Method of producing prepolymer with terminal amino groups
SUBSTANCE: invention relates to methods of producing a prepolymer with functional groups via chemical modification of oligodiene diols, which are used in chemical industry as the basis for making tyres, industrial rubber articles and paint materials. Described is a method of producing a prepolymer with terminal amino groups, involving treating oligodiene diol with a modifier, followed by separation of the reaction product, via an oligomerisation reaction of ε-caprolactam with oligodiene diol in the presence of catalytic amounts of benzoic acid with reagents in molar ratio 4:1:0.005, respectively, in a vacuum-sealed ampoule at 170°C and reaction time of 180 minutes.
EFFECT: shorter reaction time and lower temperature and, as a result, fewer thermal-oxidative and destructive processes, possibility of using industrially available starting reagents.
The invention relates to methods of producing the prepolymer with functional groups by chemical modification of oligodontia that are used in the chemical industry as the basis for the tire, rubber and paint materials.
A known method of producing prepolymers based oligodiens interaction liquid rubbers with α,β-unsaturated acids, anhydrides or their polyesters, often with maleic anhydride. The interaction of maleic anhydride with rubber in the presence of radical initiators occurs with the formation of linear (1) and crosslinked (2) structures (Chemical reactions of polymers. TRANS. from English. Ed. Zharulovna. M., Mir, 1967. Vol. 1, 503 S.):
The disadvantages of this method are receiving additional use of radical initiators, a large variety of side intermolecular reactions and processes involving disclosure of anhydrite cycle, the formation of cross-linked structures, the use of elevated temperatures of 180-220°C and, as a consequence, the appearance of products of partial resinification. In addition, the system optionally enter inhibitors gel-effect - diphenylamine, alkylhydroquinones, which complicates the process of separation of the modified reaction product from the original vexes the century
A known method of epoxidation of liquid rubbers reaction Prilezhaeva interaction of organic nagkalat with the double bonds of the olefin (Kuzminsky A.S., Kavun S.M., Kirpichev VP Physico-chemical principles of receiving, processing and use of elastomers. M, Chemistry, 1976. 368 C.):
The disadvantages of the method of obtaining are unstable and explosive peroxide compounds, corrosion activity nakilat, the use of solvent (benzene, chloroform and other), additional application of acetate and sodium bicarbonate to reduce the proportion of adverse reactions, the difficulty of separating rubber from the organic acids and disposal of sewage.
Another method to obtain prepolymers based on chemical modification of oligomeric unsaturated rubbers by partial or complete hydrogenation (Grishchenko FR, Gritsenko VK, Spirin UL Synthesis and physical chemistry of polymers. Kiev, Naukova Dumka, 1970, issue 6, p.10-16). The use of high temperatures (up to 260°C) and pressures (up to 20 MPa), solvents, and expensive complex catalysts lead to substantial difficulties in the technology of conducting hydrogenation of liquid rubbers with terminal hydroxyl groups. In this modification process is complicated by the use of a significant amount of the catalyst and the complexity of its CTD is ing from viscous polymer substrates.
A method of obtaining chain oligomers containing terminal amino groups, the oligomerization of conjugated dienes and/or vinyl monomers in the environment of the polar organic solvent followed by treatment with lithium aluminum hydride (avts 269484, IPC C08f, publ. 1970).
The disadvantages of the method of obtaining chain oligomers containing terminal amino groups, are numerous side processes at the stage of obtaining oligodontia, the need to use absolutized the original reactants, initiator. In addition, the disadvantage of this method is its multi-stage, based on subsequent recovery product with lithium aluminum hydride.
A method of obtaining orlandersmith polyethers with terminal primary amine groups as hardeners of epoxy resins (patent RF 2084467, IPC C08G 63/64, C08L 75/08, C08L 63/00. Publ. 2002). The method is characterized by numerous secondary processes and the difficulty of selection of product.
The closest is a method of producing oligomers with the primary terminal functional amine groups by reacting the oligodiens with terminal carboxyl groups with primary diamines at 150-250°C for 2-7 h (avts 323412, IPC C08f 27/08, publ. 1970):
The disadvantages of this method the floor is placed oligomers with the primary terminal functional amino groups are high temperature and long reaction time, leading to a decrease in the molecular weight of the oligomer due to thermal-oxidative, destructive processes. When not precluded by-side processes-linkage between different functional fragments of macromolecules.
Task: to develop a technologically advanced method of obtaining a prepolymer with terminal amino groups with multifunctional properties.
The technical result of the proposed method is the possibility of obtaining oligodontia with terminal amino groups technological way, characterized by the reduction of the reaction time and temperature and, consequently, reducing the share of thermal-oxidative and destructive processes and the possibility of using commercial available reagents.
The technical result is achieved by processing oligodontia modifier, followed by the separation of the reaction product, and the production is carried out by reaction of oligomerization of ε-caprolactam with oligodontia in the presence of catalytic amounts of benzoic acid at a mass ratio of reagents 4:1:0,005, respectively, in a sealed ampoule at 170°C and a reaction time of 180 minutes
The advantages of the method of producing oligodontia with terminal amino groups are the possible catalytic effect on the reaction of poly is retinoblastoma due to the presence of major primary-NH 2and secondary-NH amine groups and increase at the expense of the adhesion activity of polymeric materials to concrete and steel (Saunders JH, Frisch K. Chemistry of polyurethanes. - M.: Chemistry, 1968. - 471 C.). It is the presence of terminal primary amino groups facilitates the efficient catalysis of poliuretanovuyu due to their larger basicity compared with the secondary amino group directly linked to the carbonyl (amide group), and their relatively easy steric accessibility.
The presence pentamethylene chain -(CH2)5in the composition of the prepolymer contributes to their surface-active (lubricating) action. In this case, the prepolymer is oligodactyly ether oligomer ε-aminocaproic acid - has good compatibility with oligomeric dialami (liquid hydroxyl-containing rubbers, which are used as reagents for producing polyurethanes, as indicated, and the good solubility of the modified oligodontia in oligomeric diolah.
The developed method allows to obtain a prepolymer, without violating the structural unsaturated motive oligomannose fragment, which has a positive effect on good compatibility with polymeric and oligomeric substrates and high plasticizing nature oligodendroglioma ether oligomer ε-aminocaproic acid. The immutability of the system is entrusted structural motif in macromolecules oligodendroglioma ether oligomer ε-aminocaproic acid can be used as intermediates for the introduction of additional functional groups, provide the desired set of properties and performance characteristics of polymeric materials.
In addition, to obtain a prepolymer does not require the use of solvents, initiators, inhibitors, and the reaction of obtaining prepolymer based on the use of industrially available starting compounds and is characterized by a high yield of the prepolymer with a relatively easy separation of the reaction product from the starting materials.
Temperature obtaining prepolymer 170°C is optimal, since its increase up to 180-200°C promotes the degradation of oligomeric substances and, consequently, increase the proportion of resinous compounds, which complicates the separation and purification of the reaction product. In turn lowering the temperature of 100-150°C reduces the output of the prepolymer and makes its separation from the source oligodontia.
The mass ratio of ε-caprolactam, oligodontia and benzoic acid amounting to 4:1:0,005 is optimal, since by reducing the content of the number of ε-caprolactam is difficult separation of the reaction product. The increase in the content of ε-caprolactam in the reaction mixture promotes his side reaction with benzoic acid. This pattern holds true in the case of benzoic acid.
The response time of an EDP-1 with ε-caprolactam in the presence of catalytic amounts of benzo is Noah acid, amounting to 180 min is optimal, because the reduction of the reaction time up to 60-120 minutes contributes to the reduction of the yield of the prepolymer and the degree of conversion of the initial reagents. Increasing the reaction time up to 4-4,5 hours leads to difficulty selection prepolymer due to a sharp increase resinous products of degradation oligodontia.
The claimed method is as follows.
The ampoule is placed oligodontia, ε-caprolactam and benzoic acid, heated to 170°C and incubated for 180 min, then separated, washed and dried prepolymer.
The degree of oligomerization caprolactamate links in oligodendroglioma ether oligomer ε-aminocaproic acid evaluated by determining the content of amino reverse titration of toluene solution of the product 0.1 N. alcoholic solution of hydrochloric acid.
The way to obtain a prepolymer with terminal amino groups by acid-catalyzed reaction oligodontia with ε-caprolactam is illustrated by the following example:
Example. In a glass vial with a volume of 8-10 cm3place 1 g of 3.33·10-4mol) oligodermie - butadiene-isoprene oligomer with terminal hydroxyl groups (the content of hydroxyl groups of 0.7-1.1% of wt.) with a ratio of elementary links of 80:20 marks SOPS-1 (molecular weight 3000-3500), 4 g (0.035 mol) of ε-kaprol is Chama and 0.005 g (4,1·10 -5mol) of benzoic acid. The vial sealed and thermostatic at 170°C for 180 minutes the Product is successively washed with distilled water, ethanol and diethyl ether and dried over anhydrous calcium chloride. The degree of transformation of an EDP-1 67,5%. The output of the prepolymer 90,64%. The degree of oligomerization caprolactam units in the prepolymer m=10-14. Found: N 5,30-5.75 Per Cent. The infrared spectrum, cm-1: 3334-3244 (vN-H), 2956-2884 (vC-H), 1678 (vC=O, ester), 1618 (amide I), 1582 (amide II), 1474 (amide III). An NMR spectrum1H (CDCl3), δ, M. D.: 6,740 (1H, C(O)NH), 5,810 (1H, -HC=C<), 4,156-5,034 m (2N, CH2-, oligodontia), 1,957 d, J=6,9 Hz (2H, -CH2-NH2), 0,308-3,310 m (10H, (CH2)5). An NMR spectrum13With (CDCl3), δ, M. D.: 181,008 (1C, - >With=0), 127,678-140,896 (2C >With=With<), 41,005 (1C,-CH2-NH2).
Thus, the developed technology is a method of obtaining prepolymer with terminal amino groups of the acid-catalytic reaction of ε-caprolactam with oligodontia in the presence of catalytic amounts of benzoic acid, characterized by the reduction of the reaction time and temperature and, consequently, reducing the share of thermal-oxidative and destructive processes and the possibility of using commercial available reagents.
The way to obtain a prepolymer with terminal amino groups total f is rmula:
including processing oligodontia modifier, followed by the separation of the reaction product, wherein the receiving is carried out by reaction of oligomerization of ε-caprolactam with oligodontia in the presence of catalytic amounts of benzoic acid at a mass ratio of reagents 4:1:0,005, respectively, in a sealed ampoule at 170°C and a reaction time of 180 minutes
SUBSTANCE: polymer is soluble in a polar organic solvent and is modified in said solvent by an amine-based compound and an oxidising agent. The polymer has a structure which gives signals in the region of 150-200 h/million, determined via 13C-NMR, where the orientation of molecules according to measurement results obtained via wide-angle diffraction of X-ray radiation is 65% or higher, and specific weight is equal to or greater than 1.35.
EFFECT: fibre has high fire-resistance and strength retention value.
2 cl, 5 dwg, 30 ex
SUBSTANCE: described is a multifunctional graft copolymer-dispersant containing at least two different monomers. Each monomer is directly grafted to the polymer backbone chain having grafted sections. One monomer contains at least one ethylenically unsaturated aliphatic or ethylenically unsaturated aromatic monomer. The monomer has 2-50 carbon atoms and contains one element selected from an oxygen atom, nitrogen atom or combinations thereof. The other monomer contains at least one acylating agent, having olefinic unsaturation in at least one point and at least one amine which reacts with said acylating agent. Described also is a method of producing the multifunctional graft copolymer-dispersant, lubrication oil and a method of improving soot processing.
EFFECT: obtaining a graft copolymer, having many characteristic properties, improved soot processing and regulation lubrication oil deposits, and regulation of increase in viscosity.
41 cl, 2 tbl, 5 ex
SUBSTANCE: method for preparation of low-basic anionites by suspension copolymerisation of acrylonitrile, methylmethacrylate in amount of З-5 wt.%, content of technical grade divinylbenzene being 9-15 wt.% and concentration thereof being 50-60%, in the presence of benzoperoxide in amount of 3.0 wt.% and blowing agent (alkylbenzine, aviation kerosene, decane) in amount of 40 vol.% as regards to monomer volume in suspension media, which consists of water, 25% of sodium chloride or ammonium chloride and 1.5-2.0% of potato starch, when heated at 50°С for 1 hour, at 61-65°С for 4 hours, at 70°С for 2 hours, at 80°С for 1 hour, followed by amination with diethylenetriamine at 130-145°С for 10 hours in the presence of 1.0-1.5% of element sulphur used as a catalyst.
EFFECT: provides for high osmotic stability and high resistance to organic poisoning.
1 cl, 9 ex
FIELD: medicine, polymers, pharmacy.
SUBSTANCE: invention relates to a copolymer or its pharmacologically acceptable salt that comprises the following components as elemental links forming their: (a) one or some structural elemental links describes by the formula (I) given in the invention description, and (b) one or some structural links describes by the formula (II) given in the invention description. Disposition of these structural elements represented by the formulae (I) and (II) is chosen from the following sequences: (i) sequence with alternation "head-to-head"; (ii) sequence with alternation "head-to-tail"; (iii) mixed sequence with alternation "head-to-head" and "head-to-tail"; (iv) random sequence and taking into account that the ratio between structural links of the formula (I) and structural links of the formula (II) in indicated copolymer is in the range from 10:1 to 1:10. Also, the invention relates to a copolymer or its pharmacologically acceptable salt synthesized by addition of one or some links of carboxylic acid anhydride described by the formula (III) given in the invention description that comprises as elemental links: (a) one or some structural elemental links described by the formula (I), and (b) structural link comprising carboxylic acid anhydride link described by the formula (III) for one or some reactions chosen from the group consisting of: (i) hydrolysis; (ii) ammonolysis; (iii) aminolysis, and (iv) alcoholysis. Also, invention relates to a pharmaceutical composition used for prophylaxis or treatment of osseous metabolism disorder and comprising an acceptable excipient or carrier, at least one of above indicated copolymers or their pharmaceutically acceptable salts and at least one protein representing osteoclastogenesis inhibition factor (OCIF) or its analogue, or variant. Also, invention relates to a modifying agent comprising above said copolymers, to a complex between of one of above said copolymers and protein or its analogue, or variant, to a pharmaceutical composition comprising this complex. Also, invention relates to a method for time prolongation when OCIF is retained in blood stream after intake by a patient a complex between protein and at least one of above said copolymers. Also, invention relates to a method for treatment or prophylaxis of disorders of osseous metabolism involving intake by a patient the effective amount of complex comprising complex including OCIF or its analogue or variant and bound with at least one of the claimed copolymers. Also, invention relates to use of the complex comprising OCIF bound with at least one of the claimed copolymers designated for preparing a drug designated for prophylaxis or treatment of disorder of osseous metabolism and showing sensitivity to the protein effect. Modifying the protein, namely OCIF, by the claimed copolymers results to formation of complex possessing uniform properties being especially characterizing by reduced formation of disordered structure cross-linked with protein, improved retention of the protein activity and the excellent retaining protein in blood after intake of the indicated complex.
EFFECT: improved and valuable medicinal and pharmaceutical properties of agents.
110 cl, 13 tbl, 3 dwg, 40 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to elevated-viscosity halogenated elastomers as constituents of thermoplastic composition,. The latter comprises thermoplastic material and at least one isoolefin copolymer including unit derived from halomethylstyrene, which are mixed with at least one hindered amine or phosphine of formula R1R2R3N or R1R2R3P. In a preferred embodiment, R1,R2, andR3 represent lower and higher alkyl groups. Thus obtained ionically bound amine- or phosphine-modified elastomers are suitable for preparing thermoplastic mixed elastomeric compositions.
EFFECT: improved mixing homogeneity due to elevated viscosity of copolymer and formation of finer dispersion of one polymer system in the matrix of another polymer system.
20 cl, 10 tbl, 5 ex
FIELD: organic synthesis.
SUBSTANCE: alkenylsuccinylamides are prepared via (i) alkenylation of maleic anhydride with poly-α-olefin or polyisobutylene having 10 to 30 carbon atoms and molecular mass 800-1000 in presence of initiators at 60-100°C for 0.5-1 h and then at 165-175°C for 3.5-4.5 h, molar ration of polymeric reagent to maleic anhydride being 1:(1-1.1) followed by (ii) condensation of resulting alkenylsuccinic anhydride in presence of oil containing 5-methyl-1,4,7,10-teraaminodecane or 8 -methyl-1,4,7,10,13,16-hexaaminohexadecane first at 30-58°C for 0.5-1.0 h and then at 136-145°C for 3.5-4.0 h at alkenylsuccinic anhydride-to-amine molar ratio (1-1.5):1. In step (i), initiator is selected from t-butyl peroxide and methyl ethyl ketone peroxide in amounts 0.8-1.4% of the summary weight of initial reactants, whereas oil is industrial oil 20A or I-40A.
EFFECT: simplified technology, enabled use of accessible raw materials, and improved quality of product.
4 cl, 1 tbl
FIELD: organic chemistry, polymers.
SUBSTANCE: claimed method includes alkylation of maleic anhydride with C10-C30-poly-alpha-olefin having molecular mass of 700-1100 in presence of initiator, previously at 60-100°C for 1.0-1.5 h and further at 160-170°C for 3-4 h and holding at 175-180°C for 0.5 h in poly-alpha-olefin/maleic anhydride ratio of 1:1-1.1 followed by condensation of obtained alkylated succinic anhydride with mixture, containing polyethylene polyamines at 50-110°C for 1.-1.5 h and followed heating at 135-145 °C for 3.5-4 h in alkylated succinic anhydride/mixture (polyethylene polyamines) molar ratio of 1:1.1 in oil or aromatic hydrocarbons (such as industrial oils, ortho- or para-xylene, or solvents, such as xylene mixture, respectively). As mixture of polyethylene polyamines mixture of triehylenetetramine and tetraethylenepentamine in amount of 40-70 mass % and 20-50 mass %, respectively is used, and as initiator tert-butyl peroxide or methylethylketone peroxide in amount of 1-2.0 % based on the weight of starting poly-alpha-olefin and maleic anhydride is used.
EFFECT: simplified process; product of increased quality.
4 cl, 6 ex, 1 tbl
FIELD: organic chemistry, polymers.
SUBSTANCE: claimed method includes interaction of maleic anhydride with C10-C30-poly-alpha-olefin or C10-C30-polyisobutylene containing with molecular mass of 700-1100 in presence of initiator, previously at 70-90°C for 0.5-1.0 h and further at 165-175°C for 3-4 h in poly-alpha-olefin (polyisobutylene)/maleic anhydride ratio of 1:1-1.1 followed by condensation of obtained alkenylsuccinic anhydride in oil (such as industrial oils) with polypropylene polyamines at 40-70°C for 0.5-1.5 h then at 140-145°C for 4-4.5 hours. As initiator tert-butyl peroxide or methylethylketone peroxide in amount of 1-1.5 % based on the weight of starting poly-alpha-olefin (or polyisobutylene) and maleic anhydride is used. As polypropylene polyamines dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, as well as mixture of polypropylene polyamines containing (mass %): moisture 0.5-0.8; 1,2-diaminepropane 0.9-1.8; dipropylenetriamine 20-47; tripropylenetetramine 26-51; tetrapropylenepentamine and hentapropylenehexamine 26-28 are used.
EFFECT: simplified process (decreased energy consumption and synthetic process duration), product of increased quality.
4 cl, 8 ex, 1 tbl
FIELD: organic chemistry, polymers, medicine.
SUBSTANCE: invention describes lidocaine polyacrylate eliciting the prolonged topical anesthetic effect of the general formula: wherein n means (number of links) = 50-70; means a link of polyacrylic acid; means N,N-diethylaminoacetic acid 2,4-dimethylanilide.
EFFECT: valuable medicinal properties of compound.
1 cl, 2 tbl, 1 ex
SUBSTANCE: invention relates to a method for radical polymerisation of one or more ethylene unsaturated compounds of formula (II), characterised by that at least one radical polymerisation initiator is added in at least two steps to ethylene unsaturated compounds taken in amount of at least 80.0% of the total weight of ethylene unsaturated compounds. More polymerisation initiator is added at the second step than at the first step. The polymerisation initiator at the first and second step is added gradually and the ratio of average rate of adding at the second step to the average rate of adding at the first step is greater than 1.2:1.
EFFECT: improved method.
17 cl, 1 tbl, 8 ex
FIELD: polymerization processes and catalysts.
SUBSTANCE: invention relates to catalytic system for (co)polymerization of lactide and glycolide and to (co)polymerization process using indicated system. Catalytic system is composed of (a) trifluoromethanesulfonate of general formula (1), (b) (co)polymerization additive of general formula (2), wherein molar ratio of additive to catalyst ranges from 0.05:1 to 5:1. (Co)polymerization process of lactide and glycolide is also described as well as application of thus obtained lactide and glycolide polymer or copolymer.
EFFECT: enabled controlling chain length, nature of end units of the chain of resulting (co)polymers.
10 cl, 8 ex
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to a method for polymerization of one or some monomers one of that is vinyl chloride monomer. Method involves addition of the standard system of organic peroxides to polymerization mixture in the first step of polymerization, and one or some of additional organic peroxides and, optionally, surfactant are added to the polymerization mixture at the reaction temperature value when pressure in the polymerization reactor falls due to depletion of vinyl chloride monomer amount. Indicated additional organic peroxides have half-time value less 1 h at the polymerization temperature under condition that formed polymer is not subjected for radio-frequency dielectric heating in the presence of additional organic peroxide. The proposed method provides decreasing the polymerization time owing to higher rate value of the pressure drop in the end the polymerization reaction. Also, invention provides the enhanced effectiveness of cooling capacity of polymerization solution.
EFFECT: improved effectiveness of polymerization process.
5 cl, 1 tbl, 1 ex
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to a polymerization method of vinyl chloride monomer and optionally additional monomers by using a single or some organic peroxides. This method involves dosing at least one organic peroxide compound with half-time value from 0.0001 h to less 0.050 h at the polymerization point to the polymerization mixture. Dosing such initiating agent allows achievement of improving the polymerization rate regulation and higher rate of polymerization. By using this method vinyl chloride-base (co)polymer is prepared having less 50 mass parts of residual initiating agent per one million of mass parts of (co)polymer in measuring after polymerization and drying (co)polymer at 60°C for 1 h directly. (Co)polymer can be used in the molding process involving heating a (co)polymer to temperature exceeding its boiling point.
EFFECT: improved method for polymerization.
8 cl, 2 tbl
FIELD: polymers, rubber industry, in particular production of stereoblock polymers of conjugated dienes, such as cis-1,4-polyisoprene.
SUBSTANCE: modified cis-1,4-polyisoprene is obtained by polymerization pf isoprene in isopentane medium in presence of Ziegler-Natta catalyst. Then catalyst is deactivated; polymer is stabilized and modified with nitrogen-containing compound; polymer in isolated and dried. As nitrogen-containing compound reaction product of maleic anhydride and N-alkyl-N'-phenyl-n-phenylenediamine in amount of 0.5-2 % based on polymer is used.
EFFECT: simplified method for production of polymers having heat oxidative stability.
1 tbl, 1 ex