A method of obtaining a film-forming copolymer
(57) Abstract:The inventive obtaining a copolymer by copolymerization VAT residue of the distillation of styrene with 4 - 7 wt.% maleic anhydride and 2 to 15 wt. % fraction of pyrolysis C9 hydrocarbons with a boiling point of 130 - 220oC and certain qualitative composition. 3 table. The invention relates to methods for film-forming polymers for paints and varnishes, in particular the production of film-forming copolymer of the bottoms of the distillation of styrene (KORS) and carbonyl compounds.A known method of obtaining a film-forming copolymers by thermal copolymerization KORS with carbonyl compounds in which the carbonyl compounds using maleic anhydride (MA) /1/.The disadvantage of this method is the low impact strength of the film obtained copolymer.The closest to the essence and achieve results is a method for film-forming copolymers by thermal copolymerization KORS from 5 to 30% VAT residue of the distillation products hydroformylating olefins having a boiling point of 130 270oC (prototype) /2/. The disadvantage of such a joint venture which allows to use it for example, for the protection of offshore platforms.The purpose of the invention increase solsticetm coatings based on copolymers Kors.This objective is achieved in that according to the receiving film-forming copolymer by thermal copolymerization with AF CORSE, the reaction mixture was further added negidrirovannogo C9 fraction pyrolysis of hydrocarbons with a boiling point of 130 220oC, density 0,926 0,937 g/cm3, diene index of 11.5 13.5 g of iodine per 100 g of the sample in the amount of 2 to 15 wt. from mass KORS. The number of MA in the reaction mixture is 4 to 7 wt. from mass KORS. The process is carried out in an autoclave at 160 - 180oC for 6 hThe C9 fraction of the pyrolysis of hydrocarbons is a transparent light yellow liquid having the following composition, wt.nonaromatic hydrocarbons 5,8 6,2
monoalkylbenzenes 12,0 13,0
phenylacetylene 0,19 0,23
styrene 8,0 8,4
atitool 7,6 8,0
Olivenza 1,0 1,1
mesitylene 1,8 2,0
pseudotumor 3,6 4,0
-methylsterol+TRANS-a - methylsterol 3,1 3,3
the Dicyclopentadiene 13,5 14,1
vinylcolor 11,4 12,0
1,2,3-trimethylbenzene 1,6 1,7
Adimari cyclo - and methylcyclohexene 26,4 23,5
inden 0,9 1,0
naftalinovogo component negidrirovannah C9 fraction pyrolysis of hydrocarbons in the temperature range of boiling point 130 220oC number of 2 to 15 wt. from mass KORS, and the amount of MA in the reaction mixture is 4 to 7 wt. from mass KORS.The method is as follows.In the load capacity specified number of COURSE of different composition (table. 1), MA and C9 fraction (table.2) and heated to 160 180oC under stirring for 6 hours Then unreacted products are distilled off under vacuum at 200oC. the Remaining solid resin dissolved in xylene to obtain a 40% aqueous solution, which is used for test coverage.Carry out the determination of the softening temperature of the coating, the drying time of the applied layer.Testing cholestanol plate with a deposited coating is dipped in a glass with 3% sodium chloride solution for 24, 72, 120 and 240 hours Then determine the fraction of the area of the ruined floor.Example 1 (the prototype).In the autoclave load of 100 g Corsa, containing, by weight. 21.3 styrene, 53.1 polymer, 8,3 a-methylstyrene, 0.1 divinylbenzene, 9,3 TRANS-stilbene and phenanthrene, 2,9 high-boiling components of the inhibitor. There also placed 10 g uldehitusmaterjale faction. The synthesis is carried out at 160 190oC for 6 hours after the reaction is distilled off narora the VA which are shown in table 3. The resin dissolved in xylene to obtain a solution with a concentration of up to 40 wt. The properties of coatings obtained by applying this solution are given in table.3.Example 2. To 100 g Corsa (part 2, PL.1) add 5 g MA and 1 g C9 fraction (composition 2, PL. 2). The process is conducted as in example 1. The results are given in table.3.Examples 3 to 7. The process is conducted as in example 1, while varying the number of fractions C9 of part 2, PL.2.Examples 8 to 12. Experiments are performed as in example 1. In the reaction mixture using different compositions Corsa and C9 fraction (see table. 1, 2 and 3).Examples 13 to 15.Experiments are performed to select the optimum ratio KORS and MA in the reaction mixture.In table. 3 shows the test results of a copolymer on the basis of the COURSE and MA at different compositions KORS and C9 fraction and different ratios KORS and MA in the reaction mixture.The copolymers obtained in the MA content in the reaction mixture in amounts of 4 to 7 wt. from mass KORS, have the best properties. With increasing MA content of more than 7% coatings have good adhesion, but buy fragility. With decreasing content of MA to 3 wt. worse adhesion, which leads to reduced the tour softening of the copolymer increases the drying time of the coating. When reducing fractions C9 below 2 wt. not achieved a sufficient level of solsticetm polymer. The optimum content of C9 fraction in the reaction mixture is 2 to 15 wt. from mass KORS.The composition KORS when changing in a wide range of practically no effect on the properties of film-forming copolymer. A method of obtaining a film-forming copolymer by copolymerization VAT residue of the distillation of styrene with maleic anhydride, characterized in that the use of maleic anhydride in the amount of 4-7% by weight of the cubic residue of the distillation of styrene and optionally enter a fraction C9-pyrolysis of hydrocarbons with a boiling point of 130 220oWith having the following composition, wt.Nonaromatic hydrocarbons 5,8 6,2
Monoalkylbenzenes 12,0 13,0
Phenylacetylene 0,19 0,23
Styrene 8,0 8,4
Atitool 7,6 8,0
Olivenza 1,0 1,1
Mesitylene 1,8 2,0
Pseudotumor 3,6 4,0
-Methylsterol and TRANS - a-methylsterol 3,1 3,3
The Dicyclopentadiene 13,5 14,1
Vinylcolor 11,4 12,0
1,2,3-Trimethylbenzene 1,6 1,7
Adimari cyclo - and methylcyclopentadiene 26,4 23,5
Inden 0,9 1,0
in the amount of 2 to 15% by weight of the cubic residue rectificate the
FIELD: polymerization processes and polymerization catalysts.
SUBSTANCE: catalytic system including chromium compound deposited on silicon oxide/titanium oxide carrier, which is preliminarily reduced by carbon monoxide, and co-catalyst selected from group consisting of (i) alkyl lithium, (ii) dialkylaluminum alkoxides combined with at least one alkyl metal selected from group consisted of alkylzinc, alkylaluminum, alkylboron, and mixtures thereof, and (iii) their mixtures, can be used for polymerization of olefins to form low-density polymer with reduced melt index and/or greatly loaded melt index. Such catalyst may be used jointly with olefin polymerization Ziegler-Natta catalytic system. Polymerization processes involving above-defined catalytic systems are also disclosed. Polymers obtained via processes according to invention also show elevated volume viscosity values and find use as components in preparation of bimodal high-molecular weight resins for production of films and/or in pneumatic molding processes.
EFFECT: expanded olefin polymerization possibilities.
31 cl, 3 tbl, 3 ex
FIELD: polymerization catalysts.
SUBSTANCE: invention relates to polymerization catalyzing compounds, catalytic systems including thereof, and to their use in polymerization of ethylene and at least one more comonomer. Provided is olefin polymerization process resulting in ethylene-based polymer product, which process comprises bringing ethylene and at least one comonomer into contact with catalytic system, wherein this catalytic system contains (i) metallocene catalytic compound ensuring inclusion of a small amount of comonomer including at least one ligand based on cyclopentadienyl with condensed cycles and (ii) metallocene catalytic compound ensuring inclusion of comonomer in larger amount than compound ensuring inclusion of a small amount of comonomer, and wherein polymer product obtained is characterized by bimodal composition distribution.
EFFECT: enabled production of polymers easy to process into products, preferably into polyethylene-based films with improved properties.
25 cl, 5 dwg, 3 tbl, 5 ex
FIELD: polymer production.
SUBSTANCE: invention relates to superhigh-molecular weight copolymer constituted by an α-olefin monomer with carbon chain length 4 to 9 carbon atoms and another comonomer, which is α-olefin with carbon chain length 2 to 20 carbon atoms or containing vinylaromatic monomer. Copolymer has molecular mass above 1000000 and no more than 25 mol % monomers with carbon chain length 12 carbon atoms or more. Copolymer of invention is completely dissoluble in heavy aromatic hydrocarbons at low temperatures such as 0°C. Another advantage of the copolymer consists in that it can be transported either in stable suspension or can be preliminarily dissolved in small amount of heavy hydrocarbon. Suspension of polymer lowering resistance of a medium is stable so allowing longer storage time and thereby enabling agreement between consumer's demand and delivery time. Secondary agglomeration of polymers leading to lower resistance of medium is considerably reduced ensuring easier processing in the production process.
EFFECT: facilitated flowability control.
14 cl, 1 dwg, 2 tbl, 4 ex
SUBSTANCE: method includes contacting of (i) C4-C7 isomonoolefin and p-alkylstyrole, or (ii) C4-C6 isoolefin and multiolefin, one or more Lewis acid, one or more initiator, and solvent, including one or more hydrofluorocarbons (HFC) in reactor. As hydrofluorocarbon, compounds, represented with general formula CxHyFz, are used, where x is an integer from 1 to 40, and y and z are integers. Solvent additionally includes non-reactive olefin, one or more other hydrocarbons, and/or inert gas.
EFFECT: reduction of particle agglomeration and reactor blocking, without degradation of process parameters, conditions or components, productivity of reactor capacity and ability to produce polymers with great molecular weight.
23 cl, 25 tbl, 148 ex, 3 dwg
SUBSTANCE: invention refers to polymerisation techniques comprising diluents, including fluorohydrocarbons, and application thereof for production of new polymers essentially long-chain branching free. Produced is copolymer of isoolefine preferably of isobutylene, and that of multiolefine preferably of coupled diene, more preferably of isoprene essentially long-chain branching free. Copolymer has medium viscosity g1 exceeding or equal 0.978 as it is established with triple exclusion chromatography EXC.
EFFECT: improvement of rheological properties.
31 cl, 6 dwg, 25 tbl, 151 ex
SUBSTANCE: invention relates to isoolefin and multiolefin copolymers, copolymer possessing copolymer sequence distribution which is determined by parameter m of copolymer sequence distribution. Method of copolymer obtaining includes contacting of isoolefin, preferably isobutylene, and multiolefin, representing conjugated diene, isoprene, one or more Lewis acids, one or more initiators and thinner that includes one or several fluorohydrocarbons (FHC). As fluorohydrocarbons, one or several fluorohydrocarbons represented by general formula CxHyFz are selected.
EFFECT: reduction of particle agglomeration and reactor contamination without damage to technological parameters, conditions or components and/or without damage to productivity/throughput and/or ability to form highly-molecular polymers.
27 cl, 152 ex, 26 tbl, 4 dwg
SUBSTANCE: present invention pertains to polymerisation methods for obtaining polymers using bayonet cooled reactor systems and solvents, containing hydroflurocarbons. The method relates to obtaining (co)polymers, involving bringing isoolefine into contact with multiolefine or isoolefine with alkylstyrol using a catalyst system, containing one or more Lewis acids or one or more initiators, and a solvent, containing one or more hydroflurocarbons in a reactor, comprising a pipe or several pipes used for coolant circulation. The reactor also has connection pipes for transferring the catalyst system to the bottom part, and connection pipes for removing the polymer from the upper part, as well as a mixer axle with mixing blades, located high up the mixer axle. The given method of polymerisation allows for reducing agglomeration of particles and clogging up of the reactor, without deterioration of the parameters of the process, conditions or components, and/or without reducing output/capacity and/or capacity to produce polymers with high molecular weight.
EFFECT: reduced agglomeration of particles and clogging up of the reactor, without deterioration of the parameters of the process, conditions or components, and/or without reducing output/capacity and/or capacity to produce polymers with high molecular weight.
34 cl, 25 tbl, 148 ex, 8 dwg
SUBSTANCE: present invention pertains to polymerisation methods using hydroflurocarbons for obtaining (co)polymers. The method involves contacting (i) C4-C7 isomonoolefine and p-alkylstyrol, or (ii) C4-C6 isoolefine and multiolefine, one or more Lewis acids with a solvent, containing one or more hydroflurocarbons in a reactor, where one more Lewis acids is not a compound, with formula MX3, where M is a group 13 metal, and X is a halogen. One or more hydrofluorocarbons can be represented by general formula CxHyFz, where x is an integer from 1 to 40, and y and z are integers, one or more; x preferably lies between 1 and 10, x preferably lies between 1 and 6, and more specifically, x lies between 1 and 3.
EFFECT: reduction of agglomeration of particles and clogging up of the reactor with retention of efficiency and capacity to produce (co)polymers with high molecular weight.
23 cl, 3 dwg, 27 tbl, 148 ex
SUBSTANCE: invention relates to a poly-alpha-olefin obtained from a decene and propene and having a branching level greater than 19% and to a method of producing such poly-alpha-olefins. The decene is 1-decene. Described is a method of producing a poly-alpha-olefin from at least two monomers, where two monomers include decene and propene. Polymerisation takes place in the presence of a metallocene catalyst Ph2C(Cp-9-Flu)ZrCl2 and an aluminoxane cocatalyst. Described also is a method which involves steps, among others, of providing correlation between the total amount of propene used to form poly-alpha-olefin and at least one of the characteristics of the poly-alpha-olefin: the branching level or viscosity of the poly-alpha-olefin.
EFFECT: producing poly-alpha-olefins containing decene and propene, with predictable levels of branching and viscosity.
15 cl, 3 tbl, 9 ex
SUBSTANCE: invention relates to a method of producing norbornene oligomers (bicyclo[2.2.1]hept-2-ene) with a terminal double bond of general formula H(C7H10)n(C(R)=CH(R')), where n=6, 11, 10, 26; R=R'=H; R=H and R'=CH3 or R=CH3 and R'=H; C7H10 - norbornene repeating fragment, by reacting a nickel complex, norbornene and boron trifluoride etherate in the atmosphere of gaseous α-alkene. The method is characterised by that the complex used is bis(acetylacetonato)nickel combined with triphenylphosphine, triethylaluminium, followed by addition of methanol as a proton-donor compound, with the molar ratio Ni(acac)2:norbornene:PPh3:AlEt3:MeOH:BF3OEt2=1:2000:2:3:10:100, and the process is carried out at room temperature in toluene as an organic solvent.
EFFECT: use of the disclosed method increases efficiency of the process.
1 cl, 1 tbl, 5 ex, 1 dwg
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: chemical industry, chemical technology, polymers.
SUBSTANCE: invention relates to a method for preparing aqueous polymer dispersions of the multipurpose designation. Method for preparing an aqueous dispersion of styrene-acryl copolymer is carried out by preliminary emulsifying a mixture of acrylic monomers with styrene in the presence of emulsifying agent and the following aqueous-emulsion co-polymerization of the reaction mixture in the presence of initiating agent. Monomer mixture comprises additionally acrylamide, and method involves using ammonium persulfate and hydrogen peroxide as an initiating agent. Method involves the successive fractionally dosing feeding ammonium persulfate for two stages followed by addition of a mixture of polymethylsiloxane of molecular mass 55-1000 Da and iron sulfate in their mass ratio = (25-35):1 to the reaction mixture at stirring, cooling the reaction mass and its neutralization to pH = 5-6. Invention provides preparing the stable aqueous polymeric dispersion with diminished size of particles. Invention provides enhancing strength and water resistance of film prepared on its base.
EFFECT: improved preparing method.
1 tbl, 3 ex
FIELD: polymer production.
SUBSTANCE: invention relates to processes of producing lacquer acrylic filming agents used in manufacture of masonry, road-line, and other paints. Process of invention is realized by two-step polymerization of butyl acrylate, methyl methacrylate, styrene, and methacrylic acid at ratio (40-5):(40-45):(10-14):(1-5) in toluene-ethyl acetate mixture, while portionwise feeding monomers/initiator mixture and repeatedly ageing reaction mixture. When conversion of monomers attains 82-85%, solution of butyl acrylate/styrene/methacrylic acid copolymer is additionally charged at ratio 42:57:1 dissolved in toluene/butanol (or ethanol) mixture or toluene/acetone mixture, or in toluene/ethyl acetate/ethanol/butanol mixture. Butyl acrylate/styrene/methacrylic acid copolymer is added in amount 1.77-4.0% based on concentration of principal substance. Toluene and ethyl acetate are used in proportion (0.1-1.0):1. In the first stage, 20-30% of butyl acrylate/methyl methacrylate/styrene/methacrylic acid mixture is added and, in the second stage, 70-90%. Thus obtained filming agent is characterized by high content of nonvolatile substances at rather low viscosity, high adhesion, good strength and film drying rate, low moisture absorption, high water and wear resistance.
EFFECT: improved performance characteristics of agent.
9 cl, 4 tbl, 7 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for preparing a binding agent for a dry film photoresist of aqueous-alkaline development used in preparing a picture in making printed boards in radio- and electronic industry and as a component of paint and varnish covers and glues. Invention describes a single-step method for preparing a binding agent for a dry film photoresist of aqueous-alkaline development. At the first step method involves the copolymerization reaction of styrene with maleic anhydride in acetone medium in the presence of azo-bis-isobutyric acid dinitrile and hydroquinone at temperature 54-72°C for 2.5-3.0 h. At the second step method involves addition of 28.0-32.0 mas. p. p. of n-butanol to the reaction mixture and distilling off of 15.0-20.0 mas. p. p. of acetone followed by carrying out esterification of the copolymerization product at temperature 64-74° for 90-120 h. Prepared dry film photoresists of aqueous-alkaline development possess high stability (9-10 h) and enhanced galvanic-chemical resistance.
EFFECT: improved preparing method, improved and valuable properties of binding agent.
1 tbl, 6 ex
FIELD: polymer production.
SUBSTANCE: high molecular-weight foamable polystyrene is produced via two-step styrene polymerization, wherein, (i) in the first step, styrene is subjected to prepolymerization in presence of primary process initiator, fire-retardant - hexabromocyclododecane and its synergist dicumyl peroxide, chain growth regulator, and secondary initiator - O,O-tert-amyl-O-(2-hexyl) monoproxycarbonate, and (ii) in the second step, suspension polymerization proceeds in aqueous medium in presence of stabilizer - polyvinyl alcohol, chain growth regulator, third initiator - tert-butyl perbenzoate, and foaming agent. Invention is characterized by that, as primary process initiator, 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane is utilized and process is conducted at weight ratio of all three initiators 0.956:1:(1.14-2.5), respectively, until polymer with relative viscosity 2.1-2.3 is obtained.
EFFECT: enhanced process efficiency.