Method of producing prepolymer with terminal amino groups

FIELD: chemistry.

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.

1 ex

 

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



 

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