SU586841A3 - Method of preparing polyurethane elastomer materials - Google Patents

Description

staining with flue gases, it has improved low-temperature properties due to the use of polyester based on two atomic alcohols containing tertiary nitrogen. The polyester used in the present invention can be prepared in a conventional manner from dicarboxylic acid or its ester and dihydric alcohol. For this, a dihydric alcohol containing tertiary nitrogen is used, the formulas of which are the following: N - CH2 - C but-Us-one-Bb-one I Bs R HO-Tl.5-CH / OH / CH2-F (g) R in which m is a hydrogen atom, alkyl. or the cycloalkyl group of H2 and T4 (each of them) is an alkyl and acycioalkyl group; J and T y (each of them) - upkipenova ipi cyclopoppinna on the group; . upfix, apkylene, cycloalkipicyclo alkylene groups may have a side chain that is inert to the isocyanate group. A dihydric alcohol with too high molecular weight is not suitable for maintaining a certain concentration of tertiary nitrogen in polyurethane. A suitable molecular weight, but may be higher, if the concentration of tertiary nitrogen is kept constant. A dihydric alcohol not containing tertiary nitrogen can be partially copolymerized. Examples of dihydric alcohols containing tertiary nitrogen and having the above formulas may be the following: GNOSN HaSHCNHM / Sig / hCH3 g UnOH3 / gCCHH M / CH CH3 / Chz, LHOCHa / aCHCHgN / CH / s CHj 2 / HOCH2 / j, C / CH3 / -C.H2N / CH2CH5 / 2, / HOCH / jC / C-Hj / CHgW / CHgCHgCH / a, GNOSN / gC / CH3 / CHg N / CH, / CHjI HOSNgSNg / HOSNg / CHE / CHN /, / HOCH2CH2 // HOCH2 / CHN СН2СН2СНз / .г ЖОСН2СН // НОСН2 / СНМ / СН2СН2СН2СНз / 27 AHOCH; j / 2CHN- / CH2CHc, t / 2, h / NOSNg / gSNM / СНгСнгккккккккккккрк / 2, h / НОСНг / гСНМ / СНгСнкккккккккккрк / 2, h / НОСНг / гСНМ / СНгСнккккккккккккрк CH 3/2, HOCHaCHj CH / OH / CHgN / CH CHa / a, HOCHjCHjCH / OH / CHgW / CH CHaCHs / HOCHxCHgCH / OH / CHgN / CHgCHzCHgCH, /, Alkyl may be used as dihydric alcohols that do not impregnate tertiary nitrogen. glycols, eg ethylene, etc. opylene-, tetramethylene, pentamethylene-, hexamethylene-, octamethylene / decamethylene- and neopentane-glycol. Typical examples of dicarboxylic (dibasic carboxylic) acids may be aliphatic, such as amber, glutaric, adipic, azelaic, or sebacin, but copolymers with an aromatic or alicyclic di-1-boic acid are possible. making conventional polyester. Preferably, the reaction is carried out without a catalyst, but it can also proceed in its presence. If a catalyst is used to accelerate the reaction. It should be such that it does not have any undesirable effect on further polyurethane production. The molecular weight of the polyester dihydric alcohol used according to the present invention is preferred to CHOO-BOOi. better than 6OO-2OOO, softening temperature 60 C or less and acid number 3 or less. If a polyether based on a tertiary nitrogen-containing alcohol is used in the form of an organic or non-organic acid salt, this can be used, for example, formic, acetic, propionic, oil, valerian, capron, heptane, hydrochloric, phosphoric or nitric acid. Approach w; it is a high molecular weight polyoxide compound used in the preparation of this polyurethane elastomer containing crystalline regions having a high melting point, and noncrystalline regions with a low melting point, may be a polymer with a molecular weight of 400-6000 and a melting point not higher than 60 C, for example, polyethers based on a dihydric alcohol (for example, polyethylene-, polypropypenipipi pipetrametrypeigipicop), and polyesters based on traded alcohol (for example, popipropylene ethertrio l or polyethylene propiphenylether e trcoly) ,, nolipropylene ethertriol or propylene oxide, and (or) egklena oxide with a multifunctional alcohol, such as gpеринserin, dihydric alcohol based polyesters, obtained by glycol condensation (for example, ethylene glycol, 1,2-propylene glycol, derived from glycol condensation) 3-propylene glycol, 2,3-butylene glycol, tetramethylene glycol, 2,2-dimethyl-1, 3-propane diol, diethylene glycol, 1,5-pentamethylene glycol, 1,6-goxamethylene glycol, cyclohexane-1, -4 diol, cyclo- hexane-1,4 dimethanediol or their mixtures) with dibasic carboxylic acid, for example ipinovoy, maleic, succinic, phthalic isophthalic, terephthalic, geksagidroizo- {pgalevoy- or hexahydroterephthalic or Visly ester, or salt of hydrohalic acid: polylactones such kakiolikaprolaktondioly obtained at step polymerization. the disclosed rings of caprolactone, “an example of C-caprolactone, in the presence of glycol and the like, polylactontrioles, obtained by adding caprolactone to glycerol, trimethylolpropane, etc., and polywapprpactondiopy. As organic polyisocyanates, diisodianates can be used, for example, tetrametypiene diisopionate, hexamethylene diisocyanate, 1,4 - cyclohexanediisosulfate, 1,3-cyclohexanediisocyanate, dicyclo: hexylmethane-4, F-diisocyanate, xylylene, ycyclohexane diisocyanate. 4-pheny lendiisocyanate, 1,3-phenylenediisocyanate, 2,4-toluene diisodianate, a mixture of 2,4- and 2,6-toluene diisodianate, diphenylmethane-454 diisocyanate or naphthalene diisocyanate), polyhydric isocyanates (for example, polymethylpolyisocyanate),) polyhydric isocyanates (for example, polymethylene polyisocyanate),)) polyhydric isocyanates (for example, polymethylene polyisocyanate) or polyether polyisocyanate). so-called regenerated isocyanates which are product Aims of the addition of To / Tuipi diisocyanate to Trimetiopop 1 propane or phenopes. Typical examples of low molecular weight p. A polyfunctional compound can be low molecular weight bifunctional alginic compounds represented by diamines, for example, ethylene-, 1,2-propipen-, 1,4-butylen-, 2,3-butylene-, hexamethylen-, cyclohexanediamine, piperazine, 1,4-- diami opiperazine, xylylene ™, tolylene, phenylene diphenyl methane- or 3,3-dichlorodiphenylmethane, or 3,3-dichlorodiphenklmethanediamine; hydrazinamine, for example monoalkyl hydrazine or 1,4-dihydrazine ethylene; dihydrazides, for example, carbodihydrazide, succinate, adipic acid or terephthalate; glycols, for example, ethylene tetramethylene glycol; water, etc. This polyurethane elastomer can be obtained by the usual method. If the preferred elastomer is used in. In the form of an elastic thread, a composition for a coating, a film material, a sheet material, etc., it is preferable to obtain it by a method based on the interaction of an organic diisocyanate with a diatomic compound. An incomplete polymerization product is obtained with a terminal (closing) isocyanate group. Thereafter, the chain elongation reaction with a low molecular weight bifunctional compound in an organic solvent proceeds. In this case, any modified method can be used, in which the reaction of the prepolymerization product and the low qualification bifunctional compound is carried out in at least two stages . Examples of ferrous organic solvent are dimethylformamide, dimethyl "atamide, diethylfluoroamide, dimethyl sulfoxide, tetramethyleneurea, N-methyl-2 Gshrrolidone, hexamethylphosphoramide. The tertiary nitrogen can act as a catalyst in the reaction of the urea compound or the formation of allophanate. If there is a large amount of tertiary nitrogen in the reaction system, especially if it is necessary to obtain a substantially linear polymer, for example, in the form of an elastic thread, a three-dimensional (spatial) structure can be formed by allophanato bonding, which is of great importance. In this case, it is most preferable to use a tertiary nitrogen-containing dihydric alcohol as a salt. Reactions can be easy. made without any complications, such as gelatinization. In accordance with the present invention, the polyester should be contained in the ratio of O, 1 mol% and more to the entire high molecular weight polyoxide compound, the tertiary nitrogen should be included in the polyurethane elastomer in the amount of 10 mmol / kg and bopa h, preferably 20 mmol / kg and more. The polyurethane elastomer thus obtained possesses a good coloration and the ability to retain the dye. The intensity of dye adsorption per unit amount of tertiary nitrogen acting as a dye site is high, and therefore the amount of tertiary nitrogen in the polymer can be reduced. In addition, the polyurethane elastomer is highly resistant to ultraviolet radiation and flue gases. According to the invention, a polyurethane elastomer obtained from an organic polyisocyanate, a high molecular weight polyoxy compound and a low molecular weight polyfunctional compound can be mixed with at least one tertiary nitrogen containing polyurethane elastomer. To noncrystalline sites having a low melting point in a tertiary nitrogen-containing polyurethane elastomer, any other high molecular weight polyoxidation can be added along with a tertiary nitrogen-containing polyester. Polyether based on a dihydric alcohol, content Tertiary nitrogen can preferably contain 50% or more in relation to the entire high molecular weight polyoxy compound. An example of a co-used high molecular weight polyoxy compound can be polyethers, ethers. One of the most important factors for increasing dyeability is the concentration of tertiary nitrogen in the polyurethane elastomer. An improvement in the colourability of the product cannot be achieved if the concentration of the tertiary nitrogen is less than a certain value — 30-ZOO mmol / kg, preferably 50-15 O mmol / kg. If the concentration of tertiary nitrogen in the contained tertiary nitrogen polyurethane is low ,. then you need to add more tertiary nitrogen-containing polyurethane. If B polymer is injected with a large amount of a he-, terogenic polymer, then polyurethane. the elastomer deteriorates, and if an elastic fiber (elastic thread) is obtained from it, then the tension increases when the fiber is rolled up, and therefore the eye cannot expand, in order to increase the concentration of tertiary nitrogen in polyurethane. elastomer without increasing the amount of polymer introduced, it is necessary to raise the concentration of tertiary nitrogen. To do this, it is preferable to use low molecular weight dihydric alcohol containing tertiary nitrogen and low molecular weight dicarboxylic acid, which are used in the manufacture of the above polyether based on dihydric alcohol, and one tertiary nitrogen containing alcohol. The polyurethane elastomer obtained by the proposed method, due to its elasticity, durability: and resistance to yellowing, is used to obtain elastic fiber, microporous material for coating film, sheet material, rubber-like elastomer. polyurethane foam and the like. The invention is illustrated by examples. The method of apauiHDamiH described in these examples is as follows. Dyes: anthraquinone blue SWl (color index: 62055) of the formula SOjNft (} Method of dyeing. The product obtained in each example is washed and bleached. Ten parts of the product thus obtained are colored at 80 ° C for 1 hour in a solution of anthraquinone blue SWF ( 0.3 parts by weight) and formic acid (2.8 parts by weight) in water (1000 parts by weight). Determination of the amount of adsorbent dye. The colored product is dissolved in dimethylformamide (20 parts by weight) and precipitate are separated by ultracentrifugation. Absorbance at 570 mm top is measured by a spectrophotometer. about a layer of a solution and compare it with a previously prepared calibration curve to determine the amount of dye adsorbed. Light resistance, degree of staining After irradiation for four hours, the degree of staining of the product is determined in the A1Pa5 fadometer (the light color of the untreated polyurethane elastomer refers to to the class): 5th — unchanged 4th — yellowish, —yellow, 2nd — weak yellowish brown, 1st — yellowish brown. Coloring under the action of flue gases. To test the durability of the polyurethane elastomer in relation to gas yellowing, 1 film made of it, fiber or molded product will be placed in a 0.5 m vessel with a gas burner and a ventilation hole with a diameter of 8 cm in the upper part and for 5-10 hours they are affected by gas compropane at a temperature of 60 ° C. After selecting the material thus treated, the degree of its coloration is classified. Test the resistance to nitric oxide according to the position T IS L 1055, for which the test material is kept at 25 ° C in Teiejree for 2 hours and selected, then the degree of staining is classified, the brightness measured according to the position -1O13--5 (booster method {1 С № 12 ). The degree of staining is classified according to five classes (see below). The white color of the colored product of the polyurethane elastomer without the addition of a stabilizer, which is tested by burning propane in gas and kept in gaseous nitric oxide, is classified as first class and the white color of untreated polyurethane elastomer as fifth; The 5th is unchanged, the 4th is yellowish, the Egth is yellowish, the 2nd .W is weakly brownish, the 1st is whiteG, The intensity of elasticity recovery (coefficient of elastic recovery). The material under study is removed at a rate of 100 or ZOO% at and maintained in this state for 10 minutes, then the tension is stopped and the speed (intensity) of the elasticity reduction is calculated by the following equation: A- / B-B / xlOO where A - - length as a result of elongation, mm (ari-apinhenia on DZ (E% -15O, on lOO% -100M; b - length after reduction, mm; C - length of the material under study, mm (when pressed by 300% -5О, by 10О% iOO MM) J Speed, (intensity) of recovery at low temperatures, means vepichina, taken into account: instantaneous speed - Vepichina, taken immediately after the test material, elongated at a rate (intensity) of 60% and held for 10 minutes in this state, is released from tension. The lack of recovery of elasticity is determined as follows. at a rate (intensity) of 20O% at 20 ° C, maintained for 10 minutes in this state, then the tension is removed and the elasticity recovery is calculated by the equation; А Е / 2 where is the length of the material under study, mm о fit- length in the absence of aftereffect. Speed (intensity) of energy retention w, / w. This refers to the value obtained by dividing the energy (W), if the material under test is elongated at a rate (intensity) of 100%, the tension immediately stops at the initial energy (WJ Examples 1-6 and a comparative example concerns the production of polyether alcohol, Example 1 Adipic acid (292 g) and 2-methyl 2- (N, N-dimethylam HOMeTHn lcS-nponaHAHon (441 g) -conjugate at 20 ° C at atmospheric pressure for polyether based on a dihydric alcohol with an acid number of 2, a hydroxyl number of 147.6 and The molecular weight is 75 O in the strongest named ES -1). Example 2 Polymerization is carried out in the same manner as in Example 1 using the following materials, g: Adipic acid 292 2-Methyl-2- (N, N-dimethyl amino-methyl ) -l, 3-β-propanedyl (75 mol.%) 331 Hexamethylene glycol (25 mol.% -) 89 The resulting polyether based on a dihydric alcohol (hereinafter referred to as ES -2) has an acid number of 2.2, a hydroxyl number of 135 and molecular weight 820. EXAMPLE 3. Polymerization is carried out as in Example 1, using the following materials, g: Adipic acid 292 2-Methyl-2- (N, K-dimethylaminomethyl l ) -1, 3-propandiol (50 mol.%) 184 Hexamethylene glycol, (5O mol.%) 146 The polyether obtained in this way based on dihydric alcohols (hereinafter referred to as E -3) has an acid number of 0.5, a hydroxyl number of 98 and molecular weight 1140. EXAMPLE 4 Polymerization was carried out as in Example 1 using the following materials, g; Adipic acid219 Sebacinic acid2G1 2-Methyl-2- (N, N-diethylaminomethyl) -l, 3-propanediol 70O The dihydric alcohol-based polyester thus obtained (hereinafter referred to as E -4) has an acid number of 2.0, a hydroxyl number of 96 and mole & Coulomb weight is 1150. EXAMPLE 5 Polymerization is carried out as in Example 1 using the following materials, g: Dimethyl adipate 352 2 Methyl-2- (N, N diethylaminomethyl) -1.3-propanediol 23,5 Neopentip glycol 102 Obtained by this Thus, a polyether based on a dihydric alcohol (hereinafter referred to as E-5) has an acidic chiolo of 1.0, a hydroxyl number of 117 and a molecular weight of 95O.

eleven

EXAMPLE 6 Polymerization was carried out as in Example 1, using the following materials, g:

Sebacic acid348

2-Methyl-2 (N, N, DI-p-propylaminomethyl) -1,3-propane diol 487

Tetra. Methylene glycol54

The polyether based polyether thus obtained (hereinafter referred to as E0-6) has an acid-number of 1.5, a hydroxyl number of 100 and a molecular weight of 1100.

Comparative example V. The polymerization is carried out as described in example 1, using the following materials, g:

Adipic acid 292

Ethylene glycol140

The dihydric polyether thus obtained (hereinafter referred to as ES-CompostD) has an acid number of 1.3, a hydroxyl number of 103 and a molecular weight of 1080.

Examples 8-18 and comparative examples 19-23 relate to the preparation of a polyurethane elastomer.

PRI me R 8. Polyester based on dihydric alcohols (EE -1.25 parts by weight) is mixed with polytetramethylene glycol (mol. Weight 15OO, 250 parts by weight). To the mixture is added

12

10A weight.h. diphenylmethane-4,4-diisosulfate. The mixture is reacted at 70 ° C for 40 minutes. This forms an incomplete polymerization product having an isocyanate {group at both ends. It is dissolved in dimethylformamide, the mixture is cooled to 50 ° C and a solution of 1,2-propylenediamine (148 parts by weight) in dimethylformamide (200 parts by weight) is added with stirring to subject the chain extension reactions. With the addition of 1,2-propylenediamine, the viscosity of the solution increases. When it reaches 10OO poise, 14 weight, parts of monoethanolamine is added to the reaction mixture to stop the reaction, and then 14 weight parts. acetic acid.

The polymer solution thus obtained with a concentration of 38% has an excellent ability to thread into elastic threads. They are pulled from a spinning nozzle with 1OO holes of 0.1 mm each into the atmosphere of heated air at a speed of 210 m / min.

The filament m (fibers) is characterized by high durability and exceptional resistance to yellowing under the influence of ultraviolet radiation and flue gases. As can be seen from the table. 1, in addition, the low-temperature properties of the yarns obtained are also improved.

Table

Note: - the intensity of adsorbshsha 1OO%. EXAMPLE 9 Tertiary nitrogen contained in polyether, based on dihydric alcohols (ES -2, 1640 parts by weight), is neutralized with acetic acid and reacted with diphenylmethane-4,4-diisosphromate (194% by weight). .h,) The resulting product of incomplete polymerization (150 parts by weight) with terminal hydroxyl groups is mixed with polytetramethylene glycol (MW 150O, 150 parts by weight). The mixture is reacted with diphenylmeta-4.4-diisocyanate (100 parts by weight) at 70 ° C for 40 minutes to form a prepolymer having isocyanate groups at both ends. It is dissolved in dimethylformamide and cooled to 45 ° C. Then a solution of 1,2-propylenediamine (14.8 parts by weight) in dimethylformamide (882 parts by weight) is added to the mixture with stirring and subjected to chain extension reaction. After the viscosity of the solution is 1000 poises, monoethanolamine (1.4 parts by weight is added to stop the reaction, and then acetic acid (1.4 weight parts) is added. Gender; a polymer solution of 32% is taken into account, having a good way; —bone is drawn into the filament. It is made like in example B. to obtain an elastic fiber. The results of a study of the properties of the obtained filaments (fibers) are given in Table 1. Example 10. Polyether based on a dihydric alcohol (E-3, 228 parts by weight are reacted with diphenyl tan-4, 4-diisocyanate (1OO parts by weight), as a result which results in an incomplete polymerization product A having a terminal isocyanate group. Separately, polytetramethyl glycol (molecular weight 20OO, 400 parts by weight) reacts with diphenylmethane 4,4-diisocyanatam (100 parts by weight) to form incomplete polymerization B Having a co-isocyanate group, 164 parts by weight of product A and 250 parts by weight of product B are dissolved in 250 parts by weight of dime & formamide, the mixture is subjected to a chain extension reaction with a solution of hydrazine (4.1 parts by weight) and xylenediamine (17 | 4 weight.h in dimethylformamide (680 weight.h.) In the same way as described in Example 8, a solution of polyurethane is obtained. The polymer solution thus obtained has a concentration of 32%; it has a good ability to be drawn into nitrates. It is spun in the manner described in Clause 5, obtaining elastic yarn properties of which are examined (the results are shown in Table 1). Example. The dihydric alcohol tES -5, 62 parts by weight, polytetramethylene glycol (molecular weight 8 Op, parts by weight) and phosphorous acid (3 parts by weight) are mixed, diphenylmethane-4,4 -diisocyanate ( 100 weight.h.). The resulting mixture was reacted with a 70 ° C mixture for 40 minutes to obtain an incomplete polymerization product having terminal isocyanate groups, which is subjected to a chain extension reaction with 1,2-ps using a diamine in the same manner as described in Example 8 The polymer solution thus obtained has a good ability to be drawn into filaments, which is accomplished by that. the same way as described in example 8. The results of the study of elastic threads are given in Table. 1. Example 2. Ether based on a dihydric alcohol (HL-6, 200 parts by weight), polytetramethylene glycol (LLC molecular weight; 1000 parts by weight) and acetic acid (10 parts by weight) are mixed. The mixture was reacted with toluene diisocyanate (104 parts by weight) to obtain a partial polymerization product having terminal hydroxyl groups. 44 o weight.h, this product is brought into contact with the QO weight.h. diphenylmethane-4,4g-diisocyanate, get a long-polymer having terminal isocyanate. The prepolymer is subjected to chain stretching reaction with 1,2-propylenediamine. According to the method described in example 8. The polymer solution obtained has a good ability to stretch into elastic threads, which , form in the same way as described in example 8. The results of the study of elastic threads are given in table. 1. Example 13: Ether based on a dihydric alcohol (E -3, 187.6 parts by weight) and polytetramethylene glycol (molecular weight 1320, 47 parts by weight) are mixed and the mixture is reacted with diphenylmethane - 4, 4-diisocyanate (1OO wt.h.). An incomplete polymerization product is obtained having terminal isocyanate groups. The chain of this product is extended with hydrazine hydroxide in the same manner as described in example 8. A polymer solution is obtained that has good stretchability in the thread, which is carried out in the same way as in example 8 The results of studies of the properties of the yarns obtained are given in gabps. 1 .. Example 4. Measure the intensity of the elastic aftereffect D ji, of the elastic filaments obtained in Examples 8 and 13 and Comparative Examples 18 and 19, with

temperatures of 2O, 1O, 0, -10 and -2O C. The results of the definitions are given in Table. 1. Example 15. In Example 8, the ratio of polyether based on dihydric alcohol (CH-1) to polytetramethylene glycol is changed. Polymerization and testing is an example of Example 16. Polyester is mixed on the basis of a dihydric alcohol (acid number 1; hydroxyl number 92.5; molecular weight 12OO, 12O weight.%), Obtained according to the method described in example 1, excluding the polymerization time 9 h, with polytetramethylene glycol, molecular weight 2OOO; 20O parts by weight) The mixture is treated in accordance with Example 8, and diphenylmethane-4,4-diisocyanate (1OO parts by weight) and 1,2-propylenediamine (14.7 parts by weight) are exhausted to obtain an elastic thread.

Example17. Polyether based on a dihydric alcohol (acid number 0.7, hydroxyl number 62.2; molecular weight 1785; 5OO parts by weight) obtained from adnpinic acid, tetramethylene glycol 2-2-dimethyl-1,3-propylene glycol (molar ratio glycols 80:20) are dehydrated at a pressure of 5 mm Hg. Art. within one hour, and then mixed with diphenylmethane-4,4-diisocyanate (14O parts by weight). CMGiCb left to interact with BUT C for 9O MDA in a nitrogen atmosphere, resulting in a product of incomplete polymerization with a terminal nocyanate group.

The product obtained is dissolved in dimethylformamide (134 O parts by weight) and rapidly cooled to O C. To the cooled solution, a solution of 1,2-propylenediamine is gradually added with vigorous stirring.

The tests are carried out in a similar manner, and the content of tertiary nitrogen in the polymer is kept between 50 and 100 mmol / kg. The results of the study of the properties of the threads thus obtained are listed in Table. -2

Table 2

(20.7 wt. 4.) In dimethylformamide (2 00 weight. Parts)

When the viscosity of the solution reaches 2000 pu (25 C), the addition of the diamine is stopped and di-n-butylamine (15 parts by weight) is added thereto, as well as lbd acetic acid (about

3.2 pts.h,), to obtain a solution of polyurethane (hereinafter referred to as the solution - 2-field urethane).

Comparative example 18. Mixed on the basis of a dihydric alcohol (E $ 1

28.6 parts by weight) polyester and polytetramethylene glycol (1kly weight 15OO, 257 parts by weight) and the mixture are reacted with phenyl 1-tetan-4, 4-diisocyanate (10O parts by weight) to obtain an incomplete product polymerization

having a terminal g; isocyanate. The product is subjected to a chain extension reaction with l, 3-npt pilendiamii in the same manner as described in Example 8. The polymer solution obtained is stretched into threads

the way described in example 8 „

The results of the study of the properties of threads are given in table. one.

Comparative example 19, According to the method described in example 8, receive the product

incomplete polymerization, having a conditone idiodyate group, from polytetramethylene glycol (molecular weight iSOO, MOO weight.h)

Diphenylmethane-4,4 - diisocyanate (1OO parts.p.). The elongation of the chain of the product of full polymerization with 1,2-propylated hexamide is carried out.

1, the polymer solution thus obtained is drawn in filaments, the results of which are shown in Table 1, Cf. Exemplary Example 20. Polytetramethylene glycol (molecular weight 1,320, 132 parts by weight) is reacted with diphenyl tan-4,4- diisocyanate (50 parts by weight at 75 ° C for 1 hour without a catalyst to obtain an incomplete polymerization product having an end group. The product is dissolved in dimethylformamide and a 35% solution is obtained, which is cooled to 30 ° C. The solution is gradually introduced with stirring a solution of 1,2-propylenediamine (7.4 parts by weight) in dim When the viscosity of the solution reaches 100 poises, 0.91 parts by weight of monoethanolamine and then 0.12 parts by weight of acetic acid are added to the mixture to form a solution of polyurethane. 2-Ethyl-2- (N , N-dimethylaminomethyl) -1.3 propanediol (52.2 parts by weight) in chlorobenzene (1O, 4 parts by weight) to the mixture is added a solution of hexane diisocyanate (52.2 parts by weight) in chlorine benzene ( 10.4 weight.h

room

Energy retention rate,% example

15

Comparative example 22. Polytetramethylene glycol (molecular weight 1320, 1320 parts by weight) was reacted with diphenylmethane-4,4-diisocyanate (500 parts by weight) at 75 ° C for 1 hour without solvent to obtain a product of incomplete polymerization with terminal isocyanate groups. The product of incomplete polymerization is dissolved in dimethylformam0, 93

ABOUT

0.07

, ГК coefficient of instant elastic aftereffect,%

72

65

Before a temperature of 35 ° C is obtained, the solution is cooled to 3 ° C, six dosages of the solution are prepared. A mixture of CH / CH / CHj N I2 (diamine A) and HjNCHjCH N / t -C, I, / CH2 CH2-CH2 N H, (diamine B) is added dropwise to this solution, their ratio in polyurethane filaments is given in tab. four.

Table 4

0.7

0, C5

0,860,8

0.4

0.14O, 2

0.3 The viscous solution thus obtained is introduced separately into the two pacTBOpia of polyurethane that were obtained by the jianee, so that the content of the tertiary azogen is 50 and 100 mmol / K1, respectively. The mixture is drawn in a yarn. The properties of the obtained elastic threads are given in table 2. Comparative example 21. Polytetramethylene glycol (molecular weight 2000; 20OO parts by weight) is mixed with 2-methyl-2-. - (N J N -dimethylaminomethyl) -1,3-propanziol (54.4 parts by weight). The mixture (300 parts by weight) was treated in the same manner as described in example 8, using cyphenylmethane-4,4-diisocyanate (10O parts by weight) and hydrazine hydrate (10 parts by weight) to obtain elastic yarns. The yarns obtained in Example 16 and Comparative Example 20 measure the intensity of the energy retention, the instantaneous elastic response, and the elastic response at a low temperature. The results of the first two tests are given in Table. 3, the last in the table. 2. Tabbi AZ

nineteen

When the viscosity of the solution reaches 1OOO poise, the reaction is stopped and the final group is stabilized. The polymer extract solution thus obtained Comparative Example 23. Methylene glycol polytetra (molecular weight 1320, 1320 parts by weight) is reacted with diphenylmethane-4,4 with dysocyanate (500 parts by weight) for 1 hour without solvent. while obtaining a product of incomplete polymerization with terminal isocyanate. The product of incomplete polymerization has increased. When the viscosity of the solution reaches J.OOO poise, the reaction is stopped and the end group is stabilized. The polymer solution thus obtained is

one

90 75

2

20

woven into elastic threads t 2-6, which are well dyed, but the modulus (% ZOO elongation is extremely reduced (Table 5)

eopsnoT in dimethylformamide, a 35% solution is obtained, which is cooled to 3 seconds. Four batches of a solution of an incomplete polymerization product are prepared, where a mixture of 1,2-propylenediamine (diamine A) and 2-methyl-2- / W is added dropwise with stirring. M-dimethylaminomethyl) -1,3-propane diol (glycol B), the ratio see in table. 6

Tabsab

They are pulled into elastic threads No. 2-4, which are well dyed, but their modulus (elongation of ZOO%) is extremely low. The results of tata are given in table. 7

Table

65 45

2 4

Examples 24-26 and comparative example 27 concern the preparation of a polyurethane elastomer containing a tertiary nitrogen.

Example 24. Diphenylmethane-4,4 diy cyanate (250 parts by weight) and polyester with a terminal hydroxyl group (molecular weight 110O; 550 parts by weight), a product of adipnic acid polycondensation and 2-methyl-2 - N; N-diethylaminomethyl) -1,3-propavdiol is allowed to react at 40 ° C. for 80 minutes in dimethylformamide in the presence of acetic acid (20 parts by weight).

The resulting solution of the product of incomplete Example 25. To polylactone diol (molecular weight 1250, 250 parts by weight), which is obtained by stepwise polymerization of E -; 1 Caprolactone in the presence of tetramethylene glycol as a polymerization initiator, diphenylmethane-4,4 - is added diisocyanate (100 parts by weight) and dimethyl form MFA (350 parts by weight), and then dibutyl tin; Aurat (50 parts by weight) as a catalyst causes an immediate exothermic reaction, which lasts 2O minutes at 40 ° C. PeaKjop is rapidly cooled, then diluted with dimethylformamide (265 parts by weight). To the cooled solution, a solution of 1,2-propylenediamine (15 parts by weight) in dimethylformamide (2OOO parts by weight) and a small amount of di-ngbutylamine are gradually added with vigorous stirring to bring the solution viscosity to 2300 poises (25 ° C) . 2-4% of the polymer obtained by the reaction of diphenylmotane-4.4 g of polymerization is cooled to 5 ° C to the polymer and a 10% solution of 1,2-propylenediamine (30 parts by weight) in dimethyl form is gradually introduced, resulting in a viscous solution a polymer with a concentration of 35% and a viscosity of 600 poises (hereinafter referred to as polymer B).

Polymer B is added to the solution of 2-polyurethane, the mixture is drawn into threads, and then painted with anthraquinone blue SWF. The product using polymer B is painted in deep colors and attracts good durability during washing, as well as an excellent modulus size (300% elongation). The test results are shown in Table. eight,

Table B -diisocyanate (250 parts by weight) and polyester diol (with a molecular weight of 13OO, 65O parts by weight) is the product of sebacic acid polycondensation and the tertiary nitrogen-containing diol. HOCH-jCHjCHCHOHOH NCrt-C H), at 50 ° C for 30 minutes in dimethylformamide, cooling the resulting polymer solution to 5 C and gradually adding a 10% solution of 1,2-propylenediamine to it (30% by weight ) in dimethylformamide. Thereafter, the mixture is drawn into a yarn and dried with anthraquinone blue. The blue colored product is perfectly washable. EXAMPLE 26 Diphenylmethane-4,4.di1-cyocyanate (25O parts by weight) is reacted with polytetramethylene glycol (molecular weight 13OO, 150 parts by weight) at 80 ° C for 80 minutes, to mixtures of additives23

dimethylformamide is added, after which it is cooled to 4 ° C, a polyether with a terminal hydroxyl group (molecular weight 1100, 400 parts by weight) is added, which is the product prlicondene

adipic acid and 2-methyl-2-f W, N-dimethylaminomethyl) -1,3-propa diol. The mixture is allowed to react at 40 ° C for 30 minutes in dimethylformamide in the presence of acetic acid (20 parts by weight), 10 get a solution of the product of incomplete polymerization.

The solution of the incomplete polymerization product is cooled to 5 ° C and gradually

The amount of polymer added, g

0% 1.0

2.0

3, O

5.0

Comparative Example 27. Diphenylmethane-4, 4-diisocyanate (250 parts by weight) was dissolved in dimethylformamide to give a 35 ° / m solution. A solution of 2-methyl-2- (M in N-dimethylaminomethyl) -1,3-propanediol (147 parts by weight) and acetic acid (40 parts by weight) in dimethylformamide (the content of glycol compound 35 wt.%) to obtain a solution with a viscosity of 5OO poises (hereinafter referred to as polymer g). Reaction wire t.support the temperature of the liquid ZO-40 C.

24

a 10% solution of 1,2-propylenediamine (30 parts by weight) in dimethylformamide is introduced. The resulting viscous solution is characterized by a concentration of 35% and a viscosity of 8OO poises (hereinafter referred to as polymer B).

Polyurethane elastomer, not having a tertiary nitrogen, prepared in Example 25, is added with polymer B and the mixture is pulled into threads that are dyed with anthraquinone blue. SW P. The product is painted in deep tones, it has good durability when it is washed, it has an extremely high modulus (% ZOO elongation), see table. 9.

TablipaE

Module, kg / cm

5.5

56 15.3 60

23.5

58

28.9

57

1.0

55

Polymer D was added to the non-tertiary nitrogen polymer prepared in Example 24 to achieve a concentration of 4%, the mixture was stretched into yarns used as sample 1.

The thread obtained by adding 2.5% polymer B according to example 25 is used as sample 2.

Before or after treatment with boiling water, sample 1 and 2 are stained with anthraquinone blue and W P.

The results are shown in Table. ten.

Table 10

25

Obtained by comparative example

Claims (1)

1.J. US Patent No. 3180853, Cl, 26O-77.5, published. 1965.