High-stereospecific polybutylene and a process for production thereof

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

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The present invention relates to vysokotehnicheskoe the polybutylene and method thereof, in particular the invention relates to vysokotehnicheskoe the polybutylene and the high-level method thereof, in which the method is carried out using an inert gas that is not used during normal polymerization of 1-butene, therefore, titanium is not detected in the catalytic residues at the level of ppm wt.

In General, stereospecific polybutylene is a semicrystalline polymer with 1-butene as a monomer and high molecular polyolefin, and has a generic physical characteristics similar to those of polyethylene or polypropylene.

Stereospecific polybutylene has characteristic features such as high bending resistance, compatibility with other polymers, rheological properties, crystalline properties, etc. Also it has a density similar to the density of polypropylene and polypropylene, low density, and has a melting point, such as high density polyethylene.

Also stereospecific polybutylene has excellent stability, such that it has a very high durability even at a high temperature.

In addition, stereospecific polybutylene has the advantage that it is ready to use so the x technological processes, as extrusion, injection molding, etc. as ready for use in conventional devices for these processes, which can be used in polyolefins.

Operating temperature range of such stereospecific polybutylene - about 20-105°With, so stereospecific polybutylene can be used to manufacture various products, such as pipes for hot or cold water, soft packaging, polypropylene film, an additive to soften the fiber or component, the reinforcing adhesive capacity of hot melting adhesives, etc.

Stereospecific polybutylene can be obtained through a process in which a hydrocarbon is used as solvent, or a process in which 1-butene itself is used as the solvent.

At the present time because of the problems the Department after receipt etc. stereospecific polybutylene commercially produce the final process.

In General, stereospecific polybutylene obtained by polymerization of 1-butene in the presence of a basic catalyst based on an organic aluminum compounds of the type of diethyl-aluminum chloride and titanium trichloride.

According to this process stereospetsifichno the obtained polybutylene not high enough and therefore estereotipicas polybutylene should be separated.

In addition to the, because of its low activity, this process requires the removal phase catalytic residues, deteriorating the physical properties of the polymer.

Stereospecific polybutylene can be obtained by polymerization of 1-butene in the presence of a catalytic system consisting of internal donor of electrons and titanium on the carrier in the form of magnesium chloride.

This process, however, has a high catalytic activity compared to conventional high-level process for obtaining polyethylene or polypropylene, and therefore this process has the disadvantage that the compounds of titanium present in the polymer at the level of ppm wt.

The usual method of obtaining stereospecific polybutylene disclosed in EP 187034 A2.

According to the method for obtaining vysokotehnicheskoe of polybutylene in the form of particles in the polymerization of 1-butene at 20-45°use lower hydrocarbon type, normal butane, isobutane, normal pentane, isopentane and cyclopentane as a solvent, a catalyst of the Ziegler-Natta, organic compound of aluminum, the external donor of electrons (Lewis base). This method is designed to solve the problems of conventional processes that are used, the solvent shall be removed from the made of polybutylene.

This process has the advantage that the phase of the Department the Department asterophyllites 1-polybutene is not necessary, due to the very high stereospecificity equal to 80 or more, the obtained polybutylene, and office manufactured from polybutylene solvent is carried out quite easily.

However, since the catalytic activity in this way is low (2360 g/g-cat·4 h, i.e. 590 g/g-cat·h), it still requires the removal phase catalytic residues, deteriorating the physical properties of the polymer. Also the catalytic efficiency of this method is too low for effective commercial use.

Patent US 6306996 B1 discloses another typical way to obtain stereospecific polybutylene.

According to this method, polybutylene receive a two-step polymerization of 1-butene in the presence of a basic catalyst on magnesium chloride, and 1-butene itself is used as the solvent and the monomer, and is also used tributylamine (TBA) and diisobutyldimethoxysilane (DIPMS) is used as the donor of the external electrons. According to this method can be obtained polybutylene having satisfactory properties, such as high stereospecificity, the content of catalytic residues titanium 50 ppm wt. or less, a molecular weight distribution (Mw/Mn), is equal to 6 or more. Also, these processes show catalytic activity for homopolymer polybut the Jena 14000 g/g-cat· 4 h, i.e. 3500 g/g-cat·h

However, this method also has a much lower catalytic activity than the high-level process polyethylene or polypropylene, and therefore, the reaction takes a long time, which means poor performance of the method.

The present invention is intended to solve the above problems, and the purpose of the present invention is the provision of highly active method of obtaining vysokotehnicheskoe polybutylene, where such a polybutylene has a high stereospecificity, and titanium is not detected at the level of ppm wt., as well as possible high activity polymerization of 1-butene, similar to the highly active process of obtaining polyethylene or polypropylene.

Another objective of the present invention is to provide vysokotehnicheskoe polybutylene obtained by the method according to the present invention, which has high stereospecificity and also in which titanium is present at the level of ppm wt. unlike polybutylene obtained using conventional known methods.

To achieve the above objectives of the present invention offers a flexible way to obtain vysokotehnicheskoe polybutylene (co)polymer of 1-butene, comprising the step (S1) polymerization of the reactive monomer is 1-butene, which can IP olsavica or may not be used as a solvent, in the presence of a catalyst, an inert gas and hydrogen.

Step (S1) is characterized by increased pressure in the polymerization reactor using an inert gas with a higher pressure than the equilibrium pressure of the reagent gas-liquid at the reaction temperature.

Step (S1) is characterized by the use of inert gas, one or more selected from the group of nitrogen, helium and argon.

Step (S1) is characterized by the reaction temperature 10-110°C.

Step (S1) is characterized by the reaction temperature, which may be 20-90°C.

Visokotehnologicheskie polybutylene obtained by the method according to the present invention, characterized by the fact that is a polymer of 1-butene or a copolymer of 1-butene, comprising up to 40 wt.% α-olefins containing from 2 to 20 carbon atoms other than 1-butene, and has the following properties: 1) titanium is not detected in the catalytic residues at the level of ppm wt.; 2) stereospecificity expressed through the content of the isotactic pentad (mmmm%)determined13C-NMR, is 96 or more; 3) molecular weight distribution (Mw/Mn) is 3-6.

The method of obtaining vysokotehnicheskoe (co)polymer of 1-butene according to the present invention is characterized by the following: an inert gas, which has never been used in conventional ways to get you oosterhesselen polybutylene, used in the polymerization according to the present invention and, thus, in contrast to the well-known reactions, in which an inert gas can be obtained videostreammaterial polybutylene with high catalytic yield, like the high-level process of obtaining polyethylene or polypropylene.

The link to the polymerization process in the following description mainly focuses on the process in a batch reactor, but it is clear that the method according to the present invention is not limited to the use of this reactor, and the method according to the present invention can be implemented in all types of reactors, for example in the CSTR-type reactor, a tubular reactor or in different reactors, as well as in a batch reactor, the.

The first stage should be carried out with 1-butene, which is used as a solvent or a reactive monomer reaction in the reactor, and is a preliminary stage with the entered socialization (g) and external donor of electrons (h).

Here, after the reactor is purged by degassing and repeatedly entered the stream of inert gas, at a preliminary stage are introduced into the reactor 1-butene, socialization (g) and the external donor of electrons (h), followed by stirring.

1-Butene is polymerized during how cocatalyst is R (g) is in contact with the main catalyst (i) type of a catalyst of Ziegler-Natta etc. in the following second step. Additionally, we introduce the external donor of electrons (h)to maximize stereospecificity.

At this first stage of the reactor before polymerization must be removed anticatalyst, such as moisture, oxygen, Monokini carbon dioxide, acetylene and the like, the Removal can be performed by vacuum cleaning, purging with an inert gas (j) or their combination.

Then, in the second stage, the polymerization is carried out by introducing into the reactor a basic catalyst (i) and an inert gas (j), and then raising the temperature to the appropriate temperature polymerization with stirring. Here at the same time is added to the agent regulating the molecular weight.

The second stage is the stage at which the reaction system is introduced the main catalyst type catalyst of Ziegler-Natta and the like, which is a catalyst for polymerization is added to the agent regulating the molecular weight is attached; pressure using inert gas (j); then polymerization is carried out at an appropriate elevated temperature polymerization with stirring.

Here, the temperature of polymerization is 10-110°C, preferably 20-90°C.

The pressure in the reactor is approximately 1-1000 bar, preferably 1-60 bar.

As for the time of polymerization, that is Central time is approximately 10 min to 20 h, preferably from about 30 min to 4 h for periodic polymerization, and also about 10 min to 20 h, preferably from about 30 min to 4 h for polymerization using the CSTR reactor.

High activity polymerization can be achieved at a temperature, pressure and reaction time, as described above.

To regulate the molecular weight as agent for regulating the molecular weight, can be used hydrogen. Also the molecular weight of the polymer can be adjusted by adjusting the reaction temperature.

At this second stage, the polymerization activity is increased significantly by the implementation of the polymerization reaction at a higher pressure than the equilibrium pressure of the system gas-liquid at a given temperature, the introduction of inert gas (j), which does not participate in any reaction in the reaction system, and serves to maintain a constant pressure, as described above.

At this stage, when a suitable gas pressure is not used, the polymerization activity will be correspondingly decreased and the activity of the catalyst to obtain a polybutylene will be reduced accordingly.

At this stage, if necessary, as co monomer may be introduced a small amount of α-olefin having from 2 to 20 carbon atoms, of these type is s or propylene.

Then, in the third step, the obtained polybutylene stirred polymerization reactor or a separate tank, where injected stabilizers and additives (k).

At this stage, can be added antioxidants, etc. to reduce the decomposition of polybutylene which may occur from the heat, which is applied to the polybutylene in the process of moving polybutylene after depressurization, if the polybutylene is used for industrial purposes.

As for post-irradiation phase, as low density polyethylene (LDPE), which is conceptually similar to a polybutylene, a common feature is that the stabilizers and additives are introduced into the extractor, which is the last step, add them to the mixture (MB) during this stage. However, when the stabilizers and additives (k) is introduced at the third stage of the present invention, as described above, the stabilizers and additives (k) can be mixed with polybutylene more uniformly. Also, if the stabilizers and additives (k) can be dissolved in the hydrocarbon or if they have a particle size in the range of nanometer, even if they can't dissolve in hydrocarbons, they can be mixed at the molecular level.

In the third stage, when the polymerization reactor is a batch reactor, the, stabilizers and additives (k) can enter the us in directly without using a separate reactor, and when the polymerization reactor is a reactor with continuous mixing (CSTR), the homogeneous mixing can be accomplished by the introduction of stabilizers and additives (k) in the apparatus, which is equipped with a separate mixer or mixing device.

Then, in the fourth stage, after the pressure is reduced, remove the unreacted monomers, and polybutylene is solid.

At this point, the pressure is reduced enough and get polybutylene in solid form.

Next will be described the corresponding components used in the method of producing polybutylene according to the present invention.

As the basic catalyst (i) can be used catalyst with three-titanium chloride, ammonia-soda catalyst with titanium trichloride catalyst with titanium tetrachloride or a catalyst with titanium on the carrier in the form of silicon dioxide. Can also be used a catalyst of Ziegler-Natta or one of the catalysts of the type metallocene, or can be used catalyst with a transition metal.

To obtain high catalytic activity, it is desirable to use a catalyst with metallocenes, the catalyst with titanium on the carrier in the form of silicon dioxide, or a catalyst with titanium to magnesium carrier, including a polymerization catalyst on magnesium novtel is.

The catalyst metallocene includes pentamethylcyclopentadienyl trichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, indenyltitanium trichloride, bis(indenyl)zirconium dichloride, dimethylsilane-bis(indenyl)zirconium dichloride, (dimethylsilane)(dimethylsilane)-bis(indenyl)zirconium dichloride, (dimethylsilane)-bis(2-methyl-4-phenylindane)zirconium dichloride, (dimethylsilane)- bis(benzhydryl)zirconium dichloride, ethylene-bis(indenyl)zirconium dichloride, (ethylene)(ethylene)-bis(indenyl)zirconium dichloride, (ethylene)(ethylene)bis(3-methylindenyl)zirconium dichloride, (ethylene)(ethylene)-bis(4,7-dimethylindole)zirconium dichloride, (tert-butylamide)(tetramethyl-η5-cyclopentadienyl)-1,2-tenderloi dichloride, (tert-butylamide)dimethyl(tetramethyl-η5-cyclopentadienyl)silenzione dichloride, (methylamide)(tetramethyl-η5-cyclopentadienyl)-1,2-tenderloi dichloride, etc.

It is preferable to use the following polymerization catalyst on magnesium media, such as a catalyst of Ziegler-Natta, because its use is environmental unlike conventional catalysts platogo type as internal donor of electrons.

As for the reagents at the preliminary stage, the reaction in which galogensoderjasimi connection of magnesium reacts with organically the connection containing active hydrogen, to obtain a homogeneous solution is added to the polyamide (PA); titanium chloride is added to the homogeneous solution for the regeneration of granular stereobase media; to the regenerated carrier is added to the internal donor of electrons, which has a silicon atom in dialkylamino-1,3-W-based structures according to structural formula 1, instead of the transition metal compounds and phthalate basic internal donors of electrons, in order to obtain a polymerization catalyst on magnesium media. This catalyst can be used as a catalyst in the polymerization of α-olefin having 3 or more carbon atoms, and has a good environmental properties and high activity.

The structural formula 1

where R1and R2are aliphatic hydrocarbon having from 1 to 20 carbon atoms, or aromatic hydrocarbon including from6With20, R6is an aliphatic hydrocarbon having from 1 to 30 carbon atoms, or aromatic hydrocarbon including from6With30, a R3, R4and R5represent hydrogen or an aliphatic hydrocarbon having from 1 to 30 carbon atoms, or an aromatic hydrocarbon, including with6With30.

This is the PR of the inner electrons has environmental properties, unlike donors inner electrons on the basis phthalate, which destroy the endocrine system and is often used in conventional catalytic system. Also this composition is used as an internal donor of electrons, can be used as external donor of electrons.

The chemical structure of the polymerization catalyst on magnesium media has not yet been set, but it contains titanium 1-4 wt.%, magnesium 15-30 wt.%, halogen 60-80 wt.% and silicon (Si) is less than 1.0 wt.%.

Also the main catalyst (i) can be used after prepolymerisation with α-olefin type ethylene or propylene.

As socializaton (g) are used ORGANOMETALLIC compound of the formula RNMX3-N(where M is magnesium, boron, aluminum, zinc, etc. and represents a metal of group IA, IIA, IIB, IIIB or IVB of the periodic table, R is a linear, branched alkyl group, comprising from 1 to 20 carbon atoms, or cycloalkyl group, including with3With20, X is a halogen atom, N is an integer in the range from 0 to 3.

As specific examples of the ORGANOMETALLIC compound can be selected from the group comprising organic aluminum compounds, in particular diethylaluminium chloride (DEAH), ethylaluminum dichloride (AADH), di-n-butylamine chloride (DNBF), diisobutylaluminium chloride (DIBAH), ethylaluminum the th sesquichloride (EACH), triethylaluminium (tea), triisobutylaluminum (CHIBA), tri-n-hexylamine (TNGA), triarylamine (TNOA), renormalizability (TND), triethyltin, triethylborane, triisobutylene, methylalumoxane (MAO) and the like, or may be a mixture of two or more of the preceding compounds.

It is preferable to use diethylaluminium chloride (DEAH), triethylaluminium (tea), triisobutylaluminum (CHIBA) and methylalumoxane (MAO).

May also be entered socialization, which is the donor of the external electrons (h)to maximize stereospecificity polybutylene.

For example, can be used silane compounds, inorganic acids, servocity, esters, diesters, esters, amines, organic acids, esters of organic acids or a mixture of two or more of the preceding compounds.

As a donor of the external electrons (h) it is preferable to use alkyl-, aryl - or alkoxysilane connection silane. As specific examples may be used diphenylimidazole, phenyltrimethoxysilane, diisobutyldimethoxysilane, cyclohexanedimethanol and diisobutyldimethoxysilane.

As described above, as the donor of the external electrons (h) can be used specific internal donor of electrons, which has a silicon atom in dialkyl is open-1,3-W basic structure.

In the present invention it is important that the method was carried out with a high pressure polymerization reactor using an inert gas (j), which does not participate in the reaction, with a higher pressure than the equilibrium pressure of the reagent gas-liquid at the reaction temperature, to improve the activity of the polymerization stereospecific polybutylene.

Thus, it is possible to obtain polybutylene with a higher yield by polymerization at a higher pressure than the equilibrium pressure of the reagent gas-liquid at the reaction temperature, by introducing an inert gas which does not participate in the reaction, the reactor batch, CSTR or other type of reactor, in the presence of a catalyst of Ziegler-Natta and the like, and organic aluminum compounds.

The inert gas is a gas which does not participate in the reaction, when the polybutylene is produced by polymerization of 1-butene, and which includes nitrogen, helium, neon, argon, krypton, xenon, radon, or a mixture of two or more of the preceding gases. The preferred inert gas is any one or more selected from the group of nitrogen, helium and argon.

As stabilizers and additives (k), if necessary, can be used antioxidants on the basis of phenol, phosphorus or sulfur, the terminology is a mini-stabilizers, the nucleating etc. that are used in the polymerization of polyolefin. Can also be added and other stabilizers and additives (k).

Visokotehnologicheskie polybutylene received in accordance with the present invention is a (co)polymer of 1-butene, comprising up to 40 wt.% α-olefins containing from 2 to 20 carbon atoms other than 1-butene, and having properties as described below.

First, as shown in the following examples, the titanium is not detected in the catalytic residues at the level of ppm wt.

Also, as shown in the following examples and the attached graphic materials, stereospecificity expressed through the content of the isotactic pentad (mmmm%)determined13C-NMR, is 96 or more.

Molecular weight distribution (Mw/Mnthis polybutylene is 3-6. The distribution of molecular weight can be regulated and can be extended to the distribution of molecular weight (Mw/Mn8, or more using the following process. That is, when the polybutylene get in the CSTR reactor, the distribution of molecular weight (Mw/Mn) can be adjusted in the range of 3-6 by using only one reactor and polymerization at one stage. At the same time, when the polybutylene get in the reactor batch, CSTR, the other on obnam reactor, the distribution of molecular weight (Mw/Mn) can be adjusted to 8 or more by using two or more such reactors or reactor of a different type, which are connected in series or parallel for polymerization.

A brief description of the drawings.

Figa - range13C-NMR polybutylene, which is polymerized without external donor of electrons (Lewis base) (see example 10).

Figw - range13C-NMR polybutylene, which is polymerized with the addition of dimethoxydimethylsilane ((i-Pr)2Si(OCH3)2) as external donor of electrons (Lewis base) (see example 1).

Figure 2 - range of13C-NMR in the range 26 to 28 ppm wt. polybutylene, which is polymerized without external donor of electrons (Lewis base) (see example 10).

Figure 3 - range of13C-NMR in the range 26 to 28 ppm wt. polybutylene, which is polymerized with the addition of external donor of electrons (Lewis base) to improve stereospecificity (see example 1).

The present invention will be illustrated in more detail with the aid of the following examples, which do not limit.

Example 1: a sample of the Century

(a) Preparation of the catalyst.

In chetyrehosnuju flask with a round bottom with a capacity of 1 l, equipped with a magnetic stir bar, refrigerator and temperature probe, was added 50 ml of decane and 3.0 g of chlorine the buffer of net magnesium under a stream of nitrogen, was stirred for a few minutes, was added 1 ml of 2-ethylhexanol, increasing the temperature to 130°With over 20 minutes with stirring and then the reaction was carried out for 1 hour

After reaction for 1 h was added 1.0 g of RA. The resulting mixture was reacted for 1 h at 130°With stirring in nitrogen atmosphere. The obtained homogeneous solution was cooled to ambient temperature. The titanium tetrachloride was injected at a lower temperature over 1 h and stirred to obtain a suspension containing solid product.

The solid product was filtered, separated and washed with heptane four times.

In the resulting solid product was added 50 ml of toluene, was added titanium tetrachloride with stirring, increased temperature up to 100°S, was introduced to 0.30 g of 2-isopropyl-2-trimethylsilylmethyl-1,3-dimethoxypropane, increasing the temperature to 110°and then reaction was carried out for 2 hours

Upon completion of the reaction, the solid product was filtered, separated and washed with heptane four times. To the washed solid product was added heptane and the titanium tetrachloride and the reaction was carried out at 98°C for 2 hours resulting solid catalyst was filtered, separated and washed with heptane until then, until the connection is free of titanium is no longer detected, to obtain a solid catalyst suspended platforms is hydrated in heptane.

The composition of the obtained catalyst was analyzed by ICP-spectrometer. The results showed the presence of titanium 2-3 wt.% and magnesium 16-19 wt.%.

(b) Polymerization to obtain stereospecific polybutylene.

Used stainless steel autoclave with a capacity of 2 l was subjected to vacuum cleaning and purging with nitrogen several times. To the autoclave was added 0.01 g of the solid catalyst under paragraph (a) above, 0.01 g of diisobutyldimethoxysilane, 0.3 g diethylaluminium chloride (tea), 1.2 l of 1-butene and 200 ml of hydrogen under a stream of nitrogen, increased the pressure to 3 bar nitrogen addition increased the temperature in the autoclave to 80°and then perform the polymerization.

After one and a half hours, the autoclave was depressurized. Unreacted monomers 1-butene were removed. The obtained polymer was dried at 90°C for 12 h in a vacuum state.

Activity of dried polybutylene was 23000 g/g-cat·1.5 h, which amounted 15300 g/g-cat·h; molecular mass (Mw) was 430000; distribution of molecular weight (Mw/Mnwas 3,22; the density was 0,886 g/cm3; the melting point was 116,9°s; titanium was not detected at the level of ppm wt.

Stereospecificity was assessed by NMR and was 99.7 (mmmm%). Stereostructure polybutylene can be assessed according to the shape of the resonance peak in the range 26 to 28 ppm wt.

P is the iMER 2.

Polybutylene was obtained in accordance with the same procedure as in example 1, except that during the polymerization the pressure was increased to 6 bar nitrogen addition.

The activity of the obtained polybutylene was 32400 g/g-cat·1.5 h, which amounted to 21600 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 3,69; the density was 0,884 g/cm3; stereospecificity was 99.7 (mmmm%); melting point was 117,0°s; titanium was not detected at the level of ppm wt.

Example 3.

Polybutylene was obtained in accordance with the same procedure as in example 2, except that used 0.01 g of 2-isopropyl-2-trimethylsilylmethyl-1,3-dimethoxypropane, which was used as internal donor of electrons, as was shown in the description above, but here in the polymerization were used as external donor electrons instead of diisobutyldimethoxysilane.

The activity of the obtained polybutylene was 29700 g/g-cat·1.5 h, which was 19800 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 4,11; the density was 0,880 g/cm3; stereospecificity amounted to 96.9 (mmmm%); melting point was 115,6°s; titanium was not detected at the level of ppm wt.

Example 4.

Polybutylene received in accordance with the same procedure as in example 2, except that if the imerissia as co monomer was added propylene.

The activity of the obtained polybutylene was 30700 g/g-cat·1.5 h, which amounted 20500 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 3,45; the density was 0,881 g/cm3; methyl group in the main chain was 14 wt.%; the melting point was 134,2°s; stereospecificity amounted to 97.1 (mmmm%); titanium was not detected at the level of ppm wt.

Example 5.

Used stainless steel autoclave with a capacity of 50 l was subjected to vacuum cleaning and purging with nitrogen several times. To the autoclave was added 0.3 g of the solid catalyst obtained by the same procedure as in example 1, 0.3 g of diisobutyldimethoxysilane, 0.12 g of triethylaluminum (tea), 25 l of 1-butene and under a pressure of 10 bar of hydrogen under a stream of nitrogen increased the pressure to 4 bar nitrogen addition increased the temperature in the autoclave to 80°and then perform the polymerization.

An hour and a half polymer was moved from the autoclave in the following tank with a stirrer, was added equivalent (OSH) as an antioxidant and razgermetiziruetsya to remove unreacted monomers 1-butene. The obtained polymer was dried at 90°C for 12 h in a vacuum state.

Activity of dried polybutylene was 28300 g/g-cat·1.5 h, which was 18900 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 4,05; MFR was 0.82; stereospecificity was 98,0 (mmmm%); titanium was not detected at the level of ppm wt.

Example 6.

Used equipment including two parallel-connected reactor polymerization (50 l, autoclaves), subsequent tank with agitator (100 l) and apparatus for the reduction and recovery of pressure. Both used a 50-liter stainless steel autoclave was subjected to vacuum cleaning and purging with nitrogen several times. Into the autoclave were added 0.3 g of the solid catalyst obtained by the same procedure as in example 1, 0.3 g of diisobutyldimethoxysilane, 0.12 g of triethylaluminum (tea), 25 l of 1-butene and under a pressure of 10 bar of hydrogen under a stream of nitrogen, respectively, increased pressure 4 bar nitrogen addition increased the temperature in one autoclave to 70°C, and the temperature in another autoclave up to 80°and then spent the polymerization.

An hour and a half the polymers from the corresponding autoclaves moved into the next tank at the same time, mixed, added OSH as an antioxidant, and razgermetiziruetsya to remove unreacted monomers 1-butene. The obtained polymer was dried at 90°C for 12 h in a vacuum state.

Activity of dried polybutylene was 27800 g/g-cat·1.5 h, which was 18,500 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 7,4; MFR part is La 0,45; stereospecificity was 97,9 (mmmm%); titanium was not detected at the level of ppm wt.

Example 7.

Used 50-liter autoclave of stainless steel, equipped with automatic relay valve, subjected to vacuum cleaning and purging with nitrogen several times. To the autoclave was added 0.3 g of the solid catalyst obtained in accordance with the same procedure as in example 1, 0.3 g of diisobutyldimethoxysilane, 0.12 g of triethylaluminum (tea), 25 l of 1-butene and under a pressure of 10 bar of hydrogen under a stream of nitrogen, respectively, increased pressure 4 bar nitrogen addition increased the temperature in the autoclave to 80°and then spent the polymerization.

The time established in the amount of one and a half hours. The natural pressure drop caused by the transition of the nitrogen in the liquid is compensated by the addition of nitrogen. The number of downloads of the solid catalyst obtained in accordance with the same procedure as in example 1, and triethylamine regulated in accordance with the difference of the temperature of the reaction to maintain this temperature in the reactor constant.

An hour and a half from the beginning of the polymerization, the polymer was moved from the autoclave in the following tank with agitator. After moving a certain amount of polymer added OSH as an antioxidant and razgermetiziruetsya to remove the unreacted monomers 1-butene. The obtained polymer was dried at 90°C for 12 h in a vacuum state.

The average activity of dried polybutylene was 19200 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 4,88; MFR was 0.37; stereospecificity made up 97.5 (mmmm%); titanium was not detected at the level of ppm wt.

Example 8.

Used equipment, including two 50-liter stainless steel autoclave, equipped with an automatic relay valve, respectively, the subsequent tank with agitator (100 l) and apparatus for the reduction and recovery of pressure. Both used a 50-liter stainless steel autoclave was subjected to vacuum cleaning and purging with nitrogen several times. Into the autoclave were added 0.3 g of the solid catalyst obtained by the same procedure as in example 1, 0.3 g of diisobutyldimethoxysilane, 0.12 g of triethylaluminum (tea), 25 l of 1-butene and under a pressure of 10 bar of hydrogen under a stream of nitrogen, respectively, increased pressure 4 bar nitrogen addition increased the temperature in one autoclave to 70°C, and the temperature in another autoclave up to 80°and then spent the polymerization.

The time established in the amount of one and a half hours. The natural pressure drop caused by the transition of the nitrogen in the liquid is compensated by the addition of nitrogen. The number of downloads of the main cat is lyst and triethylaluminum regulated in accordance with the difference of the temperature of the reaction to maintain this temperature in the reactor constant.

An hour and a half from the beginning of the polymerization, the polymer was moved from the autoclaves in the next tank with a mixer and mixed. After moving a certain amount of polymer added OSH as an antioxidant and razgermetiziruetsya to remove unreacted monomers 1-butene.

The obtained polymer was dried at 90°C for 12 h in a vacuum state.

The average activity of dried polybutylene was 17900 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 4,88; MFR was 0.45; stereospecificity amounted to 96.9 (mmmm%); titanium was not detected at the level of ppm wt.

Example 9.

Polybutylene obtained by the same procedure as in example 1, except that the autoclave is not created additional pressure using nitrogen.

The activity of the obtained polybutylene was 14700 g/g-cat·1.5 h, which amounted 9800 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 3,93; the density was 0,884 g/cm3; stereospecificity were 96.7 (mmmm%); melting point was 117,4°s; titanium was not detected at the level of ppm wt., but the polymer had a shade of bright red and yellow color.

Example 10.

Polybutylene obtained by the same procedure as in example 2, except that socialization (h) diisobutyldimethoxysilane, the external donor of electrons, not in Odessa in the autoclave for polymerization.

The activity of the obtained polybutylene was 35200 g/g-cat·1.5 h, which was 23500 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 4,11; the density was 0,884 g/cm3; stereospecificity was 61,0 (mmmm%); melting point was 108,5°s; titanium was not detected at the level of ppm wt.

Example 11.

The catalyst was obtained by the same procedure as in example 1, except that 0,43 g of di-n-butylphthalate (DNBP) was introduced instead of 2-isopropyl-2-trimethylsilylmethyl-1,3-dimethoxypropane as internal donor of electrons. Polybutylene received in accordance with the same procedure as in example 2.

The activity of the obtained polybutylenepipe was 27600 g/g-cat·1.5 h, which was 18400 g/g-cat·h; distribution of molecular weight (Mw/Mnwas 3,55; the density was 0,886 g/cm3; stereospecificity was 98.2 (mmmm%); melting point was of 116.7°s; titanium was not detected at the level of ppm wt.

On figa presents a range of13C-NMR of polybutylene in the form of homopolymer, which is polymerized without external donor of electrons (Lewis base) in accordance with the present invention (see example 10). On FIGU presents a range of13C-NMR of polybutylene in the form of homopolymer, which is polymerized with the addition dimethoxy-diisopropylaniline ((i-Pr)2Si(OCH3 )2) as external donor of electrons (Lewis base) (see example 1).

Stereostructure polybutylene can be defined by the peak of the resonance of the methylene carbon, which is a branch of ethyl 1-butene (denoted as ② figure 1). As stereospecificity (isotacticity) is high, then the peak of the resonance, similar to the singlet peak falls in the range 26 to 28 ppm wt.

As shown in figa, quite complex peak resonance multiplet peak) detected in the range 26 to 28 ppm wt. due to the reduction of stereospecificity. As shown In figure 1, mainly only the peak of the resonance is detected in the range 26 to 28 ppm wt. due to the increase of stereospecificity caused by external donor of electrons (Lewis base).

Figure 2 presents a range of13C-NMR in the range 26 to 28 ppm wt. polybutylene as homopolymer, which is polymerized without external donor of electrons (Lewis base) in accordance with the present invention (see example 10). There is a range of vysokoaromatichnyj samples, dissolved in ether, and the range of nitroterephthalic samples that did not dissolve in ether with ethereal fractionation by the method of solvent extraction for the separation of the polymer obtained by stereospecific samples and asterophyllites samples. Although the objects of study were the large number of samples, all had received only a small number nitroterephthalic samples that did not dissolve in the ether.

As shown in figure 2, using the fractionation method of extraction, even stereospecific polymer that does not dissolve in ether, contains asterophyllites elements in the main chain.

Figure 3 presents a range of13C-NMR in the range 26 to 28 ppm wt. polybutylene as homopolymer, which is polymerized with the addition of external donor of electrons (Lewis base) to improve stereospecificity (see example 1).

Although we used a large number of samples was received too little nitroterephthalic samples that did not dissolve in ether, to determine the range13C-NMR.

As shown in figure 3, the obtained polymers showed only a single peak resonance in the expanded spectrum in the range 26 to 28 ppm wt. and stereospecificity expressed through the content of the isotactic pentad (mmmm%), reaching 98,7.

As described above, the method of producing polybutylene according to the present invention has a much higher activity than the activity of any other known methods for producing polybutylene, and therefore shows a high activity, very similar to the active method of producing polyethylene or polypropylene. Thus, a manufacturer who must obtain polybutylene according to the present invention is significantly improved.

The result of the implementation of the method according to the present invention can be achieved using known reactors such as CSTR, tubular reactor (TPD) and other reactors, along with the batch reactor, the.

Next, polybutylene, obtained by the method according to the present invention has such a high purity by catalytic residues that titanium is not detected at the level of ppm wt. unlike conventional stereospecific polybutylene.

1. The method of obtaining vysokotehnicheskoe (co)polymer of 1-butene, comprising the step (S1) polymerization of a reactive monomer of 1-butene in the presence of a catalyst comprising a solid component containing compound of titanium, and in the presence of inert gas, and inert gas is deliberately introduced into the reactor together with hydrogen to the inert gas could be present in the reactor during the polymerization, and step S1 is performed with high pressure in the polymerization reactor through the use of an inert gas with a higher pressure than the equilibrium pressure of the reagent gas-liquid at the reaction temperature 10-110°C.

2. The method according to claim 1, characterized in that the step S1 is carried out using one or more inert gas selected from the group of nitrogen, helium and argon.

3. Visokotehnologicheskie polybutylene, obtained the method according to claim 1, characterized in that it is homopolymer 1-butene or a copolymer of 1-butene, comprising up to 40 wt.% α-olefins containing from 2 to 20 carbon atoms other than 1-butene, having the following properties: 1) titanium is not present in the catalytic residues at the level of ppm wt.; 2) stereospecificity expressed through the content of the isotactic pentad (mmmm%)determined13C-NMR, is 96 or more; 3) distribution of molecular weight (Mw/Mn) is 3-6.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: invention relates to preparation of cellular polymer particles suited to be used in coating deposition compositions. Cellular polyesters-based polymer particle according to invention including spherical particles having numerous air hollows and long-chain aliphatic groups and/or spatially hindered branched-chain hydrophobic groups associated with surface of said spherical particles is proposed. A composition for preparing indicated cellular particles and a method of preparing the same are developed.

EFFECT: enlarged assortment of starting materials for polymeric coating compositions.

11 cl, 10 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to emulsion method for co-polymerization of acrylic monomers. Invention proposes a method involving preliminary emulsification of mixture of butyl acrylate with (meth)acrylic and/or vinyl monomer in water in the following mass ratio co-monomer : water = 1:(0.2-0.3) in the presence of 3.4-4.0 wt.-% of sulfooxyethylated alkylphenol ammonium salt wherein (C8-C10)-alkyl has the alkylation degree 18-26 wt.-%, the following emulsion co-polymerization at temperature 78-82°C for 3-10 h at continuous dosing of preliminary prepared co-monomers emulsion and 0.3-0.6 wt.-% of ammonium or potassium persulfate in the total ratio to the reaction mass co-monomer : water = 1:(0.4-0.5) followed by additional polymerization of the reaction mixture in addition of 0.1 wt.-% of ammonium or potassium persulfate after keeping the reaction mixture for 0.5 and 1.5 h and its final temperature keeping for 2 h. Invention provides increasing concentration of acrylic copolymer aqueous dispersion at low content of coagulum and improving its adhesion properties. Invention provides the development of a method for preparing highly concentrated aqueous dispersion with the content of acrylic copolymer 60 wt.-%, not less, for glues showing sensitivity to pressure.

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2 cl, 1 tbl, 13 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

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13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

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EFFECT: improved preparing method, valuable properties of copolymers.

22 cl, 6 tbl, 6 ex

FIELD: polymer production.

SUBSTANCE: invention provides elastomeric polymer composition comprising at least polymers and copolymers obtained from substituted and unsubstituted vinylaromatic monomers and from diene monomers and including 15 to 85% copolymer containing (i) at least one block formed by 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinylaromatic monomer and (ii) at least one block formed by 10 to 4000 monomer units derived from at least one diene monomer with predominant 1,4-cis structure, wherein 15-85 wt % of polymer obtained from diene monomers has molecular weight between 6000 and 600000 with content of 1,4-cis monomer units constituting at least 90%, while up to 70% of polymer obtained from substituted and unsubstituted vinylaromatic monomers has molecular weight between 10000 and 500000 and degree of syndiotacticity (expressed through syndiotactic pentads) at least 95%, a part formed by monomer units derived from diene monomer is optionally partially or completely hydrogenised. Method of preparing such elastomeric composition is also described.

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42 cl, 5 tbl, 27 ex

FIELD: polymerization processes.

SUBSTANCE: polymer containing at least one boronate substituent or its precursor is prepared by controlled living radical polymerization of monomers in presence of living chain growth control agent, in particular sulfur-containing compound having S-C(S)- bond, said monomers being represented by (i) at least one monomer having at least one boronate substituent or its precursor and selected from group consisting of acryloylbenzeneboronic acid, methacryloylbenzeneboronic acid, vinyl-4-benzeneboronic acid, 3-acrylamidophenylboronic acid, 3-methacrylamidophenylboronic acid, individually or in mixture, or in salt form, and (ii) at least having no boronate substituents nor their precursors. Also described is associate containing above-defined polymer with at least one compound ligand having at least one group capable of forming complex with the polymer containing at least one boronate substituent or its precursor.

EFFECT: narrowed molecular mass distribution and uniformity along the polymer chain.

FIELD: polymer production.

SUBSTANCE: invention is directed to production of water-soluble polymers or water-swellable hydrogels, detergents, and various composites based thereon, as well as to preparation of novel therapeutical forms. Acrylate-type polymer are obtained via light-induced polymerization of acrylate monomers in presence of metal-free porphyrins and accurately dosed quantities of molecular oxygen under irradiation by visible light within wavelength range 400-700 nm. Distinguishing feature of such a polymerization resides in high oxygen-sensitivity and concentration of porphyrin, by variation of which one can vary polymer characteristics within a wide range and. in case of acrylic acids, additionally structurize polyelectrolytes based thereon resulting in hydrogels showing different degrees of swelling in water.

EFFECT: simplified process, reduced consumption of photoinitiator, enabled polymerization of acrylic monomers in absence of their alkyl-substituted derivatives, and enabled carrying out process in bulk, in solution, or in emulsion.

6 cl, 1 tbl, 7 ex

FIELD: polymer production.

SUBSTANCE: invention is directed to production of water-soluble polymers or water-swellable hydrogels, detergents, and various composites based thereon, as well as to preparation of novel therapeutical forms. Acrylate-type polymer are obtained via light-induced polymerization of acrylate monomers in presence of metal-free porphyrins and accurately dosed quantities of molecular oxygen under irradiation by visible light within wavelength range 400-700 nm. Distinguishing feature of such a polymerization resides in high oxygen-sensitivity and concentration of porphyrin, by variation of which one can vary polymer characteristics within a wide range and. in case of acrylic acids, additionally structurize polyelectrolytes based thereon resulting in hydrogels showing different degrees of swelling in water.

EFFECT: simplified process, reduced consumption of photoinitiator, enabled polymerization of acrylic monomers in absence of their alkyl-substituted derivatives, and enabled carrying out process in bulk, in solution, or in emulsion.

6 cl, 1 tbl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to preparation of cellular polymer particles suited to be used in coating deposition compositions. Cellular polyesters-based polymer particle according to invention including spherical particles having numerous air hollows and long-chain aliphatic groups and/or spatially hindered branched-chain hydrophobic groups associated with surface of said spherical particles is proposed. A composition for preparing indicated cellular particles and a method of preparing the same are developed.

EFFECT: enlarged assortment of starting materials for polymeric coating compositions.

11 cl, 10 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to emulsion method for co-polymerization of acrylic monomers. Invention proposes a method involving preliminary emulsification of mixture of butyl acrylate with (meth)acrylic and/or vinyl monomer in water in the following mass ratio co-monomer : water = 1:(0.2-0.3) in the presence of 3.4-4.0 wt.-% of sulfooxyethylated alkylphenol ammonium salt wherein (C8-C10)-alkyl has the alkylation degree 18-26 wt.-%, the following emulsion co-polymerization at temperature 78-82°C for 3-10 h at continuous dosing of preliminary prepared co-monomers emulsion and 0.3-0.6 wt.-% of ammonium or potassium persulfate in the total ratio to the reaction mass co-monomer : water = 1:(0.4-0.5) followed by additional polymerization of the reaction mixture in addition of 0.1 wt.-% of ammonium or potassium persulfate after keeping the reaction mixture for 0.5 and 1.5 h and its final temperature keeping for 2 h. Invention provides increasing concentration of acrylic copolymer aqueous dispersion at low content of coagulum and improving its adhesion properties. Invention provides the development of a method for preparing highly concentrated aqueous dispersion with the content of acrylic copolymer 60 wt.-%, not less, for glues showing sensitivity to pressure.

EFFECT: improved preparing method, improved and valuable properties of dispersion.

2 cl, 1 tbl, 13 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to copolymers consisting of monomers comprising acid groups with double bond and other hydrophobic monomeric component used in prophylaxis of inorganic and organic deposits in water-bearing systems. Invention describes a water-soluble copolymer comprising: (a) monoethylene-unsaturated monomers chosen from group consisting of monocarboxylic acids, dicarboxylic acids and sulfoacids that can be neutralized; (b) at least copolymerizable hydrophobic acrylic, monocyclic and/or bicyclic terpene comprising unsaturated double bond wherein terpene hydrocarbon is preferable, and copolymer is prepared by free-radical copolymerization of components (a) and (b) in an aqueous phase. Also, invention describes a method for synthesis of abovementioned copolymer and methods for its using. Invention provides synthesis of nontoxic copolymer used for prevention of deposits in water-bearing systems that can be easily prepared from available components and able to store for a long time without loss of activity.

EFFECT: improved preparing method, valuable properties of copolymers.

22 cl, 6 tbl, 6 ex

FIELD: polymer production.

SUBSTANCE: invention provides elastomeric polymer composition comprising at least polymers and copolymers obtained from substituted and unsubstituted vinylaromatic monomers and from diene monomers and including 15 to 85% copolymer containing (i) at least one block formed by 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinylaromatic monomer and (ii) at least one block formed by 10 to 4000 monomer units derived from at least one diene monomer with predominant 1,4-cis structure, wherein 15-85 wt % of polymer obtained from diene monomers has molecular weight between 6000 and 600000 with content of 1,4-cis monomer units constituting at least 90%, while up to 70% of polymer obtained from substituted and unsubstituted vinylaromatic monomers has molecular weight between 10000 and 500000 and degree of syndiotacticity (expressed through syndiotactic pentads) at least 95%, a part formed by monomer units derived from diene monomer is optionally partially or completely hydrogenised. Method of preparing such elastomeric composition is also described.

EFFECT: extended temperature range for elastomeric performance of composition.

42 cl, 5 tbl, 27 ex

FIELD: polymerization processes.

SUBSTANCE: polymer containing at least one boronate substituent or its precursor is prepared by controlled living radical polymerization of monomers in presence of living chain growth control agent, in particular sulfur-containing compound having S-C(S)- bond, said monomers being represented by (i) at least one monomer having at least one boronate substituent or its precursor and selected from group consisting of acryloylbenzeneboronic acid, methacryloylbenzeneboronic acid, vinyl-4-benzeneboronic acid, 3-acrylamidophenylboronic acid, 3-methacrylamidophenylboronic acid, individually or in mixture, or in salt form, and (ii) at least having no boronate substituents nor their precursors. Also described is associate containing above-defined polymer with at least one compound ligand having at least one group capable of forming complex with the polymer containing at least one boronate substituent or its precursor.

EFFECT: narrowed molecular mass distribution and uniformity along the polymer chain.

FIELD: polymer production.

SUBSTANCE: invention is directed to production of water-soluble polymers or water-swellable hydrogels, detergents, and various composites based thereon, as well as to preparation of novel therapeutical forms. Acrylate-type polymer are obtained via light-induced polymerization of acrylate monomers in presence of metal-free porphyrins and accurately dosed quantities of molecular oxygen under irradiation by visible light within wavelength range 400-700 nm. Distinguishing feature of such a polymerization resides in high oxygen-sensitivity and concentration of porphyrin, by variation of which one can vary polymer characteristics within a wide range and. in case of acrylic acids, additionally structurize polyelectrolytes based thereon resulting in hydrogels showing different degrees of swelling in water.

EFFECT: simplified process, reduced consumption of photoinitiator, enabled polymerization of acrylic monomers in absence of their alkyl-substituted derivatives, and enabled carrying out process in bulk, in solution, or in emulsion.

6 cl, 1 tbl, 7 ex

FIELD: polymer production.

SUBSTANCE: invention is directed to production of water-soluble polymers or water-swellable hydrogels, detergents, and various composites based thereon, as well as to preparation of novel therapeutical forms. Acrylate-type polymer are obtained via light-induced polymerization of acrylate monomers in presence of metal-free porphyrins and accurately dosed quantities of molecular oxygen under irradiation by visible light within wavelength range 400-700 nm. Distinguishing feature of such a polymerization resides in high oxygen-sensitivity and concentration of porphyrin, by variation of which one can vary polymer characteristics within a wide range and. in case of acrylic acids, additionally structurize polyelectrolytes based thereon resulting in hydrogels showing different degrees of swelling in water.

EFFECT: simplified process, reduced consumption of photoinitiator, enabled polymerization of acrylic monomers in absence of their alkyl-substituted derivatives, and enabled carrying out process in bulk, in solution, or in emulsion.

6 cl, 1 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to butene-1 (co)polymers and a method of their synthesis. Except for, invention relates to articles made of butene-1 (co)polymers. Homopolymers of butene-1 are characterized by the following properties: (i) value of molecular-mass partition expressed as the ratio Mw/Mn based on measurement with using analysis carried out by gel-permeation chromatography method is less 6, and (ii) strength value of melt is above 2.8 g. These homopolymers are used for making tubes. Method for synthesis of butene-1 homopolymers is carried out in the presence of a stereospecific catalyst comprising (A) a solid component containing Ti compound and internal electron-donor compounds chosen from phthalates and applied on a carrier MgCl2; (B) alkylaluminum compound, and (C) tert.-hexyltrimethoxysilane as an external electron-donor compound. Butene-1 homopolymers possess a set of mechanical properties providing the presence both barostability after prolonged period time and their easy processing for making tubes.

EFFECT: valuable properties of (co)polymers, improved method of synthesis.

12 cl, 1 tbl, 3 ex

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