SU433687A3 - METHOD OF OBTAINING PRODUCTS STUMP POLYCONDENSATION - Google Patents

Description

one

This invention relates to chemical technology, in particular to the preparation of stepwise polycondensation products based on epoxy resins.

A known method of obtaining products.

step-by-step polycondensation by reacting polyphenyl ether polyglycidyl ether with an aliphatic dipermic diamine in a ratio of 2 modes of amino groups, per 1 mole of epoxy groups and then reacting the resulting adduct with polyepoxide in the presence of an organic solvent.

The purpose of the invention is to obtain stable step condensation products. For this, polyphenol ether and polyphenol aliphatic diphermic diamine are taken in a ratio of 3-5.5 eq. Per 1 eq of epoxy groups and the resulting adduct, beta, root in the amount of 2-eq. Per 1 eq of polyepoxide.

 polyglycindylblue ether can be obtained from polyatomic phenols or polyphenols, such as resorcinol, phenol-formaldehyde condensation products of the resol or novolac type, bis- (fl.-hydroxyphenyl) methane and especially 2h2-bis- (4-yuxiphenyl) -propane- (diomethane) .

Oco6ieHHO is suitable polyglycidyl ether of 2,2-bis- (4-oxiphenyl) propane, which contains 3.8-5.8 eq of epoxy groups per kg.

Cycloaliphatic or cycloaliphatic-aliphatic diphermic amines can be used as aliphatic dipermic amines, in which at least one of the primary amino groups is bonded to the cycloaliphatic ring carbon atom and contains 2-14 carbon atoms. Such amines include, for example. 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophorone diamine, 1-amino-2-aminomethyl-tsshoheptan and 4,4-α-diamino.-Dicyclohexylmethane. Can also be used: acyclic aliphatic diamines, for example ethylenediamine , propylenediamine or triethylentetramine.

According to the proposed method, an adduct of phenol polyglycidyl ether with amine is first fed. The reaction temperature is 3433687 1OO-120 ° C, preferably 110-12 ° C. Since the reaction is exothermic, it is sufficient to heat one of the components involved in the reaction, for example, a diamine, to 100 ° C and then enter a polyglycidipic 5 After the cycle has passed, the reaction that takes place in the absence of oxygen can be considered to be terminated. An organic solvent, for example dioxane, isopropyl, ethyl or methyl alcohol, ethylene glycol n-butyl ether, diethylene glycol monobutyl ether or basine, benzene, toluene, xylene, is added to the resulting adduct. etc. The resulting adduct at a temperature of below 100 ° C is subjected to further interaction with epoxy compounds in a ratio of 1 eq of epoxy groups to 2-5 eq of amino groups. It is preferable to use epoxy compounds; polyglycidyl polyphenols. An acid is added to the resulting product, and the sample of the reaction mixture, after dilution with water, has a pH value of 2-8. The products obtained can be applied in the textile industry, for example, in order to prevent wool and dyeing. When using the products obtained in combination with forcondensates of amine layers on textile materials, in honesty on cotton fabrics, the Soil-Re leas effect is resistant to washing. It is also possible to carry out a so-called smooth-free processing of textile materials. In addition, using compositions containing the proposed product, it is possible to achieve a good fixation of dyes on textile materials. The finishing of textile materials with the proposed product leads to the improvement of the physicomechanical properties of the treated material. The proposed interaction products are also suitable as a hair styling agent, and especially as a means for sizing paper when it is made. The use of the proposed product of the interaction is preferable primarily in the manufacture of papers that contain calcium carbonate as a filler. Example 1. 434 g (2.55 mol) of 1-amino-3-aminomethyl-3,5,5-trimetyp-cyclohexane is heated in a stirred apparatus in a nitrogen atmosphere to a temperature of about 100 ° C. With continuous stirring for 30 minutes, 191 g (1 eq of epoxy) of epoxide / 5.25 eq of epoxy are obtained in - obtained from 2., 2.-bis-(4-oxyphenyl) -propane and epichlorohydrin. The temperature is 110–10 ° C. After a further 30 minutes, 625 g of glycol monobuty are added at 110120 ° C. lovoy ether. After cooling with stirring, a medium-viscous-transparent is obtained. niy solution. The amino group content of this solution is 3.73 eq / kg. O7.2 (0.4 eq amino groups) of the solution thus obtained is heated with thorough stirring to 50 ° C. Then for 35. minutes a solution of 19.1 g (0.1 eq of epoxy groups) of the epoxide of the composition of 19.1 g of glycol-mono-butyl ether in the preceding paragraph is added dropwise. After stirring for 30 min at 50 ° C, prostavanites are distinctly soluble in dilute aqueous acetic acid. Dilute with a mixture of 24 g of glacial acetic acid and 170 g of water and stir further until cooling. A clear solution is obtained, the dry matter content of which is 20%, and the pH of Example 2. In the method indicated in Example 1, 2O6 g (1.8 mol) of 1-amino-2-aminomethylcyclopentane is reacted with 191 g (1 eq of epoxy group) of epoxide specified composition. After that, GO7 g of glycol-monobutyl ether is added. The solution obtained in this way contains amino groups of 4.38 eq / kg. 91.2 g (0.4 eq of amino groups) of this solution is heated to 51 ° C with stirring. After that, a solution of 19.1 g (0.1 eq of epoxy groups) of epoxide specified in example 1, is added dropwise within 30 minutes, 19.1 g glycol monobutyl ether. After 30 minutes of stirring at about 50 ° C, the sample is distinctly soluble in dilute aqueous acetic acid. Dilute the reaction mixture with a solution of 24 g of glacial acetic acid in 163 g of water and stir until cooled. The clear solution thus obtained contains 2O% solids and has a pH of 6.4. Example 3. 456 g (4 mol) of 1,2-diaminocyclohexane are placed in an apparatus with a stirrer and heated under nitrogen to. With stirring for. 382 g (2 eq of epoxy group) of epoxide prepared from 2,2-bis (41-hydroxyphenyl) propane and epichlorohydrin are added in 30 minutes. The reaction temperature is 100140 ° C. After 30 minutes at 1OO-120 ° C, 838 g of n-butylene glycol are added. After cooling with stirring, a medium-clear, clear solution is obtained. The amino content of this solution is 4.2 eq / kg. 95.5 g (0.4 eq amino groups) of the solution thus obtained is heated with thorough stirring to a temperature inside the reaction mass of 50 ° C. A solution of 19.1 g (0.1 eq epoxy groups) epoxy of the indicated composition of 19.1 is added dropwise within 30 minutes g n-butyl glycol. Q After the ZO min. mixing at 58 ° C, the sample is clearly soluble in dilute aqueous acetic acid. Once the reaction mass is mixed with a mixture of 1c. glacial acetic acid and 188 g of water and stirred until cooling. Get a clear solution with a dry matter content of 20% and a pH value of 7.0. Example 4. 191 g of the amino compound described in Example 1 (0.8 eq. Of amino groups) is heated with thorough stirring to an internal temperature of 50 C. Then a solution of 19.1 g (0.1 eq epoxy of the epoxide specified in sample 3) is added dropwise within 30 minutes 19.1 g of n-butylglycol. After 2O minutes the sample becomes clearly soluble in dilute aqueous acetic acid. Dilute the reaction mass with a mixture of 34 g of glacial acetic acid and 332 g of water and re-stir further to cool, THG1 is a clear solution, the content solid matter 20%, pH of the medium is 7.0. Example 5. 15O g of 4,4-diamino-dicyclohexylmethane (O, 713 mol) are placed in an apparatus with a blender and heated under nitrogen to. At this temperature for 30 minutes while stirring, 53.5 g (0.25 eq of epoxy groups) of the epoxide described in Example 3 are added dropwise, and the reaction temperature is maintained at a level of SO-120 C. Another 5 minutes after 110 minutes, adding 2 OZ, 5 g of n-butyl glycol, is added at a stirring time. the mass is cooled and a clear, medium-viscous solution is obtained. The amino group content of this solution is cocTaet em equiv / kg. 113 g (0.4 eq of epoxy groups) of the resulting solution with thorough mixing are heated to an internal temperature of 50 ° C. Then a solution of 19.1 g (19.1 g of epoxide) of the described epoxide is dropped in 30 min. -butylglycol After 1 hour, add 24 g of glacial acetic acid to 2 ° C of water and stir until cooled. A clear solution is obtained, the solids content of which is 20% and the pH of the medium. 6.4., I Example 6. 75 g of ethilendamine (1.25 mol) are heated for one hour to: 120-15 O ° C with 95.5 g (0.5 eq epoxy) of the epoxide described in Example 3. This is obtained a clear, medium-sized substance, the amino group content of which is 14.2 eq / kg. 70.4 g (1 equiv. Of amino groups) of this product are dissolved in 70.4 g of n-butyl glycol and heated to (internal) 6 ° C. Then, a solution of 38.2 g of epoxide 3 described in Proc. 3 ( 0.2 eq of epoxy groups) and 40 g of n-butyl glycol. After another 30 minutes, 40 g of glacial acetic acid and 280 g of water are added and stirred until cooled. . deni A clear, acrylate solution is obtained, the content of solid matter in which is 20%, and the pH of the medium is 7.6. Example 7. 146 g of triethylentetramine (1 mol) is stirred for one hour at 110-15 ° C together with 191 g (1 eq of epoxy groups) of the epoxide described in Example 3. After that, dilute 337 g of n-butyl glycol and mix until cooling. A clear solution is obtained, the amino group content of which is 10.3 eq / kg. 155.2 g of this solution (0.8 eq amine groups) are heated to internal temperature. The baths are 60 C. After that, 19.1 g (O, 1 equiv. of epoxy; groups) of the epoxide described in Example 3, dissolved in OO g k-butylglycol, are added in 30 minutes. Then, after another 30 minutes, 24 g of glacial acetic acid and 149 g of water are added and mixed until cooled. A flowable solution is obtained with a dry matter content of 21.5% and a pH of 8.0. Divide the solution into two parts and add 38.5 g of concentrated hydrochloric acid, due to which the pH value. Wednesday get equal to 2.0. The dry matter content is 18%. Example 8. 130 g (0.76 mol) of 1-mino-3-minomethyl-3,5, 5-trimethylcyclohexane are placed in an apparatus with a stirrer and heated under nitrogen to. While stirring, 57.3 g (O, 3 eq of epoxy groups) of the above described example of 3 epoxide were added dropwise during an MH min while the reaction temperature was maintained at the level of 10 -12 ° C. After another 30 minutes at 110-12 ° C, 187 g of n-butylglycol are added. A clear, moderately viscous solution is obtained. The amino group content of this solution is 4.0 eq / kg.

125 g of a solution (0.5 eq of amino groups) is heated to an internal temperature of 6 ° C. A solution of 2O, 6 g of phthalic acid diglycidyl ester (0.125 eq of epoxy groups) and 5O g of n-butyl glycol are added dropwise for 30 minutes. After 30 minutes, SO g of glacial acetic acid and 185 g of water are added and the mixture is stirred until cooling. A clear solution is obtained, the dry matter content of which is 20% and the pH value of the medium is 6.8.

Example 9. 217 g (1.275 mol) of 1-amino-3-aminomethyl-3,5,5-trimethylshexane are placed in an apparatus with a stirrer and heated under nitrogen to 8O C. With stirring, 80 g are added dropwise within 60 minutes ( 0.5 eq of epoxy) epoxide of the formula

I o

HgC -jCH-HgC-OHgC-tAs-CKa-O-CHa-CH-CH

OL

CH2-0-CHi-CH CHi

The temperature then rises to. Then the internal temperature is raised to 120 ° C and stirred for another hour. Following this, 297 g of n-butyl glycol is added and stirred until cooling. The amino group content of the resulting solution is 4.17 eq / kg.

12O g (0.5 eq amino groups) of the solution is heated to an internal temperature of 60 ° C. A solution of 2O, 6 g of phthalic acid diglycidyl ester (0.125 eq of epoxy groups) and 50 g of n-butyl glycol are then added dropwise for 30 minutes. After another 30 minutes, 30 g of glacial acetic acid and 169 g of water are added and stirred until cooling.

A flowable clear solution is obtained, the dry matter content of which is 20% and the pH of the medium is 6.7.

Example 10. 133 g (0.78 mol) of 1-amino-3-amine ethyl-3,5,5-trimethyl-cyclohexane is placed in an apparatus with a stirrer and heated under nitrogen to 100 ° C. While stirring, 97 g (0.57 eq of epoxy groups) described in Example 3 of epoxide are added dropwise over a DL. The reaction temperature is maintained at 110120 ° C. After 30 minutes at 11 ° -120 ° C, 23O g of butnglycol is added. Get

A medium viscous solution, the amino group content of which is 3.31 eq / kgH 75.6 g (0.25 eq amino groups) of this solution is heated to an internal temperature of 60 C. Then a solution of 19.1 g is poured in 30 minutes (O , 1 eq of epoxy groups) of the epoxide described in Example 3 in 50 g of n-butyl glycol. After another 30 minutes, 13.5 g of glacial acetic acid and 117 g of water are added and stirred further until cooling. A clear, liquid solution is obtained, the dry matter content of which is 20% and the pH of the medium is 7.0.

Example 11. In a pyrcol nionic apparatus, dyeing is carried out in a known manner with a 1OO kg: She | 5th yarn using durable dye, in particular, a reactive dye or 1: 2 chromic

or cobalt azo dye complex. At the end of the dyeing process, the wool is washed. For this purpose, 150O l of water at a temperature of 5 ° C is poured and 12 kg of the adduct solution in glycol monobutyl ether are added. If the solution is evenly distributed, a solution of 4 kg of trisodium phosphate in 20 liters of water can be supplied within 15 minutes. After another 30 minutes, 2 kgD2% gn aqueous solution of the product is added.

joining from 1 mole of octadecanol and 35 moles of ethylene oxide and treated for another 15 minutes. In conclusion, thoroughly rinse and dry for an hour at 6 ° –8 ° C. Przh is resistant to feeding and

nonshrink

Similar results are obtained when using an adduct, the process for which is described in Example 2. Example 12. In a yarn dyeing machine in skeins, 100 kg of wool is first dyed using reactive dyes. At the end of the dyeing, a thorough rinsing is carried out. After that, prepare fresh processed

This solution consists of 4000 l of water at a temperature of 40 ° С.

To the solution add 2 kg of ammonia of 25% concentration and after 5 min more than 8 kg: of the preparation obtained in accordance with

Example 7. A stable emulsion is formed in the solution bath, which is uniformly absorbed by wool for 30 minutes. After that, another 2 kg of hydrogen peroxide is introduced into the bath and after 15 minutes another

2 kg of a 12.5% aqueous solution of an adduct from 1 mol of octadecanol and 35 moles of ethylene oxide. After the next 15 minutes, a double cold rinse is performed. After drying

the coat is resistant to its own - 433 shyu and in accordance with the standards 1 W / S7B and 7C. Similar results are achieved when using the preparations obtained in accordance with Examples 3, 4, 5, 6, B and 9. Example 13. 100 kg of bleached sulfite pulp were crushed in a roll in an original way and then lowered into a mixing tank, in which as a filler, 2O kg of carbonaceous calcium. After the filler has been dispensed in the pulp suspension, add 0.3-0.7% of the product described in Example 10 based on the pulp and solids content. To increase the retention capacity of the filler, appropriate means can be injected shortly before the paper pulp is discharged. The paper obtained using this or similar mass composition is used primarily as squeezing and printing paper and is extremely resistant to the action of ink, which is a result of good sizing. Aluminum sulphate, which, in more or less significant quantities, is introduced into this system by jointly applying a paper macula, does not prevent sizing. In this system, calyx carbonate can be replaced with commercially available kaolin. The sizing effect in this case is the same as in the case of the use of calcium carbonate. Example 14. 1OO kg unbleached sulphate centrifuge was crushed by a known method in a roll and dropped into a mixer. Then 0.3-0.5% of the product described in Example 11 is added thereto, calculated on the basis of cellulose and the content of solid substance. After carefully moving, the paper mixture flows onto the papermaking machine. Paper made in this way can be used for packaging. I DMetI invention Spisob preparing polycondensation products by reacting step polyphenol polyglycidyl ether with an aliphatic diamine dipervichnym and then reacting the obtained adduct with an additional amount of polyepoxide in the presence of an organic solvent, wherein the polyglycidyl ether of polyphenol and an aliphatic diamine dipervichny taken in the ratio 3-5.5 .-eq amino groups per 1 eq of epoxy groups and the resulting adduct is taken in an amount of 2-5 eq per 1 aqua of polyepoxide.