properties such as modulus of elasticity in bending and HDT. Talc may also have the effect of okleinowania.

Nuclearmoose agents added to the compositions of the present invention in quantities fluctuating in the range of, for example, from 0.05 to 2 wt.%, more preferably from 0.1 to 1 wt.% with respect to the total mass.

The following examples provide details that are given to illustrate, without limiting the present invention.

To determine the properties listed in the detailed description and in the examples, the following analytical methods.

-Ethylene:Using IR spectroscopy.

-Fractions, soluble and insoluble in xylene at 25°C:2.5 g of polymer are dissolved in 250 ml of xylene at 135°C under stirring. After 20 minutes the solution is allowed to cool to 25°C, still under stirring and then allowed to fall to a Deposit within 30 minutes. The precipitate was filtered through filter paper, the solution is evaporated in a stream of nitrogen and the residue dried in vacuum at 80°C until constant mass is achieved. Thus, the calculated mass percentage of polim the RA, soluble and insoluble at room temperature (25°C).

-Characteristic viscosity[η]: Measured in tetrahydronaphthalene at 135°C.

-Molecular mass(): Measured by means of gel chromatography (GPC) in 1,2,4-trichlorobenzene.

-The definition of the content of the isotactic pentad: 50 mg each insoluble in xylene fraction was dissolved in 0.5 ml of C2D2Cl4.

Spectra13With NMR were obtained using the device Bruker DPX-400 (100,61 MHz, pulse 90°, the delay of 12 seconds between pulses). For each spectrum was saved about 3000 short single pulses; used as a reference peak mmmm pentad (21.8 pulses per meter).

Analysis of the microstructures was performed as described in the literature (Polymer, 1984, 25, 1640, by Y. Inoue et al. and Polymer, 1994, 35, 339, by R. Chujo et al.).

-Index polydispersity (PI): Was determined at a temperature of 200°C when using rheometer with parallel plates model RMS-800 supplied to the market by the firm RHEOMETRICS (USA), operating at a frequency generation, which increases from 0.1 rad/sec to 100 rad/sec. From the transport module, you can display P.I. by the equation:

P.I.=105/Gc

where Gc represents the transport module, which is defined as the value (expressed in PA)at which G'=G”, where G' is the storage modulus and G” is what Golem losses.

This method is used for polymers having a MFR value of 20 g/10 min or less.

-Index polydispersity: Measurement of molecular mass distribution of the polymer. To determine the value of PI is determined by the splitting module when the value of the loss modulus, for example, 500 PA, at a temperature of 200°C when using rheometer with parallel plates model RMS-800 supplied to the market by the firm Rheometrics (USA), operating at a frequency generation, which increases from 0.01 rad/sec to 100 rad/sec. From the value of the separation module can output the PI using the following equation:

PI=54,6 × (splitting module)-1,76,

where the splitting module (MS) is defined as:

MS=(frequency at G'=PA)/(frequency at G”=p),

where G' is the storage modulus and G” is the loss modulus.

This method is used for polymers having a MFR value of more than 20 g/10 minutes

-The rate of flow of the melt: Determined in accordance with method ISO 1133 (230°C and 2.16 kg).

-The modulus of elasticity in bending: Determined in accordance with method ISO 178.

-Impact strength Izod: Determined in accordance with method ISO 180/1A.

-Resistance to bleaching when voltage: Resistance to bleaching by means of a punch by punch, having a weight of 76 g, small discs, which have the dia is the EPR 4 cm and obtained by injection molding, obtained from the polymer, which should be tested. Register as a height from a minimum (h) and up to the maximum height allowable for the device necessary to obtain bleaching, and the width (diameter) square blanching.

Examples 1 and 2

The plant operating continuously in accordance with the technology of polymerization in a mixed gas-liquid phase, the experiments were conducted under the conditions detailed in Table 1.

The polymerization was carried out in the presence of a catalytic system in a series of three reactors equipped with devices for immediate transfer of the product from one reactor to another beside him.

Preparation of solid catalyst component

In chetyrehosnuju round flask with a capacity of 500 ml of purified nitrogen, injected with 250 ml of TiCl4at 0°C. While stirring, 10.0 g MgCl2·1,9C2H5OH in the form of microspheres (obtained in accordance with the method described in example 2 USP 4399054, but operating at 3,000 rpm instead of 10000 rpm) and 9.1 mmol diethyl-2,3-Diisopropylamine. The temperature was raised to 100°C. and maintained for 120 minutes and Then the stirring is stopped, the solid product allow the precipitate and the supernatant liquid is pumped out of the siphon. Then add 250 ml of fresh TiCl4. The mixture collaboration is the duty to regulate at 120°C for 60 min, and then the supernatant liquid is pumped out of the siphon. The solid residue is washed six times with anhydrous hexane (6×100 ml) at 60°C.

Catalytic system and terpolymerization processing

The solid catalytic component, described above, were in contact at 12°C for 24 minutes with triethylaluminium (TEAL) and dicyclopentadienyliron (DCPMS) as a component of an external electron donor. The mass ratio between the TEAL and the solid catalytic component and the mass ratio between TEAL and DCPMS detailed in Table 1.

The catalytic system is then subjected terpolymerization while maintaining it in suspension in liquid propylene at 20 ° C for about 5 minutes before introducing it into the first reactor for polymerization.

Polymerization

The cycle of polymerization carried out continuously in a series of three reactors equipped with devices for immediate transfer of product from one reactor to another, being with him. The first reactor is a liquid-phase reactor, and the second and third reactors are gas-phase fluidized bed reactor. The polymer (a) receive in the first reactor, while the polymers (b) and (C) receive the second and third reactors, respectively.

The temperature and pressure constant support throughout the reaction. As re is ulator molecular weight is applied hydrogen.

The gas phase (propylene, ethylene and hydrogen) constantly regulate by means of gas chromatography.

At the end of the cycle, the powder is discharged and dried in a stream of nitrogen.

Then the particles of polymer injected into the extruder with two screws (extruder of the Werner type)in which they are mixed with 635 ppm Irganox 1010, 635 ppm Irgafos 168, 2450 h/million distearyldimethylammonium and 270 ppm synthetic hydrotalcite. Previously Irganox 1010 is pentaerythritoltetranitrate-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate), while Irgafos 168 is a Tris(2,4-di-tert-butylphenyl)FOSFA, and they both sold on the market by the company Ciba-Geigy. Particles of polymer ekstragiruyut in nitrogen atmosphere in a twin-screw extruder at a speed of rotation of the rotor 250 rpm and the melting temperature of 200-250°C.

Comparative Example 1 (1C)

Example 1 was repeated except that the catalytic component was replaced catalytic component containing diisobutylphthalate instead diethyl-2,3-(aminobutiramida)succinate.

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Table 1
The polymerization process
Example121C
the mass ratio TEAL/DCPMS 2,83,43
1st liquid-phase reactor
The polymerization temperature, °C757575
Pressure, bar404040
The mass of the H2, mol. parts per million280028001300
2nd liquid-phase reactor
The polymerization temperature, °C--75
Pressure, bar--40
The mass of the H2, mol. parts per million--1300
1st gas phase reactor
The polymerization temperature, °C656560
Pressure, bar131311,5
With2-/(C2-+C3-), %303648
H2/S2-, %5,25,17,5
The 2nd gas phase reactor
The polymerization temperature, °C757575
Pressure, bar181811,4
With2-/(C2-+C3-), %99,099,096,5
H2/S2-, %18,018,014,9
Notes: mass of H2=hydrogen concentration in the liquid monomer; C2-=ethylene; C3-=p the cut.

Table 2
Analysis of the composition
Example121C
The crystalline homopolymer of propylene
The content of homopolymer, wt.%71,572,576
MFR, g/10 min553
Index polydispersity5,95,94,3
ratio8,18,16,6
ratio4,14,1a 3.9
The content of the pentad, molar %98,598,598,8
Fraction soluble in xylene, mA is.% 1,61,61,3
The copolymer of ethylene and propylene
The content of the copolymer, wt.%10,510,58
The ethylene content in the EPR, wt.%455546
Characteristic viscosity [η] soluble in xylene fraction, DL/g3,73,63,5
Fraction soluble in xylene, wt.%11(1)10,5(1)9(1)
Polyethylene
The content of polyethylene, wt.%181716
The ethylene content in PE, wt.%100100100
Characteristic viscosity [η], DL/g2,7 2,73,31
Notes: EPR: elastomeric rubber is a copolymer of ethylene and propylene; RE: crystalline polyethylene.(1)The value measured on the polymer composition obtained in the first and second reactors.

The properties of the final compositions and properties of all compositions are presented in tables 3 and 4, respectively.

Table 3
The final song
Example121C
The ethylene content, wt.%2322,423
Fraction soluble in xylene, wt.%1110,59
Characteristic viscosity [η] soluble in xylene fraction, DL/g3,73,63,5
The mass ratio PE/EPR1,711,622,00

Table 4
Properties of all songs
Examples and comparative examples121C
MFR, g/10 min1,62,02
The modulus of elasticity in bending, MPa142013701260
Impact strength Izod kJ/m2at 23°CNB1)NB1)NB1)
at -20°C10,68,56,0
Resistance to bleaching: diameter (cm) area of blanching in the fall of punch from a height:5 cm0,70,40,3
10 cm1,00,70,6
20 cm1,10,90,9
30 cm1,31,11,0
76 cm1,41,31,9
Note: not collapsed

The above data show that the polymer compositions in accordance with the present invention exhibit an improved balance between stiffness and impact resistance, particularly at low temperatures, the rigidity and the impact resistance are higher; resistance to bleaching also improves for testing, when the plunger falls from a higher altitude and is essentially the same test, when the plunger falls to a lower height.

1. Composition based on polypropylene, suitable for the manufacture of articles by injection molding and thermoforming, comprising (in wt.%):
a) 65-77% of a crystalline propylene polymer having an amount of the isotactic pentad (mmmm), measured by means of the13C-NMR of fraction insoluble in xylene at 25°C., higher than that of 97.5 mol.% and the index polydispersity determined at a temperature of 200°C using riomet is and with parallel plates at a frequency generation, increasing from 0.1 rad/s to 100 rad/s, which varies in the interval from 5 to 10;
b) from 9 to less than 12% of an elastomeric copolymer of ethylene and propylene, the copolymer has a number of structural units derived from ethylene in the range from 30 to 70%, and is partially soluble in xylene at ambient temperature; and the polymer fraction soluble in xylene at ambient temperature, has a value of the characteristic viscosity, measured in tetrahydronaphthalene at 135°C, in the interval from 2 to 4 DL/g; and
c) 10-23% of polyethylene having a value of the characteristic viscosity in the range from 1.5 to 4 DL/g and, optionally, containing structural units derived from propylene in amounts lower than 10%,
moreover, this composition exhibits the following properties:
the value of the modulus of elasticity in bending is higher than 1300 MPa in accordance with method ISO 178,
values of resistance to bleaching at a voltage corresponding to the diameter of the field of bleaching educated falling from a height of 76 cm plug of not more than 1.7 cm, and the diameter of the field of bleaching formed by falling from a height of 20 cm plug of not more than 1.2 cm and
value impact resistance Izod over 14 kJ/m2at 23°C and at least about 6.5 kJ/m2at -20°C in accordance with method ISO 180/1A.

2. The composition of the Nove propylene according to claim 1, in which crystalline propylene (a) is from 70 to 77 wt.%, the elastomeric copolymer (b) is from 9 to 12 wt.% and polyethylene (C) is from 10 to 20 wt.% with respect to the entire resin composition.



 

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1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention can be particularly used in the cable industry when making electrical cable shielding used in explosive environments, in electrical engineering when making working sheath of earthing electrodes in general-purpose protective earthing systems, protection from static electricity and electrochemical protection from corrosion in the ground, fresh and sea water etc. The rubber mixture contains the following in pts. wt: synthetic ethylenepropylene diene rubber 90-100, technical sulphur 0.3-0.5, paraffin-naphthalene oil 10-15, bis-tertbutylperoxyisopropyl benzene 5.0-6.5, zinc oxide 5-8, electroconductive technical carbon 80-100, carbon-fibre material made from hydrocellulose fibre 15-25. The electrical current conductor comprises at least one conductor which has a shielding or working sheath made from the said rubber mixture.

EFFECT: improved operational characteristics of the electroconductive rubber mixture and electrical current conductors made from the said mixture.

4 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermoplastic rubber obtained through dynamic vulcanisation, which can be used to make various elastic industrial rubber products such as hoses, sealants, linings, elastic articles for the interior and exterior of automobiles, different corrugated elastic articles. The thermoplastic rubber is made from a composition consisting of ethylenepropylenediene elastomer, polypropylene, hydrocarbon oil, fine-grained filler, curing agents which include polyhydrosiloxane which contains at least two SiH groups, and a platinum catalyst. The composition also contains a higher fatty alcohol with 12-22 carbon atoms and an organophosphorus cyano-containing compound selected from an alkylcyanoethylphosphite group of general formula (NCC2H4O)nP(OR')3-n or alkylcyanoethylphophine of general formula (NCC2H4O)nP(R')3-n, where R' is an alkyl with 2-3 carbon atoms, n=1-3.

EFFECT: increased fluidity of the molten mass while retaining good deformation and strength characteristics.

2 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a polyethylene composition with multimodal molecular weight distribution for blow moulding canisters with volume ranging from 2 to 20 dm3 and a method of preparing the said composition. The composition has density ranging from 0.950 to 0.958 g/cm3 at 23°C and melt flow rate (MFR190/5) from 0.30 to 0.50 dg/min. The composition also contains 40 to 50 wt % low molecular weight ethylene homopolymer A and 25 to less than 30 wt % high molecular weight copolymer B obtained from ethylene and another 1-olefin containing 4 to 8 carbon atoms, and 24 to 28 wt % ethylene copolymer C having ultra-high molecular weight.

EFFECT: obtained composition has good resistance to chemical effect, especially high mechanical strength, high corrosion resistance and is a naturally light material; high melt strength of the composition enables prolonged extrusion without breaking the workpiece, and an accurately selected swelling index of the composition enables optimisation of controlling thickness of the wall of the article.

10 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin substrates, for example to objects moulded from polypropylene, polyethylene or thermoplastic olefin, which is scratch resistant. Scratch resistance is achieved by adding an additive to polyolefin: maleated alpha olefin, functionalised long-chain alcohol or long-chain amine, and a primary or secondary amide of a fatty acid. The functionalised maleated alpha olefin is, for instance an ester or a partial ester of a maleated C18-C26alpha olefin with a tall fatty alcohol. The fatty acid amide is oleyl palmitate or stearyl erucamide, for example.

EFFECT: polyolefin compositions have high weather resistance, scratch resistance, good processibility, high mechanical strength, retain lustre well and are not sticky.

13 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin compositions which have high decolouration and impact resistance. The composition contains from 50 to less than 70 wt % crystalline propylene homopolymer, 13-28 wt % elastomeric ethylene and propylene copolymer and 10-22 wt % polyethylene. Total amount of the elastomeric copolymer and polyethylene in the composition is more than 30 wt %. The crystalline propylene homopolymer has polydispersity index ranging from 4 to 10 and amount of isotactic pentades (mmmm) measured using 13C-NMR method on a fraction which is insoluble in xylene at 25°C more than 97.5 mol %. The elastomeric ethylene copolymer is partially soluble in xylene at ambient temperature. The polymer fraction which is soluble in xylene has value of inherent viscosity, measured in tetrahydronaphthalene at 135°C, which ranges from 2 to 4 dl/g. Polyethylene has inherent viscosity ranging from 1 to 3 dl/g.

EFFECT: obtained polypropylene compositions have relatively low hardness, high impact resistance and high resistance to decolouration, which enables their use in the motor car industry, particularly in bumpers and interior finishing, packaging and household objects.

5 cl, 4 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing thermoplastic elastomer compositions, realised through dynamic vulcanisation of a mixture of components of a composition, meant for preparing sealing components, tubing, insulation for components of electric devices, used in aviation, automobile, cable and other industries. The method is realised by loading an ethylene-propylene-diene copolymer and target additives at the first step. Temperature is raised to 120°C and vulcanising agents are added. At temperature of 150°C, thermoplastics are added - polyethylene and polypropylene in amount of 30-50 wt % of their total content and stirring is done at temperature of 190°C. At the second step the remaining amount of thermoplastics is added to the obtained mixture.

EFFECT: obtaining a thermoplastic elastomer composition with improved mechanical, rheological and electrical characteristics.

3 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of waterproofing materials in form of profiled objects - cords, meant for sealing joints in unit construction and which provide for waterproofing through fast water regain. The polymer sealing composition contains, wt %: polymer - synthetic ethylene-propylene triple rubber - 23.78-86-80, natural bentonite - 8.68-71.34, sodium carbonate - 0.09-2.38, titanium white - 2.38-4.34 and colouring pigment - 0.09-0.12.

EFFECT: increased degree of water regain, resistance to effect of atmospheric factors, increased frost- and ozone resistance, cohesion strength and elasticity after the material dries.

1 tbl, 2 ex

FIELD: engines and pumps.

SUBSTANCE: invention relates to solid-propellant charges. Proposed charge comprises casing and propellant charge attached thereto by protective-attachment layer. The latter represents a calendered sheet material based on ethylene-propylene and comprising serpentine asbestos as filler, dioctyldecyl adipate as plastifier and n-dinitrosobenzene as adhesive additive. Note here that the surface of aforesaid layer, on boundary of contact with propellant charge, is subjected to modification by thermally-treated 4,4'-diphenyl methane diisocyanate in the amount of 5 to 20 g/m2.

EFFECT: reliable attachment of charge to engine housing that allows charge longer life.

1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: rubber composition consists of, wt %: polypropylene - 3-21, butadiene-nitrile rubber - 22-55, olefin rubber - 2.5 -9.5, modificator, cross-linking agent for rubbers - 1.5-3.5, activator - 0.18-0.3, plasticiser - 3.0-7.5, mineral oil - 8-40. The composition contains polyisocyanate containing not less than two isocyanate groups (0.05-2.3 wt %) as a modificator and polypropylene with 1-6% of grafted maleic anhydride or maleic acid - 6-20 wt %. Plasticiser solubility parametre of is not less than 18 (kJ/m3)1/2.

EFFECT: oil resistance enhancing, decrease of relative residual elongation and melt flow index.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: mixture contains two different polyolefin and ethylene/α-olefin copolymers. The ethylene/α-olefin copolymer is a block-copolymer containing at least one hard block and at least one soft block. The ethylene/α-olefin copolymer can function as a component which improves compatibility between two polyolefins which may be incompatible. The disclosed polymeric mixtures can be used in making various articles such as tyres, hoses, belts, linings, shoe soles, cast and moulded articles. Said mixtures are especially useful for applications requiring melt strength, such as big articles made by blow moulding, foam and bundled bars.

EFFECT: improved compatibility of mixtures.

27 cl, 10 dwg, 13 tbl, 40 ex

FIELD: chemistry.

SUBSTANCE: description is given of an olefin polymer composition used in pressure moulding and in hot moulding equipment, containing the following (in terms of weight): A) 60-85% crystalline propylene homopolymer characterised by polydispersity index (P.I) value ranging from 4.5 to 6 and content of isotactic pentades (mmmm) of over 96%, measured from 13C NMR in a fraction which is insoluble in xylene at 25°C; B) 15-40% partially amorphous ethylene copolymer containing from 35% to 70% propylene; the said olefin polymer composition has breaking stretching, in accordance with ISO 527, ranging from 150% to 600%. Also described is a method of preparing an olefin polymer composition through polymerisation in paragraph 1, involving at least two successive steps on which components (A) and (B) are obtained at different successive steps, carrying out each step, except the first, in the presence of the obtained polymer and the catalyst used at the previous step, and in the presence a Ziegler-Natta polymerisation catalyst containing a solid catalyst component which contains: a) Mg, Ti and a halogen and at least two electron donor compounds, said catalyst component is characterised by that, at least one of the electron donor compounds, present in amount ranging from 15 to 50 mol % of the total amount of donors, is selected from a class of succinates which are not extractable above 20 mol % and at least another electron donor compound which is extracted above 30 mol %; b) alkyl aluminium and optionally, c) one or more electron donor compounds.

EFFECT: highly elastic olefin polymer composition with high breaking elongation value is obtained.

5 cl, 3 tbl, 3 ex

Additive mixture // 2374277

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of additives to polymers, specifically to additive mixtures which are used as clarifiers for propylene homo- or copolymers. According to this invention, additive mixtures contain components (A), (B), (C) and (D). Component (A) is at least one compound of formula (I-1) , ,

and , component (B) is a compound of formula (II-1)

and component (D) is a compound of formula (III-1)

EFFECT: use of the additive mixture in accordance with this invention improves the processed propylene homo- or copolymers.

13 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin compositions with good balance of hardness and impact-resistance and high elongation rating. A hetero-phase polyolefin composition is described, containing (wt %): (A) from 50 to 80 wt % crystalline propylene polymer with polydispersity index from 5.2 to 10 and isotactic pentad (mmmm) content over 97.5 mol %, determined by 13C-NMR spectroscopy in a fraction which is insoluble in xylene at 25°C; wherein the said polymer is chosen from a propylene homopolymer or propylene copolymer and at least a comonomer, chosen from ethylene and α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical, containing at least 95 % repeating units derived from propylene; (B) from 5 to 20 % of the first elastomeric ethylene copolymer with at least a comonomer chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said first elastomeric copolymer contains from 25 to less than 40% ethylene and is soluble in xylene at room temperature in amount ranging from over 85 wt % to 95 wt %, where characteristic viscosity [η] of the fraction soluble in xylene ranges from 2.5 to 4.5 dl/g; and (C) from 10 to 40% of a second elastomeric ethylene copolymer with at elast a comonomer, chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said second elastomeric copolymer contains 50 to 75% ethylene and is soluble in xylene at room temperature in amount ranging from 50 wt % to 85 wt %, where characteristic viscosity [η] of the fraction which is soluble in xylene ranges from 1.8 to 4.0 dl/g; in which total amount of copolymer (B) and copolymer (C) ranges from 20 to 45 % of the total amount of components (A)-(C), total amount of ethylene with respect to total amount of components (A)-(C) is 23 wt %, and the ratio of ethylene content in the fraction which is insoluble in xylene at room temperature, (C2xif), multiplied by the weight percent content of the fraction which is insoluble in xylene at room temperature, (%XIF), and ethylene content in the fraction which is soluble in xylene at room temperature, (C2xsf), multiplied by weight percent content of the fraction which is soluble in xylene at room temperature (%SXF), i.e. C2xif x % XIF)/(C2xsf x % SXF), satisfies the following relationship (I): (C2xif x % XIF)/(C2xsf x % SXF)>0.01 x + 0.261, where x is total amount of ethylene. Described also is a method of polymerisation of the polyolefin composition described above, involving at least three consecutive steps, where components (A), (B) and (C) are obtained on separate consecutive steps, where operations on each step, except the first step, take place in the presence the polymer formed in the previous step and catalyst used in the previous step.

EFFECT: obtaining polyolefin compositions with high hardness, without reducing impact resistance, especially impact resistance at low temperatures and elastic properties.

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin composition which are resistant to dynamic loading and to the method of producing said composition. The composition contains A) 60 to 95 wt % propylene (co)polymer of with polydispersity index (P.I) from 4.6 to 10 and isotactic pentad content (mmmm) over 98 mol %, determined using 13C-NMR spectroscopy for a fraction which is insoluble in xylene at 25°C and B) 5 to 40 wt % ethylene copolymer, containing 40 to 70 wt % propylene or C4-C10 α-olefins or their combination and, optionally, small diene proportions. The composition has temperature rising elution fractionation (TREF) profile, obtained through fractionation in xylene with tapping fractions at temperature 40°C, 80°C and 90°C, in which ethylene content Y in the fraction tapped at 90°C satisfies relationship (I): Y≤-0.8+0.035X+0.0091X2, where X is ethylene content in the fraction tapped at 40°C, and both values of X and Y are expressed in weight percent, and value of intrinsic viscosity [η] of the fraction which is soluble in xylene at 25°C ranges from 1.8 to 4.2 dl/g.

EFFECT: obtaining olefin polymer with good balance of properties, more specifically with high hardness and good resistance to dynamic loading.

3 cl, 3 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: rubber composition consists of, wt %: polypropylene - 3-21, butadiene-nitrile rubber - 22-55, olefin rubber - 2.5 -9.5, modificator, cross-linking agent for rubbers - 1.5-3.5, activator - 0.18-0.3, plasticiser - 3.0-7.5, mineral oil - 8-40. The composition contains polyisocyanate containing not less than two isocyanate groups (0.05-2.3 wt %) as a modificator and polypropylene with 1-6% of grafted maleic anhydride or maleic acid - 6-20 wt %. Plasticiser solubility parametre of is not less than 18 (kJ/m3)1/2.

EFFECT: oil resistance enhancing, decrease of relative residual elongation and melt flow index.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polypropylene polymer composition, which has improved balance "impact resistance-rigidity" and suitable for formed products manufacturing. Composition contains a) from 50 to 90 wt % of propylene homopolymer or propylene copolymer, containing to 5% molar links, derivatives of C2-C20-alfa-olefins, b) from 5 to 25 wt % of ethylene copolymer and one or several links, derivatives of C4-C20-alfa-olefins, with content of links, derivatives of C4-C20-alfa-olefins, from 50 mol% to 92 mol % and c) from 5 to 25 wt % of copolymer of propylene and ethylene, with content of links, derivatives of propylene more than 50 mol % and less than 92 mol %. Weight ratio between ethylene copolymer(component b) and sum of component b and component c) is equal or is larger than 0.5 and smaller or equal 0.9. And component a) has polydispersibility index (PI) larger than 3, melt flow rate (MFR) larger than 1dg/min, measured at 230° C under loading 2.16 kg, and fraction, soluble in xylol at 25° C, more than 1%, it also does not contain 2,1-disturbances of location. Component b) has characteristic viscosity higher than 1.2 dl/g and lower than 6 dl/g, density within interval from 0.850 to 0.890 g/ cm3, crystallinity, expressed through melting enthalpy, lower than 25 J/g and value of copolymerisation constants product r1x r2 lower than 5. Component c) has characteristic viscocity higher than 2 dl/g and lower than 6 dl/g, density within interval from 0.850 to 0.890 g/ cm3, value of copolymerisation constants product r1xr2 lower than 1.8 and crystallinity, expressed through melting enthalpy, lower than 30 J/g.

EFFECT: creation of polypropylene composition possessing excellent rigidity, thermal stability and impact strength.

9 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: proposed composition contains a) synthetic polymer and b) one or several compounds of formula or where R1, R2 and R3 or Y1, Y2 and Y3, or Z1, Z2 and Z3 represent, for example branched C3-C20alkyl.

EFFECT: possibility of significantly reducing blushing of polymers.

41 cl, 10 tbl, 90 ex

FIELD: chemistry.

SUBSTANCE: composition contains propylene polymer 60 to 85 % with wide chain-length distribution of polydispersity index 5 to 15 and melt flow rate speed 40 to 75 g/10 min, specified according to ASTM-D 1238, provision L, at 230°C under load 2.16 kg and partially xylene-soluble polyolefin rubber 15 to 40 % containing ethylene propylene copolymer containing at least ethylene 65 wt % and xylene-insoluble components approximately 25-40 wt % specified at 25°C. Polyolefin composition is characterised with good balance of mechanical properties, particularly improved balance of bending elastic modulus and impact strength even at low temperatures, e.g., at -30°C, and also low heat settings.

EFFECT: specified property ensures high dimensional stability to the products made of polyolefin composition according to the present invention.

5 cl, 2 tbl, 2 ex

Polyolefin articles // 2342411

FIELD: chemistry.

SUBSTANCE: present invention pertains to the chemical industry and can be used for making articles from a polyolefin composition, obtained through extrusion, moulding and a combination of both. The composition contains (wt %) (1) 65-95% crystalline propylene polymer, insoluble in xylene at ambient temperature in quantity of over 85% and with heterogeneity index ranging from 4.5 to 13 and viscosity index of over 2.2 dl/g; and (2) 5-35% elastomer olefin polymer of ethylene and propylene, with ethylene content ranging from 15% to 85% and viscosity index of not less than 1.4 dl/g. The ratio of the viscosity index of component (1) to the viscosity index of component (2) ranges from 0.45 to 1.6. Single and/or multilayered pipes, films or sheets, made from the given composition can be used at relatively low pressure, have the best resistance to stretching and shock resistance at low temperature without reduction in rigidity.

EFFECT: obtaining materials with the best resistance to stretching and shock resistance at low temperature without reduction in rigidity.

13 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: composition contains polyethylene production and/or household wastes, beet pulp and bentonite as a processing additive.

EFFECT: disclosed composition has rheological characteristics which meet requirements for polymeric materials for their possible processing on conventional equipment, as well as required operational characteristics, including biodegradability.

4 ex, 2 tbl

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