Way to generate new polylithium derivatives carbosilane compounds dendritic patterns
(57) Abstract:Describes how to obtain new polylithium derivatives carbosilane compounds dendritic structure, which consists in the fact that carbosilane compounds with unsaturated groups selected from a number carbosilane dendrimer or hyperbranched carbosilane first subjected to interaction with methylmetacrylate when the molar ratio of unsaturated groups carbosilane to methylbicyclo from 2 to 1.1 in the presence of a platinum catalyst at 20-80°C, then the received methylpiperidine derived metallinou alkyllithium in the environment of an organic solvent at 20-80°C. the Technical result - the use of polylithiated derivatives carbosilane compounds as initiators of anionic polymerization, with good solubility and stability in organic solvents. 6 C.p. f-crystals. The invention relates to a method of obtaining new undescribed in the literature polylithium derivatives karbosilanovykh compounds (PLCS), which can find application in the chemical industry as intermediates for various organiseorganised materials. In particular PLCS can be the governmental groups, and heterocyclic.A method of obtaining lithium derivative of organosilicon compounds with a functionality of more than two by the interaction alkylate and allylsilanes containing from 2 to 4 allyl groups [USSR Author's certificate 311918, class C 07 F 1-02, publ. 1971]. From the structure of the compounds obtained it is obvious that in this case will be quite high degree of Association of lithium atoms that will cause polymodality polymers derived from these compounds. Another disadvantage is that this method of obtaining compounds with higher functionality is not possible.A method of obtaining laisteridge connection with a functionality of more than two on the basis of known difunctional compounds lithium type derived diphenylethylene sequential introduction of oligomers of styrene containing etinilnoy group, which is introduced next lithium atom [US Patent, US 4196153, class C 08 F 4-48, publ. 1980]. The disadvantages of this method are, first, its a multi-stage, making problematic getting a really high functionality, secondly, the structure polulation, acting as razvetvlyayushchikh centers of star-shaped polymers obtained based on them. In addition, with this structure poliitikaga connection possible Association lithium groups, which leads to a wide molecular weight distribution of the obtained polymers. Relatively high content of styrene oligomers in the composition of the compound is a disadvantage when using it as an initiator for the polymerization of compounds mesterolone nature.A method of obtaining poliitikaga compounds stitching divinylbenzene "living" polystyrene-oligomers [C. Tsitsilianis, D. Boulgaris. "A synthetic route for the synthesis of starshaped macromolecules". Macromolecular reports, A32 (suppls. 5&6), 569 - 577 (1995)]. Received star-shaped polystyrene saves live lithium group on the Central branch, is able to initiate a new process of polymerization of diene monomers. This method of getting polyfunctional compounds can be regarded only as a way to obtain star-shaped copolymers irregular structure, as obtained pollutiion connection does not have a clear structure and a known quantity of functional groups.These methods polucheniya polymerization: possess good solubility and stability in organic solvents, in the case of polyfunctional initiators to have known and a certain number of reaction centers of equal reactivity.When creating the present invention, the aim was to develop a new way of obtaining the unknown PLCS strictly defined dendritic or hyperbranched structure, in which the possibility of the Association of lithium groups would have been difficult and would have met all the requirements above. The problem is solved in that a method of obtaining new polylithium derivatives carbosilane compounds dendritic structure, which consists in the fact that carbosilane connection with unsaturated functional groups (for example, allyl, vinyl), selected from the series:
(A) Carbosilane dendrimer at least second generation,
(B) hyperbranched carbosilane containing at least 10 basic units of General formula
< / BR>where X is an unsaturated functional group;
n is the number of carbon atoms in the group X,
first is subjected to interaction with methylmetacrylate when the molar ratio of unsaturated groups carbosilane connection to methylbicyclo from 2 to 1.1 in the present is a tie, mainly butyllithium, in the environment of an organic solvent at 20 to 80oC.In the case of obtaining PLX-dendrimers at the first stage of interaction with methylmetacrylate as the source, you can use carbosilane dendrimers of limited with allyl and vinyl functional groups.In the case of obtaining PLX-hyperbranched carbosilane as a source carbosilane you can use carbosilane General formula of elementary link
< / BR>where n = 2 or 3.When interacting carbosilane dendrimers (A) or (B) methylmetacrylate as a catalyst it is possible to use a solution of hexachloroplatinic acid (catalyst SPYERA) or other complex compounds of platinum in the amount of 0.001 - 0.005% of the mass. (per Pt in relation to the amount of reagents). The reaction can be carried out in the presence of an additional component, an organic solvent, such as hexane, toluene, tetrahydrofuran, chloroform or a mixture of at least two of these solvents.In the second stage reaction of metallation as the organic solvent can be used alcamovia or aromatic prevades can be entered optionally one of the following compounds: tetrahydrofuran, dioxane, tetramethylethylenediamine, crown-ethers, dimethyl ether of ethylene glycol, dimethyl ether of diethylene glycol.The structure of the obtained compounds prove on the basis of physico-chemical methods of analysis. Data GPC obtained compounds show the preservation of monomodality and narrow molecular weight distribution throughout the entire synthesis. Data1H NMR shows the presence of CH2=CH-groups in the adduct in stage 1 and their absence in connection in stage 2, and the integral ratio of proton relevant groups coincide with theoretically calculated values.The reaction of obtaining new PLX proceed according to the following schemes (for example, the dendrimer of the second generation, obtained on the basis of allylsilanes):
< / BR>Stage 2
< / BR>The synthesized compounds according to the claimed method meets all the above specified requirements, as polyfunctional razvetvlyayushchikh centers to receive them use individual carbosilane dendrimers of limited or hyperbranched carbosilane with a known number of equivalent functional groups, and introduced decile groups comprise alkyl cover providing x is s ion groups.The invention is illustrated by the following examples.Obtaining parent compounds
Getting carbosilanes of the dendrimer of the first generation on the basis of allylsilanes. In the reactor mix 50 g (of 0.26 mole) tetraallylsilane, of 0.26 ml R-RA catalyst Speier (0,001% Pt), and introduce 119 ml (1.04 mol) of methyldichlorosilane. The reaction is carried out at a temperature of 90oC. the Reaction mixture is dispersed in vacuo (TK.240oat 1 mm RT.cent.). Next, a solution of 100 g (0,153 mol) of the obtained product and 117.3 g (1.53 mol) of allyl chloride in 250 ml of THF and 125 ml of hexane is injected dropwise to 41 g (1,68 mol) of Mg in 60 ml THF. Upon completion of the reaction the solution is filtered, evaporated in vacuum. The resulting dendrimer of the first generation (Si58All oharakterizovat using GPC: modal distribution, d = 1,02 and1H NMR: = 0,2 (m, CH3Si-), = 0,8 (m, SiCH2- ), or = 1.5 (m, -CH2-), = 4,8 (m, CH2=), = 5,7 (m, CH=).Getting dendrimer of the second generation. To 30,97 g (0,044 mol) Si58All type 49 g (0.42 mol) of methyldichlorosilane and 0.16 ml R-RA catalyst Speier (0,001% Pt) and incubated the mixture at 90oC. after the reaction solution vaccum. Further, in the reactor to 22,54 g (0,926 m) Mg and 40 ml of THF was added dropwise 68,15 g (0,042 m) Si1316Cl and 64, evaporated in vacuum. Vacuum to a constant weight at 80oand 1 mm RT. Art. the Output of the dendrimer of the second generation Si1316All is 95% (106,88 g). The purity of the product is controlled by the GPC method: modal distribution, d = 1.03 and NMR1H: = 0,2 (m, CH3Si-), = 0,8 (m, SiCH2- ), or = 1.5 (m, -CH2-), = 4,8 (m, CH2=), = 5,7 (m, CH=).The dendrimers of the following generations is obtained by repetition of the operations described upon receipt of the dendrimer of the second generation, and oharakterizovat similar methods.Dendrimers based vinylsilane receive are similar to the above methods of obtaining dendrimers, but when the first generation instead of tetraallylsilane use tetraphenylsilane, and upon receipt of subsequent generations instead of allyl chloride using vinyl chloride.Getting hyperbranched carbosilane containing 100 elementary units of the formula (II), on the basis of methyldiethylamine (n = 3). The mixture 2,52 g (0.02 m) of methyldiethylamine and 0.02 ml of toluene solution of platinum catalyst (0,001% Pt) is heated at a temperature of 80oC for 4 hours. Analysis of the product by GPC method confirms the molecular weight of the synthesized polymer. NMR1H: = 0,2 (m, CH3Si-), = 0,8 (m, SiCH2Getting polylithium compounds, PLX.Example 1. Getting poliitikaga connection-based dendrimer of the second generation
1 stage. Getting badellino derived. In the reactor with stirrer, inert gas, is mixed with 0.6 g (3.5 10-4m) Si1316All and 0.92 g (2,8 10-3m) methylpiperidine and injected 5 μl (about 0.001% weight.) catalyst PC072. Stirred at 20oC. the resulting material analyzed by GPC: modal distribution, Mp= 4360 (ex.), 4321,18 (est.) MMD: d = 1,15.1H NMR (CCl4, 200 MHz): = -0,05 (m, CH3Si-), = 0,55 (m, CH2Si-), = 0,95 (m, -CH2- ), a = 1,3 (s, -CH2-), = 4,8 (m, CH2=), = 5,75 (m, -CH=).stage 2. The metallation reaction. In the reactor, containing 1.01 g (2,3 10-4m) badellino derived enter the 1.44 ml of a 1.3 molar solution of BuLi in hexane (1,87 10-3m) and 0.28 ml (1,87 10-3m) tetramethylethylenediamine. Stirred at 20oC 5 hours and get PLX-dendrimer with a content of 8 Li atoms in the molecule.To examine the structure of sintezirovannogo is to) trimethylchlorosilane, stirred for 5 hours at room temperature. The solution was diluted with toluene and washed with water until neutral, dried and vacuum on a rotary evaporator. The resulting substance analyzed by GPC: modal distribution, MMD: d = 1,15.1H NMR (CCl4, 200 MHz): = -0,05 (m, CH3Si) = 0,55 (m, -CH2Si) = 0,9 (m, -CH2- ), a = 1,3 (s, -CH2-).Example 2. Analogously to example 1, but as the source carbosilane center are using dendrimer next (third) generation of Si2932All, and the first stage reaction is carried out at 80oC, in THF solution in the presence of a catalyst of SPYERA. Received PLX connection contains 16 of lithium atoms in the molecule.Example 3. Analogously to example 1, but as the source razorblades center, use of hyperbranched carbosilane obtained on the basis of methyldiethylamine. The first stage reaction is carried out in hexane solution in the presence of 0.005% catalyst SPYERA.Example 4. Analogously to example 1, but as the source razorblades center, use of hyperbranched carbosilane obtained on the basis of methyldiphenylamine. The first step of the reaction carried out in a solution of chloroform. As collaterals, but the first step of the reaction carried out in a solution of toluene. In the second stage of the process the reaction is carried out at 80oC and as Salvaterra additives used tetrahydrofuran.Example 6. Analogously to example 1, but as Salvaterra additives on the second stage of the process using dioxane.Example 7. Analogously to example 1, but as Salvaterra additives on the second stage of the process using dimethyl ether of ethylene glycol.Example 8. Analogously to example 1, but as Salvaterra additives on the second stage of the process using dimethyl ether of diethylene glycol.Examples of using the obtained PLCS as the initiators of anionic polymerization.Example 9. Polymerization of hexamethylcyclotrisiloxane (HMCTS) using poliitikaga compound obtained in example 1, as an initiator. To a solution of 2.6 g (1,1 10-2m) HMCTS in abs. the hexane with a concentration of 30 wt%. add to 0.62 ml PLCS with a concentration of 0.32 m/l lithium and stirred under inert atmosphere for 1 hour, then injected 2 ml of THF and continue stirring for 15 hours. Then injected into the reaction solution, the excess (0.1 ml) of trimethylchlorosilane to terminate the reaction. P is methanol. The polymer oharakterizovat using GPC: modal distribution, Mn= 20640, d = 1.26 in.Example 10. Polymerization of styrene using PLCS obtained in example 1, as an initiator. In the solution to 6.58 g (6,3 10-2m) of styrene in 64 ml of toluene is injected 1.6 ml of a solution PLX (5,12 10-4m Li) and stirred for 15 hours. The process is stopped by the addition of 0,1 ml of ethanol. The solution is diluted to 5% wt. conc. and periostat polymer 3-fold excess of methanol. The polymer oharakterizovat using GPC: modal distribution, Mn= 62470, d = 1,45. 1. Way to generate new polylithium derivatives carbosilane compounds dendritic structure, which consists in the fact that carbosilane connection with unsaturated functional groups: (A) carbosilane dendrimer, at least the second generation, (B) hyperbranched carbosilane containing at least 10 basic units of General formula
< / BR>where X is an unsaturated functional group;
n is the number of carbon atoms in the group X,
first is subjected to interaction with methylmetacrylate when the molar ratio of unsaturated groups carbosilane connection to methylbicyclo from 2 to 1.1 in prisutstvuet alkyllithium in the environment of an organic solvent at 20 80oC.2. The method according to p. 1, characterized in that as carbosilane connections use the connection with unsaturated allyl or vinyl functional groups.3. The method according to p. 1 or 2, characterized in that as alkylate use utility.4. The method according to p. 1, namely, that upon receipt polylithium derivatives carbosilane dendrimers as a source of dendrimers using dendrimers with allyl or vinyl functional groups.5. The method according to p. 1, namely, that upon receipt polylithium derivatives of hyperbranched carbosilanes, as the source of carbosilane use carbosilane General formula of elementary link
< / BR>where n = 2 or 3.6. The method according to one of paragraphs.1 to 5, namely, that the interaction polycarbosilanes connection with methylmetacrylate carried out in the presence of an organic solvent selected from the range: hexane, toluene, tetrahydrofuran, chloroform or a mixture of at least two of these solvents.7. The method according to one of paragraphs.1 - 6, implying that the metallation by alkyllithium carried out in the presence of the Sabbath., dimethyl ether of ethylene glycol, dimethyl ether of diethylene glycol.
< / BR>(patent N 4220600, CL
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention describes a method for preparing polymers. Method involves anionic polymerization reaction of vinylaromatic monomers and coupled dienes or by their copolymerization reaction in medium of hydrocarbon solvent in the presence of lithium-organic initiating agent followed by functioning ends of polymeric chains. Method involves using monofunction amine-containing lithium-organic initiating agent as a lithium-organic initiating agent wherein active lithium is stabilized with vinyl or phenyl radical of the general formula: wherein R1 and R2 are similar or different alkyl or allyl radicals; R3 means vinyl or phenyl radical. The functioning ends of polymeric chains is carried out by treatment of "living" macromolecules with a coupling agent or by the functioning break, and (co)polymerization reaction is carried out in the presence of alkaline metal alkoxides or phenolates. Invention provides preparing polymer showing reduced hysteresis losses and high mechanical strength, and improved ecological indices.
EFFECT: improved preparing method.
2 cl, 5 tbl, 11 ex
FIELD: polymerization of conjugated dienes and copolymerization with vinyl aromatic copolymers by interaction in hydrocarbon solvent medium.
SUBSTANCE: proposed method is used for copolymerization with vinyl aromatic solvent of lithium alkyl and organic amine; used as organic amine is compound of the following formula:
, where R1 and R2 are similar or different; C1-C4 are alkyl or allylic radicals; R3 is vinyl or phenyl radical. Process is performed at temperature of 20-35°C at equimolar ratio of lithium alkyl: organic amine and concentration of lithium alkyl in solution from 0.1 to 1.0 mole/l; then, diene or vinyl aromatic monomer or their mixture is fed to reaction zone continuously or in batches to mole ratio of conjugated monomer: starting lithium alkyl no less than 3 at concentration maintained at 0.05 to 0.20 mole/l. Invention is also useful to nitrogen-containing initiating agent of the following formula:
EFFECT: enhanced ecological safety with no change in polymerization of structure and composition of (co)polymers of conjugated dienes.
3 cl, 1 tbl, 8 ex
FIELD: rubber industry.
SUBSTANCE: invention relates to process of manufacturing synthetic rubber, in particular solution butadiene-styrene rubber suitable in manufacture of tires with high performance characteristics, resistance to high wheel rolling and providing long lifetime, good maneuverability, adhesion to wet pavement, and low consumption of fuel. Butadiene-styrene rubber is obtained via copolymerization of butadiene with styrene in hydrocarbon solvent and in presence of organolithium catalyst and modifying additive at catalyst-to-additive molar ratio 1:(0.2-1.0). Process comprises mixing monomers with solvent, deactivation of catalyst to stabilize polymer, degassing, and drying of rubber. As modifying additive, alkali metal alcoholates originated from hydroxyalkylated secondary amines.
EFFECT: enabled manufacture of butadiene-styrene rubber with middle and predominant content of 1,2-units in butadiene portion of copolymer.
2 tbl, 22 ex
SUBSTANCE: invention concerns process of obtaining polymerisate by anion polymerisation involving conjugated dienes and vinyl aromatic compounds. It describes obtaining of statistic polymerisates by anion polymerisation involving conjugated dienes and vinyl aromatic compounds, in inert medium, in the presence of at least one lithium-organic compound; at least one dialkyl ester represented by the formula: R1-O-CH2-CH(R3)-O-R2 (where R1 and R2 independently denote alkyl residues from methyl, ethyl, n- and isopropyl group, as well n-, iso-, di- and tributyl group, with different number of carbon atoms, while total amount of carbon atoms in both alkyl residues R1 and R2 comprises 5 to 7, and R3 stands for hydrogen, methyl or ethyl group); and at least one organic alkali compound at the ratio of more that 0.5 mol for one mol of lithium in organic lithium compound. As an organic alkali compound alkali metal alkoholate of formula M-OR is taken, where R is an alkyl group with 1-10 carbon atoms, and M is sodium.
EFFECT: production of vinyl order rubber with high styrol content with sufficient monomer randomisation.
13 cl, 1 tbl, 10 ex
SUBSTANCE: invention claims method of obtaining polybutadiene or butadiene copolymers with styrene by polymerisation of respective monomers in hydrocarbon solvent medium in the presence of initiating system, where initiating system is a complex of lithium organic compound and modifying additive obtained by reaction of alkali metal lapramolate and tetrahydrofurfurylic alcohol, metal magnesium and sodium (potassium) at molar ratio of 1 : 2-4 : 1-2 : 0-2 respectively. Polybutadiene and butadiene copolymers with styrene with 1,2-link content in diene part adjustable from 9 to 75 wt %, reduced rate of macromolecules with mass over 106 g/mol (up to 5 wt %), is obtained at temperatures over 60°C.
EFFECT: improved method of obtaining polybutadiene or butadiene copolymers with styrene.
5 cl, 5 tbl, 14 ex
SUBSTANCE: invention relates to methods of producing a polymer, having at least one functional terminal group, and a liquid polymer dispersed therein. The invention also relates to a composition and a coating containing the obtained polymer product. The method involves: (a) producing a 'living' polymer, where production of said 'living' polymer is initiated based on an anionic mechanism, and said polymer contains a cation; (b) adding a functional initiator precursor of the formula FI-H, where H is hydrogen and FI is a functional group, said H terminates said 'living' polymer resulting in a liquid polymer, and FI and said cation form a functional initiator; (c) adding a monomer, where said functional initiator initiates anionic polymerisation of said monomer; and (d) terminating the polymerisation reaction initiated at step (c). Steps (a) through (c) may be conducted in a single reactor, allowing a liquid polymer to be dispersed in a functionalised polymer in a single polymerisation step.
EFFECT: liquid polymer does not have to be handled separately and processing efficiency is improved.
15 cl, 2 tbl, 7 ex
SUBSTANCE: invention relates to functionalised multi-branched polymers which include a reaction product of a cross-linking agent and a polymer synthesised by anionic polymerisation and subsequently hydrolysed, a synthesis process thereof and different versions of use thereof.
EFFECT: structure of polymers disclosed herein provides the polymers with improved processing properties and makes said polymers suitable for use in hot-melt adhesives.
16 cl, 8 tbl
SUBSTANCE: invention relates to method of obtaining functionalised polymer. Method includes anion-initiated polymerisation of ethylene-unsaturated monomers. Monomers include one or larger number of polyene types. polymer with active chain terminal group is obtained. Polymer interacts with compound of general formula with obtaining functionalised polymer. Also described are: functionalised polymer, composition, vulcanisate and alkali metal compound.
EFFECT: obtaining polymer, demonstrating excellent interaction with ordinary and non-traditional fillers .
15 cl, 4 tbl, 32 ex
SUBSTANCE: invention relates to functionalised polymers and method for their manufacture. A method for preparing a functionalised polymer comprises the steps of: polymerising diene monomer, and optionally co-diene monomer, using an anionic initiator to form a reactive polymer and the reactive reaction of the polymer with a compound containing a nitrile protected amino group. The protected amino group is selected from the group, consisting of acyclic fragments, heterocyclic fragments and non-aromatic cyclic fragments.
EFFECT: invention can reduce hysteresis of rubber vulcanisates.
12 cl, 1 dwg, 3 tbl, 25 ex
SUBSTANCE: invention relates to a method of producing diene (co)polymers. A method of producing diene polymers or vinylarene-diene statistical copolymers includes anionic (co)polymerisation in hydrocarbon solvents, at least one conjugated diene monomer, optionally in the presence of a vinyl aryl monomer, and using a compound belonging to a group of alkyl lithium compounds as an initiator, the method being characterised by that the entire alkyl lithium initiator is modified onsite through a reaction with a compound of general formula (I): Rm-(X-H)n (I), where R is (C2-C20)-(cyclo)alkyl or (C6-C20)-aromatic radical, X is a heteroatom belonging to the VIA group of the periodic table, n is an integer equal to or greater than 1, m is an integer ≥1, which depends on the valence of the heteroatom X.
EFFECT: high stability of the active end of the chain, enabling regulation of the macrostructure of (co)polymers with respect to reduction of polydispersity or reduction of branching.
12 cl, 5 tbl, 14 ex
FIELD: chemical technology.
SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR1 2 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).
EFFECT: improved preparing method.
1 tbl, 9 ex
FIELD: organosilicon polymers.
SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.
EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.
2 dwg, 1 tbl, 5 ex
FIELD: organosilicon polymers.
SUBSTANCE: novel polycyclic poly- and copolyorganocyclocarbosiloxanes with variable cycle size including structural motif of general formula: , wherein (1) x=3 or 4 and y=1, (2) x=2 and y=2, (3) x=3, and suitable as preceramic templates for manufacturing oxygen-free silicon carbide ceramics are prepared by Würtz reaction in toluene via interaction of chloro-derivatives of organocarbosilanes with metallic sodium in the form of suspension.
EFFECT: enlarged assortment of preceramic templates.
2 cl, 1 tbl, 3 ex