SU616269A1 - Polyarylate-butadiene-isoprene block copolymers possessing vibration damping properties - Google Patents

Description

(54) POLYARILATOBUTEDIENE ISOPRENE UNIT OF POLYMERILES OWNED WITH VIBRATION DIFFERENCE BY I2 PROPERTIES

0-C-N- (1% II II II

IT h-N- / L-5-y-kJ, / II / j ION 5 h-CH2 CH "SI-CHgm - 5-25

q - 3-7,

with mos. at. 45000-58000 is obtained by low-temperature polycondensation of oligomeric polyarylate b of cyan and dichlorangiprid iaophgalic acid with terminal acid chloride groups with oligomeric butadiene and isoprene with terminal hydroxyl groups in the medium of an organic solvent in the presence of a toetic amine.

SNSNz

/ A-c- / Vo-c N4R) eN-c-o - VoH

/ I / II I I II / I

snzon no-CH,

 {CHg-CH dH-CH-CH-C CH-CH2

as said copolymer

It is also possible to use the product of the interaction of an excess of the ligomeric macrocy isocyanate. with diaminodiphenylsulfone followed by condensation with an excess of diane. If heated in chlorobenzene in the presence of a catalyst, ibutyldichloride

SNS

15 as the oligomeric copolymer of butadiene and isoprene with terminal hydroxyl groups use the condensation product of an excess of diane with oligomeric macrodisocyanate, which is 20 with a copolymer of butadiene with isoprene

and having terminal isocyanate groups in chlorobenzene when heated in the presence of a catalyst - dibutyl dichloridol (A). The reaction proceeds according to the scheme

ON-OS5CH) G8 NCO

tin (B), the reaction takes place in two stages.

In the first stage, a significant excess of the oligomeric macrodisocyanate reacts with diaminodiphenylsulfone in chloro-benzene at 100 ° C for 2 hours according to the scheme C-11% C-C-O- / CP II 1I I ONNOSE CB2-C CH-CHg -;

 H2 "

ng -I- 2ocNiTi-) 7c WCO

C-N-S- / N-C-N4R. NCO

II I OH

non

In the second stage, the resulting oligomer with terminal iocyanate groups interacts with the cyano excess in the presence of a catalyst — aibutyldOCK4lt) 28 NCW I II I / I non Vo-c-i4i-H, c-II III CB OHH 0 tt The structure of oligomeric compounds with terminal hydroxyl groups proved by elemental analysis and IR spectroscopy. The process for the preparation of polyarylate butadiene isoprene block copolymers consists of two stages. In the first stage, the interaction of an excess of isophthalic acid dichloride with Dian at 45 ° C in an organic solvent (for example, chloroform) in the presence of triethylamine with stirring for 1 hour yields the terminal acid chloride group. By changing the ratio of the reagents, oligomers of a molecular weight are obtained. In the second stage, the oligomer with terminal acid chloride groups in solution reacts with an oligomer containing terminal hydroxyl groups, t, e, A or B, which is introduced into the reaction flask in a solution of chloroform with triethyl amine. An equimolecular ratio of oligomers is taken to provide maximum yield and viscosity for block copolymers. The synthesized block copolymers identified by elemental analysis, IR spectroscopy, turbidimetric titration. The examples given describe the preparation of oligomeric bifunctional products and polyarylate butadiene isoprene block copolymers based on them, Example 1, Oligomer with terminal hydroxyl groups based on oligomeric and cyaaa – i ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– (A In a three-necked conical flask, equipped with a stirrer, a cooler, and VOLA nitrogen, dissolved at a stirring, not 20.0 g (0.0052 mol) of the complete BuTaPaOIA with isoprene with terminal NGOs - and protein groups (Y -28) at 50.0

Chloridol - within 2 hours with the formation of an oligomer with terminal hydroxyl groups according to the scheme N-e-N Chi NOI th NCO-f 2NO N-C-N. K-C-0 chlorobenzene, there is added g (0, O1 weight,% of the total starting material) of the dibutyl dichloridol catalyst. - raise the temperature to 1OO C and add 2,632 g (0.011 mol) of diane to the flask. After stirring under nitrogen for 5 hours, the reaction mixture is cooled to room temperature and the resulting product is precipitated with isopropyl alcohol. After that, it is dried in air and in vacuum. 19.0 g (yield 84%) of a light yellow viscous product, mol. at. 437O determined by the percentage of hydroxyl groups found according to the method of Berle, Example 2: An oligomer with terminal hydroxyl groups based on oligomeric macro-diisocyanate, au. "Aminodiphenylsulfone and diane (B). In a three-necked flask equipped with a stirrer, condenser and feed for nitrogen, 127.5 g (O, O334 mol) of isoprene-terminated isoprene-butadiene oligomer (-28) in 6O mg of chloroform are dissolved with stirring, 0 g , 0161 mol) diaminodiphenylsulfone and 10O, 0 ml of dimethylsulfoxide (to completely dissolve diaminodiphenylsulfone), raise the temperature to 10OO C and mix in a stream of nitrogen for 2 hours, after which BUTH2,525 g (0.0415 mol) of diane A 0.141O g (0, OO1 wt.% of the sum of the starting materials) of the catalyst - dibutylcylchloride. The mass is stirred for 3 hours at 10 ° C in a stream of nitrogen. After cooling the reaction, the resulting oligomer is precipitated with isopropyl alcohol, filtered, dried in air, then in vacuum. The yield of oligomer B is 87%, mul. 833G. EXAMPLE 3: OOPilmsr block based on oligomeric asIlpts) iU (una with terminal chlorohydriyanate groups and oligomer with terminal hydroxyl groups, prepared as described in Example 1. -In a four-necked flask equipped with a stirrer, a condenser and nitrogen for nitrogen; solution 2.7848 g (0.0122 mol of dian in BO, O ml of chloroform, 3.09 ml (0.0246 mol) of triethylamine and 2.9780 g {0.0127 mol) of d-chloro phthalic acid dichloride in solid The mixture is stirred for 1 hour, after which a solution of 10 g (p, O 24 mol of the oligomer prepared by Example 1, dissolved with 0.654 ml (0.0048 mol of triethylamine in 30.0 ml of chloroform. Stir the reaction mass for 3 hours. After cooling, the precipitated precipitate is obtained and the resulting block copolymer is isopropyl alcohol, dried in air at 7 ° Sivacuum. Get 12 (yield 80%) of a block copolymer with 2 bp 0.56 al / g, determined for O, 5% solution in tetrachloroethane, mol. 4500 and softening point 182-185 ° C. The resulting block copolymer has the structural formula I, where the tangent of the angle of mechanical loss of the block copolymer is in the range of values 0.1-0.3 prd1 meas The temperature is: i N N-CI If but the molecular weight of the block copolymer, determined by the light scattering method, in chloroform is 58000, the tangent of the angle of mechanical loss lies in the range of values 0, О7 - 0.18 when the temperature changes from minus 6 O to plus 160 ° C, the dynamic modulus of elasticity is in the range of values. 10 5 10 kg / cm at the same temperature conditions. The high elasticity interval found from the thermomechanical curve minus 6O - plus 220 ° C. The block copolymers obtained by this method are readily soluble in chlorine P1 hydrocarbons, such as chloroform, methylene chloride, and others, from minus 60 C to plus 1OO C, the dynamic modulus of elasticity I-IO210. Kg / cm under the same temperature conditions . The high elasticity interval found from the thermomechanical curve, minus 60 - plus 16 O C. Example 4: A block copolymer based on oligomeric arylate diana with terminal chlorohydride groups and oligomer with terminal hydroxyl groups, prepared according to example 2. In a four-neck flask equipped with a stirrer, a condenser and an inlet for nitrogen, dissolve 5.622 g (0, O246 mol) of diane in 120.0 ml of chloroform with stirring, 4.98 g (0.0492 mol) of triethylamine are added and 5.272 g are added at 45 ° C. (0.0259 mol) of isophthalic acid dichloride in solid form. The mixture was stirred for 1 hour, after which 10 g (0, OO12 mol) of the oligomer obtained in Example 2 diluted in 70 ml of chloroform with 0.230 g (0, OO24 mol) of triethylamine were introduced into the reaction flask. Stir the reaction mass for 3 hours, after which the cooling down to room temperature, washed with 0.3 n. with a solution of hydrochloric acid, then with water until neutral, dried in air at 70 ° C and in vacuum. A block copolymer with 0.77 dl / g, a yield of 87% and a softening temperature of 25 O-262 C is obtained. The obtained block copolymer has the structural formula T, where N-C-0 hch II solutions, in which by means of a watering form strong transparent films. Polyarylate butadiene isoprene block copolymers have constant physical and mechanical properties over a wide temperature range (for example, the mechanical loss tangent for a block copolymer obtained in example 3 is in the range of values 0.1 - 0.3 when the temperature changes from minus 60 to plus 10 ° С and within the range of 0.07–0.18 when the temperature varies from minus BO to + 16 ° С for the block: polymer, obtained in Example 4, the elasticity interval found from the thermomechanical curve for the block copolymer was obtained. For example 3, minus 60 - plus: 160 C.