RU1816769C - Polyoxyalkylene copolymers grafted on polyalkyleneguanidine as surface-active substances and cationic polyelectrolyte - Google Patents

Abstract

Usage: detergents, demulsifiers of oil emulsions. SUMMARY OF THE INVENTION: grafted copolymers of polyoxyalkylene on a polyalkylene guanidine of the general formula LCHOS2H jRC2H30) mH f (CH2) 6N (jjN CH2l6 H-fOC2H5R) m-N where R H, CH3, m 2-10, n 4-280, s mol.m. 1000-50000, 5 tab. Yo

Description

The invention relates to the synthesis of surface active compounds, in particular to the synthesis of polyalkylene oxide grafted copolymers on polyalkylene guanidine of the general formula

 (RC2H30) mH

i (SIAM H-fOC2H3R) m-N

where R N. SNs, m 2-10, n 4-280, with the properties of surface-active substances (surfactants) and cationic polyelectrolyte.

The purpose of the invention is to impart the properties of a surfactant and cationic polyelectrolyte.

The goal is achieved by the chemical structure of the grafted copolymers of polyoxyalkylene on polyalkylene guanidine of the General formula

00

(Ј

2

Yu

H-t ° W} m С2Н30) tN

f (CH2) 6NCN3-niCH2) 6 H-fOC2H3R) m-N

where R H, CH3, t 2-10, n 4-280.

The new copolymers are colorless or slightly colored oils, soluble in water and alcohols, practically odorless and non-toxic (Dlbo is oral at 10000 mg / kg according to the 1st Moscow Medical Institute).

The inventive copolymers are prepared by hydroxyalkylation without using any solvent of the polyalkylene gaunidines in the form of bases or salts by heating the epoxide under slight pressure for several hours. About

cess is controlled by pressure reduction

in the reactor. Polyalkylene guanidines, available as aqueous solutions or slightly watered polymers, can be used for oxyalkylation without preliminary drying or dehydration. Varying over a wide range of reagent ratios - epoxide and polyalkylene guacidine - allows copolymers of various structures and with different hydrophilic-hydrophobic balances (cm .tab. 1). The synthesis of copolymers is described in more detail in the examples. The properties of copolymers of various compositions are presented in table.2.

Lz table, 2 shows that the copolymers of the proposed structure have the ability to strongly reduce the surface tension of water.

The new copolymers have high surface activity both in pure form and in aqueous solutions, due to the comb-like structure of the macromolecules, which repeats the Langmuir stockade, high and easily regulated molecular weight, regulated by hydrophilic-hydrophobic balance. The polymeric nature of new surfactants provides them with the unification at a interatomic distance of a large number of elementary fragments — guanidine moieties with suspended hydrophobic polyester substituents. Due to the excellent water solubility of copolymers of any composition and the ability to control the composition and properties over a wide range, including surface activity, the scope of their practical application is extremely wide: from textile auxiliary substances to the demulsification of anode-oil mixtures. The practical absence of toxicity makes polyalkylene oxide guanidines a valuable surfactant for the production of shampoos. In this case, it is very important that guanidine compounds have antiseborrhoeic activity.

The cationic nature of new surfactants, due to the presence of a fragment of the structure of polyalkylene guanidine, gives them the ability to coagulate dispersions, and the hydrophobic nature of the side polyalkylene oxide chains makes them particularly effective flocculating for water-oil dispersions, which is especially

0

fifty

5

0 5 0. 5 0

5

important when used for refining crude oil. When introduced into shampoos as a detergent, cationic copolymers are able to control the electrical charge of the hair, which is usually achieved by adding a cationic polyelectrolyte.

The degree of graft copolymerization of epoxides on polyhexamethylene guanidine is determined by taking into account the equal reactivity of all amino groups in the guanidine units of the polymer by dividing the number of moles of bound epoxide by the total number of such amino groups in the starting polyhexamethylene guanidine. The absence of a significant amount of homopolymerization of epoxides under copolymerization conditions was established by the absence of a noticeable binding of the water introduced into the reaction mixtures. The degree of polymerization of the starting polyhexamethylene guanidine is determined quite accurately from its intrinsic viscosity data using the Kuhn-Mark-Hauwink empirical relationship.

It was noted above that combining the properties of a cationic polyelectrolyte with the properties of a surface-active polymer in one substance makes it effective as a flocculant for the purification of oil-containing effluents, for which the use of two substances of a cationic polyelectrolyte and a surfactant is known. The presence of hydrophobic polyalkylene oxide side chains in macromolecules of copolymers, their means to drops of dispersed oil products in wastewater increases and its purification efficiency (see table H).

The introduction of polyalkylene oxide side chains into a polyhexamethylene guanidine molecule substantially increases its surface activity (st. 34-36 mN / m for copolymers and 47 mN / m for the initial polyhexamethylene guanidine).

Thus, in comparison with the known surfactants, the new copolymers have a wider range of useful properties, providing a more significant and complex positive effect when using them.

The invention is illustrated by the following examples.

Example 1. In an autoclave equipped with an electrically heated bath, a mechanical stirrer, a thermometer, a manometer, a bubbler with a micro-valve and a pressure relief valve, 53.3 g of polyhexamethylene guanidine base with a molar mass of about 10 thousand cu were charged. 25% humidity (content of the main substance in the sample

40 g). The autoclave was sealed, purged with nitrogen, heated to 40 ° and ethylene oxide, which was absorbed by the reaction mass, was gradually introduced. The pressure in the autoclave was maintained at 2.8-3 atm. The process is illustrated in Table 4.

Measurements of temperature and pressure were made at the time of feeding a new portion of ethylene oxide. From the data of Table 1 it is seen that a total of 420 ml (3375 g) of ethylene oxide was introduced into the reaction mixture. After the ethylene oxide supply was stopped, the reaction mixture was kept at the synthesis temperature for another 1 hour. Then, the autoclave was cooled and the obtained grafted polyethylene oxide copolymer was unloaded on PHMG. The copolymer (420 g of 2.5% humidity) is a transparent, viscous liquid miscible with water. Drying in vacuum obtained an anhydrous copolymer, which the court according to elemental analysis (table 5) has the following structure and composition:

HtthV NX- C-N X- HKOS2N4

Nx

where m 10, p 0, n 70 (the general structural formula A is given, the numerical values m, p, n are indicated below,

Example 2. According to example 1, the outcome of 53.03 g of irrigated base PHMG with mol.m. 10 thousand conventional units, the grafted polypropylene oxide copolymer was synthesized on PHMG. As a catalyst, an additive of 0.4 g KOH was used. A total of 596 ml (494 g) of propylene oxide was added. According to elemental analysis, the resulting copolymer has the following structure

A (t 0. p 10, n -56).

Example 3. According to example 1, the outcome from 48 g of a 75% aqueous base of PHMG (mol.m. 10 thousand conventional units) and 515 ml of propylene oxide (452 g) was synthesized in the presence of 1 g of KOH, 500 g a grafted copolymer of polypropylene oxide on PHMG, close to the previous structure. The copolymer was used to build the surface tension isotherm. The curves have the characteristic form of surfactant isotherms for liquid-gas systems.

A (t 0, p 10, n 56).

Example 4. A sample of 100 g of the grafted copolymer of polypropylene oxide on PHMG from the previous experiment was hydroxyethylated according to the procedure of Example 1 using 77 ml (68.6 g) of ethylene oxide. According to elemental analysis, the resulting grafted terpolymer of polyethylene oxide and

polypropylene oxide on PHMG has the structure

A (t 10, p 3, p 70) Example 5. A portion of 100 g of the grafted copolymer obtained in Example 3 was hydroxyethylated in Example 1 using 116 ml of ethylene oxide. According to elemental analysis (see table 5), the resulting terpolymer has the following structure 0A (t 16, p 3, p 70).

Example 6. A weighed portion of 100 g of the copolymer obtained in Example 1 was hydroxypropylated using 142 ml of propylene oxide and 0.3 g of KOH. According to elemental analysis 5, the resulting terpolymer has the structure

A (t 10, p 9, p 70). Example 7. A weighed portion of 100 g of the copolymer obtained in Example 3 was hydroxyethylated with 0 using 77 ml (68.6 g) of ethylene oxide and 0.1 KOH at 125 ° for 4 hours. The terpolymer obtained in this way has the structure according to elemental analysis:

A (gp 10, p-10, p 56).

5 PRI me R 8. According to example 1, the outcome of 76.8 g of a 75% aqueous base of PHMG (mol.m. 50 thousand standard units) and 412.4 g (463 ml) of ethylene oxide synthesized 489 g of grafted copolymer of polyethylene oxide on PHMG of the following structure:

A (t 10, p 0, n 280). Example 9 A weighed portion of 100 g of the copolymer obtained in Example 8 was oxypropylated at 135-140 ° C using 222.4 5 g (268 ml) of propylene oxide. The resulting terpolymer (328.3 g, 1.453 each) has the structure

A (t 10, p 25, p 280). Example 10. According to example 1, 187 g of oxyethylated 75% aqueous base of PHMGsmol.m were hydroxyethylated. Yuty.s usl. At 125 ° C for 5.5 hours, 220 g of ethylene oxide were added and 388 g of a copolymer of the following structure was obtained: 5 A (m 16, p 0, n 70).

Example 11. Nav, esku 203.5 g of the copolymer obtained in Example 10 were hydroxypropylated with 145 g (175 ml) of propylene oxide in the presence of 0.4 g of KOH. Synthesized 349.6 0 g of terpolymer of the following composition: A (t 16, p 70). Example 12. A weighed portion of 43.53 g of the copolymer obtained in Example 10 was hydroxypropylated at 95 ° using 31 g of 5 (37.5 ml) of propylene oxide. Received 60 g of terpolymer composition similar to the experience of example 11.

Example 13. In Example 1, 168 g of a 75% aqueous base of PHMG with a mol.m. were ethoxylated at a temperature of 125 ° C. fifty

thousand standard units Within 2 hours 10 minutes, 192.6 g (222 ml) of ethylene oxide were absorbed and 344.5 copolymers of the structure were obtained

A (t 1.6, p 0, n 280).

Example 14. A weighed portion of 43.6 g of the copolymer obtained in Example 13 was hydroxypropylated at 130 ° C. Within 3.5 hours, 203.3 (245 ml) of propylene oxide was taken up. As an initiator, 1 g of KOH was used. The resulting terpolymer has the structure

A (t 1.6, p 280)

Example 15. According to example 1, 93.5 g of PHMG base with a mol.m are hydroxypropylated at 130 ° C. 10 thousand. In two hours, the absorption of propylene oxide was 145 g (174.7 ml). According to the data of elemental analysis, the following structure can be prescribed for the obtained copolymer:

A (t 0, p 1.6, p 56)

Example 16. At 110-130 ° C, the PHMG base with mol.m. 50 thousand standard units in the form of a 75% aqueous solution. Within 3 hours, a weighed portion of 100.9 g of PHMG absorbed 156.5 g (188.5 ml) of propylene oxide and obtained 230 g of a copolymer of the structure

A (t 0, p 1.6, p 280)

Example 17. A portion of 64.3 g of the copolymer obtained in Example 16 was hydroxyethylated at 125-130 ° using 114.3 g (1-28.4 ml) of ethylene oxide and 1 g of KOH as a catalyst. Synthesized 176.7 g of terpolymer structure:

A (t 5.7, .6, p 280)

Example 18. A portion of 75.7 g of the copolymer of Example 16 was hydroxyethylated at 100 °. Within 1 h, 34.9 g (39.2 ml) of ethylene oxide was absorbed and 107 g of a terpolymer of the structure obtained:

A (t 1.5 .6, p-280)

Example 19. In the reactor of the device described in Example 1, 30 g of PHMG hydrochloride, 100 ml of distilled water were charged, and ethylene oxide was injected into the resulting solution at 70-90 ° C. Within 3 hours, 226.0 (225 ml) of ethylene oxide or 30 ml per one unit of PHMG was absorbed. The resulting copolymer has the structure A (, p 0, p 5b)

Example 20. According to example 1, 50 g of PHMG hydrochloride dissolved in 100 ml of water were oxyethylated at 75-90 ° C. For 3 hours, the absorption of ethylene oxide was 185.9 g. 338.3 g of an aqueous solution of a copolymer of the structure were obtained.

A (t 4.7, p 0, n 56)

An IR spectrum was taken for the copolymer. In parallel, the spectrum of the initial PHMG is shown. From the analysis of the spectra, we can conclude that along with the characteristic bands

the spectrum of PHMG in the spectrum of the copolymer, a band of ether oxygen is observed (at 1126) and a small number of NH groups of the initial PHMG are retained (weak band at 1590 cm).

The latter circumstance is confirmed by a qualitative reaction to NH groups with polytrichlorobutadiene (red-violet staining when standing).

Example 21. A portion of 40 g of PHMG hydrochloride was hydroxypropylated according to the procedure of Example 1 at 100 ° C. Within 14 hours, the absorption of propylene oxide was 194.5 g, which corresponds to 5-fold hydroxypropylation of all amino groups contained in the PHMG element. Accordingly, the structure of the obtained copolymer can be represented as

A (m 0, p 5, n 56). The IR spectrum of the resulting copolymer is taken off.

It contains, along with methylene and guanidine absorption bands (at 2930 and 1590, respectively), bands of ethereal oxygen (at 1126 cm) and a band at 1730 attributed to the aldehyde carbonyl, the occurrence of which can be explained by the partial isomerization of propylene oxide.

Thus, the proposed grafted copolymers of polyoxyalkylene on polyalkylene gaunidine with different m and n, but within m 2-10 and n 4-280 s mol.m. (10f50) 103 conventional units Compared with the prototype, they have the properties of surfactants and cationic polyelectrolyte.

Claims (1)

SUMMARY OF THE INVENTION Grafted copolymers of polyoxyalkylene on polyalkylene guanidine of the general formula HiOC2H3R (RC2H30) mH ftCH2)) 6 H-fOC2H3R) m7N where R is H, CH3: m 2-10; n 4-280, with a mol.m. 10000-50000 cu as surfactants and cationic polyelectrolyte. Synthesis and properties of polyoxyalkylene copolymers on polyhexamethylene guanidine ) Like m. of polyhexamethylene guanidine is equal to 50,000 sr .. in all other cases x 10,000 sr 111816769 12 Table 2 Surface tension of 0.1% aqueous copolymer solutions Oxyethylation of the PGMG base Table 3 Table 4 Elemental analysis of grafted copolymers of polyalkylene oxide on polyhexamethylene guanidine Oj