SU740793A1 - Structurally coloured water-soluble epoxy resin as film-producing agent of paint-varnish coatings - Google Patents

Description

actrapiridine, benzanthrone, - isothiaeolantrone, pyrazolanthrone, phthaloyl acridone, phthaloylbeneimidazole, and so forth. - One of the most important problems in dyeing in bulk is the dyeing of the dye in the resin. The dye injected into the resin does not provide a sufficiently even color tone, and therefore the problem of choosing the most effective method of dispersing the dye arises. to ensure the required dispersion, a special pigment nepeTVij is required for a sufficiently long period of time. Staining water-soluble resins that can be used as aqueous film-forming agents poses special difficulties due to the fact that water and aqueous solutions of resins do not wet pigments worse, which makes it difficult for the pigment to bind with the binder; the introduction is special ;; wetting reduces the quality of forming coatings. The coatings with dispersed dye possessed a rather high chalking caused by the interaction of the CG dye with light and film-forming agent, leading to sweating of the dye or pigment on the surface of the coating 1,: The purpose of the invention is to synthesize colored water soluble sdolk. suitable for color lacquer coatings with reduced grinding. This goal is achieved by carrying out the process of joint polycondensation of epichlorohydrin, propane chloride, sodium salt of propanchlorine hydrinsulfonic acid, and an anthraquinone series dye capable of coping with haloalkyl-sh, the content of paint in the starting reaction mixture with Si is 15-50% by weight. the content of the dye is due to the possibility of reactions between ag / shnoxo derivatives of anthraquinone to the sodium salt of propanchlorohydrin sulfoxide in chlorine in an alkaline medium. Anthraquinone dye dyes are primed Yes oaz of personal colors About Nliv I AMUHO OH CU anthraquinone (ffpac b / u ZC) NHdHjCHaOH HO 0 WHdH CHgOH i; t-L I9n a - olamino-5, S di JOHcuoHri-ipa. x blue - AS fievifc /) 0 UN, GL HHj ZD -, 11, yamino - anmpa) fuHO j ffiuonemoSotu C) NHdHociH-cHj v „oiH 0 imdHjdH-dH.a 0 1, Diama 5 Z-Memoffcuaffm - paxuf OM Snorsc uSupoSaHi-ffffu KKdHjdH- dHg 0 i HdHodH-CH i - Leah loasiamiio - antrahino O nn, a irf gfffii fH intezyrovapiyz ene resin employed for psshucheni colored paint coatings from aqueous oro in lux in a better understanding of the invention are ML-track toadae examples half-painted water-soluble epoxy resins, p and m er 1, a three-neck gauge with a stirrer, a reverse ODILE and a thermometer, will absorb 39.32 g (0.2 mol) sodium salt propanchlorhydro-sulfonic acid, 35.34 g (0 , 1 mole) rasitel -dietanolamnns 5, 8 - dioksiantraona, 8 g (0.2 mol L) th to Attr caustic and dissolved obavl 500. g- / l of water. iPeAKUHOHHsn j jumbo baring: t at 100 ° C for 1 hour, after which 22.83 g (0.1 mol) of diphenylolpropane 8 g (0.2 mol) of caustic soda and 4b, 2 (0.5 mol) of epichlorohydrin are charged, Conducted to condense These compounds are then distilled off for 1 hour, then water and excess epichlorohydrin are distilled off and the product obtained is dried. After separation from sodium chloride, 82 g (82%) of product are obtained, which is a blue powder. The molecular weight of the obtained compound is 1001.0, epoxy resin is 11.40%, the sulfur content is 6.40, the maximum absorption wave E of an aqueous solution is 650 nm. When grown in water, the product gives a 22% solution. The structural formula of the resulting compound can be represented by formula I, where X ,, Xa is NHCH, CH20-, Vr. one,, . Calculated: C 54.00; H 5.03 S 6.41; N 2.80, Found,%: C 53.20; H 4.91; 56 N2.91. Example 2. In a three-neck flask equipped with a stirrer, a reflux condenser and a thermometer, 58.98 g (0.3 mol) of sodium salt of propanchlorohydrin sulfonic acid, 47.84 g (0.2 mol) of 1-amino-4-hydroxyanthraquinone dye, 12 g (0, 3 mol of sodium hydroxide, 500 ml of water and hold the reaction mixture for 1 hour. Then, 22.83 g (0.1 mol) of diphenylolpropane, 8 g (0.2 mol) of caustic soda and 46.25 g are loaded into the flask. (0.5 mol) of epichlorohydrin and condensation is carried out for a period of 1 hour, after which excess epichlorohydrin is distilled off and the product is dried. moreover, sodium is obtained 110 g (86%) of a solid colored in claret color. The molecular weight of the obtained compound is 1279.3, the epoxy number is 8.92%, the sulfur content is 7.51%, the maximum absorption wavelength in water Thief 550 nm. When dissolved in water, the compound gives; 30% solution. The structural formula of the obtained compound can be represented by the formula I, where X is NH-, X "- 0-, W 2, 1, p 0. Calculated,% : C, 54.45; H, 4.18; S7.52; N2.19. NaIDE,%: C 54.00; H 3.98; in 7.42, N2.28. Example 3. In a three-necked flask equipped with a reflux condenser, Tept "MeTpoM and a stirrer, load 39.32 g (0.2 mol) of the sodium salt of propanchlorohydrin sulfonic acid 8 g (0.2 mol) of caustic soda. 68.49 g (0.3 mol) of diphenylolpropane, 500 ml of water and incubate the reaction mixture for 1 hour. Then load into the flask 35, .04 g (0.1 mol) of the dye epoxidized 1,4-diaminoanthraquinone, 8 g (0.2 mol) of caustic soda and 46.25 g (0.5 mol) of epichlorohydrin. Condensation of these compounds is carried out for 1 hour, after which the water and KZ 3 distilled epichlorohydrin are distilled off and dried. After separation of the sodium chloride, 121 g (83%) of a violet colored solid is obtained. The molecular weight of the obtained compound is 1465.6, the epoxy number is 7.78%, the sulfur content is 4.37%, the maximum absorption wavelength in an aqueous solution is 565 nm. The resulting compound is dissolved in zodia to form a 15% purple solution. The structural formula of the obtained compound can be represented by the formula I, Q where X-J, is NH-CHo-CH-CH, -, W 0, and 2, p 1. Calculated,%: C 63.10; H 5.64, S 4.38; A 1.91. Found,%: C 64.20; H 5.68; , 21; L / 1.85. Example 4. In a three-necked flask,., Equipped with a reflux condenser, a thermometer, and a stirrer, 19.58 g (0.1 mol) of sodium salt of propanchlorohydrinsulfonic acid, 4 g (0.1 mol) of caustic soda, 68.49 g (0, 3 mol) of diphenylolpropane, 500 ml of water and incubated the reaction mixture for 1 hour. Then, 76.08 g (0.2 mol) of an epoxidized dye 1,4-diamino-2-label 1-anthraquinone, 8 g (0.2 mol of caustic soda and 46.2bg (0.5 mol) of epichlorohydrin. These compounds are condensed for 1 hour, after which water and excess epichlorohydrin are distilled n and dried. After separation of the sodium chloride, 139 g (81%) of a bright pink colored substance is obtained. The molecular weight of the product obtained is 1718, the epoxy layer is 6.64%, the sulfur content is 1.86%, the maximum wavelength is absorbed, and in one solution is 565 nm. Compound. A 6% aqueous solution. The structure of the compound obtained can be represented by the formula 1, where X-, - - NH-CH -CH, VTl, P2. Calculated,%: C 67.11; H 5.92; 51.86 W 3.2 7. Found, 4; C, 67.28; H 5.98; S 1.72; N3,32. Example 5. A thermometer and a blender of 78.64 g (0.4 mol) sodium salt of propanchlorohydrine sulfoxanol 47 (0.2 mol) dye, 5-diaminoan raquinoneEr 16 g (O, 4 mod) caustic n The mixture was stirred at 100 ° C for a period. After which the mixture was charged with 3 g (0.2 mol) of caustic soda and 16.25 g (0.5 mol) of epichloric. Condensation was carried out. These substances are for 1 hour; the water and excess epichlorohydrin are then distilled off and the product obtained is dried. After separation of spx chloride and three receive 142 g (86%) of the product, represented by a red powder, the molecular weight of the obtained product is 1647.7, the epoxy number is 6.92%, the sulfur content is 7.78%, the maximum length of the absorption wave is 505 im. The resulting product is dissolved in water in red; red with a color of 32%. The structural formula of the obtained Compound can be represented by Formula I, where X X, -NH -, Up-2, K1-2, p 0 Calc-1Sleno, %: C 55.40; H 4.52; 5 7.78; N 3.39, Found,%: C 55.61; H 4.61; S 7.68; N 3.42. Evidence of the structural staining of the resin may be a shift in the maximum wavelength of the lamination (L max.) Of the dyed product with respect to the dye, sho, h due to a change in the nature of the chain associated with the chromophore group. For the dilute aqueous solutions of the dyes and the aqueous solutions of the resins, the following values of the maximum wavelengths were absorbed: L max. Resin according to example 1650 Dye 1,4-dietano amino-5,8-dioxyanthraquinone630 Resin according to example 2550 Dye 1 amino-4-oxyanthramine. UH530 Resin according to example 3565 Dye 1,4-diaminanthraquinone .545 Resin according to use- :: 4565: .: r - a - 1,4 -; - 1Io shno-2-methoxyanthraquinone 540 Resin according to Example 5505 Dye 1,5 diaminoanthraquinone 490 The obtained resins are precipitated from an aqueous solution with barium chloride to form barium lacquers by sulfo groups. At the same time, solids of the corresponding colors, which are polymeric pigments, are not soluble in water. The formation of colored precipitates with complete decolouration of aqueous solutions can also serve as evidence of the dye entering the oligomer molecule with the chemical bond formed. The structure of the synthesized resins is confirmed by elemental analysis and infrared spectra, removed. (On a two-beam infrared X-22 trophotometer. The resins obtained give color films from aqueous solutions. Films were cured at 120 s for 1 hour. Dethylentetramine, tetrabromophthalic anhydride were used as hardeners , polyethylene polyamine (in the amount of 7-10% by weight of the resin). The coatings obtained under the described conditions, 20–40 µm thick and containing 8090% of the three-dimensional product, were tested according to the following methods: the thickness of the coatings is determined at WASHING of the ITP-.1 thickness gauge, the determination of the strength of the films upon impact is given on the pr-t selection of the U-Y brand according to GOST 4765-73; the strength test on the GTP on the SHG device according to GOST 6806 -73; test of hardness - on the instrument of mark M-3 in accordance with GOST .52.33-67; test for melee. - on the instrument (described in the article by MI Karinoy and Goncharova I, S. The pneumatic stationary portable instrument for determination of the degree of chalking of paint and varnish coatings, published in the journal Paintwork materials and their application, 1963, No. 4, as well as in book 3 Livsh Itsa M.L. Technical analysis and control of the production of varnishes and paints, M., Higher School; 1973 ,, p. 197-200, according to GOST 6992-68.

Samples of coatings obtained from resins with different ratios of the starting components:

1. Structure-colored water-soluble epoxy resin based on epichlorohydrin (ECG), diphenylol propane (DFP), sodium salt of propanchlorohydrin sulfonic acid (Na - PHGSK)

and the dye 1,4-diethanolamino-5,8-dioxyanthraquinone.

The molar ratio of the components; ECG: DFP: On-PHC: dye 0, 5: 0.1: 0.2: 0.1

2. The same. The dye is 1-amino-4-axianthraquinone ECG: DFP: Na-PHGSK: dye-0.5: 0.1: 0.3: 0.2.3. The same. The dye is epoxidized 1,4-diaminoanthraquinone ECH: DFP: Ma - PHGSK: the dye is 0.5: 0.3; 0.2: 0.1.

Comparative physicomechanical properties of coatings based on structurally-painted water-soluble epoxy resin and water-soluble epoxy resins with dispersed dye

Coatings based on structurally dyed epoxy resins

4. The same. Dye-epoxidized 1,4-diamino-2-methoxyanthra, and non.

ECG: DFP: Na - PHGSK: dye 0, 5: 0.3: 0.1: 0.2.

5. The same. Dye - 1,5-diamine anthraquinone ECH: DFPsA - PHGSK: dye -0,5: 0,2: 0,4: 0,2.

To compare coatings based on the water content of the resins pigmented by bound dyes, coatings obtained from aqueous solutions of unpainted resins with dispersed dye were tested, the free dye content being equal to the content of the bound dye in the structure-colored resins.

The test results are given in. the table.

Water-based coatings

epoxy resin dispersed

dye

The test results show that coatings are based on structured, water-soluble epoxy coatings; resins are superior in their properties to pigmented coatings based on 55 grams

-E

HdKrHs

H

.CHi

Claims (1)

1. USSR author's certificate in application number 2414695, class, C 08 G 59/02, 1977,