RU2767530C1 - Polypropylene composition with high melt strength and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polymer compositions suitable for making articles by foaming. Disclosed is a polymer composition for foaming, containing the following components (wt. %): A. powdered or granular propylene homopolymer, or random copolymer of propylene with ethylene and/or higher α-olefins, or block copolymer of propylene with ethylene and/or higher α-olefins, or combinations thereof (48.5–99.4765); B. coagent (COAG) or a mixture of COAG, which are vinyl monomers (0.5–3); C. peroxide initiator (0.001–1.0); D. hindered cycloaliphatic amine stabilizer (HALS) (0.0025–1.5); E. antioxidant and/or heat stabilizer (0.02–1.0); F. polyolefin elastomer (0–25); G. other additives (0–20). Also disclosed is a method of producing said composition, use thereof and obtained foamed article.

EFFECT: obtaining a polypropylene composition with high melt strength, which enables to obtain foamed articles with improved foam shape stability and uniformity thereof.

100 cl, 1 dwg, 5 tbl, 40 ex

Description

Field of technology to which the invention relates

The present invention relates to high strength thermoplastic polymers and/or compositions for foaming by any of the known methods to produce high strength materials for a wide range of applications.

Due to their high functional properties, polypropylene foam materials replace other previously actively used foam materials. In particular, polypropylene foam materials have better stiffness, strength and heat resistance than polyethylene, impact strength and hygienic properties - compared to polystyrene, chemical resistance - compared to polyurethane.

The composition disclosed in this invention can be used in the construction, transport, cable, pipe industries, in the production of packaging materials and products with high heat, sound and waterproofing properties, preferably obtained by foaming, as well as in the form of a film material obtained inflatable or in any other way known from the prior art.

Basic conventions and abbreviations

MFR - melt flow index

PP (PP) - polypropylene

MS - melt strength

HMS PP - High Melt Strength PP

SOAG - coagent (as part of a peroxide modifying system, which is a mono, di-, tri- or polyfunctional vinyl monomer)

HALS - Hinder Amine Light Stabilizer

cN - centinewton

State of the art

Foaming is one of the simplest methods for obtaining foam and sponge-like materials. The special properties of materials obtained in this way - light weight, shock-absorbing ability, high rates of heat, sound, waterproofing properties, make them attractive for use, expanding their scope. Traditional foaming polymers are polyurethanes, polystyrene, epoxy polymers, polyvinyl chloride. However, polypropylene, despite a number of its unique properties, and applications in various industries, has not currently found obvious recognition for use in foamed products due to its low strength and extensibility of the melt.

There are several ways to produce foam materials. One of the main ones is to pass a gas mixture (air, nitrogen) through the molten polymer compound to the required degree of foaming, extrusion, and subsequent cooling to room temperature, at which the material solidifies in a foamed state. The foam materials obtained as a result of this method, from ordinary highly linear polypropylene, synthesized according to standard industrial technology on Ziegler-Natta catalysts, are characterized by a low ability to maintain the volume of gas bubbles (pores or cellular structure) and the shape of the foam upon cooling. The retention of bubble volume (pore or honeycomb structure) is influenced by polymer properties such as melt extensibility (mm/s) and melt strength MS (cN). To improve these properties - the strength and extensibility of the polypropylene (PP) melt, various approaches are used. All of them are associated with the modification of the linear structure of isotactic polypropylene, the purpose of which is its significant branching and/or partial or even complete crosslinking.

Currently, the following polypropylene-based systems are most widely used to produce foams:

1. Linear bimodal polypropylene obtained by multi-stage polymerization in the reactor or the reaction of polypropylene with cross-linking agents;

2. Branched polypropylene obtained by peroxide or radiation treatment or copolymerization of propylene with dienes in the presence of a metallocene catalyst. According to the type of branching, long-chain polypropylene is distinguished: multi-branched (a), double-stranded (ladder) (b) and polypropylene with short branches (c), shown in Fig. one.

To assess the degree of branching of the polymer, the branching index g' is used, which is defined as the ratio of [IV] _{branched polymer} / [IV] _{linear polymer} , where [IV] _br is the intrinsic viscosity of branched polypropylene and [IV] _lin is the intrinsic viscosity of linear polypropylene with a similar molecular weight mass. A material suitable for the production of foam must have a g' index of less than 0.9.

An analysis of the prior art allows us to distinguish three main methods for producing polypropylene, which has a high melt strength and is used to produce products by foaming: radiation, reactor and post-reactor.

The radiation method makes it possible to achieve the highest melt strength values, however, it entails significant economic costs due to the need to use expensive devices - electronic accelerators.

The disadvantages of reactor methods for producing polypropylene with high melt strength are the complexity of the technology, as well as, in some cases, the required additional modification of the product.

Post-reactor melt modification of polypropylene using crosslinking and/or modifying agents is currently the most widely used technology for producing high melt strength polypropylene.

Patents in the field of post-reactor modification to obtain high melt strength polypropylene are presented by such companies as Akzo Nobel, Atofina Research (Total Petrochemical), Borealis AG, Dow Global Technologies.

The basis of post-reactor modification for the production of polypropylene with increased melt strength is the modification of polypropylene powder or melt with organic peroxides, cross-linking and/or branching agents using standard mixing equipment.

Known approaches related to the modification of the linear structure of PP with various variants of commercially available peroxide, diazonium, sulfonyl azide or other radical initiators, disclosed in documents US5416169A (JNC), US6103833B (AkzoNobel (Nld)), US6204348B (Borealis AG (AT)), US6323289B (AkzoNobel (Nld)), KR2018065303А (HANWHA Total Petrochemical Co Ltd (KR)), CN104072874A (Zhang Xishun (CN)), US6800669B (Dow Global Technologies (US)) and a number of others, have common disadvantages associated with the difficulty of achieving and maintaining a set of key properties of the PP composition, such as melt strength, flow and extensibility.

Another well-known approach that allows more targeted influence on the above properties of polypropylene compositions with increased melt strength is the use of modifying systems based on mixtures of a radical initiator with a mono- and/or di- and/or polyfunctional vinyl monomer, which allows, due to the chain transfer reaction, to significantly reduce the concentration of the radical initiator in the system, thereby helping to reduce the likelihood of a side competitive reaction of the destruction of polypropylene macrochains. A wide range of class of vinyl monomers - coagents (VOAGs) available on the market has contributed to the emergence of numerous application materials and patents devoted to methods for producing polypropylene with increased melt strength.

Document US5082869A (Ausimont SA (US), April 15, 2001) discloses a polypropylene composition for foamed products obtained by peroxide "dynamic" vulcanization in the presence of a bifunctional monomer - a derivative of furan. The resulting composition consists of 3 to 75% by weight of crosslinked polypropylene dispersed in non-crosslinked polypropylene in the form of particles with a diameter of 0.5 to 100 µm. With the addition of a foaming agent to the composition, the process of molding the final product can be combined with the stage of dynamic vulcanization.

Documents JP7242762, KR1877249, WO2017170907, WO2018062443 of the Japanese company Sekisui Chem. describes a method for producing peroxide-crosslinked foams from polypropylene using mono- or polyfunctional aromatic vinyl monomers or polyolefin elastomer additives as SOAGs. The materials obtained with the addition of foaming agents are intended for lamination, or injection molding, or the production of food containers. The main disadvantage of such compositions is the impossibility of their recycling due to excessive crosslinking, which is difficult to control during their synthesis.

In documents JP20000289082A, JP2000143856A, JP03634935B2, JP10168214A, JP10158424A, JP11035724A, JP03561078B2. conjugated dienes: 1,3-butadiene and isoprene, or their combination with aromatic vinyl monomers, were used as SOAGs in the preparation of foamable PP compositions: The issues of controlling the fluidity of final compositions in these reactive extrusion methods are also difficult, given the high tendency to crosslink highly active conjugated dienes. Difficulties in technological terms are also provided by the high volatility of diene monomers.

From the prior art, attempts are known to solve the above problems, where diene oligomers deposited on a special porous polypropylene are used as SOAG. Trigonox BPIC peroxide from Akzo Noobel is added to the polypropylene composition in the form of a concentrate. The melt strength of the composition containing 9 wt.% oligomer reaches 20.1 cN at an extensibility of 250 mm/s.

WO2012049690 (Reliance Industries (IN), 10/11/2011) proposes a wide range of COAGs for the production of polypropylene with high melt strength. Preferably, however, the use of such SOAGs as triallyl cyanurate, divinylbenzene and acrylic series monomers: trimethylol propane triacrylate (TMPTA) pentaerythritol triacrylate, hexadecyl methacrylate, etc. in the concentration range from 0.1 to 1.0 wt.%. The non-conjugated system of double bonds of the acrylate nature in these monomers apparently contributes to a decrease in the contribution of crosslinking processes in favor of macrochain branching. The increase in melt strength achieved in this case is from 30 to 60% of the initial one.

Document CN101418064B (Univ of China, (CN), 02.12.2008) proposes a method for producing long-chain branched polypropylene with increased melt strength, in which the control of side processes of polypropylene degradation is carried out by adjusting the ratio of polypropylene, initiator, polyfunctional monomer, changing the residence time a mixture of ingredients in the extruder, as well as additional input of a monofunctional styrene monomer and a processing additive - calcium stearate.

In patent CN102432762B (East china university (CN), 09/02/2011) a similar goal is achieved by using a three-component mixture of monomers of different functionality: maleic anhydride, styrene and isoprene, introduced into a certain zone of the extruder. The melt strength of polypropylene reaches 24 cN at 190°C. WO2012174965 (East china university (CN), June 22, 2011) describes a method in which linear bifunctional siloxanes are used as branching agents for polypropylene, along with the introduction of diene monomers, styrene, etc. Melt strength also reaches 24 cN at 190 °C.

A known approach to achieve a balance between melt strength and tensile strength is to use a bimodal polypropylene blend. So, in the patent US6723795B (Atofina, from 06/08/2000) describes a method for obtaining a bimodal mixture based on isotactic polypropylene by mixing a high molecular weight component (from 55 to 65 wt.%) and a component with a low molecular weight (MM) (from 45 to 35%) in an extruder under nitrogen at 220°C. The first component has an MFR of _{230 °C/2.16 kg} less than 0.5 g/10 min, the second one - more than 6 g/10 min. The mixture has a polydispersity index equal to 8 and the ratio of average MM to number average MM (Mz/Mn) equal to 10. The resulting composition can be used to produce foamed and extruded materials, as well as fibers, thermoformed products. Crosslinking agents such as allyl methacrylate, divinylbenzene, in combination with a radical initiator, can be used to improve product performance.

A common disadvantage of all peroxide-SOAG modifying systems used in the post-reactor synthesis of polypropylene compositions with increased melt strength is the need for continuous monitoring of the degradation and/or crosslinking of polypropylene macrochains. Such control during the modification process is extremely difficult, but without it it will not be possible to maintain the balance of the main properties of the composition.

In international application WO2013086757 (KINGFA SCI TECH (CN), 12/23/2011), companies attempt to solve the above post-reactor synthesis difficulties by using an additional additive, the so-called organic peroxide degradation regulator, designated FRS (free radical stabilizator). various compounds of rare earth elements (REE) act as FRS.These additives can be, for example, REE oxides and carboxylates, as well as their complexes with naphthenic and dithiocarbamic acids.As stated in the application, FRS regulates the processes of destruction and grafting of polypropylene macromolecules and serves to control ratio of polypropylene-initiator-COAG, increase the time of grafting to polypropylene, inhibition of degradation of polypropylene and prolongation of free radicals The melt yield strength of the obtained products can vary from 0.1 to 50 g/10 min, preferably up to 3.2 g/10 min Glycol-diacrylates, TMPTA, pent aerythritol triacrylate (PETA). The obvious disadvantage of this technical solution is the use of expensive, hard-to-reach and unsafe compounds of rare earth elements from the point of view of toxicology.

The closest in technical essence to the present invention is the solution described in the document CN101434681B (Changchun institute of applied chemistry, 12/17/2008), in which organosulfur compounds - dithiocarbamates are used as a peroxide decomposition regulator in the post-reactor synthesis of polypropylene with high melt strength widely used in agriculture as fungicides. Preferably, trimethylol propane triacrylate (TMPTA) is used as SOAG. It is revealed that dithiocarbamates not only reduce the intensity of the process of destruction of polypropylene macrochains, but also contribute to an increase in the strength of the polymer melt. The melt strength of the modification products is in the range from 16 to 36 cN, while the melt yield strength is from 0.5 to 2.0 g/10 min. The disadvantage of this invention is the reduced fluidity and extensibility of the products at high melt strengths (MS = 36 cN, MFR _{230 ° C / 2.16 kg} = 0.5 g / 10 min), possibly due to the tendency to cross-link the products of polypropylene modification when using organosulfur additives. In addition, the very use of such organosulfur compounds is a disadvantage, due to their toxicity to the human body. In addition, a number of dithiocarbamates significantly impair the organoleptic and sanitary-hygienic properties of modification products, which significantly limits their scope, in particular for the production of polypropylene products that are in contact with food products.

Thus, the issues of increasing the efficiency of systems for the post-reactor modification of polypropylene in terms of improving control over all the main stages of the reaction modification process remain highly demanded, which will improve the quality and balance of the main properties of the resulting products with high melt strength.

Essence of the Invention

The objective of the present invention is to obtain a composition of polypropylene with increased melt strength, which is decisive in the production of foamed products by any known method, with improved stability of the shape of the foam and its uniformity.

Technical result The present invention consists in obtaining a composition of polypropylene with increased melt strength by reactive extrusion, with melt strength values from 20 to 50 cN (16-36 cN for the prototype), in combination with improved flow characteristics of modification products: MFR_{230°C/2.16kg} in the range from 0.5 to 3.0 g/10 min (0.5-2.0 g/10 min in the prototype).

An additional technical result lies in the environmental friendliness of the resulting product.

In addition to the achieved technical result in terms of melt strength and other properties mentioned above, the composition has a unique chemical, heat and weather resistance.

The composition according to the invention is also characterized by:

- drawing speed at which the polypropylene thread breaks in the rheometer from 60 to 350 mm/s.

This technical problem is solved and the achievement of the desired technical result is ensured due to the use of a peroxide modifying system in the composition of PP, consisting of a mixture of organic peroxide and a vinyl monomer of various nature and functionality - a coagent, in particular SOAG. A mixture of peroxide with SOAG can be used both in the form of a pre-prepared concentrate, including a powdered base polymer, and directly in the preparation of the charge, or using any dosing devices as part of an extrusion line. To significantly increase the efficiency and effectiveness of the process of chemical modification of polypropylene, the composition additionally includes sterically hindered cycloaliphatic amines, known in practice due to their use as photostabilizing additives for polymeric materials, the so-called HALS, followed by reaction compounding of such compositions in the melt in suitable equipment.

The additional introduction of HALS into the composition of the above-described PP compositions intended for post-reactor modification with peroxide systems in order to obtain high-strength polypropylene, as was unexpectedly found by the inventors, has a significant positive effect on the further process of reactive compounding of the polypropylene composition with an obvious increase in melt strength, while maintaining values of the index of fluidity and extensibility. The supposed reason for this result is the influence of both the HALS molecules themselves and the intermediate products of their oxidation on the process of reactive extrusion of PP in the presence of the peroxide/COAG modifying system. Probably, this contributes to a certain regulation of the processes of peroxide decomposition and the associated destruction reactions competing with each other, modification with SOAG coagent, followed by branching and crosslinking of polypropylene macromolecules with the formation of structures that provide increased strength of the PP melt, while maintaining the required values of its fluidity and extensibility.

Achieving the listed properties provides the possibility of obtaining materials based on this composition by foaming with a wide range of applications, ranging from thermal and waterproofing material to high-tech packaging products.

Detailed description of the invention

In accordance with the present invention, a composition is claimed that includes the following components:

A. from 48.5 to 99.4765 wt.% powdered or granular propylene homopolymer, or propylene random copolymer with ethylene and/or higher α-olefins, or propylene block copolymer with ethylene and/or higher α-olefins, or their combinations;

B. from 0.5 to 3 wt.% SOAG or a mixture of SOAG;

C. from 0.001 to 1.0 wt.% initiator;

D. 0.0025 to 1.5 wt% HALS;

E. 0.02 to 1.0% by weight of an antioxidant and/or heat stabilizer;

F. from 0 to 25 wt.% (optional) polyolefin elastomer;

G. 0 to 20% by weight (optional) of other additives.

Ascomponent A uses isotactic propylene homopolymer, preferably isotactic propylene homopolymer with MFR_230/2.16kg from 1.5 to 3.5 g/10 min, or random copolymer of propylene with ethylene and/or with C₄-FROM₁₀ an α-olefin, preferably a propylene/ethylene and/or C random copolymer₄-FROM₁₀ α-olefin with PTR_{230°C/2.16kg} from 0.27 to 3.5 g/10 min, or block copolymer of propylene with ethylene and/or with C₄-FROM₁₀ α-olefin, preferably a block copolymer of propylene with ethylene and/or with C₄-FROM₁₀ α-olefin with MFR_{230°C/2.16kg} 0.27 to 3.5 g/10 min. Examples of industrial grades of propylene homopolymer: PPH030GP, PPH020GP, produced at the Tomskneftekhim LLC enterprise of Sibur Holding PJSC. Examples of industrial grades of random copolymer of propylene with ethylene and/or C₄-FROM₁₀ α-olefin: PPR003, PPR007 and PPR015, produced at the enterprise LLC "Tomskneftekhim" of PJSC "Sibur Holding". Examples of commercial grades of block copolymer of propylene with ethylene: Balen 02015 produced by OAO Ufaorgsintez, PP 1500J produced by PJSC Nizhnekamskneftekhim. The content of these polymers, both separately and in any combination with each other, varies from 48.5 to 99.4765 wt.%, more preferably from 75 to 98.75 wt.%.

As component B, vinyl monomers of various nature and functionality are used, which, due to unsaturated bonds, are capable of participating in the reactions of polymerization, grafting, and cross-linking of polymer macromolecules, as well as being used as coagents (COAG) of peroxide systems for the modification and vulcanization of rubbers, thermoplastic polymers, and compositions on their basis. Any combination of SOAG is also acceptable, both two- and multi-component. Examples of such monomers produced by the industry are: monofunctional - maleic anhydride (MA) and other anhydrides of unsaturated acids, (meth)acrylic acid and / or its derivatives, N-vinylpyrrolidone, styrene, unsaturated silanes: vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (VTES ), methacryloxypropyltrimethoxysilane (MES), etc.; bifunctional - divinylbenzene (DVB), conjugated and non-conjugated dienes of different classes, aliphatic and aromatic dimaleimides, (meth)acrylate derivatives of glycols, etc.; trifunctional - triallyl isocyanurate (TAIC), trimethylol propane triacrylate (TMPTA), trivinylcyclohexane (TVCH) and others; polyfunctional - pentaerythritoltetraacrylate (PETA), sorbitolpentaacrylate, etc. Examples of SOAG combinations: isoprene - styrene, butyl acrylate - TMPTA, MA - styrene - isoprene, etc. The content of SOAG in the composition is from 0.5 to 3.0 wt.%, more preferably from 0.7 to 1.5 wt.%.

Ascomponent C, initiators known from the prior art are used, preferably peroxy, most preferably virtually any mono-, di- and polyfunctional peroxide compounds used in the vulcanization of rubber compounds and melt processing of hydrocarbon polymers. Examples of peroxides used may be products known under the trademarks Trigonox 301, Luperox DCP, Luperox DI, Luperox DTA, Luperox F, Luperox 101, Luperox 801, etc. The concentration of peroxide in the final composition is from 0.001 to 1.0 wt.% , preferably from 0.005 to 0.5 wt.%, most preferably from 0.01 to 0.2 wt.%.

As component D, hindered cycloaliphatic amines are used, known in practice due to their use as photostabilizing additives for polymeric materials - HALS. All classes of HALS known today: secondary amines, tertiary amines and ether derivatives of hydroxylamines, have comparable efficiency as promoters of the peroxide modifying system in the process of obtaining high-strength polypropylene. Examples of secondary amine class HALS are: Tinuvin 770, Chimassorb 622, Chimassorb 944, Chimassorb 2020, Uvasil 299, ADK Stab LA 52, mixtures thereof Tinuvin 791, Tinuvin 783. Examples of tertiary amine class HALS are: Chimassorb 119, Chimassorb 1:1 mixture 119 and Tinuvin 622 - Tinuvin 111, Uvasorb HA 19, Everstab 119, Todosorb 119. Tinuvin 123 is an example of a class of hydroxylamine ether derivatives. .01 to 1.0 wt.%, even more preferably from 0.05 to 0.7 wt.%. The concentration of HALS in relation to SOAG in the composition can vary from 0.5 to 50 wt.%, preferably from 5 to 30 wt.%, even more preferably from 5 to 20 wt.%.

As component E, the present composition according to the invention may contain primary antioxidants, secondary antioxidants and heat stabilizers or mixtures thereof. Primary antioxidants of the phenol type, for example, ester of 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid and pentaerythritol under the trademark Irganox 1010, secondary antioxidants of the phosphite type, for example, tri-(phenyl -2,4-di-tert-butyl)phosphite under the trademark Irgafos 168, and / or heat stabilizers of other brands, as well as other types of stabilizers or mixtures of stabilizers under such trademarks as Irganox B225, Irganox B215, etc. The content of these additives in the composition may range from 0.02 to 1.0 wt.%, preferably from 0.05 to 0.5 wt.%, most preferably from 0.1 to 0.3 wt.%.

As component F - olefin elastomer - industrial grades of random copolymers of propylene with ethylene or terpolymers of propylene with ethylene and butene-1 (propylene based copolymers) are used. Examples of such copolymers are products marketed by Exxon Mobil under the Vistamax brand. The preferred copolymer is Vistamax 6102.

In another embodiment of the invention, copolymers of ethylene with α-olefins containing from 4 to 8 carbon atoms, obtained on metallocene catalyst systems, are used as an elastomer. Preferably, an ethylene-octene-1 copolymer is used.

Said elastomer has a density of 0.855 to 0.890 g/cm ³ , preferably 0.857 to 0.885 g/cm ³ . The elastomer is also characterized by an MFR of _{230°C/2.16 kg} from 1 to 30 g/10 min., preferably from 3 to 13 g/10 min., even more preferably from 3 to 7 g/10 min. Examples of such elastomers may be products known under the trademarks Engage 8452, Engage 8842, Engage 8137, Exact 8210 and others.

The content of elastomer F is 0 to 25% by weight, preferably 0 to 20% by weight, based on 100% by weight of the polypropylene composition. It is possible to use mixtures of the two above classes of elastomers.

As a component G, the proposed composition may additionally contain other functional, including polymer additives, for example, high-flow grades of propylene homopolymer with MFR _{230/2.16 kg} more than 20 g/10 min, for example, PPH270GP, PPH450GP, etc., lubricating additives, processing additives, nucleators, mineral fillers, pigments, etc.

The high strength polypropylene composition of the invention can be produced by any of the known thermoplastic melt processing methods on any suitable equipment, including single or twin screw extruders, internal rotary mixers, and the like. The preferred equipment is a twin screw extruder with an L/D of at least 30, preferably at least 35.

The order and method of loading all the ingredients of the composition can be any, based on the capabilities of a particular extrusion line. Powdered components B, C, D, E and G are preferably premixed in a suitable dry mixer at room temperature, partially or completely with the base powder component A and component F (if necessary). In the presence of weight automatic dispensers of dry ingredients, it is advisable to carry out the dosing of bulk components of the composition using them. Liquid components B, C, D, E and G are most appropriately introduced into the composition during the compounding process using liquid ingredient weighers of appropriate capacity.

The mixing temperature of the components is determined by the properties of a particular component of the composition, and more specifically -. the mixing of the components is carried out at a temperature above the melting point of the components included in the composition, and below the temperature of their decomposition. Preferably, the mixing temperature of the components is from 200 to 260°C, most preferably from 210 to 250°C.

The processing modes of the resulting composition (compounding) do not differ from the standard modes used depending on the rheological characteristics. The most preferred processing method is melt extrusion.

The compositions produced by the method of the invention are suitable for use as foam materials ranging from thermal and waterproofing material to high-tech packaging products.

The invention will be further explained by examples, which are given to illustrate the present invention and are not intended to limit its scope.

Implementation of the Invention

The following propylene homopolymer was used as component A: PPH030GP (granules) with MFR _{230°C/2.16 kg =} 3.0 g/10 min, produced by Tomskneftekhim LLC; Statistical copolymer of propylene with ethylene grade PPR003 in the form of a powder with an MFR of _{230°C/2.16 kg} from 0.3 to 0.5 g/10 min, produced by OOO Tomskneftekhim. Block copolymer of propylene with ethylene brand Balen 02015, produced by OAO Ufaorgsintez with MFR _{230/2.16 kg} 1.5 g/10 min.

Component B was Nexamit A48 hexamethylenedimaleimide manufactured by Nexam Chemical (Sweden); meta-phenylenedimaleimide (PDM), maleic anhydride (MA), trivinylcyclohexane (TVCH), 1,9-decadiene, manufactured by Shanghai Amino-Chem (China); butyl acrylate (BA), TMPTA, PETA produced by Evonik (Germany).

Component C was Triganox 301 organic peroxides manufactured by Akzo Nobel (Netherlands) and Luperox F40 and Luperox 101 peroxides manufactured by Arkema (France).

As component D, various variants of sterically hindered cycloaliphatic amines - HALS, in particular, secondary amines - Tinuvin 770, Chimassorb 944, Chimassorb 2020, manufactured by BASF (Germany) were used; tertiary amines - Uvasorb HA 19, manufactured by 3V Sigma; ester derivatives of hydroxylamine Tinuvin 123, manufactured by BASF (Germany).

As component E, we used a synergistic mixture of phenol and phosphite AO, Irganox B215 brand, manufactured by BASF, Germany.

Component F, an olefin elastomer, was Vistamax 6102 available from Exxon Mobil and Engage8842 available from Dow Chem.

As component G, a propylene homopolymer of the PPH270FF brand with an MFR of _{230°C/2.16 kg} 27.0 g/10 min, produced by OOO Tomskneftekhim, was used.

The determination of the melt flow index was carried out at a temperature of 230°C and a load of 2.16 N according to ASTM D 4101.

Melt strength was measured using a Smart Rheo 2000 capillary rheometer. The melt was forced through the capillary, loaded into a puller, and pulled out at constant acceleration. When a certain drawing speed was reached, the thread being drawn broke. The force recorded at the moment of thread rupture on the strain gauge was considered as the strength of the melt. The value of the thread winding speed at the moment of rupture at the rheometer piston speed = 0.30 mm/s was taken as the extensibility of the melt. To determine the strength of the polyethylene melt, a capillary with a diameter of 2 mm was used, the measurement temperature was 210°C.

Examples

Getting compositions:

In a number of embodiments of the present invention, a mixture of all components included in the composition - the charge - was prepared manually, or using any known mixing equipment at room temperature until the components were evenly mixed. The resulting charge for the polypropylene melt compounding stage was loaded into a funnel or other dosing device of an extruder, preferably a twin-screw extruder with an L/D of at least 30, preferably at least 35, and processed into a finished product - granules or crushed pieces - by standard methods. The liquid ingredients of the composition, in particular the acrylate-based SOAG, can more preferably be dosed by special weight dispensers for liquid materials, either into the hopper or into one of the extruder zones, depending on the design features of the extrusion line. The maximum melt processing temperature of the extrusion equipment is 200 to 260°C, preferably 210 to 250°C. The product pellets are used for further rheological testing.

In other embodiments of the present invention, a dry concentrate consisting of peroxide, SOAG, and random propylene copolymer powder was pre-prepared at room temperature. The compositions of the compositions are shown in Table 1. Then the resulting concentrate is mixed manually, or using any known mixing equipment, with the remaining ingredients of the final polypropylene compositions at room temperature until all components are uniformly mixed, with further use of the resulting mixture for melt compounding.

The test results of the obtained polypropylene compositions are shown in Table 2, including Examples 1-40. These examples are provided only to illustrate the present invention and do not limit it.

Example 1 (comparative).

The polymer material for testing is prepared by melt processing on the line of a laboratory twin-screw extruder LTE-20-44 of a charge consisting of 98.85 wt.% powder of a random copolymer of propylene with ethylene grade PPR003, 1.0 wt.% Nexamit A48 dimaleimide, 0.05 wt.%, peroxide Trigonox 301 and 0.1 wt.% JSC Irganoks B215 at a maximum temperature in the cylinder zones of 230 °C and a screw speed of 250 min ^-1 .

The resulting material is characterized by an average melt strength MS _210/2/12 = 17.5 cN, a maximum value MS = 17.9 cN and an MFR of _{230°C/2.16 kg} = 2.10 g/10 min.

Example 2 (comparative)

The polymer material for testing is prepared by melt processing on the line of a laboratory twin-screw extruder LTE-20-44 of a charge consisting of 89.0 wt.% powder of a random copolymer of propylene with ethylene grade PPR003, 10 wt.% concentrate K-1 (Table 1) and 0.1 wt.% JSC Irganoks B215 at a maximum temperature in the cylinder zones of 230°C and a screw speed of 250 min ^-1 .

The resulting material is characterized by an average melt strength MS _210/2/12 = 18.5 cN, a maximum value MS = 19.8 cN and an MFR of _{230°C/2.16 kg} = 2.18 g/10 min.

Example 3

The polymer test material was prepared in the same manner as Example 1 (comp.), except that an additional 0.05 wt% HALS brand Chimassorb 2020 was used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 27.0 cN, a maximum value MS = 29.1 cN and an MFR of _{230°C/2.16 kg} = 2.05 g/10 min.

Example 4

The polymer test material was prepared in the same manner as in Example 3, except that an additional 5.0% by weight of PPH270FF high index PP was used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 29.0 cN, a maximum value MS = 31.5 cN and an MFR of _{230°C/2.16 kg} = 2.15 g/10 min.

Example 5

The polymer test material was prepared in the same manner as Example 2 (comp.), except that 0.05 wt% Chimassorb 2020 brand HALS was additionally used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 27.3 cN, a maximum value MS = 29.6 cN and an MFR of _{230°C/2.16 kg} = 2.02 g/10 min.

Example 6

The polymer material for testing is prepared similarly to Example 5, except that instead of concentrate K-1, concentrate K-2 is used in the same amount.

The resulting material is characterized by an average melt strength MS _210/2/12 = 25.6 cN, a maximum value MS = 27.0 cN and an MFR of _{230°C/2.16 kg} = 1.89 g/10 min.

Example 7

The polymer material for testing is prepared similarly to Example 5, except that instead of concentrate K-1, concentrate K-3 is used in the same amount.

The resulting material is characterized by an average melt strength MS _210/2/12 = 24.5 cN, a maximum value MS = 26.0 cN and an MFR of _{230°C/2.16 kg} = 1.72 g/10 min.

Example 8

The polymer material for testing is prepared similarly to Example 4, except that instead of 1.0 wt.% Nexamit A48 it is used in an amount of 1.5 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 35.8 cN, a maximum value MS = 42.0 cN and an MFR of _{230°C/2.16 kg} = 1.19 g/10 min.

Example 9

The polymer test material is prepared in the same manner as in Example 4, except that instead of 1.0 wt.% Nexamit A48, it is used in an amount of 2.0 wt.%. .

The resulting material is characterized by an average melt strength MS _210/2/12 = 39.3 cN, a maximum value MS = 43.0 cN and an MFR of _{230°C/2.16 kg} = 1.10 g/10 min.

Example 10

The polymer test material is prepared in the same manner as in Example 4, except that instead of 1.0 wt.% Nexamit A48, it is used in an amount of 2.5 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 41.2 cN, a maximum value MS = 44.5 cN and an MFR of _{230°C/2.16 kg} = 1.09 g/10 min.

Example 11

The polymer test material is prepared in the same manner as Example 4, except that instead of 1.0 wt.% Nexamit A48, it is used in an amount of 3.0 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 42.0 cN, a maximum value MS = 45.0 cN and an MFR of _{230°C/2.16 kg} = 1.05 g/10 min.

Example 12 (comparative)

The polymer material for testing is prepared similarly to Example 4, except that instead of 1.0 wt.% Nexamit A48 it is used in an amount of 5.0 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 32.5 cN, a maximum value MS = 33.2 cN and an MFR of _{230°C/2.16 kg} = 0.89 g/10 min.

Example 13 (comparative)

The polymer material for testing is prepared similarly to Example 4, except that instead of 1.0 wt.% Nexamit A48 it is used in an amount of 0.4 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 12.5 cN, a maximum value of MS = 14.2 cN and an MFR of _{230°C/2.16 kg} = 4.10 g/10 min.

Example 14 (comparative)

The polymer material for testing is prepared similarly to Example 1 (comparative), except that instead of Nexamit A48, the same amount of TMPTA SOAG is used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 18.5 cN, a maximum value MS = 19.2 cN and an MFR of _{230°C/2.16 kg} = 1.55 g/10 min.

Example 15

The polymer test material was prepared in the same manner as Example 14 (comparative) except that 0.10 wt% Chimassorb 944 HALS was additionally used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 33.8 cN, a maximum value MS = 34.5 cN and an MFR of _{230°C/2.16 kg} = 1.60 g/10 min.

Example 16

The polymer material for testing is prepared similarly to Example 15, except that instead of 1.0 wt.% TMPTA it is used in an amount of 1.5 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 40.5 cN, a maximum value MS = 42.5 cN and an MFR of _{230°C/2.16 kg} = 1.24 g/10 min.

Example 17

The polymer material for testing is prepared similarly to Example 15, except that instead of 1.0 wt.% TMPTA it is used in an amount of 2.0 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 43.8 cN, a maximum value MS = 45.2 cN and an MFR of _{230°C/2.16 kg} = 1.23 g/10 min.

Example 18

The polymer material for testing is prepared similarly to Example 15, except that instead of 1.0 wt% TMPTA it is used in an amount of 2.5 wt/%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 45.5 cN, a maximum value MS = 48.0 cN and an MFR of _{230°C/2.16 kg} = 1.20 g/10 min.

Example 19

The polymer material for testing is prepared similarly to Example 15, except that instead of 1.0 wt% TMPTA it is used in an amount of 3.0 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 46.0 cN, a maximum value of MS = 48.5 cN and an MFR of _{230°C/2.16 kg} = 1.17 g/10 min.

Example 20

The polymer test material was prepared as in Example 8, except that 0.30 wt% Chimassorb 944 was used instead of 0.05 wt% Chimassorb 2020, and 0.085 wt% was used instead of 0.075 wt% Trigonox 301.

The resulting material is characterized by an average melt strength MS _210/2/12 = 35.2 cN, a maximum value MS = 42.0 cN and an MFR of _{230°C/2.16 kg} = 0.85 g/10 min.

Example 21

The polymer test material was prepared similarly to Example 20, except that the same amount of Luperox F40 was used instead of Trigonox 301 peroxide.

The resulting material is characterized by an average melt strength MS _210/2/12 = 44.3 cN, a maximum value MS = 50.0 cN and an MFR of _{230°C/2.16 kg} = 0.50 g/10 min.

Example 22

The polymer test material was prepared similarly to Example 20, except that instead of 0.30 wt.% Chimassorb 944 it was used in an amount of 0.50 wt.%, and instead of 0.085 wt.% Trigonox 301 it was used in an amount of 0.100 wt.% .

The resulting material is characterized by an average melt strength MS _210/2/12 = 39.2 cN, a maximum value MS = 50.0 cN and an MFR _230/2.16 = 0.85 g/10 min.

Example 23

The polymer test material was prepared similarly to Example 8, except that 0.10 wt% of its Chimassorb 944 analogue was used instead of 0.05 wt% Chimassorb 2020, and the same amount of Luperox 101 was used instead of Trigonox 301 peroxide.

The resulting material is characterized by an average melt strength MS _210/2/12 = 26.9 cN, a maximum value MS = 30.2 cN and an MFR of _{230°C/2.16 kg} = 0.69 g/10 min.

Example 24

The polymer test material was prepared similarly to Example 8, except that 0.10 wt% Tinuvin 770 was used instead of 0.05 wt% Chimassorb 2020.

The resulting material is characterized by an average melt strength MS _210/2/12 = 24.6 cN, a maximum value of MS = 28.0 cN and an MFR of _{230°C/2.16 kg} = 2.10 g/10 min.

Example 25

The polymer test material was prepared in the same manner as in Example 24, except that 0.50 wt% Tinuvin 770 was used instead of 0.10 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 31.8 cN, a maximum value MS = 38.0 cN and an MFR of _{230°C/2.16 kg} = 1.84 g/10 min.

Example 26

The polymer test material was prepared as in Example 24, except that the same amount of Uvasorb HA 19 tertiary amine grade HALS was used instead of Tinuvin 770 secondary amine grade HALS.

The resulting material is characterized by an average melt strength MS _210/2/12 = 28.8 cN, a maximum value MS = 36.0 cN and an MFR of _{230°C/2.16 kg} = 1.96 g/10 min.

Example 27

The polymer test material was prepared similarly to Example 26, except that instead of 0.10 wt.% Uvasorb HA 19, it was used in an amount of 0.30 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 30.5 cN, a maximum value MS = 41.0 cN and an MFR of _{230°C/2.16 kg} = 1.38 g/10 min.

Example 28

The polymer test material was prepared as in Example 26, except that the same amount of hydroxyl ether class HALS Tinuvin 123 was used instead of Uvasorb HA 19 tertiary amine class HALS.

The resulting material is characterized by an average melt strength MS _210/2/12 = 27.5 cN, a maximum value MS = 35.0 cN and an MFR of _{230°C/2.16 kg} = 2.06 g/10 min.

Example 29

The polymer material for testing is prepared similarly to Example 28, except that instead of 0.10 wt.% Tinuvin 123 use it in an amount of 0.30 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 29.9 cN, a maximum value MS = 37.0 cN and an MFR of _{230°C/2.16 kg} = 1.64 g/10 min.

Example 30

The polymer material for testing is prepared similarly to Example 15, except that instead of the base polymer consisting of PPR003 powder with the addition of 5 wt.% PPH270FF, PPH030GP granulate is used, instead of 0.05 wt.%, 0.0125 wt.% Trigonox 301 is used. , and instead of 0.10 wt.% using 0.02 wt.% Irganox B215.

The resulting material is characterized by an average melt strength MS _210/2/12 = 22.9 cN, a maximum value of MS = 25.0 cN and an MFR of _{230°C/2.16 kg} = 2.61 g/10 min.

Example 31

The polymer material for testing is prepared similarly to Example 30, except that instead of 1.0 wt.% TMPTA, a mixture of 0.8 wt.% TMPTA and 0.2 wt.% Nexamit A48 is used, and instead of 0.0125 wt.% use 0.01 wt% Trigonox 301.

The resulting material is characterized by an average melt strength MS _210/2/12 = 28.4 cN, a maximum value MS = 36.0 cN and an MFR of _{230°C/2.16 kg} = 1.95 g/10 min.

Example 32

The polymer test material was prepared similarly to Example 30, except that 0.0075 wt% Trigonox 301 was used instead of 0.0125 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 29.8 cN, a maximum value MS = 32.5 cN and an MFR of _{230°C/2.16 kg} = 1.35 g/10 min.

Example 33

The polymer material for testing is prepared similarly to Example 30, except that instead of the PPH030GP granulate, the granulate of the block copolymer of propylene with ethylene of the Balen 02015 brand is used, instead of SOAG TMPTA, the same amount of Nexamit A48 is used, instead of 0.0125 wt.%, 0 05 wt.% Trigonox 301, and instead of 0.02 wt.% use 0.05 wt.% Irganox B 215.

The resulting material is characterized by an average melt strength MS _210/2/12 = 24.3 cN, a maximum value MS = 27.2 cN and an MFR of _{230°C/2.16 kg} = 0.89 g/10 min.

Example 34

The polymer material for testing is prepared similarly to Example 30, except that PETA is used instead of TMPTA, and 0.0075 wt.% Trigonox 301 is used instead of 0.0125 wt.%.

The resulting material is characterized by an average melt strength MS _210/2/12 = 27.3 cN, a maximum value MS = 29.5 cN and an MFR of _{230°C/2.16 kg} = 1.23 g/10 min.

Example 35

The polymer material for testing is prepared similarly to Example 3, except that Vistamax 6102 elastomer is additionally added to the composition due to the base PPR003 in an amount of 20.0 wt.%, and instead of 0.05 wt.% Chimassorb 2020, 0.10 wt. .% of its counterpart Chimassorb 944.

The resulting material is characterized by an average melt strength MS _210/2/12 = 32.9 cN, a maximum value MS = 37.0 cN and an MFR of _{230°C/2.16 kg} = 1.78 g/10 min.

Example 36

The polymer test material was prepared similarly to Example 35, except that the same amount of Engage 8842 elastomer was used instead of Vistamax 6102.

The resulting material is characterized by an average melt strength MS _210/2/12 = 23.5 cN, a maximum value MS = 27.0 cN and an MFR of _{230°C/2.16 kg} = 0.88 g/10 min.

Example 37

The polymer test material was prepared as in Example 35, except that a mixture of 0.10 wt% Vistamax 6102 and 0.10 wt% Engage 8842 was used instead of 0.20 wt% Vistamax 6102.

The resulting material is characterized by an average melt strength MS _210/2/12 = 20.7 cN, a maximum value MS = 23.4 cN and an MFR of _{230°C/2.16 kg} = 0.99 g/10 min.

Example 38

The polymer material for testing is prepared similarly to Example 15, except that instead of 0.10 wt.% TMPTA, a mixture of 0.5 wt.% TMPTA and 0.5 wt.% BA is used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 27.6 cN, a maximum value MS = 30.2 cN and an MFR = 3.0 g/10 min.

Example 39

The polymer material for testing is prepared similarly to Example 38, except that instead of a binary mixture of TMPTA and BA, a three-component mixture of monomers is used: 0.5 wt.% TMPTA + 0.5 wt.% MA + 0.5 wt.% TVCG, and instead of HALS Chimassorb 944, Tinuvin 123 is used in the same amount.

The resulting material is characterized by an average melt strength MS _210/2/12 = 30.5 cN, a maximum value MS = 33.0 cN and an MFR of _{230°C/2.16 kg} = 0.95 g/10 min.

Example 40

The polymer test material was prepared similarly to Example 39, except that a ternary monomer mixture consisting of 0.5 wt% TMPTA + 0.5 wt% MA + 0.5 wt% 1,9-decadiene was used.

The resulting material is characterized by an average melt strength MS _210/2/12 = 32.1 cN, a maximum value MS = 35.0 cN and an MFR of _{230°C/2.16 kg} = 1.10 g/10 min.

Table 1-4 shows the compositions of the concentrate, which is pre-prepared to the stage of mixing with the main polymer

Table 1. Compositions of concentrates (wt.%) from K-1 to K-3

Components K-1 K-2 K-3 PPR003 powder Up to 100 Up to 100 Up to 100 Nexamit A48 10.0 10.0 - Meta-phenylenedimaleimide (PDM) - - 10.0 Trigonox 301 0.5 - - Luperox F40 - 0.5 0.5

Tables 2-5 show the compositions of polypropylene compositions with increased melt strength (Examples 1-11)

Table 2. Compositions (wt.%) and properties of compositions of polypropylene with increased melt strength according to examples 1-11

Components Example No. one
(compar.) 2
(compar.) 3 4 five 6 7 8 nine 10 eleven PPR003 powder 98.85 89.0 98.80 91.9 89.85 89.85 89.85 93.275 92.75 92.24 91.73 PPH270FF - - - 5.0 - - - 5.0 5.0 5.0 5.0 Nexamit A48 1.0 - 1.0 1.0 - - - 1.5 2.0 2.5 3.0 K-1 - 10.0 - - 10.0 - - - - - - K-2 - - - - 10.0 - - - - - K-3 - - - - - - 10.0 - - - - Chimassorb 2020 - - 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Trigonox 301 0.05 - 0.05 0.05 - - - 0.075 0.100 0.110 0.120 Irganox B215 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Properties MFR _{230ºС/2.16kg} , g/10 min 2.10 2.18 2.05 2.15 2.02 1.89 1.72 1.19 1.10 1.09 1.05 melt strength,
(cN) Wed value at different piston speeds 17.5 18.5 27.0 29.0 27.3 25.6 24.5 35.8 39.3 41.2 42.0 Maximum value (winding speed at break, mm/s) 17.9
(98-159) 19.8
(108-147) 29.1
(75-92) 31.5
(72-90) 29.6
(75-85) 27.0
(75-89) 26.0
(86-94) 42.0
(62-85) 43.0
(66-77) 44.5
(65-73) 45.0
(62-70)

Table 3. Compositions (wt.%) and properties of compositions of polypropylene with increased melt strength according to examples 12-22

Components Example No. one
(compar.) 2
(compar.) 3 4 five 6 7 8 nine 10 eleven PPR003 powder 89.8 94.4 93.85 93.75 93.225 91.485 92.205 91.695 93.015 93.015 92,800 PPH270FF 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Nexamit A48 5.0 0.4 - - - - - - 1.5 1.5 1.5 TMPTA 1.0 1.0 1.5 2.0 2.5 3.0 - - - Chimassorb 2020 0.05 0.05 - - - - - - - - - Chimassorb 944 - - - 0.10 0.10 0.10 0.10 0.10 0.30 0.30 0.50 Luperox F40 - - - - - - - - - 0.085 - Trigonox 301 0.05 0.05 0.05 0.05 0.075 0.085 0.095 0.105 0.085 - 0.100 Irganox B215 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Properties MFR _{230ºС/2.16kg} , g/10 min 0.89 4.10 1.55 1.60 1.24 1.23 1.20 1.17 0.85 0.5 0.85 melt strength,
(cN) Wed value at different piston speeds 32.5 12.5 18.5 33.8 40.5 43.8 45.5 46.0 35.2 44.3 39.2 Maximum value (winding speed at break, mm/s) 33.2
(68-79) 14.2
(108-147) 19.2
(75-89) 34.5
(70-82) 42.5
(66-80) 45.2
(65-78) 48.0
(63-75) 48.5
(60-72) 42.0
(65-77) 50.0
(60-72) 50.0
(67-88)

Table 4. Compositions (wt.%) and properties of compositions of polypropylene with increased melt strength of examples 23-33

Components Example No. 23 24 25 26 27 28 29 thirty 31 32 33 PPR003 powder 93.225 93.75 93.35 93.75 93.55 93.75 93.55 - - - - PPH030GP granules - - - - - - - 98.8675 98.87 98.8725 - Balen 02015 granules - - - - - - - - - - 98.8 PPH270FF 5.0 5.0 5.0 5.0 5.0 5.0 5.0 - - - - Nexamit A48 1.5 1.0 1.0 1.0 1.0 1.0 1.0 - 0.2 - 1.0 TMPTA - - - - - - - 1.0 0.8 1.0 - Chimassorb 2020 - - - - - - - - - - - Chimassorb 944 0.10 - - - - - - 0.1 0.1 0.1 0.1 Tinuvin 770 - 0.10 0.50 - - - - - - - - Uvasorb HA 19 - - - 0.10 0.30 - - - - - - Tinuvin 123 - - - - - 0.10 0.30 - - - - Luperox 101 0.075 - - - - - - - - - - Trigonox 301 - 0.05 0.05 0.05 0.05 0.05 0.05 0.0125 0.01 0.0075 0.05 Irganox B215 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.02 0.02 0.02 0.05 Properties MFR _{230ºС/2.16kg} , g/10 min 0.69 2.10 1.84 1.96 1.38 2.06 1.64 2.61 1.95 1.35 0.89 melt strength,
(cN) Wed value at different piston speeds 26.9 24.6 31.8 28.8 30.5 27.5 29.9 22.9 28.4 29.8 24.3 Maximum value (winding speed at break, mm/s) 30.2
(78-89) 28.0
(80-110) 38.0
(77-87) 36.0
(81-95) 41.0
(72-87) 35.0
(90-102) 37.0
(85-94) 25.0
(90-95) 36.0
(85-91) 32.5
(80-92) 27.2
(110-155)

Table 5. Compositions (wt.%) and properties of compositions of polypropylene with increased melt strength of examples 34-40

Components Example No. 34 35 36 37 38 39 40 PPR003 powder - 78.75 78.75 78.75 93.75 92.8 92.8 PPH030GP granules 98.8725 - - - - - - PPH270FF - - - - 5.0 5.0 5.0 Vistamax 6102 - 20.0 - 10.0 - - - Engage 8842 - 20.0 10.0 - - - Nexamit A48 - 1.0 1.0 1.0 - - - TMPTA - - - - 0.5 0.5 0.5 PETA 1.0 - - - - - - BA - - - - 0.5 - - MA - - - - - 0.5 0.5 TVCG - - - - - 0.5 - 1,9-decadiene - - - - - - 0.5 Chimassorb 944 0.1 0.1 0.1 0.1 0.1 - - Tinuvin 123 - - - - - 0.1 0.1 Trigonox 301 0.0075 0.05 0.05 0.05 0.05 0.05 0.05 Irganox B215 0.02 0.1 0.1 0.1 0.1 0.1 0.1 Properties MFR _{230ºС/2.16kg} , g/10 min 1.23 1.78 0.88 0.99 3.0 0.95 1.10 melt strength,
(cN) Wed value at different piston speeds 27.3 32.9 23.5 20.7 27.6 30.5 32.1 Maximum value (winding speed at break, mm/s) 29.5
(77-88) 37.0
(90-105) 27.0
(125-190) 23.4
(210-350) 30.2
(100-115) 33.0
(70-82) 35.0
(75-90)

The results of testing polypropylene compositions with increased melt strength, shown in Table 2, indicate the advantages of the proposed method for their preparation, which consists in the implementation of the promoting effect of HALS molecules on the operation of the peroxide modifying system during the reactive extrusion of PP compositions, leading to a sharp increase in the melt strength values of products without significant reduction in their fluidity and extensibility. Examples 3-7, 15 and Comparative Examples 1, 2 and 14 demonstrate a significant effect of increasing the melt strength (MS) values of compositions based on random copolymer of propylene with ethylene, subjected to reactive extrusion in the presence of peroxide modification systems with Nexamit A48 SOAG and TMPTA, with the introduction they contain a small amount of HALS brands Chimassorb 2020 and Chimasssorb 944 (0.05 and 0.10 wt.%, respectively). It can be seen that, in this case, the values of the MFI and extensibility (winding speed at breakage) of the products change insignificantly.

The following Examples 8-11 and 16-19 show the nature of the effect of increasing the dosage of SOAG: TMPTA and Nexamit A48 dimaleimide within the allowable interval of their dosing on the increase in the melt strength index (MS) and the change in the value of the melt flow index (MFR) of the resulting compositions. Comparative Examples 12 and 13 demonstrate the nature of the change in the values of MS and MFI of polypropylene compositions when exceeding, or going beyond the lower level of the allowable values of the SOAG concentration using the example of Nexamit A48.

Examples 20-22 demonstrate the nature of the change in the properties of polypropylene compositions with increased melt strength (HMS-PP) with an acceptable increase in the dosage of HALS using Chimassorb 944 as an example. The possibilities of a significant increase in the melt strength of the compositions with an increase in the dosage of HALS with a slight decrease in their fluidity are visible.

Examples 23 and 8 show how the properties of HMS-PP compositions change when Trigonox 301 peroxide is replaced with Luperox 101.

Examples 7, 24-29 demonstrate the nature of the effect of HALS additives of various brands and classes with varying their concentrations on the melt strength and flowability of the resulting HMS-PP compositions. The wide possibilities of the proposed approach are visible.

Examples 30-33 demonstrate the nature of the change in the properties of HMS-PP compositions when using another polymer base in the form of granules instead of the PPR003 random propylene-ethylene copolymer powder: PPH030GP grade propylene homopolymer (Examples 30-32) and Balen 02015 block copolymer (Example 33).

Examples 35-37 demonstrate the effect of adding polyolefin elastomers on MS, extensibility and MFI values of HMS-PP compositions. One can see the influence of the nature of the elastomer, as well as their combination in a 1:1 ratio, on the properties of these compositions.

Examples 31, 34, 38 - 40 demonstrate the possibility of using SOAG of various nature, both separately (Example 34), and in binary (Examples 31, 38) and triple (Examples 39, 40) combinations in HMS-PP compositions with HALS: Himassorb 944 and Tinuvin 123.

Claims (114)

1. Polymer composition for foaming, containing in relation to the total weight of the following components: A. from 48.5 to 99.4765 wt.% powdered or granular propylene homopolymer, or propylene random copolymer with ethylene and/or higher α-olefins, or propylene block copolymer with ethylene and/or higher α-olefins, or their mixture; B. from 0.5 to 3 wt.% coagent (SOAG) or a mixture of SOAG, which use vinyl monomers; C. from 0.001 to 1.0 wt.% of the initiator, which is used as a peroxide system; D. 0.0025 to 1.5% by weight hindered cycloaliphatic amine stabilizer (HALS); E. 0.02 to 1.0% by weight of an antioxidant and/or heat stabilizer; F. from 0 to 25 wt.% polyolefin elastomer or mixture of elastomers; G. 0 to 20% by weight of other additives. 2. The polymer composition according to claim 1, where the content of powdered or granular propylene homopolymer, or propylene random copolymer with ethylene and/or α-olefins, or propylene block copolymer with ethylene and/or higher α-olefins, or mixtures thereof in relation to to the total weight of the composition is from 75 to 98.75 wt.%. 3. Polymer composition according to claim. 1, where the content of SOAG in relation to the total mass of the composition is from 0.7 to 1.5 wt.%. 4. The polymer composition according to claim 1, wherein the content of the initiator relative to the total weight of the composition is from 0.005 to 0.5% by weight, preferably from 0.01 to 0.2% by weight. 5. The polymer composition according to claim 1, wherein the content of HALS relative to the total weight of the composition is from 0.01 to 1.0% by weight, preferably 0.05 to 0.7% by weight. 6. The polymer composition according to claim 1, where the content of the primary phenolic antioxidant or a mixture of the primary phenolic antioxidant and the secondary phosphite stabilizer, relative to the total weight of the composition, is from 0.05 to 0.5 wt.%. 7. The polymer composition according to claim 6, where the content of the primary phenolic antioxidant or a mixture of the primary phenolic antioxidant and the secondary phosphite stabilizer, relative to the total weight of the composition, is from 0.1 to 0.3 wt.%. 8. The polymer composition according to claim 1, wherein the content of the olefin elastomer or mixture of elastomers relative to the total weight of the composition is from 0 to 20 wt.%. 9. The polymer composition according to claim 1, where the content of HALS in relation to SOAG in the composition is from 0.5 to 50 wt.%. 10. Polymer composition according to claim 9, wherein the content of HALS in relation to SOAG in the composition is from 5 to 30 wt.%, preferably from 5 to 20 wt.%. 11. The polymer composition according to claim 1, wherein C ₄ -C ₁₀ α-olefin is used as the higher α-olefin in the propylene-α-olefin random copolymer. 12. The polymer composition according to claim 1, wherein C ₄ -C ₁₀ α-olefin is used as the higher α-olefin in the propylene-α-olefin block copolymer. 13. The polymer composition according to claim 1, where monofunctional and/or bifunctional and/or trifunctional and/or polyfunctional monomers are used as SOAG or mixture of SOAG. 14. The polymer composition according to claim 13, where the monofunctional monomers are selected from the group including maleic anhydride, anhydrides of unsaturated acids, methacrylic acid and / or its derivatives, N-vinylpyrrolidone, styrene, unsaturated silanes, in particular vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane. 15. The polymer composition according to claim 13, where the bifunctional monomers are selected from the group containing divinylbenzene, conjugated and non-conjugated dienes, aliphatic and aromatic dimaleimides, (meth)acrylate derivatives of glycols. 16. The polymer composition according to claim 13, where the trifunctional monomers are selected from the group containing triallyl isocyanurate, trimethylol propane triacrylate, trivinylcyclohexane. 17. The polymer composition according to claim 13, where the polyfunctional monomers are selected from the group containing pentaerythritoltetraacrylate, sorbitolpentaacrylate. 18. The polymer composition according to claim 1, where combinations of monomers are used as a SOAG mixture: isoprene-styrene, butyl acrylate-trimethylol propane triacrylate, maleic anhydride-styrene-isoprene. 19. The polymer composition according to claim 1, where peroxide systems are used as the initiator. 20. The polymer composition according to claim 1, wherein hindered cycloaliphatic amines are used as HALS. 21. The polymer composition according to claim 1, wherein secondary amines are used as HALS. 22. A polymer composition according to claim 1, wherein tertiary amines are used as HALS. 23. The polymer composition according to claim 1, where ester derivatives of hydroxyalamines are used as HALS. 24. The polymer composition according to claim 1, where HALS functions as promoters for peroxide systems. 25. The polymer composition according to claim 1, where primary antioxidants of the phenolic type are used as antioxidants. 26. The polymer composition according to claim 1, wherein secondary antioxidants of the phosphite type are used as antioxidants. 27. The polymer composition according to claim 25, wherein 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid ester is used as the primary antioxidant. 28. The polymer composition according to claim 26, where tri-(phenyl-2,4-di-tert-butyl) phosphite ester is used as a secondary antioxidant. 29. The polymer composition according to claim 1, wherein the polyolefin elastomer is a propylene-ethylene copolymer. 30. The polymer composition of claim 1, wherein the polyolefin elastomer is a propylene-ethylene random copolymer. 31. The polymer composition according to claim 1, wherein the polyolefin elastomer is a terpolymer of propylene with ethylene and butene-1. 32. The polymer composition according to claim 1, wherein the polyolefin elastomer is an ethylene-α-olefin copolymer. 33. The polymer composition according to claim 32, where the α-olefin contains from 4 to 8 carbon atoms. 34. The polymer composition of claim 32, wherein the α-olefin is produced on metallocene catalyst systems. 35. The polymer composition according to claim 34, where the α-olefin, which is part of the polyolefin elastomer, is octene-1. 36. The polymer composition according to claim 1, where other additives are selected from the group including lubricating additives, processing additives, nucleators, mineral fillers, pigments. 37. The polymer composition according to claim 1, where a propylene homopolymer with an MFR of _{230/2.16 kg} of more than 20 g/10 min is used as an additive. 38. The polymer composition according to claim 1, where the MFR _{230 / 2.16 kg} for propylene homopolymer is from 1.5 to 3.5 g / 10 min. 39. The polymer composition according to claim 1, where the MFR _{230/2.16 kg} for the copolymer of propylene with ethylene and/or C ₄ -C ₁₀ with α-olefin is from 0.27 to 3.5 g/10 min. 40. The polymer composition according to claim 1, wherein the density of the polyolefin elastomer is from 0.855 to 0.890 g/cm ³ . 41. The polymer composition according to claim 1, where the density of the polyolefin elastomer is from 0.857 to 0.855 g/cm ³ . 42. The polymer composition according to claim 1, where the MFR _{230°C/2.16 kg} for the polyolefin elastomer is from 1 to 30 g/10 min. 43. The polymer composition according to claim 1, where the MFR of _{230°C/2.16 kg} for the polyolefin elastomer is from 3 to 13 g/10 min. 44. The polymer composition according to claim 1, where the MFR _{230°C/2.16 kg} for the polyolefin elastomer is from 3 to 7 g/10 min. 45. A method for producing a polymer composition for foaming according to claim 1, including mixing and processing into a melt the following components, taken in relation to the total mass of the composition in an amount: A. from 48.5 to 99.4765 wt.% powdered or granular propylene homopolymer, or propylene random copolymer with ethylene and/or higher α-olefins, or propylene block copolymer with ethylene and/or higher α-olefins, or their mixture; B. from 0.5 to 3 wt.% SOAG or a mixture of SOAG; C. from 0.001 to 1.0 wt.% initiator; D. 0.0025 to 1.5 wt% HALS; E. 0.02 to 1.0% by weight of an antioxidant and/or heat stabilizer; F. from 0 to 25 wt.% polyolefin elastomer or mixture of elastomers; G. 0 to 20% by weight of other additives. 46. The method of obtaining a polymer composition according to p. 45, where the content of SOAG in relation to the total mass of the composition is from 0.7 to 1.5 wt.%. 47. The method of obtaining a polymer composition according to p. 45, where the content of the initiator in relation to the total mass of the composition is from 0.01 to 0.2 wt.%. 48. The method of obtaining a polymer composition according to p. 45, where the content of HALS in relation to the total weight of the composition is from 0.01 to 1.0 wt.%. 49. A method for producing a polymer composition according to claim 45, where the content of a primary phenolic antioxidant or a mixture of a primary phenolic antioxidant and a secondary phosphite stabilizer relative to the total weight of the composition is from 0.05 to 0.5 wt.%. 50. The method for producing a polymer composition according to claim 45, where the content of the primary phenolic antioxidant or a mixture of primary phenolic antioxidant and secondary phosphite stabilizer in relation to the total weight of the composition is from 0.1 to 0.3 wt.%. 51. The method for producing a polymer composition according to claim 45, where the content of the olefin elastomer or mixture of elastomers in relation to the total weight of the composition is from 0 to 20 wt.%. 52. The method of obtaining a polymer composition according to p. 45, where the content of HALS in relation to SOAG in the composition is from 0.5 to 50 wt.%. 53. The method of obtaining a polymer composition according to p. 52, where the content of HALS in relation to SOAG in the composition is from 5 to 30 wt.%. 54. A method for producing a polymer composition according to claim 45, wherein C ₄ -C ₁₀ α-olefin is used as the higher α-olefin in the propylene-α-olefin random copolymer. 55. The method for producing a polymer composition according to claim 45, where C ₄ -C ₁₀ α-olefin is used as the higher α-olefin in the composition of the propylene block copolymer with α-olefin. 56. A method for producing a polymer composition according to claim 45, where vinyl monomers are used as SOAG or a mixture of SOAG. 57. A method for producing a polymer composition according to claim 45, where monofunctional and / or bifunctional and / or trifunctional and / or polyfunctional monomers are used as SOAG or a mixture of SOAG. 58. A method for producing a polymer composition according to claim 45, where monofunctional monomers are selected from the group including maleic anhydride, anhydrides of unsaturated acids, methacrylic acid and / or its derivatives, N-vinylpyrrolidone, styrene, unsaturated silanes, in particular vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane . 59. A method for producing a polymer composition according to claim 45, where the bifunctional monomers are selected from the group containing divinylbenzene, conjugated and non-conjugated dienes, aliphatic and aromatic dimaleimides, acrylate derivatives of glycols. 60. The method for producing a polymer composition according to claim 45, where the trifunctional monomers are selected from the group containing triallyl isocyanurate, trimethylol propane triacrylate, trivinylcyclohexane. 61. The method for producing a polymer composition according to claim 45, where the polyfunctional monomers are selected from the group containing pentaerythritoltetraacrylate, sorbitolpentaacrylate. 62. A method for producing a polymer composition according to claim 45, where combinations of monomers are used as a SOAG mixture: isoprene-styrene, butyl acrylate-trimethylol propane triacrylate, maleic anhydride-styrene-isoprene. 63. A method for producing a polymer composition according to claim 45, where peroxide systems are used as an initiator. 64. A method for producing a polymer composition according to claim 45, where sterically hindered cycloaliphatic amines are used as HALS. 65. A method for producing a polymer composition according to claim 45, where secondary amines are used as HALS. 66. A method for producing a polymer composition according to claim 45, where tertiary amines are used as HALS. 67. A method for producing a polymer composition according to claim 45, where ester derivatives of hydroxyalamines are used as HALS. 68. A method for producing a polymer composition according to claim 45, where HALS acts as a promoter for peroxide systems. 69. A method for producing a polymer composition according to claim 45, where primary phenol-type antioxidants are used as antioxidants. 70. A method for producing a polymer composition according to claim 45, where secondary antioxidants of the phosphite type are used as antioxidants. 71. A method for producing a polymer composition according to claim 69, where 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid ester is used as the primary antioxidant. 72. A method for producing a polymer composition according to claim 70, where tri-(phenyl-2,4-di-tert-butyl) phosphite ester is used as a secondary antioxidant. 73. A method for producing a polymer composition according to claim 45, where a propylene-ethylene copolymer is used as a polyolefin elastomer. 74. A method for producing a polymer composition according to claim 45, where a propylene-ethylene random copolymer is used as a polyolefin elastomer. 75. A method for producing a polymer composition according to claim 45, where a terpolymer of propylene with ethylene and butene-1 is used as a polyolefin elastomer. 76. A method for producing a polymer composition according to claim 45, where an ethylene-α-olefin copolymer is used as a polyolefin elastomer. 77. The method of obtaining a polymer composition according to p. 76, where the α-olefin contains from 4 to 8 carbon atoms. 78. The method of obtaining a polymer composition according to p. 76, where the α-olefin is obtained on metallocene catalyst systems. 79. The method for producing a polymer composition according to claim 76, where the α-olefin, which is part of the polyolefin elastomer, is represented by octene-1. 80. The method of obtaining a polymer composition according to p. 45, where other additives are selected from the group including lubricating additives, processing additives, nucleators, mineral fillers, pigments. 81. A method for producing a polymer composition according to claim 45, where a propylene homopolymer with an MFR of _{230/2.16 kg} of more than 20 g/10 min is used as an additive. 82. A method for producing a polymer composition according to claim 45, where the MFR _{230 / 2.16 kg} for propylene homopolymer is from 1.5 to 3.5 g / 10 min. 83. A method for producing a polymer composition according to claim 45, where the MFR _{230 / 2.16 kg} for a copolymer of propylene with ethylene and / or C ₄ -C ₁₀ with an α-olefin is from 0.27 to 3.5 g / 10 min. 84. A method for producing a polymer composition according to claim 45, where the density of the polyolefin elastomer is from 0.855 to 0.890 g/cm ³ . 85. The method of obtaining a polymer composition according to p. 45, where the density of the polyolefin elastomer is from 0.857 to 0.855 g/cm ³ . 86. The method for producing a polymer composition according to claim 45, where the MFR _{230 ° C / 2.16 kg} for the polyolefin elastomer is from 1 to 30 g / 10 min. 87. A method for producing a polymer composition according to claim 45, where the MFR of _{230 ° C / 2.16 kg} for a polyolefin elastomer is from 3 to 13 g / 10 min. 88. A method for producing a polymer composition according to claim 45, where the MFR of _{230 ° C / 2.16 kg} for a polyolefin elastomer is from 3 to 7 g / 10 min. 89. A method for producing a polymer composition according to clause 45, where a mixture of all components that make up the composition is simultaneously prepared - a charge. 90. A method for producing a polymer composition according to claim 45, where a concentrate is preliminarily prepared, consisting of an initiator, SOAG and a propylene random copolymer. 91. The method of obtaining a polymer composition according to p. 45, where COAG, initiator, HALS, antioxidant and / or heat stabilizer and other additives are pre-mixed. 92. The method of obtaining a polymer composition according to p. 91, where the mixture of COAG, initiator, HALS, antioxidant and / or heat stabilizer and other additives are pre-mixed in the form of a powder. 93. The method of obtaining a polymer composition according to p. 92, where the mixture of SOAG, initiator, HALS, antioxidant and / or heat stabilizer and other additives are introduced into the composition in liquid form. 94. A method for producing a polymer composition according to claim 45, where the mixing of the components that make up the composition is carried out at a temperature above their melting point and below their decomposition temperature. 95. The method of obtaining a polymer composition according to claim 45, where the mixing of the components that make up the composition is carried out at a temperature of from 200 to 260°C. 96. The method of obtaining a polymer composition according to p. 45, where the mixing of the components that make up the composition is carried out at a temperature of from 210 to 250°C. 97. A method for producing a polypropylene composition according to claim 45, where mixing and processing into a homogeneous melt of all components is carried out using mixing equipment and an extruder. 98. The use of a polypropylene composition according to any one of paragraphs. 1-44 or a composition obtained by the method according to any one of paragraphs. 45-97, as a composition for obtaining products by foaming. 99. The product obtained by foaming from the composition according to any one of paragraphs. 1-44 or a composition obtained by the method according to any one of paragraphs. 45-97. 100. The product according to claim 99, which is a product selected from packaging, cable, thermal and waterproofing.

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