Using terpolymers of propylene and butylene with nucleating agent to form sterilising films obtained via extrusion blowing

FIELD: chemistry.

SUBSTANCE: invention relates to use of terpolymers of propylene/butylene/ethylene with a nucleating agent to form sterilising films obtained via extrusion blowing. A film is obtained from a polymer composition containing (i) and (ii) 0.001-1.0 wt % of one or more phosphorus-containing and/or polymeric α-nucleating agents. The terpolymer of propylene, ethylene and butylene consists of 86.0-98.0 wt % propylene, 2.0-12.0 wt % butylene and 0.1 to less than 1.0 wt % ethylene. The obtained films have a) turbidity according to ASTM D 1003-92 for a 50 mcm film less than 8% before and after steam sterilisation at 121°C for 30 minutes and b) lustre at 20° according to DIN 67530 for a 50 mcm film of at least 55% before steam sterilisation at 121°C for 30 minutes and at least 60% after steam sterilisation at 121°C for 30 minutes. The films are sterilisable and have excellent optical and mechanical properties.

EFFECT: improved method of obtaining films.

16 cl, 4 tbl, 3 ex

 

The present invention relates to the use of terpolymers propylene/butylene/ethylene with a nucleating agent to obtain sterylizowane films obtained by extrusion blow.

Film obtained by extrusion blow obtained from these polymers are sterilized and have excellent optical and mechanical properties.

Background of invention

Polyolefins have received wide acceptance and use in many industrial applications due to their relatively low cost and desirable properties.

Such industrial applications include polymer films, such as films, obtained by irrigation, a film obtained by extrusion blown, one - and biaxially oriented films and coating. These polymer films may, for example, be used for a variety of flexible and rigid packaging, for example, for food, medical products, flowers, etc.

In a constantly increasing part of the market, especially in the pharmaceutical industry, and in food packaging material is sterilized one way or another. Adverse use of heat (steam), radiation or chemicals for sterilization is usually significantly affects the mechanical and optical properties of the material.

The polypropylene for a film n is currently used almost exclusively for films, receive irrigation. In the method of obtaining a film watering cooling roller is achieved very rapid cooling of the melt in order to use a potentially good optical and mechanical properties of polypropylene for film applications.

Until recently, the polypropylene could be used in the method of obtaining a film extrusion blown, only when it was possible to use the cooling upon contact with water in order to achieve the same rapid cooling, as in the method of producing films watering.

In the traditional method of obtaining a film extrusion blown using air cooling, the polymer melt and the film obtained from it cools only slowly. This gives insufficient optical and mechanical parameters, because the process of slow cooling causes uncontrolled growth of crystalline and spherolites patterns. A polypropylene film obtained by extrusion blown with air cooling, are as dull, and brittle.

The problem of opacity, respectively, turbidity and fragility polypropylene film obtained by extrusion blown, tried to improve by using a combination of statistical copolymers of propylene or inorganic nucleating agent or with carbetapentamine paradisebet what aalami, which gives improved optical and mechanical properties to a very limited extent. So there is a need for more improvements in air-cooled films obtained by extrusion blow, of polymers of propylene.

In the examples of WO 2005/026240 treated film obtained by extrusion blow-containing polypropylene composition comprising a homopolymer of propylene or a copolymer of propylene with 4.8 wt.% ethylene, the composition of propylene copolymer containing 0.2 wt.% clarifier containing phosphate-containing α-nucleating agent, respectively, arbitrade α-nucleating agent.

In these examples it is shown that the film obtained by extrusion-blow process, of a copolymer of propylene and ethylene containing phosphate-containing α-nucleating agent, has better optical properties (gloss and turbidity compared with the film obtained by extrusion-blow process, of a copolymer of propylene and ethylene containing arbitrade α-nucleating agent. The film obtained by extrusion-blow process, according to example 1 also shows the modulus of tensile elasticity of about 925 MPa (longitudinal direction) and, respectively, approximately 972 MPa (transverse direction).

WO 02/44252 considers the use of polymer compositions consisting of propylene terpolymer the erucic acid amide and/or amide of oleic acid as an additive, reducing friction, for films, for example films obtained by spray, or a film obtained by extrusion-blow process, which show the following properties:

a) dynamic friction coefficient after storage for 3 days (72 hours) at 23°C less than 0.30 (measured according to DIN 53375);

b) characterization of turbidity, measured in values of turbidity in accordance with ASTM D 1003-92 after storage for 14 days (336 hours) at 40°C, which shows the deterioration of not more than 100% of the original value, measured after storage for 4 days (96 h) at 23°C.

Furthermore, it describes that the laminated film obtained from the above polymer compositions show a smaller loss of optical properties compared to films from statistical copolymers, propylene-butylene or propylene-ethylene after sterilization at 121°C for 30 minutes

The modulus of tensile elasticity of the films obtained by the irrigation technology, is in the range 385-440 MPa.

WO 03/040202 consider, for example, a film obtained by extrusion blow out (among other polymers) copolymers, propylene/1-butylene and terpolymers propylene/ethylene/1-butylene.

These films contain at least 50 wt.% propylene and at least 5 wt.% ethylene and/or one or more unsaturated comonomers and have a turbidity less than about 10 and a gloss at 45° more primerno.

In the examples of WO 03/040202 describes the basic resin for studying mixing to obtain a film obtained by extrusion-blow process, using commercially available propylene Ziegler-Natta (N-02Z: minimalistically PP Ziegler-Natta containing 0.5 wt.% ethylene-nucleating - methylene-bis(4,6-di-tert-butylphenyl)hospitalaria salt supplied by the company The Dow Chemical Company). The resulting film obtained by extrusion-blow process, considered as a comparative example, shows less favourable properties than mixtures containing special copolymers of propylene/ethylene claimed in WO 03/040202.

Therefore, the aim of the present invention is to provide an improved water - and air-cooled films obtained by extrusion-blow process, preferably, the air-cooled films obtained by extrusion blow derived from terpolymers propylene/butylene/ethylene, which are sterilized and have superior mechanical properties and excellent optical properties, which are even improved after sterilization.

The objective is achieved through the use of a polymer composition, including:

(i) terpolymer propylene/butylene/ethylene, which consists of

86,0-98,0 wt.% propylene,

2.0 to 12.0 wt.% 1-butylene and

0.1 to less than 1.0 wt.% ethylene and

(ii) 0.001 to 1.0 wt.% odgovori more phosphorus-containing and/or polymer of α-nucleating,

to obtain sterylizowane water - and air-cooled films obtained by extrusion-blow process, which have the following properties:

(a) the turbidity according to ASTM D 1003-92 for a 50 μm film of less than 8% before and after steam sterilization at 121°C for 30 min; and

b) gloss at 20° acc. to DIN 67530 for a 50 μm film of at least 55% to steam sterilization at 121°C for 30 min and at least 60% after steam sterilization at 121°C for 30 minutes

Suddenly these films combine high stiffness (modulus of tensile elasticity, and excellent optical properties, which are even improved after sterilization.

The use of these compositions terpolymer propylene to obtain sterylizowane films obtained by extrusion-blow process, preferably, the air-cooled films obtained by extrusion blow with the above required benefits that are not considered in the existing technique.

According to other variants of the present invention ethylene, preferably present at levels less than 1.0 wt.%, more preferably, less than 0.5 wt.%, and, most preferably, in the range of 0.1 to 0.4 wt.%

According to other variants of the present invention butylene, preferably present at levels of more than 5 wt.%, more preferably, more than 6 wt.%, and, most preferred is entrusted, in the range of 7-12 wt.%

In addition, the composition may contain other polymers, such as HDPE, LDPE, LLDPE, PEEP, PAOP or other polymers or copolymers containing ethylene and other α-olefin.

The polymer composition further comprises 0.001 to 1.0 wt.% one or more alpha-nucleating. Is introduced, preferably, 0.005 to 0.5 wt.%, more preferably, 0.01 to 0.3 wt.% one or more alpha-nucleating. The number of alpha-nucleating less than 0.001 wt.% usually do not give the desired effect, whereas with quantities of more than 1 wt.%, although obtaining the desired effect, the resulting film obtained by extrusion blown become too expensive due to costly nucleating.

Alpha-nucleating agent, which can be used for polymeric compositions of the present invention includes an organic nucleating selected from the group of phosphorus-containing nucleating, for example, metal salts of phosphoric esters represented by the formula I:

in which

R1 represents an oxygen atom, a sulfur atom or a hydrocarbon group having 1-10 carbon atoms;

each of R2 and R3 represents H, a hydrocarbon or a hydrocarbon group having 1-10 carbon atoms; R2 and R3 can be the ü the same or different from each other, two R2, two R3 or R2 and R3 may be joined together forming a ring;

M is an atom monovalent, divalent, trivalent metal;

n is an integer from 1 to 3;

and m represents either 0 or 1, provided that n > m.

Preferred examples of alpha-nucleating represented by formula I, include :

sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate,

sodium-2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate,

lithium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate,

lithium-2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate,

sodium-2,2'-ethylidene-bis-(4-isopropyl-tertbutylphenyl)-phosphate,

lithium 2,2'-methylene-bis-(4-methyl-6-tert-butylphenyl)phosphate,

lithium 2,2'-methylene-bis-(4 - ethyl-6-tert-butylphenyl)phosphate,

calcium-bis[2,2'-thio-bis(4-methyl-6-tert-butylphenyl) phosphate],

calcium-bis[2,2'-thio-bis(4-ethyl-6-tert-butyl-phenyl)phosphate],

calcium-bis[2,2'-thio-bis-(4,6-di-tert-butylphenyl)phosphate],

magnesium-bis[2,2'-thio-bis-(4,6-di-tert-butylphenyl)phosphate],

magnesium-bis[2,2'-thio-bis-(4-tert-octylphenyl)phosphate],

sodium-2,2'-butylidene-bis-(4,6-dimetilfenil)phosphate,

sodium-2,2'-butylidene-bis-(4,6-di-tert-butylphenyl)phosphate,

sodium-2,2'-tert-octylamine-bis-(4,6-dimetilfenil)phosphate,

sodium-2,2'-tert-octylamine-bis-(4,6-di-tert-butylphenyl)-phosphate,

calcium-bi is-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)-phosphate],

magnesium-bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate],

barium-bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate],

sodium 2,2'-methylene-bis-(4-methyl-6-tert-butylphenyl)phosphate,

sodium 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenyl)phosphate,

sodium-(4,4'-dimethyl-5,6'-di-tert-butyl-2,2'-biphenyl)phosphate,

calcium-bis-[(4,4'-dimethyl-5,6'-di-tert-butyl-2,2'-biphenyl)phosphate],

sodium-2,2'-ethylidene-bis-(4-meta-butyl-6-tert-butylphenyl)-phosphate,

sodium 2,2'-methylene-bis(4,6-di-tert-ethylphenyl)phosphate,

potassium-2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate,

calcium-bis[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)-phosphate],

barium-bis[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)-phosphate],

aluminiumhydride-bis-[2,2'-methylene-bis(4,6-di-tert-butyl-phenyl)phosphate],

aluminum-Tris[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)-phosphate].

The second group of phosphate nucleating includes, for example, aluminumhydroxide-bis[2,4,8,10-tetrakis-(1,1-dimethylethyl)-6-hydroxy-N-dibenzo[d,g]-dioxa-fosfory-6-oxidate] and mix with Li-myristate or Li-stearate.

Of the phosphorus-containing nucleating especially preferred are sodium-2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate or aluminiumhydride-bis-[2,2'-methylene-bis(4,6-di-tert-butyl-phenyl)phosphate], or aluminumhydroxide-bis - 2,4,8,10-tetrakis-(1,1-dimethylethyl)-6-hydroxy-N-diben what about the[d,g]-dioxa-fosfory-6-oxidate] or mixture with Li-myristate or Li-stearate.

Other suitable alpha-nucleating are polymeric nucleating selected from the group consisting of vinylcyclohexane polymers and vinylalcohol polymers. The nucleation with the specified polymeric nucleating performed either by a special reactor technology, where the catalyst terpolymerization monomers, such, for example, vinylcyclohexane ((VCG)(VCH)), or by mixing a propylene polymer with vinyl(cyclo)alkanoyl polymer. These methods are described in more detail, for example, in EP A and WO 99/24479.

Suitable alpha-nucleating for Propylenediamine compositions of this invention are the nucleating the joining, as described for example, in Macromolecules, 2005, 38, 3888-3695.

The nucleating such as ADK NA-11 (methylene-bis(4,6-di-tert-butylphenyl)hospitalaria salt) and ADK NA-21 (aluminumhydroxide-bis[2,4,8,10-tetrakis-(1,1-dimethylethyl)-6-hydroxy-N-dibenzo[d,g]-dioxa-fosfory-6-oxidate]), are commercially available from the company Asahi Denka Kokai and, preferably, introduced into Propylenediamine composition of the present invention.

Among all alpha-nucleating mentioned above, especially preferred are the nucleating containing aluminumhydroxide-bis[2,4,8,10-tetrakis-(1,1 - Imereti)-6-hydrox the-N-dibenzo-[d,g]-dioxa-fosfory-6-oxidate], such ADK NA-21, NA-21E, NA-21F, etc., sodium 2,2'-methylene-bis(4,6-di-tert-butyl-phenyl)phosphate (ADK NA-21), aluminiumhydride-bis-[2,2'-methylene-bis(4,6-di-tert-butyl-phenyl)phosphate] and polymeric nucleating selected from the group consisting of vinylcyclohexane polymers and vinylalcohol polymers.

The most preferred nucleating are ADK NA-21 and ADK NA-11.

Propylene compositions used for the films according to the present invention may contain various additives that are commonly used in the propylene compositions, such as stabilizers, antioxidants, collateralisation, oiling agents, UV absorbents, additives that prevent adhesion, antistatic agents, additives that prevent clouding, etc., provided that they do not impair the desired properties of the composition.

The preferred antioxidants are spatial employed phenolic antioxidants, such as 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-METHYLPHENOL, 2,6-di-tert-butyl-4-isoamylene, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-diisopropylphenol, 2,6-dicyclopentyl-4-METHYLPHENOL, 2,6-di-tert-butyl-4-methoxyethanol, 2-tert-butyl-4,6-dioctadecyl, 2,5-di-tert-butylhydroquinone, 2-tert-butyl-4,4-hexadecyloxypropyl, 2,2'-methylene-bis(6-tert-butyl-4-METHYLPHENOL), 4,4'-thio-bis(6-tert-butyl-2-methylphe the ol), 2,2'-thiodiethanol-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl-3--(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-Tris(3',5'-di-tert-butyl-4-hydroxy-benzyl)benzene, 2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltin-decyl)chroman-6-ol, pentaerythrityl-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Antioxidants, which are commercially available, for example, from the company Ciba Specialty Chemicals, are Irganox 1010, Irganox 1330, Irganox 1076, Irganox 1035, Irganox E201 etc.

The preferred stabilizers are hospitalarias stabilizers, for example, Tris(2,4-di-tert-butylphenyl)-pofit, bis-(2,4-di-tert-butylphenyl)pentaerythritol-diphosphite, bis(2,4-dokumenter)pentaerythrityl etc.

Commercially available stabilizers, for example, from the company Ciba Specialty Chemicals, are Irgafos 168, Irgafos 126, etc. or from the firm Dover Chemical Corporation - stabilizers Doverphos S-9228CT etc.

Collateralisation and/or oiling agents are, for example, salts of carboxylic acid, where the metal is selected from the 1st or 2nd group of the periodic system of elements or transition metals such as zinc. Preferred carboxylates are Li-stearate, stearate, Li-myristate, Na-myristate, CA-stearate, Mg stearate, CA-12-hydroxystearate, Mg-12-hydroxy-stearate, Ca-myristate, CA-palmitate, CA-laurate, Mg-myristate, Mg-palmitate, Mg-La the rat and Zn-stearate.

Can also be used zeolite structures (hydrotalcite, both natural and synthetic), magnesium oxide or zinc oxide.

Preferably, the injected synthetic hydrotalcite ((BHT) (SHT)), more preferably, Mg4,5Al2(OH)13(CO3)3,5H2O.

In addition, the particularly preferable to use the above-mentioned resin composition to obtain sterylizowane films obtained by extrusion-blow process, preferably, the air-cooled films obtained by extrusion blow to turbidity in accordance with ASTM D 1003-92 for a 50 μm film of less than 8%, preferably less than 7%, more preferably less than 6%, and most preferably, less than 5%, before and after steam sterilization at 121°C for 30 minutes

In addition to the above characteristics, it is preferable to use the above-mentioned resin composition to obtain sterylizowane films obtained by extrusion-blow process, preferably, the air-cooled films obtained by extrusion blow with the gloss at 20° acc. to DIN 67530 for a 50 μm film of at least 55%, preferably at least 58%, to sterilization and at least 60%, preferably at least 65%, more preferably at least 70%, after steam sterilization at 121°C for 30 minutes

Film obtained by extrusion blow obtained from polymer compositions, used according to the present invention, have STC (SIT) (initial temperature welding) ≤ 130°C, preferably ≤ 125°C, for a 50 μm film obtained by extrusion-blow process.

According to another variant of a film obtained by extrusion-blow process, have the following property:

the modulus of tensile elasticity ((md) longitudinal direction) according to ISO 527 of at least 1000 MPa to 50 μm film obtained by extrusion-blow process.

Especially preferable to use the above-mentioned polymer composition to obtain a film obtained by extrusion-blow process, with a modulus of tensile elasticity (longitudinal direction) above 1150 MPa and, more preferably, above 1200 MPa.

According to the present invention, it is preferable to use a polymer composition consisting of terpolymer propylene/butylene/ethylene, which is the proportion of the polymer soluble in cold xylene at 23°C, not more than 5%, preferably not more than 4.5%, and more preferably not more than 4.0%.

The film obtained from the polymer compositions containing these terpolymer, meet the requirements of solubility, which is needed for application in food packaging.

The film according to the present invention have a preferred thickness of from 5 to 1500 μm, more preferably up to 1000 μm, and most preferably, d is 200 μm.

Films produced according to the present invention, are preferably used to obtain sterylizowane films.

Another aspect of this invention relates to the use of the polymer compositions of the invention for a multi-layered film obtained by extrusion-blow process, where at least one layer consists of a polypropylene film obtained by extrusion-blow process, according to the invention.

Description get terpolymer propylene/butylene/ethylene

The specific method used for polymerization is not required for implementation of the present invention, and methods of polymerization, now considered traditional, are suitable for the method of the invention.

The method of polymerization for polymers according to the present invention can be a continuous method or a batch method using known methods.

The polymer composition of the present invention can be obtained by one - or multi-stage method for the polymerization of propylene, 1-butene and ethylene, such as polymerization in mass, gas-phase polymerization, suspension polymerization, polymerization in solution or combinations thereof. Such methods are well known to the person skilled in the technical field.

The preferred method is a combination of a reactor (re the Ktorov) circulation polymerization in mass and reactor (reactor) gas-phase polymerization. The polymer composition of the invention can be obtained either in the reactor with circulation or in combination reactor with circulation and gas-phase reactors. Specialist in the art knows various possibilities of obtaining copolymers and terpolymers propylene and easily find a suitable technology for the production of suitable polymers that are used in the present invention.

The method preferably is carried out in the presence of catalytic systems stereoregular polymerization.

Can be used all the catalysts suitable for the polymerization of propylene to butylene and ethylene, such as catalysts of the Ziegler-Natta and single center catalysts, including metallocene and demetallized.

As one of the catalyst can also be any metallocene catalyst capable of catalyzing the formation of copolymer or terpolymer propylene and butylene. Suitable metallocene catalyst contains a reaction product of metallocene/activator which is impregnated porous substrate with a maximum internal volume of pores. The catalytic complex contains a ligand, which is usually the bridge, and a transition metal of groups IVa, VIa, and alumoorganic connection. The catalytic metal connection is typically a metal halide.

In p edocfile variant of the method, the method as described above is performed with the use of a catalyst of Ziegler-Natta, in particular high-performance catalyst of Ziegler-Natta (so-called type fourth and fifth generation, derived from low-productivity of the catalysts of the Ziegler-Natta so-called second generation). Suitable catalyst of the Ziegler-Natta used in accordance with the present invention, contains the catalytic component (optional, vinylacetylene catalytic component), socialisticheski component and at least one electrondonor (internal and/or external electrondonor, preferably, at least one external electrondonor). Preferably, the catalytic component is Ti-Mg-containing catalytic component, and usually acetalization is Al-alkylesters connection.

Such catalytic systems are described, for example, in US 5234879, WO 92/19653, WO 99/33843, WO 02/60962 etc., and such systems containing vinylacetylene catalytic components, in WO 92/24478 and WO 99/24479.

An integral component of such catalysts are solid catalytic components containing compound of titanium with at least one communication titanium-halogen, an internal electron-donor compound and a magnesium halide in active form as a carrier as iconologia component, and donor compounds. The catalysts may contain internal electrondonor - compounds selected from ethers, ketones, lactones, compounds containing N atoms, P and/or S, and esters of mono - and dicarboxylic acids.

Another integral component of the catalyst is alumoorganic connection, such as alkylamines connection.

In addition, commonly used external electrondonor. Preferred external electrondonor are known selectabase donors, preferably, dicyclopentadienyliron or cyclohexanedimethanol.

To obtain terpolymer propylene and butylene is preferable to use a polymerization method based on the combination of one or more reactor (reactors) polymerization in mass, and one or more reactor (reactor) gas-phase polymerization.

Preferably, the method also includes terpolymerization with the selected catalytic system. Preferably, the propylene polymer composition of the present invention receive in the reactor with circulation or in combination reactor with circulation and gas-phase reactor. Such methods are well known to the person skilled in the technical field.

"Suspension reactor" means any reactor, such as a simple capacitive reactor with stirring nepreryvnogo periodic operation or reactor with circulation, with work in bulk or in suspension, and where the polymer is formed in a solid dispersion form. "In bulk" means a polymerization in a reaction medium, which contains at least 60 wt.% the monomer. According to a preferred variant of the suspension reactor comprises a reactor with a circulation of polymerization in mass.

You can also use several reactors of each type, for example, one reactor with circulation and two or three gas-phase reactor or two reactors circulation and one gas-phase reactor connected in series.

"Gas-phase reactor" means a reactor with mechanical agitation or fluidized bed. Preferably, the gas-phase reactor comprises a reactor with a fluidized bed with mechanical agitation speed gas of at least 0.2 m/s

Particularly preferred variant of the present invention includes performing polymerization in the method containing the reactor with circulation and gas-phase reactor.

The preferred multi-stage method is defined above the suspension-gas-phase method, such as developed by Borealis and is known as Borstar technology. In this respect, reference is made to European application EP I and EP A, shown here as a reference.

In respect of the above preferred suspensio the aqueous-gas phase method may be represented by the following General information in relation to technological conditions.

The temperature is in the range from 40°C to 110°C, preferably in the range from 60°C to 100°C, in particular in the range from 70°C to 90°C, with a pressure in the range from 20 to 80 bar (2000-8000 kPa), preferably 30 to 60 bar (3000-6000 kPa), with the option of introducing hydrogen in order to regulate the molecular weight of a way known as such.

The reaction product of suspension polymerization, which is preferably performed in a reactor with circulation, then overload in subsequent gas-phase reactor in which the temperature is preferably in the range from 50°C to 130°C, more preferably 60-100°C, at a pressure in the range from 5 to 50 bar (500-5000 kPa), preferably 15-35 bar (1500-3500 kPa)over 6000 kPa), with the option of introducing hydrogen in order to regulate the molecular weight, with the option of introducing hydrogen in order to regulate the molecular weight way known as such.

In the reaction zones identified above, the residence time can vary. In one embodiment, the residence time in the suspension reactor, such as reactor with circulation, is in the range from 0.5 to 5 hours, for example 0.5-2 h, whereas the residence time in the gas-phase reactor is usually from 1 to 8 hours

If desired, the polymerization can be carried out in a known manner in supercritical conditions in suspe the audit, preferably, the reactor with circulation and/or as a condensed version in the gas-phase reactor.

The method of polymerization provides high get and additional development propylene polymer compositions of the invention. For example, the properties of the polymeric composition may be adjusted or regulated in a known manner, for example, adjusting or regulating one or more of the following parameters: temperature, hydrogen power, comonomers power, propylene power, for example, in gas-phase reactor, catalyst, type and amount of external donor (if used), cut between the components. Accurate control of the polymerization conditions and parameters of the reaction is in the competence of the art.

After ending the polymerization in the first and optional second reactor, through known stages of the post, including the stage of deactivation of the catalyst, removal of residual catalyst and drying, can be obtained given the copolymer or terpolymer.

The resulting polymer particles can be granulated in a traditional compounders extruder with various additives that are commonly used in thermoplastic polymer compositions, such as stabilizers, antioxidants, kilomeetrit the Torah, antistatics and so on, provided that they do not impair the desired properties of the composition.

In addition, the polymeric material contains at least one alpha-nucleating agent, which is derived from phosphate-containing and/or polymeric nucleating that can be entered directly at the stage compounding or in the process of obtaining films by external masterbatches.

Application

Terpolymer propylene and butylene can be used for all extrusion technologies.

Preferably, it is used for extruded two - and-axis-oriented and non-oriented films obtained by extrusion blow with the thickness of the films from 5 to 1500 μm.

More preferably, it is used for the production of rigid undirected and two - and-axis-oriented films with a thickness of 5-1000 μm on the technology of film extrusion blown.

Most preferably, it is used to obtain a non-oriented film obtained by extrusion-blow process, a thickness in the range of 5-200 μm.

Description for the films technology of blown

The polymer compositions of the invention are able to be processed in the film obtained by extrusion blown with water or air cooling, preferably, in the film, developed the s-extrusion blown with air cooling, on conventional equipment to produce plastic films obtained by extrusion blow.

Technology of production of films by extrusion blow with the contact ring water cooling

Through the technology of polymeric films molten polymer is extruded through a tubular extrusion head (usually single-screw extruder) and swells in the sleeve. Film sleeve is in contact on the outside with a ring of water cooling and cools quickly. Already hardened film sleeve after it is folded into a flat double tape tension rollers and is discharged on a bobbin.

A more detailed description see the reference “Polypropylene Hanbook”, published by Edward P. Moore, Jr., Hanser Publishers, 1996.

Technology of production of films by extrusion blow air cooled

At this stage for the films by extrusion blow air cooled film is obtained using the degree of blowing at least 1.5 times, preferably, the degree of blowing at least a 2.0, more preferably, the degree of blowing at least a 2.5.

Technology of production of films by extrusion blown with air cooling are well known to produce thin polymer films. In a preferred method, the polymers such as low density polyethylene, linear polyethylene nor the coy-density and high-density polyethylene, is extruded through an annular extrusion head with the formation of the film. Air is introduced through the center of the mouthpiece to maintain the film in the form of a sleeve, which increases the diameter of the film is about 1.5 to 6 times, after which the sleeve is formed on the rolls. There are several variants of this method in the art. Most of the links on films obtained by extrusion-blow process, discusses the methods used for polyethylene, but they are applicable to polymer compositions of the present invention with minor modifications in the art without undue experimentation.

For example, cooling often, preferably, modified, because the specialist in the art knows that the polypropylene is cooled and crystallized at a speed different from the speed of polyethylene.

Therefore the adjustment of the cooling parameters often provide a more stable sleeve when desired performance.

In forming films obtained by extrusion-blow process, the molten polymerization composition (melt) enters the annular extrusion head through the bottom or side. The melt is pumped through a spiral groove around the surface of the mandrel inside the extrusion head and extruded through the extrusion head as a thick-walled pipe. Pipe rasshiryaet the sleeve of the desired diameter and, accordingly, reduces the thickness as described above.

The film obtained from the polymer composition according to the present invention have very good optical properties, high toughness, good weldability and a good ability to fold flat. In addition, they are sterilized with steam at 121°C for 30 minutes

As for the method of sterilization, the film according to the present invention have a higher superior optical properties after steam sterilization compared with the films of random copolymers or terpolymers polypropylene and ethylene in accordance with the current level of technology, where these properties deteriorate after steam sterilization.

Therefore, these films are mainly used in pharmaceutical industry and in food packaging.

Test methods

Properties of polymers

The rate of flow of the meltdetermined under a load of 2.16 kg and 230°C. the flow Rate of the melt (MFR) represents the number of polymer in grams which the device for testing, standardized according to ISO 1133, extradiol for 10 minutes at a temperature of 230°C. under load of 2.16 kg

The content of the co monomer(ethylene-butylene) determine the method of IR spectroscopy with Fourier-transform ((IXFP) (FTIR)) c calibration13C-NMR.

u> Soluble in xylenedetermined at 25°C according to ISO 6427.

Properties of the film obtained by extrusion blow

Glitter and turbidityas the performance of the optical appearance of the film obtained by extrusion-blow process, determined according to DIN 67530 (Shine) and ASTM D1003-92 (turbidity), both on the sample film obtained by extrusion-blow process, a thickness of 50 μm.

The modulus of tensile elasticityas an indicator of the stiffness of the films obtained by extrusion blow, determined according to ISO 527 on the sample film obtained by extrusion-blow process, a thickness of 50 μm.

The tear resistance in Elmendorfdetermined according to ISO 6383/2 sample film obtained by extrusion-blow process, a thickness of 50 μm.

The onset temperature of thermal welding ((TNTS)(SIT))

1. Total

The method determines the temperature interval welding polypropylene film obtained by extrusion-blow process. Temperature range welding is a temperature range in which the film can be welded in accordance with the terms below.

The lower limit (the onset temperature of thermal welding (TNTS) (SIT)) is the temperature of the welding, which guarantees the strength of the weld > 5 km N. The upper limit temperature after welding (TCS)(SET)) is achieved when the film starts to gamerbase.

Samples get in the longitudinal direction of the extrusion. The sample size is 25.4 mm × 250 mm, film thickness is 50 μm.

3. Device for welding

To use welding lab welding device DTC Hot tack tester. Before testing the device check on a parallel position welding clamps.

4. The welding parameters

Set the following welding parameters:

Effort welding:0,66 N/mm2
Welding time:1
Welding clamps:50×5 mm, flat + fluoropolymer film
Heating:both clamp, accuracy +/- 1°C
Initial temperature:100°C
Sample rate:42 mm/s

5.Welding procedure

- Tape stack size 125×25.4 mm and inserted between the welding clamps.

The clamps are heated to welding temperature.

Immediately after welding, the sample is removed from device.

For each temperature weld 5 samples./p>

6.Test

To determine the initial strength 5 samples welded at one set temperature, and using devices DTC Hot tack tester determine the strength of the weld.

If the average of 5 tests (as described above) is > 5 H, then reached the initial temperature welding. If not, then the welding temperature increase of 2°C and the test repeated.

After reaching TNTS (SIT) temperature welding additional increase in increments of 2°C until, when the film begins to gamerbase.

After exposure time 30 s after welding the stretch film with a speed of 42 mm/s with the determination of the strength of the weld is in Newtons. TNTS (SIT) represents the temperature is achieved when the weld strength > 5 N.

Examples

Example 1 (invention)

Getting terpolymer propylene/ethylene/1-butylene

To obtain terpolymer propylene using the method containing the stage of terpolymerization and main stage polymerization.

Temperature, pressure, catalyst, monomer and hydrogen in the individual stages of polymerization and the concentration of polymer in the main reactor constant support. The molecular weight of terpolymer regulate the introduction of gaseous hydrogen. The concentration of hydrogen in the mixture of liquid monomers continuous is measured by gas chromatography. The technological parameters and the results of the analyses of the obtained polymer are shown in tables 1 and 2.

The catalyst is highly stereoregular preterition catalyst of Ziegler-Natta on MgCl2-the media.

The catalyst is in contact with triethylaluminium (TEAl) as socializaton, cyclohexylmethoxy the silane (donor) as an external electrondonor obtaining catalytic system and then terpolymerization in a known manner in the presence of propylene in a small reactor (equipped with a stirrer and cooling system).

The prepolymer (product a) is continuously removed from the reactor terpolymerization and pass into the main reactor system (equipped with a stirrer and cooling system), where the excess liquid mixture of monomers propylene and 1-butylene adding ethylene formation of an end terpolymer (In). In addition, in the main reactor continuously serves a mixture of monomers (propylene/1-butylene/ethylene) and hydrogen (to regulate the molecular weight). The concentration of the polymer support constant.

Part of the contents of the reactor (the polymer with an excess of monomer) continuously withdrawn from the reactor in the installation of degassing for the Department formed terpolymer () from unreacted monomer mixture by evaporation.

The separation of the hydrated terpolymer (C) is subjected to a steam treatment to remove unreacted monomers and volatile substances, and then dried. The polymer powder is mixed with 0.18% of nucleating agent ALR NA-21 from the company Asahi Denka Kokai.

Next, enter the following supplements:

300 hours/million Mg4,5Al2(OH)13(CO3)3,5H2O as a neutralizer,

500 hours/million Irganox 1010 (Ciba Specialty Chemicals) as an antioxidant and

500 hours/million Irgafos 168 (Ciba Specialty Chemicals) as a stabilizer.

This mixture then granularit traditional line compounding.

The properties of the polymer are shown in table 3.

Obtaining films

Granular materials used for film extrusion blown on industrial lines for the films by extrusion blow Alpine 35.

Film obtained by extrusion blow receive a single screw extruder with a cylinder diameter of 70 mm and extrusion cylinder of circular cross section 20 mm with a gap of the extrusion head 1 mm in combination with odnokromochnye cooling ring and the inner cooling sleeve (THIEF)(IBC). The temperature of the melt in the extrusion head is 210°C; the temperature of the cooling air is maintained at 15°C, and the degree of drawing ((ST)(BUR)) is 3:1. The film thickness 50 microns adjusted by selection of the ratio between the output of the extruder, speed selection and ST.

Film properties are presented in table 3.

Comparative examples 2 and 3

As the e of the comparative examples 2 and 3 use industrial grade statistical copolymer Borclear RB709CF and Borclear RB707CF.

Table 1
unitExample 1
TEAl/donor D[yoy]5
TEAl/Ti[yoy]0,82
TEAl/Ti[mol/mol]1,36

Table 2
unitExample 1
The reactor terpolymerization/liquid monomer phase
Power catalyst[g/h]≈ 1,2
Pressure[bar]
(kPa)
34
(3400)
Temperature[°C]20
Average duration of stay[min]≈ 90
The main reactor/liquid monomer phase
Pressure[bar]
(kPa)
34
(3400)
Temperature[°C]64
Average duration of stay
catalyst
[min]≈ 90
The concentration of polymer in the reactor[g/l]≈ 0,52
Food mix
propylene/1-butylene*)
[kg/h]127-133
Contents 1-butylene in the monomer feeding[% vol.]≈ 20,5
Nutrition ethylene[kg/h]0,5
The concentration of H2in Monomeric nutrition[h/mn ]410-420
The performance of the receiving polymer (product)[kg/h]27-43
*)General nutrition liquid polymer mixture in the reactor C is theme.

Table 3
The properties of the polymerExamples
12
(RB709CF)
3
(RB707CF)
The concentration of ethylene[wt.%]0,3the 5.74,5
The concentration of 1-butylene[wt.%]6,9--
The nucleating agent NA-21[h/mn]180018001800
Soluble in xylene[wt.%]3,577
Melting point[°C]143135144
The rate of flow of the melt MFR g/10 min1,71,51,5

Table 4
Film propertiesExamples
12
(RB709CF)
3
(RB707C)
Turbidity ds.*)[%]4,53,57,1
Turbidity PS*)[%]4,89,48,3
Gloss at 20° outside ds.*)[%]59,160,143,7
Gloss at 20° outside PS*)[%]71,413,637,2
Gloss at 20° inside ds.*)[%]61,061,6 44,1
Gloss at 20° inside PS*)[%]72,320,535,9
*)JS - prior to sterilization
*)PS - after sterilization
Steam sterilization was performed at 121°C for 30 minutes
The modulus of tensile elasticity (longitudinal direction)[MPa]12507391127
The modulus of tensile elasticity (transverse direction)[MPa]12197181127
The temperature of the welding SIT[°C]122112124
Welding temperature[°C]115105120

These examples show that the values of the optical properties of turbidity and Shine in example 1 improved after sterilization, then ka is in the case of examples 2 and 3 they are getting worse.

In addition, the film of example 1 has a much higher modulus of tensile elasticity in comparison with example 2 and higher modulus of tensile elasticity in comparison with example 3.

1. The use of polymeric compositions, including
(i) terpolymer propylene and butylene, which consists of
86,0-98,0 wt.% propylene,
2.0 to 12.0 wt.% butylene and
from 0.1 to less than 1.0 wt.% ethylene, and
(ii) 0.001 to 1.0 wt.% one or more phosphorus-containing and/or polymer of α-nucleating,
to get sterilized films obtained by extrusion blown with water or air cooling, which have the following properties:
a) the turbidity according to ASTM D 1003-92 for a 50 μm film of less than 8% before and after steam sterilization at 121°C for 30 min; and
b) gloss at 20° acc. to DIN 67530 for a 50 μm film of at least 55% to steam sterilization at 121°C for 30 min and at least 60% after steam sterilization at 121°C for 30 minutes

2. The use according to claim 1, characterized in that the α-nucleating agent contains one or more phosphorus-containing α-nucleating and/or polymer of α-nucleating selected from the group consisting of vinylcyclohexane polymers and vinylalcohol polymers.

3. The use according to claim 2, characterized in that the α-nucleating agent selected from the group aluminumhydroxide-bis[2,4,8,10-tetrac the s-(1,1-dimethylethyl)-6-hydroxy-N-dibenzo[d,g]dioxa-fosfory-6-oxidate]containing nucleating, sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate, aluminiumhydride-bis-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate] and polymeric nucleating selected from the group consisting of vinylcyclohexane polymers and vinylalcohol polymers.

4. The use according to claim 1, characterized in that the films have the following property: the modulus of tensile elasticity (longitudinal direction (md)according to ISO 527 of at least 1000 MPa to 50 μm film.

5. The use according to claim 2, characterized in that the films have the following property: the modulus of tensile elasticity (longitudinal direction (md)according to ISO 527 of at least 1000 MPa to 50 μm film.

6. The use according to claim 1, characterized in that the polymer has a part of the polymer soluble in cold xylene (25°C), not more than 5%.

7. The use according to claim 1, characterized in that the films have a thickness of from 5 to 1500 μm.

8. The use according to claim 2, characterized in that the films have a thickness of from 5 to 1500 μm.

9. The use according to claim 1 to obtain a sterilized films obtained by extrusion blown with air cooling.

10. The use according to claim 2 to obtain sterilized films obtained by extrusion blown with air cooling.

11. The use according to claim 1 for receiving the sterilized film for pharmaceutical and food packaging.

12. The use according to claim 2 d is I get sterilized films for the pharmaceutical industry and food packaging.

13. The use according to claim 1 for the multilayer films obtained by extrusion-blow process, where at least one layer includes polypropylene film obtained by extrusion-blow process, according to claim 1.

14. The use according to claim 1 for the multilayer films obtained by extrusion-blow process, where at least one layer includes polypropylene film obtained by extrusion-blow process, according to claim 2.

15. Film obtained by extrusion-blow process, when applied according to any one of claims 1 to 14.

16. The film obtained by extrusion-blow process, where the film obtained by extrusion-blow process, contains a polymer composition that includes
(i) terpolymer propylene and butylene, which consists of
86,0-98,0 wt.% propylene,
2.0 to 12.0 wt.% butylene and
from 0.1 to less than 1.0 wt.% ethylene, and
(and of) 0.001-1.0 wt.% one or more phosphorus-containing and/or polymer of α-nucleating,
where the film has the following properties:
a) the turbidity according to ASTM D 1003-92 for a 50 μm film of less than 8% before and after steam sterilization at 121°C for 30 min; and
b) gloss at 20° acc. to DIN 67530 for a 50 μm film of at least 55% to steam sterilization at 121°C for 30 min and at least 60% after steam sterilization at 121°C for 30 minutes



 

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15 cl, 1 dwg, 2 tbl, 10 ex

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Pressure pipe // 2310789

FIELD: mechanical engineering; transportation of liquids and gases.

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FIELD: polymer production.

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EFFECT: increased hardness and tensile strength of the composition.

10 cl, 1 dwg, 2 tbl, 4 ex

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