SU777045A1 - Coloured polyester resins for porous polyurethans with high photosensitiveness and their preparation method - Google Patents

Description

((H2) 2-o-d - ((H: 2)

00

p, CHj

I 0- (CHj 2-0- {Hj) 2-0-YCh U (; - (t j 00% 0 0- /

-Go - ((; H2) 2-0- {CH212-0-Y-1 (H214-4 fR-C-KH li-C ln-l L Jx (il

0O - 00

{o- (H2) 2-0-No. 2) 2-0- (| - ((Hg) 4- (| -0- (CH2) 2-0- (CH2)

00- /

e / Tt-l,; j l,, y l, n j tO-li, - f tep-r -: i 2

0 NflNH -HK 0 CHj

in AtfKj, -N02 -H;

 , -DVH-, -0-, and the method of their preparation, which consists in carrying out. Condensation of phthalic anhydride with diphenylolpropane at 145-155 ° C, followed by interaction of the obtained product with adipic acid, diethylene glycol, trimethylolpropane, catalyst and dye in the amount of 4.6-9.9% of the total weight of the components at 195-205 ° C. As dyes, bifunctional dyes of anthrachos of the “on-new and posicyclic series are used: 1,4-diaminoanthraquinone (dispersed purple K) 1 -Amino-4-oxyanthraquinone (dispersed red 2C) 1-amino-2-methoxy-4-oxyanthrahino (dispersed pink G) 1,4-Diamino-2-methoxyanthraquinone (dispersed bright pink) 1,5-Diaminoanthraquinone (dispersed orange, intermediate product for the production of vat dyes) 1,5-Dioxy-2-bromo-4,8 - diami α-norathraquinone (polyester blue) 1,8-dioxy-4,5-di- (methylamino) - anthraquinone (dark blue) 1,4-dioxy - (ethylamino) -5.8 - dio xianthraquinone (dispersed blue-green) 1,4-diamino-5 - nitroanthraquinone (purple 2C dispersed) Dioxyviolantrone (intermediate product for the bottom green dyes)

fa

(n2-s - (; H2-o - (- (dH2i4 - (; - fIIll I rf

CH20H 00-0 0 KlI (; il2CH20H -1Ш 0- OH

d 6 KHCHjdHjOH OH 0 NII Example 1. A three-neck flask with a capacity of 250 ml, equipped with a Liebig condenser, contact thermometer and mechanical stirrer, was charged with 7.4 g (0.05 mol) of phthalic anhydride, and the melting point (131 ° C) and melt were heated are kept at this temperature to avoid sublimation. With constant stirring, the flask is flushed with nitrogen for 5 minutes, then 5.71 g (0.025 mol) of diphenylolpropane is charged, the mass is heated to 150 ° C and maintained at this temperature for 3 hours in a stream of nitrogen. After this, 45.1 g (0.425 mol) of diethylene glycol is slowly charged, not significantly lowering the temperature during the charging process, and stirred for 1 hour, at the same time bringing the mass to 150 ° C, then 3.35 g (0.025 mol) of trimethylolpropane are charged. , 5.96 g (0.025 mol) of 1,5-diaminoanthraquinone, 62.11 g (0.425 mol) of adipic acid, 0.0002 g of tetrabutoxytitanium, 0.0002 g of iron powder, 0.001 g of ammonium molybdate. The flask is purged with nitrogen for 10 minutes, the temperature is raised for 0.5 hours to 200–205 ° C, and maintained at this temperature for 4 hours. After the indicated time has passed, a vacuum of 300–500 mm. the temperature of the reaction mass is 205–207 ° C,

t p n +.

The average molecular weight of the polyester formed, determined by the method of ebulioscopy (the molecular masses of all the formations of their polyesters are determined by the method of ebulioscopy) is 4450. The calculated molecular weight is 4536.88,

max 505 NM.

Found,%: C 58.03; H 7.12; N 0.66. Calculated,%: C 58.51; H 7.02; N 0.62. Example 2. The process is carried out as in Example 1, using the following amounts of substances, g (mol):

Phthalic anhydride 8.89 (0.06) Diphenylolpropane6.85 (0.03)

Diethylene glycol 47.75 (0.45)

Trimethylolpropane4.02 (0.03)

1,4-DiamI | NoanthraquinOH 7.15 (0.03) Adipic acid 65.76 (0.45) Catalyst charges remain the same. Polycondensation is carried out at 195-200 ° C.

Get 118.2 g (yield 84.2%) resin red-purple color of the formula 1, where

about y; p y; y +, with a molecular weight of 4200. The calculated molecular weight is 4105.43. Hmake 480nm. Calculated,%: C 58.82; H 6.98; N 0.68. Found,%: C 58.04; H 7.10; N 0.65. Example 3. The process is carried out as in Example 1, using substances in the following amounts, g (mol):

Phthalic anhydride 8.89 (0.06) Diphenylolpropane6.85 (0.03)

Diethylene glycol 41.39 (0.39)

Trimethylolprotsan4,02 (0,03)

1 -Amino-4-oxyanthraquinone 7, 18 (0.03)

Adicic acid 56.99 (0.39) 104.5 g (yield: 83.4%) of a red gum is obtained, whose composition is expressed by the formula 1, where

RII

0,

with a molecular weight of 3720. 1max. 535nm. The calculated molecular weight is 3672.93. Found,%: C 59.51; H 7.00; N 0.39. Calculated,%: C 59.19; H 6.89; N 0.38. Example 4. The process is carried out as described in example 1, using substances in the following amounts, g (mol):

Phthalic anhydride 7.4 (0.05) Diphenylolpropane 5.71 (0.025) Diethylene glycol 45.10 (0.425) Trimethylolpropane 3.35 (0.025) 1,4-Diamino-2-methoxyanthraquinone 6, 71 (0.025)

Adipic acid 62.11 (0.425) 107.4 g (yield 84.3%) of a red-violet polyester are obtained, whose composition is expressed by: formula 1, where t + (

(

Xq25

4490. I, max. With a molecular mass of 520 NM. Computed

molecular weight 4566.903. Found,%: C 58.39; H 7.00; N 0.57. Calculated,%: C 58.39; H 7.02; N 0.61. Example 5. The process is carried out similarly to onHcaHHOMLy in example 1, using substances in the following amounts, g (mol):

Phthalic anhydride7.4 (0.05)

Diphenylolpropane5.71 (0.025)

Diethylene glycol42.45 (0.4)

Trimethylolpropane3.35 (0.025)

1 -Amino-2-methoxy-4-oxyanthraquinone 6, 73 (0.025)

Adipic acid 58.46 (0.4) 104.4 g (yield 84.2%) of a red-brown polyester are obtained, whose composition is expressed by the formula 1, where

about other From,

050

t p x n +,

with a molecular weight of 4480. max. 510nm

Calculated molecular weight 4351.65

Found,%: C 58.57; H 7.25; N 0.31. Calculated,%: C 58.51; H 6.93; N 0.32.

Example 6. The process is carried out as described in example 1 with the following amounts of components, g (mol):

Phthalic anhydride 8.89 (0.06) Diphenylolpropane6.85 (0.03)

Diethylene glycol 47.75 (0.45)

Trimethylolpropane4.02 (0.03)

1,4-Diamino-5-nitro-anthroquinone 8, 02 (0.03) Adipic acid 65.76 (0.45) Obtain 118.7 g (yield 84.0%) of a violet-colored polystyrene, the composition of which is expressed by the formula 1, where this p n +, with a molecular weight of 4220. Lmax. 620 nm. The calculated molecular weight is 4133.42. Found,%: C 58.28; H 6.89; N 1.02. Calculated,%: C 58.27; H 6.93; N 0.97. Example 7. The process is carried out analogously to example 1 with the following quantities of substances, g (mol): Phthalic anhydride 8.89 Diphenylolpropane 6.85 Diethylene glycol 44.57 Trimethylolprocane 4.02 1,8-Dioxy-4,5-di- (methylamine) -anthraquinone 8.95 Adipic acid 61.38. 113.6 g (yield 84.3%) of a dark blue polyester are obtained, whose composition is expressed by the formula 1, where -о о 0m is p I; n +, with a molecular weight of 4090. Yamax. 615 nm. The calculated molecular weight is 3948.23. Found,%: C 58.65; H 7.15; N 0.69. Calculated,%: C 58.71; H 6.95; N 0.71. Example 8. The process is carried out as described in example 1 with the following amounts of substances, g (mol): Phthalic anhydride 8.89 (0.06) Diphenylolpropane 6.85 (0.03) Diethylene glycol41.39 (0.39) Trimethylolpropane4.02 (0.03) 4,8-DiaminO-2-bromo-1,5-dioxyanthraquinone 10, 47 (0.03) Adipic acid 56.99 (0.39) 108.5 g (yield 84.5%) of polyester are obtained blue, whose composition is expressed by formula I, where m p n +, with a molecular weight of 3695, Yamax. 610 nm. The calculated molecular weight is 3782.85. Found,%: C 57.21; H 7.10; N 0.78. Calculated,%: C 57.47; H 6.69; N 0.74. Example 9. The process is carried out similarly as described in tsimer I, using the following amounts of substances, g (mol): 5 10 20 25 30 40 45 50 55 60 65 Phthalic anhydride 8.89 (0.06) Diphenylolpropane 6.85 (0, 03) Diethylene glycol 44,57 (0,42) Trimethylolpronane 4,02 (0,03) 1,4-Dioxyethylamino-5,8 Dioxyanthraquinone 10.75 (0.03) Adipic acid 61.38 (0.42) Obtain 115.4 g (yield 84.6%) of a blue-green polyester, whose composition is removed by pho / rmulo 1, where KHClijCHjOtl is about XHCHjCHjOH and pn + q, with a molecular weight of 4030. Yamax. 600 nm. The calculated molecular weight is 4008.28. Found,%: C 57.53; H 7.15; N 0.69. Calculated,%: C 57.83; H 6.74; N 0.70. Example 10. The process is carried out as described in example 1 with the following amounts; substances: Phthalic anhydride 8.89 (0.06) Diphenylolpropane 6.85 (0.03) Diethylene glycol47.75 (0.45) Trimethylolpropane 4.02 (0.03) Dioxyviolanthrone 14.66 (0.03) Adinic acid 65.76 (0.45) 124.1 g (yield: 83.8%) of a dark green polyester are obtained, the composition of which is expressed by the formula 1, where tr pn +, with a molecular weight of 4425. Yamax. 585 nm. The calculated molecular weight is 4354.08. Found,%: C 60.76; H 6.70; Calculated,%: C 60.96; H 6.71. The structure of the obtained polyesters is proved by IR spectra. The resulting resins are bright colored and have a high solubility in polyester resins. The duration of the combination of the short polyester resin with the unpainted one is no more than a few minutes during the propulsion. On the basis of the proposed, painted polyester resins with high lightfastness get polyurethane foam. The compositions for polyurethane foams include the proposed colored polyester resins with enhanced light resistance, polyester P-2200, toluene diisocyanate, activator mixture of the following composition (per 100 g of polyester resins), ml: Urea (50% height) Z.P. Privocell1.27 Sulfuricinate1,19 Vaseline oil0,17

To compare the properties of the synthesized resins with known ones, colored resins according to prototye were obtained, and based on them polyurethane foams of similar composition.

The tests were carried out on samples in the form of bars of size 100x50X25 cut from polyurethane foam blocks so that their height (25 mm) coincided with the direction of foaming. Irradiation is carried out with PRK-4 mercury-quartz lamps at a distance of 16 cm to the irradiated surface for 25-175 h at 20 ° C.

The resistance of polyurethane to UV rays is assessed by the color change of the irradiated layer. The irradiated samples are compared with the original polyurethane foam, the change in color is expressed in a five-point system (5 — the film does not change color).

The test results are shown in the table.

As follows from the data given in it, polyurethane foams based on the proposed and known resins have a high uniformity of color.

However, polyurethane foams based on the proposed dyed polyester resins have a higher resistance to visible light and UV irradiation.

Thus, the use in polyurethane foams of small quantities of the proposed colored polyester resins significantly increases their light resistance and paints products in strong, stable colors.

Fofmula of the invention 1. Colored polyester resins of general formula

G1

n4- (СН2) 2-о - (; н2} 2-о - (- 1сн2) 4th 4 -fО-CH -c-CHj-o-O-tCHjU-iff

tl I L fTJ

00СНгОн 0o

G. 1

I o- (CH,) 2-0 - (“H,), - 0-c-; - - С-fy- «4

  II / II y I II II I.

-00CH; 00 f

- | --- (C1G2) 2-0- (CH2) 2-0 - {; - 1 (12)) (i,

-Go (C112) 2-0-1C 12) 2-0 - (- SI214 - (- 0- (C) D) 2-0- (CK2) 2-o4n

-ii0g e / nl ,, xl, t / l, l + 5 10-14g,

0 N11,

Claims (2)

I II II II NH 0 AI -tlH 0 CHj "Hj B- -OCll ,, -N02 .- f i p- -Nil-, -0-, with a molecular weight of 3700-4500 for polyurethane foam with increased light fastness. 2. A method of producing polyester resins according to claim 1, concludes: that the condensation of phthalic anhydride with diphenylolpropane is carried out at 145-155 ° C, followed by the reaction of the obtained product with adipic acid, diethylene glycol, trimethylolpropane, catalysis and dye in the amount of 4.6-9.9% of the total weight of the components at 195-205 ° C. Sources of information taken into account in the examination 1. The patent of England No. 838716, cl. 2 (5) R, pub. 06/22/60. 2. USSR author's certificate for application No. 2503131, cl. C 08 G 63/68, 07/05/77 (prototype).