Method for synthesis of functionalised poly(1,3-alkadienes) and use thereof in producing impact-resistant vinyl aromatic polymers

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of functionalised poly(1,3-alkadienes) and use thereof in producing impact-resistant vinyl aromatic polymers. Described is a method for synthesis of functionalised poly(1,3-alkadienes), which involves anionic polymerisation of at least one 1,3-alkadiene monomer with 4-8 carbon atoms in the presence of an organolithium compound and a non-polar solvent with a low boiling point and carrying out a step for chain termination of the 1,3-alkadiene-based polymer at the end of polymerisation by adding a bromoalkane to the polymerisation mixture, where the alkane contains 1-12 carbon atoms, after which a product containing a stable nitroxyl radical, characterised by presence of a -NO• group, soluble in said non-polar solvent, is added. The invention also describes functionalised poly(1,3-alkadienes), obtained using said method. Described is a method of producing vinyl aromatic (co)polymers that are grafted on unsaturated poly(1,3-alkadiene) in a controlled manner, involving: a) dissolving said functionalised poly(1,3-alkadiene) in a liquid phase consisting of a mixture of vinyl aromatic monomers and a polymerisation solvent in a weight ratio ranging from 60/40 to 100/0, preferably from 60/40 to 90/10; b) adding at least one radical initiator to the mixture containing the functionalised poly(1,3-alkadiene) in a solution, and polymerising the obtained mixture at a temperature equal to higher than 120°C; c) extracting the vinyl aromatic (co) polymer obtained at the end of polymerisation, and removing volatile components therefrom in a vacuum in order to extract the solvent and unreacted monomers, and d) recycling the mixture of solvent and monomers obtained when removing volatile components to step (a). Described also is an impact-resistant vinyl aromatic (co)polymer, which contains a continuous phase essentially consisting of a matrix containing at least 50 wt % vinyl aromatic monomer, and a dispersion phase essentially consisting of said functionalised elastomer in amount of 1-25 wt % relative total weight, wherein elastomer particles have a "core/cladding" morphology, and average diameter thereof ranges from 0.1 mcm to 1 mcm.

EFFECT: obtaining a functionalised compound which can then be used to produce an impact-resistant vinyl aromatic copolymer with the morphology of an elastomer phase of the core-cladding type.

9 cl, 2 tbl, 4 ex

The present invention relates to a method of synthesis of functionalized poly(1,3-alkadienes) and to their use in obtaining high-impact vinylaromatic polymers and copolymers.

More specifically, the present invention relates to a method for vinylaromatic polymers or copolymers, more (co)polymers grafted adjustable manner on functionalityand poly(1,3-alkadiene), and Acadiana group contains from 4 to 8 carbon atoms.

More specifically, the present invention relates to a method for producing styrene (co)polymers grafted on functionalized polybutadiene in the presence of a system suitable for living radical polymerization.

The term "living radical polymerization"used in the present description and in the claims, means the traditional radical polymerization, which is carried out in the presence of chemical substances that can enter into a reversible reaction with the radical of the growing polymer chain. These chemical substances are, for example, stable nitroxyl radicals or alkoxyamine. More detailed information about the living radical polymerization can be found in U.S. patent No. 4581429, in European patent No. 869137 or in the book "Handbook of Radical Polymerization" Wiley Interscience 2002.

In the present description of the invention the CoE mentioned conditions should be considered as preferred conditions, even if it is not stated directly.

Methods of obtaining vinylaromatic (co)polymers grafted on an elastomer (rubber) adjustable manner known in the literature. For example, in U.S. patent No. 6262179 describes a method for reinforced rubber vinylaromatic polymer, characterized by a modal or bimodal morphology; this method involves the polymerization vinylaromatic monomer in the solution containing the rubber, using an initiating system comprising a source of stable radicals. At the end of the polymerization receive the product, consisting of a rigid polymer matrix, in which the dispersed rubber particles, however, the morphology of these particles is still determines the type of rubber, as in traditional methods that use unstable polymerization initiators.

In U.S. patent No. 6255402 described a method of obtaining a composition consisting of a polymer vinylaromatic matrix, in which the dispersed rubber particles, the morphology of which is different from the morphology, known as "salami", but refers to the types of "labyrinth", "the onion" or, preferably, a "core/shell"that provides high-impact final product with improved characteristics of surface gloss. In the same U.S. patent given information about the meaning of terms that indicated above morphol the policy form.

The difference of this method is that it managed to get a different morphology by applying homopolymer 1,3-butadiene (hereinafter butadiene) rubber, which traditionally gives the morphology of the creature type "salami".

The method described in this U.S. patent, involves the dissolution of polybutadiene rubber in a solvent in the complete absence of the monomer and the functionalization of dissolved rubber with initiating system consisting of a conventional radical initiator, such as peroxide, and a stable radical initiator, for example, 2,2,6,6-tetramethylpiperidine-1-oxyl (known as TEMPO), which is carried out in the temperature range from 50 to 150°C with stirring for several hours.

At the end add vinylaromatic monomer, and then conducting the polymerization to the desired degree of conversion. The disadvantage of this patent is the implementation of functionalization of the elastomer in the presence of solvent.

In the patent applications WO 00/14134 and WO 00/14135 described the synthesis of reinforced rubber vinylaromatic polymers with the use of polybutadienes, functionalized nitroxyl radicals or nitroxyl esters using reactive extrusion. Then, the elastomer is dissolved in styrene and solvent is, and then polimerizuet. At the end of the polymerization receive the product, consisting of a rigid polymer matrix, in which the dispersed rubber particles, the morphology of which does not depend on the type of rubber, and depends only on the amount of nitroxyl radical or nitroxyl of ester applied at the stage of the reactive extrusion process.

The disadvantage of these patent applications is adding another operation in the method of obtaining styrene materials, reinforced rubber.

Now discovered a method of obtaining vinylaromatic (co)polymers grafted on an elastomer orderly manner, with the use of elastomers, functionalized nitroxyl radicals obtained directly during the synthesis of the elastomer with the use of bromoalkanes and nitroxyl radicals, such as, for example, 1,1,3,3-Tetraethylenepentamine-2-yloxyl (TEDIO), which is soluble in non-polar solvents.

The present invention also relates to the production of poly(1,3-alkadienes), preferably, the polybutadiene obtained by polymerization of at least one of 1,3-alkadiene, such as butadiene, in solution in an aliphatic or cycloaliphatic solvents or their mixtures, using alkyllithium initiators.

In General, the polymerization of this type can be made in reactors periodic activities the civil action or in reactors with continuous action. In reactors of periodic action initiator, which usually consists of a primary or secondary utility, added to the reaction mixture, consisting of solvent and monomer, taken in an amount such that the total content of the solid product at the end of the polymerization is not more than 20 wt.%. Specialists in this field it is known that this reaction can be performed in the presence of Lewis bases in an amount which depends on the content of vinyl or 1,2-units, which must be present in the polymer chain. Among the Lewis bases are most widely used ethers, in particular tetrahydrofuran, which is already in the amount of 100 ppm (parts per million) relative to the solvent can significantly accelerate the reaction, maintaining the vinyl content of the links below 12 mol.%. At higher concentrations of THF microstructure gradually changing; for example, when the amount of THF equal to 5000 ppm (parts per million), the content of vinyl units exceeds 40%. A large number of vinyl units is not necessary and may even be harmful, for example, for the application of polybutadiene in the field of modification of plastics. Preferably the content of these links does not exceed 15%, while increasing the efficiency of the graft copolymerization can be applied polybutadiene with a higher content is of 1,2-units.

Specialists in this field is also known that the reaction is carried out in the absence of ethers or tertiary amines, is fast enough to ensure complete polymerization of the monomer for a time not exceeding 1 hour, at finite temperatures not exceeding 120°C, and, in any case, is governed by the initial temperature of the reaction mixture, which may not be less than 35-40°C, as the initial reaction must be fast enough and incompatible with normal production cycles.

To achieve the above purpose, the reactor can be equipped with cooling jackets, which is not particularly effective due to the unfavorable ratio of surface/volume, typical of the industrial reactors, the volume of which is always at least 20 m³. More effective temperature control is achieved through partial evaporation of the solvent, which condense, and then fed into the reactor in which carry out the reaction. A reactor of this type, which is called "boiling water reactor", is very effective to control the reaction temperature, and in the prior art the use of such a reactor is the best way to effectively limit the natural temperature rise due to heat of polymerization of monomers, such as butadiene.

The implementation of polymerization in re Torah periodic action leads to the formation of the polymer, which, before the possible addition of a binding agent has a modal molecular weight distribution, where the relationship between the mass-average molecular weight (Mw) and srednekamennogo molecular weight (Mn) is very close to 1, usually, from 1 to 1.2.

Conversely, if the polymerization is carried out in the reactor of the continuous type reactor with constant stirring (CSTR) or in several reactors continuous operation of the CSTR type arranged in series, receive a polymer having a modal molecular weight distribution, where the ratio Mw/Mn is from 1.8 to 2.5.

In both cases, the polymer at the end of the polymerization is linear and includes still active ends of the chain, and these ends of the chain consist of groups polyamideimide (polybutadiene, in the case of butadiene monomer). Possible add proteogenic agent (e.g., alcohol) or halogen derivatives of silicon, where the ratio between the halogen and silicon is equal to 1 (non-limiting example is trimethylchlorosilane, TMHS), leads to deactivation bufadienolides end of the chain and at the same time preserves the linear structure of the molecule.

Adding polyfunctional substances that can react with the active ends of the chain leads to the formation of branched macro is out, characterized in that it includes a branching point, from which comes a number of branches, the number of which is equal to the number of functional groups in the polyfunctional substance. As a non-limiting example, professionals in this field know that adding to the reaction medium of silicon tetrachloride in a ratio of Si:Li=1:4 leads to the formation of radial polymer, which, in the case of a polymer obtained in the batch reactor, the, includes four branches of equal length, whereas in the case of a polymer obtained in the reactor continuous action, four branches are different.

The use of halogenoalkanes, preferably, bromoalkanes, and even more preferably, the primary bromoalkanes, for the generation of primary radicals in situ by the reaction of these bromoalkanes with butyllithium added at the end of the reaction, it is also known, for example, from U.S. patent No. 6858683. Primary alkyl radicals of the type after the formation of the react (move) with protons present in the polymer chain, for example, polybutadiene, in the allyl position, with the formation of a secondary polymer macroradicals allyl type. Branched structures are formed as a result of subsequent combinations of polymer macroradicals, is able to modify the rheological properties of elastomers (polymers, which carried out the above reaction. The reaction mechanism described Viola G.T. article Coupling reaction of polyisoprenillithium with 1,2 dibromoethane, Journal of Polymer Science: Part A: Polymer Chemistry, Vol.35, 17-25 (1997), the findings of which can also be applied to statistical butadiene-styrene, the copolymers.

In U.S. patent No. 6858683 described obtaining butadiene-styrene copolymer with a high modulus of elasticity compared to a linear polymer with improved properties from the point of view of the distribution of the filler consisting of carbon black. This method can be applied to polymers that are still active (with butadienestyrene the ends of the chains), and to polymers with inactive end groups with monofunctional and polyfunctional substances, in this case with the formation of a more coherent structures.

Now unexpectedly been found, as better shown in the claims that these secondary allylic the macroradicals to their mutual connections can react with substances belonging to the group "acceptor radicals" or "spin traps". The speed with which these substances react with secondary allylic radicals, indeed, by several orders of magnitude higher than the connection speed is the same allyl radicals, to complete which usually takes a few minutes, bude what is shown in the illustrative examples (examples 2 and 4). From this it follows that the addition of stoichiometric quantities of "acceptor radicals" immediately after the formation of macroradicals allyl prevents the last connection and branching of the chain, keeping the polymer structure is almost identical to the structure of the polymer prior to the formation of macroradicals. In the prior art there are known various substances that can react with the audience of allyl radicals with such speed that they could be used as specific inhibitors of polymerization or, in General, reactions, which are spread via the radicals: the presence of an odd number of electrons characterizes a group of products, which are defined as "living radical", because these substances are distinguished by the presence of unpaired electrons that can react with other radicals present. In the case of substances which contain the group N-O (also known as N-oxides or nitroxyl radicals), in which the nitrogen atom is linked simple connections with two methylene groups, it is known that the unpaired electron is attributed to the nitrogen atom can interact with the unpaired electron of the carbon radical with the formation of communication, which, depending on temperature rebuilds the original two radical by hemolysate polymer solution, including deactivated or active radicals, butyllithium, and then bromoalkanes leads to the formation of allyl of macroradicals, which after addition of compounds containing N-oxide group, still have the same structure as the original polymer, but are functionalized, because the polymer chains are N-O-C, and the nitrogen atom is part of a saturated cyclic structure, and the carbon atom is part of Polivanova patterns in the allyl position.

The usual method of production, for example, polybutadiene, in this case, functionalized polybutadiene, includes, after adding a couple of antioxidants consisting of a primary phenolic antioxidant type and a secondary antioxidant, typically an organic compound of trivalent phosphorus, removal of the solvent, which is carried out by the joint action of water and steam in vessels with agitators. Receive a suspension of pellets of the elastomer in water, from which, after discharge of water on meshes elastomer is directed to a stage of drying, which is carried out in two mechanical extruders. In the first extruder (screw press) perform the operation of squeezing to eliminate most of the water through the side slit of the extruder, while the final drying is carried out in the second e is struture (the extender), in which the elastomer, which is subjected to mechanical handling, heated to a temperature of 160-180°C. a Certain amount of steam comes out through the hole (vent valve), located at the end of the extruder, while the portion of the steam exits through the outlet head. Then the pellets of the elastomer is sent via conveyor belts or other means of transportation in a packaging machine, where they are Packed in packages.

After fabrication of functionalized elastomer, preferably, functionalized polybutadiene, can be used to obtain impact-resistant thermoplastic polymers, for example, shockproof vinylaromatic polymers, also known as high impact polystyrene (HIPS). In these polymers, polybutadiene is present in the form of dispersed phase particles with the morphology of type "core/shell", and the average diameter of these particles is from 0.1 to 1 μm. This result is highly unexpected, as specialists in this area is well known that in applications of this type elastomer, such as defunctionalizing polybutadiene, always leads to the formation of particles with a morphology type "salami", the average diameter of which ranges from 2 to 5 μm. Although this morphology provides the possibility of achieving good impact resistance of the final polymer has in the SMA unsatisfactory optical properties.

The nature of the polybutadiene (unsaturated elastomer or rubber) requires a strict control of the conditions final treatment, as experts in this field are aware of the disadvantages arising from the formation of lumps of insoluble matter (gel), which are usually formed at the final stage, in particular, the extender. These gels lead to lower quality of rubber, designed for use in the modification of plastics, because of the formation of large surface defects. Therefore, great attention should be paid to defining the conditions final treatment polybutadiene, followed by the need to process large numbers of analyses for process control and quality control of the product.

Therefore, an object of the present invention relates to a method for vinylaromatic (co)polymers grafted to the unsaturated elastomer orderly manner, including:

a) dissolving the elastomer, functionalized bromoalkane and nitroxyl radicals, soluble in non-polar solvents in the liquid phase consisting of a mixture of vinylaromatic monomers and a polymerization solvent in a weight ratio of from 60/40 to 100/0, preferably from 60/40 to 90/10;

b) feeding at least one radical initiator in a mixture containing options is analiziropany elastomer in solution, and the polymerization of the thus obtained mixture at a temperature above or equal to 120°C;

C) removing vinylaromatic (co)polymer obtained at the end of the polymerization, and the implementation of the removal of volatile components under vacuum to extract the solvent and unreacted monomers and

g) feeding the recycling stage (a) of the mixture of solvent and monomers obtained by removing volatile components.

According to the present invention, a method of obtaining vinylaromatic (co)polymer can be performed in a batch reactor or in the reactor of a continuous action. In the first case, the dissolution of the functionalized elastomer together with conventional additives in the liquid phase consisting of a mixture of vinylaromatic monomers and a polymerization solvent, and the subsequent polymerization of the monomers is carried out in a single vessel, for example, in the mixer with the mixer, equipped with heating systems, which collect the polymerization mixture to extract the final (co)polymer and send it to the stage of removal of volatile components, when the solids content reaches a level of from 60 to 80 wt.%. In the second case, the dissolution of the elastomer together with conventional additives in the liquid phase (vinylaromatic monomers + polymerization solvent) is carried out in smesitel is with a stirrer, which continuously supplies the resulting solution in one or more reactors with agitators, selected vessels with agitators, such as CSTR (the reactor with constant stirring) and/or tubular reactors (ideal displacement). In this second case, removing the final (co)polymer is also carried out through a stage of removal of volatile components after the solids content reaches the above-mentioned levels. The continuous method described, for example, in European patent EP 400479, is the preferred method according to the present invention.

The term "vinylaromatic (co)polymer used in the present description and in the claims, essentially means a (co)polymer obtained by (co)polymerization of at least one monomer represented by the following General formula (I):

where R represents hydrogen or methyl group, the index n is zero or an integer from 1 to 5, a Y is a halogen, such as chlorine or bromine, or alkyl or CNS radical containing from 1 to 4 carbon atoms.

Examples vinylaromatic monomers having the above General formula include styrene, α-methylsterols, methylsterol, atillery, butalbiral, dimethylstyrene, mono-, di-, tri-, Tetra - and pentachlorophenol, Postira, m is oxysterol, acetoxystyrene etc. Preferred vinylaromatic monomers are styrene and/or α-methylsterol.

Vinylaromatic monomers having General formula (I), can be applied separately or in a mixture in an amount up to 50 wt.% with other copolymerizing monomers. Examples of these monomers are (meth)acrylic acid, C₁-C₄alkyl esters of (meth)acrylic acid, such as methacrylate, methyl methacrylate, acrylate, methacrylate, isopropylacetate, butyl acrylate, amides and NITRILES of (meth)acrylic acids such as acrylamide, methacrylamide, Acrylonitrile, Methacrylonitrile, butadiene, ethylene, divinylbenzene, maleic anhydride, etc. Acrylonitrile and methyl methacrylate are preferred copolymerizing monomers.

Any elastomer, suitable for use as a reinforcing product in vinylaromatic (co)polymer can be functionalitywith and it can be used in the method, the object of the present invention. However, the preferred product, based on economic considerations, is a homopolymer of polybutadiene with srednekamennogo molecular weight (Mn) of 50,000 to 350,000 and mass-average molecular weight (Mw) of 100,000 to 500,000.

Other elastomers that can be used instead of polybutadiene or a mixture of them, you can choose from homopolymer and copolymers of 1,3-alkadienes, containing 40-100 wt.% 1,3-alkadiene monomer, such as butadiene, isoprene or pentadiene, and 0-60 wt.% one or more monoethylene unsaturated monomers selected from styrene, Acrylonitrile, α-methylstyrene, methyl methacrylate and ethyl acrylate with a molecular weight Mw or Mn, equal to the molecular mass of homopolymer polybutadiene. Non-limiting examples of copolymers of 1,3-alkadienes are butadiene-styrene block copolymers, such as double linear elastomers of the type S-B, where S represents a polystyrene block with an average molecular weight Mw of from 5000 to 80000, whereas B is a block of polybutadiene with an average molecular weight Mw from 2000 to 250,000. In these elastomers number of unit S is from 10 to 50 wt.% relative to the total mass of the S-B elastomer. The preferred product is a butadiene-styrene block copolymers, in which the styrene content is 40 wt.%, and for which the viscosity of the solution, measured at 23°C in a solution concentration of 5 wt.% in styrene, is from 35 to 50 JV. Other examples of elastomers that can be used in the method, the object of the present invention, described in European patent No. 606931.

The above functionalityand the elastomer is dissolved in the liquid phase comprising the monomer(s) and a polymerization solvent. The preferred R is storyteller according to the present invention is ethylbenzene, but it is also possible to use other aromatic solvents, such as toluene or xylene, or aliphatic solvents such as hexane or cyclohexane.

In the solution, thus prepared, you can add at least a catalytic system for the polymerization in an amount of from 0 to 0.5 wt.% respect to the total mass, preferably from 0.02 to 0.5 wt.%, consisting of one or more free radical initiators. Free radical initiators chosen, in particular, of free-radical initiators, for which the activation temperature higher than 50°C. Typical examples of the polymerization initiators are isoprostane, such as 4,4'-bis(Diisobutylene), 4,4'-bis(4-cyanobacteria acid, dihydrochloride 2,2'-azobis(2-amidinopropane), or peroxides, hydroperoxides, percarbonates and paroxetine. In General, the preferred free radical initiators are peroxides selected from tert-utilization.paroxetine, tert-butyl-2-ethylhexylcarbonate, dicumylperoxide, di-tert-butylperoxide, 1,1-di(tert-butylperoxycyclohexyl), 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, di-tert-butylperoxycyclohexyl, tert-peroxyacetate, Cumyl-tert-butylperoxide, tert-butyl peroxybenzoate, and t-BUTYLPEROXY-2-ethylhexanoate.

The other is their supplements which can be added to the polymerization mixture, are known conventional additives, which are used in obtaining transparent, impact-resistant vinylaromatic copolymers. For example, the polymerization mixture may include a molecular weight regulator, such as a mercaptan selected from n-artilleryman, n-dodecylmercaptan, tert-dodecylmercaptan, mercaptoethanol, etc. Other additives chosen from, for example, antioxidants, UV stabilizers, antistatic agents, etc.

Stable nitroxyl radical, characterized by the presence of the group-NO•, is chosen from radicals, soluble in nonpolar solvents and having the General formula (II)

where the group R₁, R₂, R₅and R₆identical or different, represent a linear or branched, substituted or unsubstituted alkyl radicals containing from 1 to 20 carbon atoms, or alkylaromatic radicals, where the alkyl group contains from 1 to 4 carbon atoms while the group R₃and R₄the same or different, identical groups R₁, R₂, R₅and R₆or R₃-CNC-R₄refers to a cyclic structure, for example, with 4 or 5 carbon atoms, and this cyclic structure may form a condensed system with the aromatic ring is, or saturated ring, containing from 3 to 20 carbon atoms.

Examples of initiators having the General formula (II)which are particularly preferred and can be used in the method, the object of the present invention are, for example, TEDIO (the synthesis of which is described in the patent application WO 2004/078720) and an ester of palmitic acid and N-TAMRA (4-hexadecanoyl-2,2,6,6-tetramethylpiperidine-1-oxyl).

After functionalization of the elastomer carry out the final stage, after which start the polymerization process vinylaromatic (co)polymers grafted on an elastomer, as in conventional methods known from the prior art, by dissolving the elastomer in the monomers and the solvent, and start the polymerization reaction by raising the temperature in one or several stages. Upon completion of the polymerization to produce the removal of volatile components from polymer to extract the unreacted monomers and solvent, the ratio between them is such that they can be direct recycle to the mixer without having to separate them from each other. In the end receive shockproof vinylaromatic (co)polymer comprising a continuous phase consisting of a rigid vinylaromatic matrix in which is distributed functionalized elastomer, for example, preferably, functionalized polybutadiene, the number is e from 1 to 25 wt.% respect to the total mass as the dispersed phase in the form of particles with the morphology of type "core/shell", the average diameter of which ranges from 0.1 to 1 μm.

For a better understanding of the present invention and its embodiments proposed several illustrative and non-limiting examples.

Characterization of the SYNTHESIZED POLYMERS

1. Determination of the microstructure of the bound styrene and polybutadiene

The method is based on measuring the intensity of the bands attributed to the three isomers of butadiene (TRANS-, vinyl - and CIS-). For analytical determination of isomers of CIS-, TRANS - and 1,2-butadiene used the following spectrum: 1018 and 937 cm^-1for the TRANS-isomer, 934 and 887 cm^-1for the 1,2-isomer and 800 and 640 cm^-1for the CIS isomer. Measurement of the absorption maxima and the knowledge of the values of the extinction coefficient, measured on standard polymers defined using¹H-NMR, provides the possibility of calculating the number of structures of butadiene and quantity of styrene using the law of Lambert-Baer.

2. Determination of molecular mass distribution (MMD)

Determination of molecular mass distribution was performed using gel permeation chromatography (GPC), also known as size-exclusion chromatography, which is carried out by passing the polymer solution, which is the volume of the volume analysis, in THF through a series of columns containing a solid phase consisting of cross-linked polystyrene with pores having different sizes.

Equipment:

Chromatograph: HP 1090;

Solvent: THF;

Temperature: 25°C;

Column: PL-Gel 105-105-104-103;

IR detector: HP 1047 A.

Determination of molecular masses was carried out according to the method of the universal calibration using the following values of k and a:

k=0,000457 a=0,693.

3. Determination of average molecular mass and measuring the degree of branching using technology exclusive chromatography / scattering of laser radiation from multiple angles (SEC/MALLS)

According to the internal methodology, taken from the work described in the Application Note, n° 9, Wyatt Technology e Pavel Kratochvil, Classical Light Scattering from Polymer Solutions, Polymer Science Library, 5, Elsevier Science Publishers B.V., 1987, by combining detector scattering of laser radiation from multiple angles (ROKU) with normal suantai system SEC/RI you can make an absolute measurement of molecular weight and radius of gyration of the macromolecule separated chromatographic system. The amount of light scattered by macromolecules in solution, can be used directly to obtain their molecular weight, whereas the change of the scattering angle is directly correlated with the average size of molecules in solution. Usually apply the following basic soo is wearing:

$$\frac{\text{K*c}}{{\text{R}}_{\text{θ}}}=\frac{\text{1}}{{\text{M}}_{\text{w}}{\text{P}}_{\text{θ}}}+{\text{2A}}_{\text{2}}\text{c}\text{(1)}$$

where:

K* is an optical constant that depends on the wavelength of the used light, the values of dn/dc of the polymer used solvent;

M_w- mass-average molecular weight of the polymer;

c - concentration of the polymer solution;

R_θ- the intensity of scattered light measured at an angle 0;

P_θ- the function describing the change in the angle scattered light;

A₂the second virial coefficient for the solvent, equal to 1 for the angle θ of zero.

At very low concentrations (normal for system exclusive chromatography) formula (1) is reduced to

$$\frac{\text{K*c}}{{\text{R}}_{\text{θ}}}=\frac{\text{1}}{{\text{M}}_{\text{w}}{\text{P}}_{\text{θ}}}\text{(2)}$$

and, as a result of measurements at multiple angles, extrapolation to zero angle dependence function K*c/R_θfrom sin 20/2 directly gives the molecular mass of the magnitude cut, cut along the ordinate axis, and the radius of gyration of the tangent of the slope of the straight.

In addition, since the measurement is carried out for every area of the chromatogram, it is possible to obtain the molecular weight distribution and the distribution of radius of gyration.

The size of macromolecules in solution is directly correlated with the degree of branching, with the same molecular weight, the smaller the size of macromolecules in relation to the linear counterpart, the higher the degree of branching. As the macromolecule, in the inner part which has a branch point (radial structure and a branched structure), with the same molecular mass has a smaller hydrodynamic volume compared to a linear molecule, the slope of the above line (coefficient a) will be more or less depending on whether less or more degree of interconnectedness of structures. In particular, for linear macromolecules factor is proporcjonalnosci between radius of gyration and molecular weight were equals 0.58, whereas for branched molecules, this value gradually becomes lower with increase in the number of branching points that are present in the macromolecule. For example, for statistical butadiene-styrene copolymer obtained by radical polymerization in emulsion (E-SBR), value and equal to 0.35-0,38. Equipment:

IR-spectrometer: HP 1047 A of MALLS Wyatt Technology DAWN model-DSP;

Differential Refractometer: KMX16-CROMATIX.

4. Determination of Mooney viscosity

Determination of the Mooney viscosity was carried out at 100°C with the use of the rotor L and over time (1+4) (ASTM D1646).

5. Determination of the solution viscosity in styrene

The method involves the preparation of a solution of polybutadiene in styrene concentration of 5 wt.% and subsequent measurement of the viscosity at 25°C using a capillary tube Cannon Fenske, the size of which should be chosen in such a way as to avoid elution time through a capillary in the interval 100-200 C.

In the case under consideration polymers used viscometer Model 300, suitable for interval viscosity 50-250 SP.

6. Determination of the average molecular weight of the polystyrene matrix determination of the average molecular weight of the polystyrene matrix was performed on chromatographic equipment, consisting of: degassing system, pump, injector: WATERS Alliance 2695, set Phenogel columns (300×7.6 mm) 5 μm, porosity 106, 05, 104, 103 angstroms, differential refractometric detector (Waters 410, UV detector Waters 2487, software for chromatographic analysis: Millenium 32 version 3.2 (Waters).

7. Determination of the morphology of the elastomeric phase, raspredelenie in high-impact polystyrene

The size and morphology of the elastomeric phase, distributed in a matrix of polystyrene was determined using TEM (transmission electron microscopy) according F.Lenz, A.Wiss-Mikroscopie 63, 1956, page 56. The morphology of the particles of the elastomer was determined by inspection of the micrographs, and the characterization of various structures was carried out according to the classification described in the publication of Adolf Echte "Teilchenbildung bei der Herstellung von Kautschukmodifiziertem Polystyrol" 58/89 (1977), page 175-198 and in patent EP 716664. For calculation of such statistics as the mean volume diameter DV of particles, used the following formula:

$${\text{D}}_{\text{v}}=\frac{{\text{Σ}}_{\text{i}}{\text{N}}_{\text{i}}{\text{D}}_{\text{i}}{\text{4}}^{}}{{\text{Σ}}_{\text{i}}{\text{N}}_{\text{i}}{\text{D}}_{\text{i}}{\text{3}}^{}}(3)$$

where D_irepresents the diameter of the i-th particle, then how to calculate the percentage of particles of type "core/shell" or "mixed" patterns (such as "labyrinth" or "brain") was applied stereological method described in the publication C.Maestrini et al. Journal of Material Science, Vol.27. Analysis using TEM was performed on a transmission electron microscope Philips CM.

8. Determination of other characteristics

The concentration of the remaining styrene monomer and other volatile organic compounds were determined using gas chromatography.

Mineral oil contents were determined using infrared spectroscopy with Fourier transform (FTIR). Some experimental values are always slightly smaller than the calculated values, since a certain quantity of oil Argonauts during the stage of removal of volatile components.

The concentration of polybutadiene in high-impact polystyrene was determined using iodometric titration according to the method described in the publication Wijs, Berichte, 1898, Vol.31, page 750.

The content of the gel phase (after thermal crosslinking of the elastomer) and the degree of swelling (without heat with the air traffic management elastomer) was determined using the test Ruffing (Ruffing test) described in U.S. patent No. 4214056.

The melt flow index (RTD) was determined according to standard method ASTM D 1238 at 200°C at a load of 5 kg

Impact strength Izod specimens with notch (samples for testing manufactured using injection molding) was determined according to standard method ISO 180/1A ISO 179 (value expressed in kJ/m²). Another parameter related to the resistance of the materials was determined using the strength tests when struck by falling cargo (Ball Drop), which were conducted according to standard method ISO 6603/2 samples for testing with two different thicknesses (2 mm and 3 mm).

Properties characterizing the tensile strength (yield strength, the elongation at yield point, ultimate stress, ultimate elongation, modulus of tensile elasticity and bending strength (ultimate stress, elastic modulus)was determined according to standard methods ASTM D 638, ISO 527 ISO 178 samples for testing manufactured using injection molding, and the results were expressed in MPa, except for elongation at yield strength and ultimate elongation, expressed in percent.

The Shine of the material was determined according to standard method ASTM D523 at either of two angles read (20° and 60°) using gloss meter Dr. Lange. The measurements were carried out on the samples to use the tests with three steps manufactured using injection molding; zone sizes dimensions: 95 mm × 75 mm × 3 mm Conditions injection molding in the manufacture of test specimens were as follows: melt temperature 220°C, the temperature of the mold 29°C.

Example 1 (comparative)

In a reactor with a volume of 100 l, which support anhydrous environment, equipped with a stirrer and a heating jacket in which circulating thermal oil at a temperature of 50°C, was introduced in order, in a stream of nitrogen, the following products: 50 kg anhydrous cyclohexane, 6.5 kg of anhydrous butadiene without inhibitor and acetylene hydrocarbons and 5 g of THF. When the temperature of the reaction mixture reached 40°C, was added 2.6 g of utility in solution concentration of 15 wt.% in cyclohexane. When the transformation was completed, at a temperature of 105°C, the reactor was introduced a certain number of trimethylchlorosilane equal 2,77 g for full decontamination of end groups in the polymer chain.

Then the mixture of chemicals released into the hermetic vessel, which added a mixture of antioxidants consisting of Irganox® 565 and Irgafos® 168 in such quantity that the content in the elastomer was 0.1 and 0.4%, respectively.

The solvent is then separated from the polymer by distillation in steam flow, after which the polymer was dried by mechanical means in the calender. Determination of molecular mass distribution, sushestvennee using gel permeation chromatography (GPC), gave value srednekamennogo molecular weight Mn equal to 256000, and the value of the index polydispersity (Mw/Mn)equal to 1.02. Analysis by GPC method-ROKU (GPC-MALLS) showed the value of α, equals 0.58, which is typical for a linear polymer. Analysis by the method of IR spectroscopy showed the content of 1,2-units, amounting to 11.5%.

The Mooney viscosity (4+1 at 100°C) is equal to 42, whereas the viscosity in styrene equal to 97 SDR.

1.8 kg thus obtained polybutadiene was dissolved at 60°C for 6 h in 25,8 kg of styrene monomer, 1.8 kg of ethylbenzene, 0.8 kg of oil Primoil 382 and 14 g Tx22E50 (1,1-di(tert-BUTYLPEROXY)cyclohexane). Thus obtained solution was sent to the first reactor of ideal displacement (PFR), equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 125°C to 135°C; in this reactor was carried out preliminary polymerization graft copolymerization and inversion phases.

15 g of NDM (n-dodecylmercaptan) was added to the mixture leaving the first reactor, which was then applied to the second reactor of ideal displacement (PFR), also equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 135°C to 160°C.

The resulting mixture is sent to a device for removing volatile components operating in a vacuum at a temperature of 235°C, removed what I unreacted styrene and solvent from the polymer; thus obtained end product whose characteristics are given in Tables 1 and 2.

Example 2

In a reactor with a volume of 100 l, which support anhydrous environment, equipped with a stirrer and a heating jacket in which circulating thermal oil at a temperature of 50°C, was introduced in order, in a stream of nitrogen, the following products: 50 kg anhydrous cyclohexane, 6.5 kg of anhydrous butadiene without inhibitor and acetylene hydrocarbons and 5 g of THF. When the temperature of the reaction mixture reached 40°C, was added 2.16 g of utility in solution concentration of 15 wt.% in cyclohexane. When the transformation was completed, at a temperature of 105°C, the reactor was introduced a certain amount of utility equal 0,83 g, in solution in cyclohexane concentration of 5%, and, after holding for 5 minutes, put the second a certain amount of utility equal to 6.6 g, in solution in cyclohexane concentration of 5%. Immediately after the second addition of utility added 20 g of activated in solution concentration of 20% in cyclohexane, and then immediately added to 25.6 g of 1,1,3,3-Tetraethylenepentamine-2-yloxyl (TEDIO).

Then the mixture of chemicals released into the hermetic vessel, which added a mixture of antioxidants consisting of Irganox® 565 and Irgafos® 168 in such quantity that the content in the elastomer was 0.1 and 0.4%, respectively.

The solvent is then CTD is Lily from the polymer by distillation in steam flow, then the polymer was dried by mechanical means in the calender. Determination of molecular mass distribution, carried out by gel permeation chromatography (GPC)gave the value srednekamennogo molecular weight Mn equal to 250000, and the value of the index polydispersity (Mw/Mn)equal to 1.03. Analysis by GPC method-RIKU showed the value of a, equals 0.58, which is typical for a linear polymer. Analysis by the method of IR spectroscopy showed the content of 1,2-units, amounting to 11.2%. The Mooney viscosity (4+1 at 100°C) is equal to 40, whereas the viscosity in styrene of 103 JV.

1.8 kg thus obtained polybutadiene was dissolved at 60°C for 6 h in 25,8 kg of styrene monomer, 1.8 kg of ethylbenzene, 0.8 kg of oil Primoil 382 and 14 g The. Thus obtained solution was sent to the first reactor of ideal displacement (PFR), equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 125°C to 135°C; in this reactor was carried out preliminary polymerization graft copolymerization and inversion phases.

15 g of NDM added to the mixture leaving the first reactor, which was then applied to the second reactor of ideal displacement (PFR), also equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 135°C to 160°C.

The final with the offer sent to the device for removing volatile components, working in a vacuum at a temperature of 235°C. to remove unreacted styrene and solvent from the polymer; thus received a final product whose characteristics are given in Tables 1 and 2.

Example 3 (comparative)

In a reactor with a volume of 100 l, which support anhydrous environment, equipped with a stirrer and a heating jacket in which circulating thermal oil at a temperature of 50°C, was introduced in order, in a stream of nitrogen, the following products: 50 kg anhydrous cyclohexane, 6.5 kg of anhydrous butadiene without inhibitor and acetylene hydrocarbons and 5 g of THF. When the temperature of the reaction mixture reached 40°C, was added 1.5 g of utility in solution concentration of 15 wt.% in cyclohexane. When the transformation was completed, at a temperature of 102°C, the reactor was introduced a certain number of trimethylchlorosilane equal to 2 g for the complete decontamination of end groups in the polymer chain.

Then the mixture of chemicals released into the hermetic vessel, which added a mixture of antioxidants consisting of Irganox® 565 and Irgafos® 168 in such quantity that the content in the elastomer was 0.1 and 0.4%, respectively.

The solvent is then separated from the polymer by distillation in steam flow, after which the polymer was dried by mechanical means in the calender. Determination of molecular mass distribution made by GE is ü permeation chromatography (GPC), gave value srednekamennogo molecular weight Mn equal to 360000, and the value of the index polydispersity (Mw/Mn)equal to 1.02. Analysis by GPC method-RIKU showed the value and equal 0,59, which is typical for a linear polymer. Analysis by the method of IR spectroscopy showed the content of 1,2-units, amounting to 11.7%.

The Mooney viscosity (4+1 at 100°C) is equal to 60, whereas the viscosity in styrene equal to 204 SP.

1.8 kg thus obtained polybutadiene was dissolved at 60°C for 6 h in 25,8 kg of styrene monomer, 1.8 kg of ethylbenzene, 0.8 kg of oil Primoil 382 and 14 g The. Thus obtained solution was sent to the first reactor of ideal displacement (PFR), equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 125°C to 135°C; in this reactor was carried out preliminary polymerization graft copolymerization and inversion phases.

15 g of NDM added to the mixture leaving the first reactor, which was then applied to the second reactor of ideal displacement (PFR), also equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 135°C to 160°C.

The resulting mixture is sent to a device for removing volatile components operating in a vacuum at a temperature of 235°C. to remove unreacted styrene and solvent from the polymer; it is m the way I received the final product, characteristics of which are given in Tables 1 and 2.

Example 4

In the reactor, the configuration of which is entirely similar to that described in Examples 1 and 2, of 1.57 g utility added to the reaction mixture, consisting of 50 kg of cyclohexane, 6.5 kg of butadiene and 5 g of THF, at a temperature of 40°C.

When the transformation was completed, at a temperature of 101°C, the reactor was added 0,80 g utility in solution in cyclohexane concentration of 5% and, after holding for 5 min, added a second certain number of utility equal to 9.5 g, in solution in cyclohexane concentration of 5%. Immediately after the second addition of utility added 28.5 g of activated in solution concentration of 20% in cyclohexane, and then immediately added 36,4 rTEDIO.

The solvent was removed by distillation in steam flow of a mixture of reagents containing a mixture of antioxidants consisting of Irganox® 565 and Irgafos® 168 in such quantity that the content in the elastomer was 0.1 and 0.4%, respectively, and then the polymer was dried by mechanical means in the calender. Determination of molecular mass distribution, carried out by gel permeation chromatography (GPC)gave the value srednekamennogo molecular weight Mn equal 355000, and the value of the index polydispersity (Mw/Mn)equal 1,07. Analysis by GPC method-RIKU showed the value of α, equals 0.58, which is typical for a linear polymer. EN is Liz by the method of IR spectroscopy showed the content of 1,2-units, average of 11.5%.

The Mooney viscosity (4+1 at 100°C) is equal to 58, while the viscosity in styrene equal to SDR 198.

1.8 kg thus obtained polybutadiene was dissolved at 60°C for 6 h in 25,8 kg of styrene monomer, 1.8 kg of ethylbenzene, 0.8 kg of oil Primoil 382 and 14 g The. Thus obtained solution was sent to the first reactor of ideal displacement (PFR), equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 125°C to 135°C; in this reactor was carried out preliminary polymerization graft copolymerization and inversion phases.

15 g of NDM added to the mixture leaving the first reactor, which was then applied to the second reactor of ideal displacement (PFR), also equipped with a stirrer and temperature regulation system, with a temperature profile in the reactor increases from 135°C to 160°C.

The resulting mixture is sent to a device for removing volatile components operating in a vacuum at a temperature of 235°C. to remove unreacted styrene and solvent from the polymer; thus received a final product whose characteristics are given in Tables 1 and 2.

From the results listed in Tables 1 and 2, it is easy SDE is the substance of the conclusion what functionalization of polybutadiene made by the reaction between bromaline, n-butyllithium and stable nitroxyl radicals, soluble in non-polar solvents, provides an opportunity for high impact polystyrene with the morphology of the elastomeric phase type "core/shell" and with excellent surface gloss, which otherwise can be achieved with the use of particularly expensive butadiene-styrene blockcopolymer. However, when applying the same polybutadiene, not functionalized with the application of the described technology, get high impact polystyrene with the morphology of the dispersed phase type "salami" and with extremely poor aesthetic properties (luster).

1. The method of synthesis of functionalized poly(1,3-alkadienes), including anionic polymerization of at least one monomer 1,3-alkadiene 4-8 carbon atoms in the presence of organolithium compounds and non-polar solvent with a low boiling point and the implementation stage of the chain breakage of the polymer based on 1,3-alkadiene at the end of the polymerization by adding a polymerization mixture bromaline, where the alkane contains from 1 to 12 carbon atoms, and then add a product containing a stable nitroxyl radical, characterized by the presence of group-NO•soluble in the indicated non-polar solvent.

2. The method according to claim 1, where 1,3-alkadiene represents butadiene.

3. The method according to claim 1, where the organolithium compound is utility.

4. The method according to claim 1, where bromelin is a 1-bromooctane.

5. The method according to any one of claims 1 to 4, where a product containing a stable nitroxyl radical, characterized by the presence of group-NO•, which are selected from compounds having General formula (II):

where the group R₁, R₂, R₃and R₆identical or different, represent a linear or branched, substituted or unsubstituted alkyl radicals containing from 1 to 20 carbon atoms, or alkylaromatic radicals, where the alkyl group contains from 1 to 4 carbon atoms while the group R₃and R₄the same or different, identical groups R₁, R₂, R₅and R₆or R₃-CNC-R₄refers to a cyclic structure, for example, with 4 or 5 carbon atoms, and this cyclic structure may form a condensed system aromatic ring or a saturated ring containing from 3 to 20 carbon atoms.

6. Functionalityand poly(1,3-alkadiene)obtained according to the method according to any one of claims 1 to 5.

7. The method of obtaining vinylaromatic (co)polymers grafted to the unsaturated poly(1,3-alkadiene) reg the dummy way including:
a) dissolving poly(1,3-alkadiene) according to claim 6 in the liquid phase consisting of a mixture of vinylaromatic monomers and a polymerization solvent in a weight ratio of from 60/40 to 100/0, preferably from 60/40 to 90/10;
b) feeding at least one radical initiator in a mixture containing functionalized poly(1,3-alkadiene) in solution, and the polymerization of the thus obtained mixture at a temperature that is greater than or equal to 120°C;
C) removing vinylaromatic (co)polymer obtained at the end of the polymerization, and the implementation of the removal of volatile components under vacuum to extract the solvent and unreacted monomers and
g) feeding the recycling stage (a) a mixture of solvent and monomers obtained by removing volatile components.

8. The method according to claim 7, where vinylaromatic monomers are styrene and/or α-methylsterol.

9. Shockproof vinylaromatic (co)polymer comprising a continuous phase essentially consisting of a matrix containing at least 50 wt.% vinylaromatic monomer, and a disperse phase, essentially consisting of a functionalized elastomer according to claim 6 in an amount of from 1 to 25 wt.% respect to the total mass, and elastomer particles have a morphology type "core/shell", and their average diameter is from 0.1 to 1 μm.