RU2252943C2 - Method of production of a polyetherurethaneacrylate oligomer - Google Patents

Abstract

FIELD: rocketry; methods of a synthesis of a polyetherurethaneacrylate oligomer.

SUBSTANCE: the invention is pertaining to the field of rocketry, in particular, to a method of a synthesis of a polyetherurethaneacrylate oligomer being the basis for production of non-saturated polyester compositions used for formation of the potting armoring compositions. The indicated method provides for interaction of a monomethacrylic ether of ethylene glycol with a polyester macrodiisocyanate containing 4.0-7.0 % of isocyanate groups, produced by interaction of polyoxypropylene glycol of Laprola 1052 or polyfurite, with toluylene diisocyanate 102Т in presence of dibuthyldilaurate of stannous-product 222-09 or 222-08 at the temperature of 60-70°C, intensive stirring with a rate of 125-158 rpm and a residual pressure of no more than 1333.3 Pa within 3.5-7.0 hours and at following ratio components: 82.14-89.64 mass % of the above indicated polyester macrodiisocyanate 9.8-17.7 mass % of the monomethacrylic ether of ethylene glycol, 0.16-0.56 mass % of dibuthyldilaurate of stannous-product 222-09 or 222-08. The offered method allows to improve quality of produced polyetherurethaneacrylate oligomer for potting armoring compositions, to produce a conditioned raw material with a long term of its storage - up to 12 months, to reduce labor input and to expand a source of raw materials for production of the armoring materials.

EFFECT: the invention allows to improve quality of produced polyetherurethaneacrylate oligomer for potting armoring compositions, to produce a conditioned raw material with a long term of its storage, , to reduce labor input, to expand a source of raw materials.

4 ex, 3 tbl

Description

The present invention relates to the field of rocketry and relates to a method for the synthesis of polyether urethane acrylate oligomer, which is the basis for obtaining unsaturated polyester compositions used to create armored compositions.

Currently, in the preparation of the casting composition for booking long charges from dibasic ballistic fuel, oligoesterurethanes with polyester resins are used as the basis for the compositions. However, there is no production of polyether urethane oligomers in Russia. It is well known that the raw material problem is currently one of the urgent. One of the main ways to solve this problem is to develop a method for producing polyetruurethane acrylate oligomer directly at the enterprise. And such a path has been found. The method of obtaining the necessary polyether urethane acrylate oligomer from polyester macrodiisocyanate (urethane rubber SKU-L-1052M TU 84-07509103.440-95), including polyoxypropylene glycol (laprol 1052 or polyfurite) and toluene diisocyanate (product 102T).

Closest to the claimed technical essence is a method for producing polymeric materials with urethane groups by reacting in bulk unsaturated hydroxyl-containing monomer with polyester macrodiisocyanate (SU No. 273424, IPC C 08 G 22/08) - prototype. One of the disadvantages of this method of producing polymeric materials with urethane groups according to the prototype is the frequency of obtaining materials for the single use of this mixture and the long curing time of the compositions (at 80 ° C from 3 to 20 hours).

In this prototype, an intermediate product is obtained in the synthesis of 1 mole of oligodiols with 1.5-2.2 moles of toluene diisocyanate and this product is not analyzed for indicators that are crucial in the formation of the polymer structural network.

The technical problem solved in this invention is the development of a method for producing a polyether urethane acrylate oligomer, which is the basis of casting compositions for booking long charges from high-energy ballistic fuel.

The technical result is achieved due to the fact that, in contrast to the known method for producing saturated or unsaturated oligodiols, diisocyanates and unsaturated monomers with an active hydrogen atom in the mass, for the synthesis of polyester urethane acrylate oligomer, polyester macrodiisocyanate (SKU-L-1052 urethane rubber is taken as the starting component) ), obtained on the basis of polyoxypropylene glycol - laprol 1052 or polyfurite and toluene diisocyanate - product 102T, with the content of isocyanate groups in the range of 4.0-7.0% and with viscosity up to 200 Pa · s.

The novelty and inventive step of the invention lies in the fact that the synthesis of polyether urethane acrylate oligomer is carried out at a temperature of 60-70 ° C for 3.5-7.0 hours at a residual pressure of 1333.3 Pa (10 mm Hg) by interaction in mass using ethylene glycol monomethacrylic ester and tin dibutyl dilaurate activator - product 222-09 or 222-08 with polyester macrodiisocyanate with vigorous stirring in a mixer with a stirrer speed of 125-158 rpm.

The polyether urethane acrylate oligomer is obtained in the following ratio of components, wt.%:

- macrodiisocyanate SKU-L-1052M - 82.14-89.64

- ethylene glycol monomethacrylic ester (MEG) - 9.8-17.7

- tin dibutyl dilaurate -

product 222-09 or 222-08 - 0.16-0.56

The achieved positive effect is obvious, because as a result of the proposed chemical modification, a completely new polyether urethane acrylate oligomer with terminal double bonds is obtained. Using this oligomer, a casting composition is arranged having high mechanical, adhesive and operational characteristics for armor compounds.

The claimed limits of the ratios between the components are determined by calculation and are optimal from the point of view of the formation of the structure of the polymer matrix, ensuring the achievement of a high complex of physico-mechanical characteristics of the finished polymer, as well as the technical characteristics of the polyester urethane acrylate oligomer itself. The indicated ratios (wt.%) Between macrodiisocyanate (SKU-L-1052M urethane rubber) and ethylene glycol monomethacrylic ester (MEG) take into account their molar ratio of 2.0-2.2 mol of MEG and 1.0-1.05 mol of prepolymer SKU-L-1052M. The optimal ratio between the SKU-L-1052M prepolymer and ethylene glycol monomethacrylate is 1 mol: 2.10 mol, respectively.

The synthesis of the polyether urethane acrylate oligomer was carried out by a chemical reaction using ethylene glycol monomethacrylic ester and an activator of the reaction of dibutyl dilaurate - product 222-09 or 222-08 with macrodiisocyanate based on polyoxypropylene glycol - laprol 1052, or polyfurite and toluene di-tytomethane-usual rubenitreisitomethane with usual rubenitene diisocyanate vacuum line and mixing device. The synthesis was carried out until the isocyanate groups (NCO groups) were completely consumed.

In appearance, the obtained oligomer is a viscous transparent yellow liquid with a viscosity of 289-350 Pa · s (at a temperature of 20 ° C according to Stokes).

The technical characteristics of the synthesized oligomer were determined, on which casting compositions were subsequently prepared and cured.

The technical essence of the invention is illustrated by the following experimental data:

Example 1

To 1 mole (89.64 wt.%) Of macrodiisocyanate (SKU-L-1052M urethane rubber) containing 6.6% NCO groups, 1.05 mole (9.8 wt.%) Of ethylene glycol monomethacrylic ester and 0.00089 were added. mole (0.56 wt.%) of the tin dibutyl dilaurate reaction activator, product 222-09 or 222-08, was stirred at a temperature of 60 ° C for 3.5 hours with a stirrer speed of 125-158 rpm. The mixture was evacuated at a residual pressure in the reactor of not more than 1333.3 Pa (10 mm Hg). The content of NCO groups in the polyether urethane acrylate oligomer is 0.08%.

Hardeners were then added to the polyether urethane acrylate oligomer, after which the resulting reaction mass was poured into a metal slit mold for curing at a temperature of 80 ° C for 30 minutes, the viability of the reaction mixture was evaluated by studying its rheological properties on a Reotest-2 device in the temperature range 17 -60 ° C.

Example 2

2.2 moles (17.7% by weight) of ethylene glycol monomethacrylic ester and 0.00025 were added to 1 mole (82.14 wt.%) Of macrodiisocyanate (SKU-L-1052M urethane rubber) containing 6.0% NCO groups mole (0.16 wt.%) of the tin dibutyl dilaurate reaction activator, product 222-09 or 222-08, was stirred at a temperature of 60 ° C for 7 hours with a stirring speed of 125-158 rpm. The mixture was evacuated at a residual pressure in the reactor of not more than 1333.3 Pa (10 mm Hg). The content of NCO groups in the polyether urethane acrylate oligomer is 0.01%.

The polyether urethane acrylate oligomer was cured by the addition of polyester resin and initiators.

Example 3.

2.1 moles (14.0 wt.%) Of ethylene glycol monomethacrylic ester and 0.00025 were added to 1 mole (85.84 wt.%) Of macrodiisocyanate (SKU-L-1052M urethane rubber) containing 6.6% NCO groups mole (0.16 wt.%) of the tin dibutyl dilaurate reaction activator, product 222-09 or 222-08, was stirred at a temperature of 70 ° C for 5 hours with a stirring device rotational speed of 125-158 rpm. The mixture was evacuated at a residual pressure in the reactor of not more than 1333.3 Pa (10 mm Hg). The content of NCO groups in the polyether urethane acrylate oligomer is absent.

Example 4

To a mole (87.7% by weight) of macrodiisocyanate (SKU-L-1052M urethane rubber) containing 5.9% NCO groups, 2.05 mol (12.1% by weight) of ethylene glycol monomethacrylic ester and 0.00025 were added. mole (0.16 wt.%) of the tin dibutyl dilaurate reaction activator, product 222-09 or 222-08, was stirred at a temperature of 65 ° C for 6 hours with a stirrer speed of 125-158 rpm. The mixture was evacuated at a residual pressure in the reactor of not more than 1333.3 Pa (10 mm Hg). The content of NCO groups in the polyether urethane acrylate oligomer is 0.005%.

Table 1 shows the formulation of the polyether urethane acrylate oligomer, and in Tables 2 and 3 the comparative technical, physicomechanical, and adhesive characteristics of the oligomers and casting armor formulations obtained with different molar ratios of components.

Table 1 Name of components and their ratio Content in prototype, mole fractions Content, molar fractions (% by weight) Example 1 Example 2 Example 3 Example 4 Oligodiol: diisocyanate (prepolymer): unsaturated monomer with an active hydrogen atom (MEG) 1.0-1.5: 2.2-1.1: 6.0 1: 1.05 (89.64: 9.8) 1: 2.2 (82.14: 17.4) 1: 2.1 (85.84: 14.0) 1: 2.05 (87.7: 12.1) Tin Dibutyl Dilaurate - Product 222-09 or 222-08 - 0.56 0.16 0.16 0.16 table 2
Technical characteristics of the synthesized polyether urethane acrylate oligomer and prototype The name of indicators Prototype Example 1 Example 2 Example 3 Example 4 1 2 3 4 5 6 1. Appearance Yellow viscous clear liquid 2. Stokes viscosity at 20 ° С, Pa • s 200-300 350,0 289.4 326.0 316.0 3. Density at 20 ° C, g / cm ³ 1.105 1,112 1,101 1,111 1,111 4. The content of NCO-groups,% not determined 0.08 0.01 are absent 0.005 5. Shelf life, months An intermediate product of 6 months in a conditionally sealed container, in an environment of dry compressed nitrogen or air 12 12 12 12

Table 3 Specifications Prototype Example 1 Example 2 Example 3 Example 4 1 2 3 4 5 6 1. The content of NCO-groups,% not determined 0.08 0.01 are absent 0.005 2. The viability of the reaction mixture of the finished casting armor, min at 17 ° C - 360 375 360 310 22 ° C 360 275 270 300 200 40 ° C - 240 210 220 230 60 ° C - fifty 35 thirty 40 3. Tensile strength at (23 ± 2) ° С and speed 500 mm / min, kgf / cm ² 77-500 79.6 86.0 89.5 94.6 4. Relative deformation at break at (23 ± 2) ° С and speed 500 mm / min,% 50-685 23.0 24.2 25,4 25.0 5. The adhesion strength of the armor to ballistic fuel type NDP-2MK at (23 ± 2) ° C and a speed of 500 mm / min, kgf / cm ² 45 89.9 89.1 91.2 87.6 6. The temperature of the mechanical glass transition, ° C plus 5 minus 22 minus 22 minus 21 minus 22

From table 1 it is seen that the complete synthesis of obtaining polyether urethane acrylate oligomer is achieved when the ratio of the components: 1 mol of urethane rubber: 2.1 mol MEG. In this case, the synthesis proceeds until the isocyanate groups are completely consumed (Example 3), and in other cases they fluctuate within acceptable limits from 0.005 to 0.08%.

Tables 2 and 3 show that the polyester urethane acrylate oligomer synthesized in the laboratory meets all the requirements for the feedstock (oligomers, rubbers, diols) for the preparation of armor or fastening casting compounds. The polyether urethane acrylate oligomer has an acceptable viscosity, satisfactory density, long shelf life and high mechanical and adhesive characteristics. From table 3 it is seen that the armor compositions prepared on the basis of the synthesized polyester urethane acrylate oligomer have high strength at a level of ~ 80-90 kgf / cm ² , high adhesion to ballistic fuel type NDP-2MK (~ 91.2 kgf / cm ² ) and sufficient elastic properties (~ 25%).

The main advantage of the synthesized polyester urethane acrylate oligomer is the possibility of its use in the arrangement of armor compositions for booking long products from dibasic ballistic fuel, operated in a wide temperature range from plus 50 to minus 50 ° С.

Using polyester urethane acrylate oligomer obtained by the present method, the process of booking long charges of complex configuration from dibasic fuels has been worked out.

The proposed method for producing a polyether urethane acrylate oligomer was introduced at the experimental research plant of FSUE NIIPM.

Obtaining a polyether urethane acrylate oligomer according to the proposed method allows:

- improve the quality of filling armored personnel;

- get conditioned raw materials with a long storage time;

- reduce the complexity;

- expand the raw material base for the production of armored materials.

Claims (1)

A method of producing a polyether urethane acrylate oligomer by reacting ethylene glycol monomethacrylic ester with a polyester macrodiisocyanate, characterized in that polyester macrodiisocyanate SKU-L-1052M with an isocyanate group content of 4.0 to 7.0 polyapropyl is used; or polyfurite and toluene diisocyanate - product 102T, the oligomer is synthesized in the presence of the tin dibutyl dilaurate activator - product 222-09 or 222-08 at a temperature of 60-70 ° C, a residual pressure of not more than 1333.3 Pa (10 mm Hg) and with vigorous stirring of the mass in the mixer with a stirring device rotational speed of 125-158 rpm for 3.5-7.0 hours in the following ratio components, wt.%: the above polyester macrodiisocyanate SKU-L-1052M 82.14-89.64 ethylene glycol monomethacrylic ester (MEG) 9.8-17.7 tin dibutyl dilaurate - product 222-09 or 222-08 0.16-0.56