SU1120045A1 - Polyamidepolybutadiene block-copolymer as material for face coating of imitation leather and method of producing same - Google Patents

Abstract

1. Polyamide polybutadiene block copolymer of the general formula LEBE-p, S (L LJ / 7 Jy 45.0) wt.% And molecular weight 4 10,000-30000 as the material for the artificial leather surface coating, 2. The method for producing the polyamide poly- . a butadiene block copolymer by reacting a polybutadiene, a diisocyanate and a component forming a polyamide block in the presence of an organometallic catalyst, characterized in that, in order to improve the hygienic properties of an artificial skin, the polybutadiene is

Description

And OC NTgj-NH-C-O-CHrCHfiCHrdHH, d where y 29-80, as a component forming H0 | C-fCHg-S-NH-fCH where X C-60, and as the organometallic catalyst is an organotin compound, the reaction is carried out in one oH-CHffyCHa-CH -O NH-T JI-CO ch, polyamide block, polyamide is used PA-b / bb-3 of the formula) NH-df СНг-иН- | -Н, stage at a ratio of NCO: (NHj + cOOH) groups of reagents 1: G in N, N dimethylformamide or 5% LiUlB solution, L-dimethylformamide at 80-IOOC.

The invention relates to the production of artificial leather, in particular to block copolymer, used as a face coating for art leather, and a method for its preparation. Triple-block polyamide butadiene-polyamide block copolymers obtained from polybutadiene with terminal acidic rpynnawi and E-caprolactam 1J, as well as on the basis of the sodium salt of C-caprolactam, chlorine-substituted isocyanate, live polybutadiene, and g-caprolactam, are known. Also known are tri-block polybadi-thiene-polyamide-poly-butadiene block copolymers obtained by polymerization of butadiene in the presence of polyamide C 3 iJ. However, these block ss opimers consist only of three blocks and the polyamide block contains only polyamide-6, which practically excludes the variation of their properties. In addition, these copolymers have low hygienic properties. The closest to the technical essence and the achieved effect of the invention are three-block polyamide polybutadiene polyamide block copolymers obtained on the basis of isocyanate-terminated polybutadiene and E-caprolactam Cj However, artificial skin with a face coating of the known block copolymer has a low vapor-permeability C j. the production of polyacid polybutadiene polyadonic block-co. polymers by polymerizing E-caprolactam in the presence of polybutadiene with terminal acid groups ij. However, with this method of synthesis, the reaction of formation of block copolymers proceeds in the melt at a high temperature (240-260 ° C). In addition, only three-block block copolymers are formed that do not contain polyamide-6 / 66-3 blocks. Three-block polyamide poly-butadiene-polyamide block copolymers are known that can be made in several herds. In the first stage, sodium salt of caprulactam is reacted with chlorine-substituted diisocyanate, in the second, interaction with live polybutadiene and in the third interaction of polybutadiene with terminal isocyanate groups with caprolactam 2. However, with this method of synthesis, the reaction proceeds in several Stages which significantly complicates the process formation of block copolymers. Three-bedded polybutadiene polyamide polybutadiene block copolymers are known, which can be obtained by polymerization of butadiene in the presence of polyamide h. . 311 However, with such a synthesis process, three-block copolymers with terminal elastic blocks are formed, which negatively affects the deformation-strength properties of the block polymer. : The closest to the invention and the technical effect achieved SU15NOSTI tm ots method prlucheny poliamidpolybutadienovogo block copolymer by reacting po-, libutadiena terminated with amine groups, followed by boiling dnizotsianatom papimerizatsiey caprolactam obtained in the presence of an isocyanate-terminated polibutadietta grupnaitu. The TeAc formation of a block with polymers is carried out in Goxane in the presence of organolithium compounds at C43. 2 d "-o | d- (CH% (R -C-NH-R KH-Cj; -. - II .-.. ---- li - (- 9nby; y i9-80, .c by matching the blocks of polyamide and 0 "C -r HH-C-oAjHf- Hff -.: H, -. - ;: ::; ::..: ::;:; beats in 29-80, as a component, forming

Ho | tiftiH2 d-NH CH2 NH- (NHJ-H

where X 9-60,

and as an organometallic meta-catalyst, organotin is the compound; the reaction is carried out in one stage with the ratio of NCO: (NHj + COOH) groups of 1: 1 reagents in the medium

S, K-dimethylformamide or 5% solution of LiCl in M, N-dimethylformamide at 80-10b ° C.

, Properties; the iolibutadiene block oopomers are determined mainly by the content of polyamide blocks. However, the known method requires the use of low temperatures, two stages, which complicates the process of formation of block copolymers.  In addition, artificial leathers containing block copolymers obtained by a known method as a face coating are characterized by low hygienic properties (low vapor permeability, hygroscopicity and moisture return).  The aim of the invention is to improve the hygienic properties of the artificial goat.  This goal is achieved by the synthesis of HOBcfro poly (d) poly (butadiene) block copolymer of the general formula (i) LKbE-1I.    ,:  ABOUT .  .  .    . .  n ((J- (CH2V-HH j- "dH-dH CHr Yngo - 1 polybutadiene (A: B) (99.0: 1.0) - (45.0) May.  % and a molecular weight of 30 10,000-30000, as a material. For facial pokrggy artificial.  ; / skin.  ;.  .    .  ,: According to the process for the preparation of poly (i) 1 dibolybutadiene block copolymer by reacting polybutadiene, diisulfate and the component forming the polyamide block c. the presence of an organometallic catalyst as polybutadiene is.  .   . -. - 40 use a polymer of formula V. . -,: 0.  -.   -.  М-С-О; ::;:::: - -:.    ; .  .     ; polyamide block, polyamide PA-6 / 66-3 of formula yes or polybutadiene is used, and not the molecular weight of these blocks.  However, this is true if the molecular weights of the blocks have a molecular weight comparable to the molecular weight of the segment.  Therefore, it is advisable to use a polyamide with a molar mass of 3000-20000 (x 9-60) to synthesize polyidic polybutadiene block copolymers, since blocks of polyamide with such a molecular mass provide the basic properties of the polyamide in the block copolymer.  If a polyamide with X 9 is used, the properties of the polyamide in the block copolymer are poorly developed.  In addition, polyamides mol.  weighing 3000 are not issued by the domestic industry.  Using polyagshd with mol.  weighing 20,000 (t. e.  60) is impractical because their use makes the process of producing block copolymers difficult: with an increase in the molar mass of the polyamide, the compatibility of the solution of polyamide and nojmbutadiene deteriorates, the reaction mass becomes heterogeneous and the molecular weight of the block copolymers decreases.  In the case of the polybutadiene component, as well as for the popiamide blocks, it is important that the weight of the blocks of field b of the utadiene be comparable to the mol.  mass of the segment. .  Polybutadiene blocks with a molar mass of 200 r (in 29) poorly exhibit the properties of popibutadena, and the use of polyb utadiene with mol.  a mass of 5000 (80) is not advisable, since its use leads to heterogeneity of the reaction solution and the survival of p 1} molecules of the mass of the block copolymer. .  The relative content of the blocks of polyamide and polybutadiene has a significant impact on the hygienic properties of block copolymers.  With a block content of 99% g; .  The chemical properties are deteriorating (a pure polyamide-based artificial leather front coating (PA-6 / 66-3 - 100% polyamide blocks obtained from dimethyl phosphorus solution cracks In block-polymer, containing 55% optic blocks, in turn, also contains reduced hygienic.  properties, therefore use block9 containing olimers. 55% of polyamide blocks, as facial pok1) it is impractical to imitate artificial skin.  The hygienic properties of polyamide polybutadiene block copolymers, depending on their composition, pass through a maximum (composition 95: 5%) and remain at a rather high level up to 55% polyamide block content.  The amount of diisocyanate used in the synthesis of the block copolymer, as well as its chemical structure, does not have a noticeable effect on the hygienic properties of the face coating of artificial leather.  Apparently, this is due to the fact that the properties of block copolymers are mainly determined by the ratio of the blocks of polyamide and polybutadiene, and also by the fact that the content of diisocyanate residues in the copolymers is small and is only 0.57-3.86 %  Therefore, the composition of the block copolymers is calculated in such a way that the residues of diisocyanates belong to a rigid, polyamide block.  In this case, the elastic blocks of polybutadiene, the main modifying component in block copolymers, are precisely indicated. The reaction to obtain block copolymers is carried out at an equimolar ratio of reactive groups; CSR (diisocyanate and end groups / polybutadiene) and W + COOH polyamide groups.  It is also possible to carry out the reaction without the addition of a low molecular weight diisocyanate.  In this case, the formation of a block copolymer occurs only at the expense of terminal NCO-ri ynn polybutadiene.  As an organic tin catalyst, for example, tin octoate, tin dibutyldilurinate tin or diethyl dicaprylate tin in a quantity of 0.005-0.01 wt. % by weight of the final product.  At the end of the reaction, it is desirable to introduce into the solution of the obtained polymer, M% by weight of an antioxidant copolymer, for example, 2,6-di-1 T-1-4-methylphenol (ionol).  Synthesis of block copolymers is carried out in a three-necked flask equipped with a mechanical stirrer, refrigeration and tubes for inlet and outlet.  dry argon.  If the synthesis is carried out using LlCl, then LiCl is charged to the flask and dissolved at dry temperatures of 120 ° C in dry H, H-dimethylformamide.  Polyamide is charged into the prepared solution and dissolved at 120 ° C.  In the temperature range of 80-100 seconds, polybutadiene with isocyanate terminal groups mixed with the calculated amount of diisocyanate is added dropwise to the resulting solution.  Next, the flask is made from 0.005 to 0.01 wt. % (from 10% of the mass of the final product) of an organotin catalyst; I conduct the reaction for 3.5 h at 80–100 ° C.  30 minutes before the end of the reaction, 1% of the mass of the antirxidant copolymer was introduced into the flask.  After the reaction, the contents of the flask are used to make materials such as artificial leather.  If, upon receipt of the indicated block copolymer, LiCl is not used, the synthesis will be carried out as follows.  .  In a three-bulb flask equipped with a mechanical stirrer, a cooler and tubes for injecting and discharging dry argon, the polyamide is loaded and carried out at 120 ° C its dissolution in dry N, N-dimethylformamide.  Polybutadiene with terminal iso-cancanate groups mixed with the calculated amount of diisocyanate is added dropwise to the resulting solution in the temperature range from 80 to dropwise.  Next, the required amount of organic ovarian catalyst is introduced into the flask.  The reaction is carried out for 3.5 hours in the temperature range of 90-100 G.  30 minutes before the end of the reaction, 1% of the mass of antioxidant copolymer (ionol) was added to the flask.  After the reaction, the contents of the flask are poured into water.  Precipitation. filtered off, washed and dried for 24 hours under vacuum; 1 mm Hg, st over PjOg.  PRI me R t.  In a three-necked 300 ml flask, equipped with a non-agitated stirrer, a cold bottle (with both input and lance tubes of dry argon, 10 g of LiCl and 80 mp of dry g, H, H-dimesh1 fbromma are loaded; solution. , 39.6 (66 U g-mol) PA-6/66 3 (m.  mass 6000, X 18) and too et dry N, N-dimesh1formamida.  Ynr pry 1 58 remeshing carried out the dissolution of platinum before forming a homogeneous solution.  0.4 g (1.67 10 g-mol) of polybutadiene (mol.  mass 2500, 38) with terminal isocyanate groups, mixed with 0.001 g (0.005 wt.  to the mass of the final product) octoate olRva.  Next, 1.61 g (64.33 10 g-mol) of 4,4-diphenylmethane diisocyanate (mol.  weight 250.25) and additionally administered 20 ml of dry K, L-dimethylforma mda.  The reaction is carried out for 3.5 hours.  at.  Thirty minutes before the end of the reaction, 0.4 g (1% by weight, copolymer) of antioxidant (2,6-datretbutyl-4-met1shphenol) was introduced into the flask.  At the end of the reaction, the contents of the flask are cooled and the suspension obtained is used to make materials such as artificial leather.  The output of the obtained block copolymer with a ratio of bpdok pryalshda and polybutadiene 99, O: t, 00 wt. % is 38, t) g or 93.0% of theoretical.  The polyamide-poly-butadiene block copolymer obtained is soluble in N, N-dimethyl-forming in a mixture of methanol chloroform (80:20 vol. %).  .  The intrinsic viscosity of the block copolymer solution in H, K-dimerformamide at 1-, 86 dl / g, which corresponds to the average viscosity mol. , mass MV 30000.   The structure of the synthesized block copolymer is confirmed by a high yield of the target product, which is brisk; theoretical, as well as data of electroplating and IR spectroscopy.  Found,%: C 63.81; H 10.12; I N 13.68.  22573, 4e 3t 5tiMjt57. 6T Calculated,%: C 64.28i And 9.65;  N 12.28.  The infrared spectra of the block copolymer show characteristic stretching vibrations for the polyamide blocks (at 1520, 1340, V1360, 3080, 3300 cm to W-gr and R 1640) and blocks of no ibutadiene (at 730 1.4) 5 910 1 , 2 cis and at 970 1.4 trans).  PRI me R 2 ;.  Analogously to Example 1, the synthesis was carried out under the following loads: to a solution of 36.4 g.  ; (6, 1-S g-mop) PA-b / bb W (mol.  mass 6000, X 18) in 180 ml of dry N, I-dimethylformamide was added dropwise 4.0 g (1.60 1C g-mol) of polybutadiene (mol. weight 2500, at 38) with end | aocyanate groups, mixed pro with 0.002 g (0.01 wt. % by weight of the final product) dibutildyl urin and tin.  Next, 1.14 (4.5510 g-mol) L, diphenylmethane daneocyanate are added to the flask and additional 20 ml of dry H, N-dimethylformamide is added.  The reaction is carried out for 3.5 hours.  30 minutes before the end of the reaction in a flask yn t 0.4 g antiyoxy-.  danta ionopa.  At the end of the reaction, the contents of the flask are cooled and the resulting suspension is used for preparing prepared materials such as leather.  The output of the obtained block copolymer with the ratio of blocks of polyamide and polybutadene 90,0: 10, About wt. % is 38.6 g or 96.5% of the theoretical.  The resulting polyamino block polymeric copolymer is soluble in N, Nb dimethyl formamide and 4-ethanol-chlorophor mixture (80; 20 vol. %).  The characteristic viscosity of the solution of the batch resin in H, H-dimethylformamide is 1.43 dl / g, which corresponds to the average viscosity mol.  yassi My 26000.  The structure of the synthesized block block is confirmed by the high yield of the target product, which is close to the theoretical, as well as the data of elemental analysis and IR spectroscopy.  Found,%: C 64.51; H 9.81, N 11.96.  SEZ ,, 1 4 “D, Oz44, L5 N 547, l Calculated,%: C 65.86; H 9.74; N 11.44.  In the IR spectra of the block copolymer, observauggs characteristic vibrational bands of vibration mat for polyamide blocks (at 1520, 1540, 1560, 3080 and 3300 cm for H-termes and 1640 cm for) and blocks for polybutadene (at 730 cm-t, 4 cis ; 910 1,2 cis. and at 970 1,4 trans).  Example 3  AT.  A three-necked 500 MP flask equipped with a mechanical stirrer, a cooler, and tubes for injecting and draining dry argon was charged with 6.0 g (1.06 t f-Monb Pa-6 / 66-3 (mol.  mass 6000, x 18) and 120 ml of dry N, K-dimethyl form vada With stirring, the polyamide is dissolved to form a homogeneous solution.  2.65 g (1.0610 g-mol) of polybutadiene (mol. mass 2500, at "38) with terminal isocyanate groups, mixed with 0.01 g (0.005 wt. % by weight of the final product) tin dystildicaprylate (the reaction is carried out for 3.5 hours at).  About 30 minutes before the end of the reaction, 0 g of the antioxidant ionol was added to the flask.  At the end of the reaction, the contents of the flask are drunk into water.  A solid precipitate is filtered off, washed with water and dried at, for 24 hours, under vacuum.   d mm Hg, Art.  above .  The output of the resulting block copolymer with the ratio of blocks of polyamide and poputadiene 70,0: 30,0 wt. % is 8, tg or 93.6% of theoretical.  The polyamide polybutadiene block copolymer obtained is soluble in N, N-dimethylformamide and, methanol-chloroform mixture (80:20 vol. %) The characteristic viscosity of the block copolymer solution in N, H-dimethylformamde is 0.81 dl / g, which corresponds to an average viscosity mass of fiv of 18,000.  The structure of the synthesized block copolymer is confirmed by the high yield of the target product, close to the theoretical, as well as by data. elemental analysis and infrared spectroscopy.  Found,%: C 67.5; H, 9.65; N 10.11, 497 Calculated,%: C 68.8; H 9.81; N 9.36.  In the IR spectra of the block copolymer, characteristic bands of valence oscillations are observed for polyatz blocks (at 1520, 1540, 1560, 3080, and EEPO for B-groups and at 1640 cm for) and blocks of polybutadiene (at 730 1.4 cis} 910 , 2 cis and at 970 1.4 trans) ;.  EXAMPLE 4 Analogously to Example 3, the synthesis was carried out at the following loads: to solution 6, O g (2.0. 10-3 g-mol) PA-6 / 66-3 (chalk i mass 3000, X 9) to 120. MP dry N, N-dimethylformacdda added dropwise 4.74 g (2.0-10 g-mol) of polybutadiene (mol.  mass 2500, 38) with terminal isocyanate groups, mixed with 0.001 g (0.005 wt. % by weight of the final product) dibutyl Dilaurinat tin.  The reaction is carried out at within 3.5 hours  30 minutes before the end of the reaction, 0.1 g of anti-oxidant ionol was added to the flask.  Upon completion of the reaction, the contents of the flask are poured into water.  The precipitate is filtered off, washed with water and dried at 25 ° C for 24 h shade under vacuum “1 mm Hg. st over pjo.  Output received. a block copolymer with a block ratio of polyamide and polybutadiene 55,0: 45,0 wt. % soot is 10.2 g or 94.2% of theoretical.  The resulting polyamide polybutadiene vii block copolymer is soluble in N, N (dimethylformamide and a mixture of methanol and chloroform (80:20 about. %).  The intrinsic viscosity of the block copolymer solution in N, N-dimeshimformayde at SEA is 0.65 dl / g, which corresponds to Mu 10,000.  The structure of the synthesized block copolymer was confirmed by a viewpoint of the target product, close to the theoretical content, as well as by elemental analysis and IR spectroscopy.  .  Found,%: C, 70.97; H 9.88i N 8.47.  LOT + ,, 4N M. B; %: C 72.57- H 10.03; N 7.99.  In the IR spectra of the block copolymer, characteristic stretching vibration bands are observed for polyamide blocks (at 1520.1540.1560.3080 and 3300 cm for W-groups and at 1640 dl) and polybutadiene blocks (at 730 1.4 cis; 910 1.2 qi and at 970 1.4 trans).  Example 5  Similarly to Example 1, 10 LlCl, 60 ml dry H, K-dimethylformamide are loaded into a 50 ml three-necked flask equipped with a mechanical stirrer, a refrigerator, and tubes for injecting and discharging dry argon. homogeneous solution.  6.3 g (2.27 10-g-mol) PA-6 / 66-3 (mol.  mass 3000, x 9) and 35 ml of dry H, K-dimethylformamide.  With stirring, the polyamide is dissolved to form a homogeneous solution.  To the resulting solution, 4.23 (2.110 g-mol of polybutadiene with terminal isocyanate groups) are added dropwise (mol.  mass 2000, 29), mixed with 0.001 g (0.005 wt. % by weight of the final product) dibutyldilaurate tin.  Then, 1 g (0.5710 g-mol) of 2,4-toluylene diisocyanate was added to the flask and 15 ml of dry N, H-dimethylformamide were additionally introduced.  The reaction is carried out at 80 ° C for 3.5 hours.  30 minutes before the end of the reaction, 0.1 g of anti-oxidant ionol was added to the flask.  At the end of the reaction, the contents of the flask are cooled and the resulting suspension is used to make materials such as artificial leather.  The output of the obtained block copolymer with a ratio of blocks of polyamide and polybutadiene 60,0: 40,0 wt. % is 9.3 g of the share 93.0% of the theoretical.  The resulting polyamide polybutadiene block copolymer is soluble in N, N-dimethylformamide and a mixture of methanol / chloroform (80:20 vol. %).   The intrinsic viscosity of the solution of the block copolymer in H, L-dimethylformam more when it is equal to O, 73 dl / g, which corresponds to the average viscosity mol.  mass 13000 m.  The structure of the synthesized block copolymer is confirmed by the high yield of the target product, close to the theoretical, as well as by the data of elemental analysis and IR spectroscopy.  Found,%: C 67, 12; H 8.87; N 11.03.   1157, E4 P96, E40) 5T, 25 -5E, T2 Calculated,%: C 68.31; H 8.90; N 10.58.  In the IR spectra of the block copolymer, characteristic stretching vibration bands are observed for polyamide blocks (at 1520, 1540, 1560, 3080, and 3300 dp of W-groups and at 1640) and blocks of polybutadiene (at 730 1.4 cis, 910, 2 cis and at 970 1.4 trans).  Example 6  Analogously to Example 1, the synthesis was carried out under the following loads: to a solution of 36.3 g (710 g-mol) pA-6 / 66-3 (mol. mass, 6000, X 18) in 180 MP of dry N, N da1 methylformamide was added dropwise 4.2 g.  (1.68-10 g-mol) of polybutadiene (mol. mass 2500, at 38) with terminal AND: isocyanate groups, mixed with 0.001 g (0.005 wt. % by weight of the final product) dibutshsaurinate.  olo, wa.  Next, 0.74 g (4.4-10 g-mol) of 1,6-hexamethylene diisocyanate is added to a cobba and further 20 ml of dry N, N-dimethylformamide are added.  The reaction is carried out at 90 ° C for 3.5 hours.  Thirty minutes before the end of the reaction, 0.4 g of the ionol antioxidant was added to the flask.  At the end of the reaction, the contents of the flask are cooled and the resulting suspension is used to make materials such as artificial leather.  The output of the obtained block copolymer with a block ratio of polyamide and polybutadiene 90,00: 10.0 wt. % is 38.1 g or 93, 1% of the theoretical.  The resulting polyamide polybutadiene block copolymer is soluble in N, N-dimethylformamide and a mixture of methanol / chloroform (80:20 vol. %).  The characteristic viscosity of the block copolymer solution in N, N-dimethylformamide at 1.12 dl / g, which corresponds to the average viscosity mol.  mass RV 23000.  The structure of the synthesized block copolymer is confirmed by the high yield of the target product, which is close to the theoretical, as well as by the data of elemental analysis and IR spectroscopy. Found: C 64.56; H 9.73; N 11.61.  -229l, 3fc 48 i. -tz 343.8 6.65; H 9.85) Calculated,%: C N 11.49, characteristic spectra are observed in the IR spectra of the block copolymer. Oscillation bands for polyamide blocks (at 1520.1540.15560.30080 and 3300 MN-groups and at 1640 cm for dl) and blocks of polybutadiene (at 730 1.4 cis 1 910 cm-1.2 qi and at 970 1 , 4 trans).  .  Example 7  Similarly to Example 1, the synthesis was carried out under the following charges: to a solution of 36.0 g (6 10 g mol) PA-6 / 66-3 (mol. mass 6000, X 18) in 180 ml of dry N, N-dimethylformamide was added dropwise 4.2 g (1.2 pLa-mol) of polybutadiene (mol mass 3500, 53) with terminal isocyanate groups mixed with 0.001 g (0.005 May. . % by weight of the final product) tin dibutyldilaurinate.  Then 1.22 g was introduced into the flask.  (4.810 gmol) 4,4-diphenylmethane diisocyanate and additionally administered 20 ml of dry K, H-dimethylformamide.  The reaction is carried out for a period of 3.5 hours.  30 minutes before the end of the reaction 9, the flask was introduced with 0.4 g of the antioxidant ionol.  At the end of the reaction, the contents of my flask are cooled and the resulting suspension is used to make materials such as artificial leather.  The output of the obtained block copolymer with a block ratio of polyamide and polybutadiene 90:10 wt. % is 38.4 or 92.7% of theoretical.  The resulting polyamide polybutadiene block copolymer is soluble in N, K-di-; methylformamide and methanol-chloroform mixtures (80:20 vol. %).  The characteristic viscosity of the block copolymer solution in N, N-dimethylformamide. when it is 0.98 dl / g, which corresponds to the average viscosity - mol.  mass of MV 20000.  The structure of the synthesized block copolymer is confirmed by a high yield of the target product, close to the theoretical, as well as by elemental analysis and IR spectroscopy.  Found,%: C 60.21; H 10.98j N 12.96.  18 74 × 4012, 4 Calculated,%: C b 1.42, H 11, u4j N 12.93.  In the IR spectra of the block copolymer, characteristic valence vibration bands are observed for the polyamide blocks (at 1520.1540.1560.30.30 and 3300 cm-length X-groups and at 1640 dl) and polybutadiene blocks (at.  thirty.  1,4 CIS-, 910 1,2 cis and at 970 1,4 trans).  Example 8  Analogously to Example 1, the synthesis was carried out under the following loads: to a solution of 36.0 g (1.76-10 g-mol) PA-6 / 66-3 (mol.  a mass of 20,400, x 60) in 180 mp of dry N, N-dimethophormamide is added dropwise 4.0 (0.8310 g-mol) of polybutadiene (mol.  mass 4770, 80) with terminal isocyanate groups, mixed with 0.001 g (0.005 wt. % by weight of the final product) dibutyl-dilaurin and tin.  Next, 0.23 g (0.9310 g-dl) of 4,4-diphenylmethane diisocyanate was added to the flask and additional 20 ml of dry H, H-dimethylformamide was added.  The reaction is carried out at 90 ° C for 3.5 hours.  Thirty minutes before the end of the reaction, 0.4 g of the ionol antioxidant was added to the flask.  At the end of the reaction, the contents of the flask are cooled and the resulting suspension is used to make materials. type of artificial leather.

The yield of the obtained block copolymer with a ratio of blocks of polyamide and polubitadiene is 90:10 wt%: 37.6 or 93.5% of theoretical ;. go The resulting polyamide polybutadiene block copolymer is soluble in S, N-dimethylformamide and a mixture of methanol-chloroform (80:20 vol.%). The characteristic viscosity of the solution of the block copolymer in N, M-dimethylformamide is 1.23 for / ri which corresponds to the average acoustic mass of MV 24000.

The structure of the synthesized block-polymer is confirmed by the high yield of the target product, which is close to the theoretical one, as well as by the data of elemental analysis and the IR spectroscope.

Found,%: C 64.43; H 9,

N12.09.

, e5 i4lO; 5 Oj28 9

Calculated,%: C 65.93; H 9.85; N 11.27.

In the infrared spectrum of the block copolymer

The characteristic bands of the vibrational vibrations of dp of polyamide blocks (at 1520, 1540, 1560, 3080 and 3300 cm for H-groups and at 1640 cm for) and blocks of polybutadiene are given (at 730 1.4 "HCj 910 1.2 cis and at 970 1,4 trans) Synthesized polyamide polybutadiene block copolymers are dissolved by heating in S, H-dimethylformaine and, at room temperature, in a mixture of methanol: chloroform (80: 20 vol.%) ./ Films based on them are transparent and elastic. According to the data of thermo-mechanical analysis (load. 9.6 kgf, / cm), the block copolymers are two-phase and have two glass transition layers: at -80 and.

The composition of the BSP, wt.%

W "MMLTsMMMM

L PA I P8

 "M m | y1" "

99 95 90 70

t 5

to

thirty

45

55

The resulting prliamide polybutadiene block copolymers are promising for use as a front coating for artificial leather intended for the manufacture of inner parts of footwear (insoles, lining, etc.).

The hygienic properties of the samples of artificial leather with a face coating of polyamide polybutadiene block copolymers are given in table 1.

As can be seen from the above examples, the proposed one-step method for the preparation of polyblock polyblock polyblock. polybutadiene block copolymers are simple, based on the use of industrial products and can be carried out on serial equipment. Samples of artificial sozh with the front coating of the proposed block copolymers have higher HYGIO-. have better skin properties than face leather with a coating of known copolymers or a Sanprene E-18 urethane block copolymer (Table 1).

In addition, polyacdprolibutadieNew block-conojHiMep, containing 5 wt% polybutadiene blocks, is promising as an additive to industrial polyetherrethane of the brand Sanpren E-18, which increases the sorption properties of the gray-haired one (twice) (Table 2). Moreover, the indicated increase in sorption properties is achieved with a low content of the additive (5 hours per 100 hours of polyether: urethane).

Hygienic properties of samples of artificial leather with facial coating based on polyester-; The urethane grades Sanprene E-18 and polyag Shdpolybutadiene block copolymers are given in Table. 2

Table

4, n

4.06

2.89

4.35 5.27 3.21

 2.96 3.47. 2.50

0.85 0.66 3.50

2.97 0.54

1.03

2.97

6 (Sanpren E-18 ROM)

7PA-PB-PA bloc copolymer of composition 5: 5 mue. (Well-known).

3.56

1.01

0.65

1.00

0.63

0.52

3.46

il.OO

Claims (2)

1. Polyamide polybutadiene block copolymer of the General formula 45.0) May. 7 and a molecular weight of 10000-30000 as a material for the facial coating of artificial leather. 2. A method of producing a polyamide poly-, butadiene block copolymer by reacting polybutadiene, a diisocyanate and a component forming a polyamide block in the presence of an organometallic catalyst, characterized in that, in order to improve the hygienic properties of artificial leather, a polymer of the formula ’is used as polybutadiene SU „„ 1120045> And ⁰ ° “ ^C “ ^M -TOG ^NH ~ ^C ~ ° “ ^CH r ^CH ff CHfCHHJH-CH ^ CHj-CHiHKnH N = C — 0 H ₃ c CH J where y = 29-80, polyamide block, watering is used as a component forming the amide PA-6 / 66-3 of the formula 0 0 o HO ^ C-fCH, ^ NH-d-fCHg ^ - hhJ-h _? where x ^and C-60, la as the organometallic catalyst is an organotin compound, the reaction is carried out in one stage with the ratio of the NCO groups: (NHj + COOH) of the reagents 1: ί on the average, д of dimethylformamide or a 5% solution of Liclв, Ν- dimethylformamide at 80-100С.