PL220887B1 - Derivative polyampholyte of dimethylphosphinic acid and ammonia and a method for its manufacture - Google Patents

Description

The subject of the invention is a new polyampholyte derived from dimethylphosphinic acid and ammonia, which is a universal buffer for pH adjustment.

The essence of the invention is a polyampholyte, which is a derivative of dimethylphosphinic acid and ammonia of formula 1.

The polyampholyte derived from dimethylphosphinic acid and ammonia has not been described in the scientific and technical literature so far.

The polyampholyte is intended to be used as a universal buffer for pH correction, to bind hydroxide ions, protons and metal ions, to stabilize process water, and other applications.

Polyampholytes derived from dimethylphosphinic acid and ammonia are stronger acid than polyampholytes containing carboxylic acids and weaker acid than commonly used polyampholytes containing phosphonic or sulfonic groups. Poly dimethylphosphine ampholytes form numerous cyclic fragments in their structures, therefore they are structurally similar to polymers containing azacorone ethers.

Polyampholyte derived from dimethylphosphinic acid and ammonia of formula 1 is obtained in a three-stage reaction of phosphinic acid with ammonia and formaldehyde, carried out at a temperature of

273-373 K, in water, in the presence of an activator, the obtained aminomethylphosphinic acid is subjected to a polycondensation reaction with formaldehyde in the second stage, and a cross-linking with formaldehyde in the third stage.

The invention is presented in the preparation examples.

P r z k ł a d 1

To a solution of ammonium phosphinate (4.15 g, 0.050 mol) in water (5 cm ³ ), about 298 K 37% formalin (4.10 cm ³ , 0.055 mol) is added dropwise at ₃ , and the mixture is kept at temperature. 31 1 31 turn about 298 K and a series of measurements using the spectra ¹ H, ³¹ P ^{1 H} and ³¹ P NMR, which showed that after 96 hours of the main components of the mixture are: acid aminometylofosfinowy (47%) acid phosphine (41%). The obtained results are presented in Table 1.

P r z k ł a d 2

The procedure is as in Example 1, except that ₃ is added before the formalin is introduced

12M aqueous HCl (1.25 cm ^3, 0,30x0,050 mol) and the resulting mixture was analyzed by 1 31 31 PO1 power spectra ¹ H, ³¹ P ^{1 H} NMR and ^31P. The measurements show that after 96 hours the main components of the mixture are: aminomethylphosphinic acid (51%), phosphinic acid (19%) and 30% of various phosphine compounds, including polymers. The obtained results are presented in Table 1.

P r z k ł a d 3

The procedure is as in Example 1, except that ₃ is added before the formalin is introduced

12M aqueous HCl (2.50 cm ^3, 0,60x0,050 mol) and the resulting mixture was analyzed by 1 31 31 PO1 power spectra ¹ H, ³¹ P ^{1 H} NMR and ^31P. The measurements show that after 96 hours The main components of the mixture are: aminomethylphosphinic acid (26%), phosphinic acid (15%) and 59% of various phosphine compounds, including as much as 57% of polymers. The obtained results are presented in Table 1.

P r z k ł a d 4

The procedure is as in Example 1, except that ₃ is added before the formalin is introduced

12M aq. HCl solution (5.00 cm ³ , 1.20 x 0.050 mol) and the resulting mixture is analyzed at 31 L 31 ¹ H, ³¹ P { ¹ H} and ³¹ P NMR. The measurements show that after 96 hours the main components of the mixture are: aminomethylphosphinic acid (21%), phosphinic acid (39%) and 30% of various phosphine compounds, including 25% of polymers. The obtained results are presented in Table 1.

P r z k ł a d 5

The procedure is as in Example 1, except that ₃ is added before the formalin is introduced

12M aqueous HCl solution (7.50 cm ³ , 1.80 x 0.050 mol) and the resulting mixture was analyzed at 31 L 31 ¹ H, ³¹ P { ¹ H) and ³¹ P NMR. The measurements show that after 96 hours the main components of the mixture are: phosphinic acid (86%) and hydroxymethylphosphinic acid (12%), no other phosphinic compounds and polymers. The obtained results are presented in Table 1.

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T a b e l a 1. Mixture composition [%] depending on the nHCl / nH2PO2H ratio at 298 K.

HCI / H2PO2H [mol / mol] H2PO2H [% molP] H2NCH2PO2H2 [% molP] Other [% molP] 0.00 41 47 12 0.30 19 51 thirty 0.60 15 26 59 (57 polymers) 1.20 39 21 30 (25 polymers) 1.80 86 0 12 HMPA

HMPA = HOCH2PO2H2.

Examples 1-5 show that the optimum for the synthesis of aminomethylphosphinic acid, which is the basic substrate for the next polycondensation, is 0.3 mole HCl per mole of phosphinic acid, and the optimum for the degree of conversion of aminomethylphosphinic acid and polymerization is 0.6 mole HCl per mole phosphinic acid. Increasing the amount of HCl over this value inhibits the aminomethylation of phosphinic acid and reduces the yield of aminomethylphosphinic acid, and thus also the degree of subsequent polycondensation. At 1.8 moles of HCl per mole of phosphinic acid, no more aminomethylation products of phosphinic acid are observed.

P r z k ł a d 6

To a solution of ammonium phosphinate (4.15 g, 0.050 mol) in water (5 cm ³ ), about 298 K 37% formalin (4.10 cm ³ , 0.055 mol) is added dropwise at ₃ , and the mixture is kept at temperature. 31 1 31 turn about 323 K and a series of measurements using the spectra ¹ H, ³¹ P ^{1 H) and ³¹ P NMR, which showed that after 4 hours the major constituents of the mixture are: acid aminometylofosfinowy (46%) and acid phosphine (35%). The obtained results are presented in Table 2.

P r z k ł a d 7

The procedure is as in Example 6 except that ₃ is added before the formalin is introduced

12M aqueous HCl (1.25 cm ^3, 0,30x0,050 mol) and the resulting mixture was analyzed by 1 31 31 PO1 power spectra ¹ H, ³¹ P ^{1 H} NMR and ^31P. These measurements show that after 4 hours the main components of the mixture are: aminomethylphosphinic acid (42%), phosphinic acid (12%), 29% of various aminomethylphosphinic compounds and about 11% of compounds containing an NCPCN moiety. The obtained results are presented in Table 2.

P r z k ł a d 8

The procedure is as in Example 6 except that ₃ is added before the formalin is introduced

12M aqueous HCl (2.50 cm ^3, 0,60x0,050 mol) and the resulting mixture was analyzed by 1 31 31 PO1 power spectra ¹ H, ³¹ P ^{1 H} NMR and ^31P. These measurements show that after 4 hours the main components of the mixture are: aminomethylphosphinic acid (30%), phosphinic acid (16%), 37% of various aminomethylphosphinic compounds and about 16% of compounds containing an NCPCN moiety. The obtained results are presented in Table 2.

P r z k ł a d 9

The procedure is as in Example 6 except that ₃ is added before the formalin is introduced

12M aq. HCl solution (5.00 cm ³ , 1.20 x 0.050 mol) and the resulting mixture is analyzed at 31 L 31 ¹ H, ³¹ P { ¹ H} and ³¹ P NMR. These measurements show that after 4 hours, the main components of the mixture are: aminomethylphosphinic acid (21%), phosphinic acid (29%), 31% of various aminomethylphosphinic compounds and 11% of compounds containing an NCPCN moiety. The obtained results are presented in Table 2.

P r z k ł a d 10

The procedure is as in Example 6 except that ₃ is added before the formalin is introduced

12M aqueous HCl (7.50 cm ^3, 1,80x0,050 mol) and the resulting mixture was analyzed by 1 31 1 31 aid spectra ¹ H, ³¹ P ^{1 H} NMR and ^31P. These measurements show that after 4 hours the main component of the mixture is phosphinic acid (96%). No other phosphine compounds or polymers were found. The obtained results are presented in Table 2.

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T a b e l a 2. Mixture composition [%] depending on the ratio of nHCl / nH2PO2H at 323 K.

HCl / H ₂ PO2H [mol / mol] H2PO2H [% molP] H2NCH2PO2H2 [% molP] Other [% molP] 0.00 35 46 7NCPH + 1NCPCN 0.30 12 42 29NCPH + 11NCPCN 0.60 16 thirty 37NCPH + 16NCPCN 1.20 29 21 31NCPH + 11NCPCN 1.80 95 0 5HMPA

HMPA = HOCH ₂ PO ₂ H ₂ , NCPH = compounds containing the N-CH ₂ -PH fragment, NCPCN = compounds containing the N-CH ₂ -P-CH ₂ -N fragment.

Examples 6-10 show that the optimum for the synthesis of aminomethylphosphinic acid, which is the basic substrate for subsequent polycondensation, at 323 K is variable. After one hour it is 0.3 mole HCl per mole of phosphinic acid, and after 4 hours it is 0.0 mole HCl per mole of phosphinic acid. The optimum degree of conversion of aminomethylphosphinic acid is 0.3-1.2 moles of HCl per mole of phosphinic acid. Increasing the amount of HCl above these values inhibits the aminomethylation reaction of phosphinic acid and significantly reduces the yield of aminomethylphosphinic acid. At 1.8 moles of HCl per mole of phosphinic acid, no more aminomethylation products of phosphinic acid are observed.

P r x l a d 11

The procedure is as in Example 1, except that after 96 hours is added to the reaction mixture ₃

37% formalin (4.10 cm ^3, 0.055 mol), the mixture is maintained at a temperature of about 298 K and wyko1 31 1 31 nuje a series of measurements using the spectra ¹ H, ³¹ P ^{1 H} NMR and ³¹ P, of which it appears that after 70 h the main components of the mixture are polymeric aminomethylphosphinates containing the moiety

N-CH ₂ -P-CH ₂ -N (48%), N-CH ₂ -PH (28%). The spectra showed no presence of either _3- nomethylphosphinic acid or phosphinic acid. Then 37% formalin (4.10 cm ³ , 0.055 mol) is added, then the mixture is kept at a temperature of about 298 K for 24 hours to obtain a polyampholyte solution from which water and other volatile components are distilled off at a pressure of about 20 hPa with a water bath. 373 K. poliamfolit obtained as a white powder, whose structure is confirmed by ¹ H spectra and ³¹ P ^{1 H} NMR.

P r z k ł a d 12

The procedure is as in Example 2, except that after 96 hours is added to the reaction mixture ₃

37% formalin (4.10 cm ^3, 0.055 mol) and the mixture is maintained at a temperature of about 298 K

31 1 31 and a series of measurements using the spectra ¹ H, ³¹ P ^{1 H} and ³¹ P NMR which showed that 70 hours after the main components of the mixture are polymeric aminometylofosfiniany containing moiety

N-CH ₂ -P-CH ₂ -N (43%) and N-CH ₂ -PH (34%). The spectra showed no presence of either _3- nomethylphosphinic acid or phosphinic acid. Then 37% formalin (4.10 cm, 0.055 mol) is added and the mixture is kept at a temperature of about 298 K for 24 h and a polyampholyte solution is obtained, from which water and other volatile components are distilled off at a pressure of about 20 hPa from a water bath with a final temperature of 373 K. Polyampholyte is obtained in the form of a white powder,

31 1 whose structure is confirmed by H and P {H} NMR spectra.

P r z l a d 13

The procedure is as in Example 3, except that after 96 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 about 298 K and a series of measurements are made using the ¹ H, ³¹ P { ¹ H) and ³¹ P NMR spectra, which show that after 70 h the main components of the mixture are polymeric aminomethylphosphinates containing the N-CH ₂ moiety - P-CH ₂ -N (61%) and N-CH ₂ -PH (17%). No presence of aminomethylphosphinic acid or phosphinic acid was found on the spectra. Thereafter, 37% formalin ₃ (4.10 cm ³ , 0.055 mol) was added, and the mixture was kept at a temperature of about 298 K for 24 h. Water and other volatile components were distilled off from the resulting polyampholyte solution at a pressure of about 20 mbar.

31 1

A white powder poliamfolitu, whose structure is confirmed by ¹ H spectra and ³¹ P ^{1 H} NMR.

P r z k ł a d 14

The procedure is as in Example 4, except that after 96 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

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31 1 31 about 298 K and a series of measurements are made using the ¹ H, ³¹ P { ¹ H} and ³¹ P NMR spectra, which show that after 70 h the main components of the mixture are polymeric aminomethylphosphates containing the N-CH ₂ moiety - P-CH ₂ -N (59%), N-CH ₂ -PH (30%). The spectra no longer detectable aminometylofosfinowego acid or phosphinic acid, but poliamfolit contains about 7% of sour su ₃ hydroksymetylofosfinowego. Then also added 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture is maintained at a temperature of about 298 K for 24 h poliamfolitu solution is obtained from which distilled water and other volatile components under a pressure of about 20 hPa a water bath with a final temperature of 373 K. A polyampholyte is obtained in the form of a white powder

The structure is confirmed by the H and P {H} NMR spectra.

P r z k ł a d 15

The procedure is as in Example 5, except that after 96 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 about 298 K and a series of measurements are made using the ¹ H, ³¹ P { ¹ H} and ³¹ P NMR spectra, which show that after 70 h the main components of the mixture are phosphinic acid (49%) and hydroxymethylphosphinic acid ( 23%), which shows that the addition of 1.8 moles of HCl per mole of phosphinic acid almost completely inhibits the formation of aminomethylphosphinates and the formation of polyampholytes.

P r x l a d 16

The procedure is as in Example 6, except that after 14 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 about 323 K and a series of measurements are made using the ¹ H, ³¹ P { ¹ H} and ³¹ P NMR spectra, which show that after 4 h the main components of the mixture are polymeric aminomethylphosphates containing the N-CH ₂ moiety - P-CH ₂ -N (51%), N-CH ₂ -PH (21%). The spectra showed no presence of aminomethylphosphinic acid or phosphinic acid. Then added are 37% formalin ₃ (4.10 cm ^3, 0.055 mol) and the mixture was maintained at about 323 C for 9 h and the solution obtained poliamfolitu, containing 99% total polymers, of which distilled water and other volatile components at a pressure of about 20 hPa from a water bath with a final temperature of 373 K.

31 1

Poliamfolit obtained as a white powder, whose structure is confirmed by ¹ H spectra and ³¹ P ^{1 H} NMR.

P r z k ł a d 17

The procedure is as in Example 7, except that after 14 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 about 323 K and a series of measurements is made using the H, P {H) and P NMR spectra, which show that after 4 h the main components of the mixture are polymeric aminomethylphosphinates containing the N-CH ₂ -P-CH ₂ moiety -N (54%) and N-CH ₂ -PH (32%). No presence of aminomethylphosphinic acid or phosphinic acid was found in the spectra. Then 37% formalin ₃ (4.10 cm, 0.055 mol) is added and the mixture is kept at a temperature of about 323 K for 9 h and a polyampholyte solution is obtained, containing a total of 96% polymers, from which water and other volatiles are distilled off components under a pressure of about 20 hPa from a water bath with a final temperature of 373 K.

31 1

The resulting polyampholite in the form of a white powder, the structure of which is confirmed by the H and P {H} NMR spectra.

P r z k ł a d 18

The procedure is as in Example 8 except that after 14 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 about 323 K and a series of measurements are made using the ¹ H, ³¹ P { ¹ H} and ³¹ P NMR spectra, which show that after 4 h the main components of the mixture are polymeric aminomethylphosphates containing the N-CH ₂ moiety - P-CH ₂ -N (67%) and N-CH ₂ -PH (23%). No presence of aminomethylphosphinic acid or phosphinic acid was found in the spectra. Then added are 37% formalin ₃ (4.10 cm ^3, 0.055 mol) and the mixture was maintained at about 323 C for 9 h and the solution obtained poliamfolitu, containing 97% total polymers, of which distilled water and other volatile components at a pressure of about 20 hPa from a water bath with a final temperature of 373 K.

31 1

Poliamfolit obtained as a white powder, whose structure is confirmed by ¹ H spectra and ³¹ P ^{1 H} NMR.

P r z k ł a d 19

The procedure is as in Example 9 except that after 14 hours is added to the reaction mixture ₃

37% formalin (4.10 cm ^3, 0.055 mol) and the mixture is maintained at a temperature of about 323 K

31 1 31 and a series of measurements using the spectra ¹ H, ³¹ P ^{1 H} and ³¹ P NMR, which showed that after 4 hours the major components of the mixture are polymeric aminometylofosfiniany containing moiety

N-CH ₂ -P-CH ₂ -N (73%), N-CH ₂ -PH (22%). The spectra showed no presence of either _3- nomethylphosphinic acid or phosphinic acid. Then an additional 37% formalin (4.10 cm,

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0.055 mol), then the mixture is kept at a temperature of about 323 K for 9 hours and a polyampholyte solution is obtained, containing a total of 98% polymers, from which water and other volatile components are distilled off at a pressure of about 20 hPa from a water bath with a final temperature of 373 K Is obtained

31 1 polyampholyte in the form of a white powder, the structure of which is confirmed by H and P {H} NMR spectra.

P r z k ł a d 20

The procedure is as in Example 10 except that after 14 hours is added to the reaction mixture ₃ 37% formalin (4.10 cm ^3, 0.055 mol) and the mixture was maintained at a temperature

31 1 31 of about 323 K, and a series of measurements using the spectra ¹ H, ³¹ P ^{1 H} and ³¹ P NMR, which showed that after 4 hours the major components of the mixture are polymeric aminometylofosfiniany containing moiety N-CH ₂ - P-CH ₂ -N (76%), N-CH ₂ -PH (17%). The spectra showed no presence of aminomethylphosphinic acid or phosphinic acid. Then an additional 37% for ₃ raspberry (4.10 cm ³ , 0.055 mol) is added and the mixture is kept at a temperature of about 323 K for 9 hours to obtain a polyampholyte solution with a total of 97% polymers, from which water is distilled off and other volatile components at a pressure of about 20 hPa from a water bath with a final temperature of ₁

373 K. poliamfolit obtained as a white powder, whose structure is confirmed by ¹ H spectra ³¹ P ^{1 H} NMR.

Example 21 ₃

In the first step, to a solution of ammonium phosphinate (8.30 g, 0.10 mol) in water (10 cm ³⁾ ₃ was added dropwise carefully at approximately 300-310 K 12M hydrochloric acid (5.0 cm, 0.060 mol) and ₃ was then 37% formalin (8.2 cm ^3, 0.11 mol). The mixture is heated to approximately 353 K

31 1 31 for an hour, and then performs H, P {H} and P NMR spectra measurements, which show that after an hour, the main components of the mixture are aminomethylphosphinic acid derivatives (78%) and polymeric aminomethylphosphinates containing the N-CH ₂ moiety - P-CH ₂ -N (14%). Further heating of the mixture no longer changes its composition, this is added to a second portion of 37% formalin ₃ (8.2 cm ^3, 0.11 mol) and the mixture was heated to a temperature of about 353 K for 3 hours, resulting thick gel. 0.10 g of gel is taken and suspended in 0.60 g of water, and then 31 1 31 ¹ H, ³¹ P { ¹ H} and ³¹ P NMR spectra of the solution above the gel are not measured, showing that in part soluble, there is no phosphinic acid or aminomethylphosphinic acids, and only a small amount (as evidenced by the low signal-to-noise ratio) of polymeric compounds containing the N-CH ₂ -P-CH ₂ -N moiety (99%), indicating that wbudowały all the substrate ₃ in the structure of the resin. A third portion of 37% formalin (8.2 cm ³ , 0.11 mol) is added to the gel, and then the mixture is heated to a temperature of about 353 K for 6 hours, which causes the gel to harden, from which water and other volatile components are distilled off at a pressure of about 20 hPa from a water bath with a final temperature of 373 K. A polyampholyte in the form of a white powder is obtained, the structure of which is supported by the P {H} NMR spectrum (in D ₂ O) [AK010], where only broad signals from 15 to 18 ppm.

Example 22 ₃

Water (10 g) was added a 14M aqueous solution of ammonia (7.1 cm ^3, 0.10 mol), followed by dropping funnel ₃ beach cautiously at a temperature of about 300-310 F, 12M hydrochloric acid (7.5 cm ^3, 0.090 mole), then

50% phosphinic acid (15.6 cm ^3, 0.15 mol) and 37% formalin (9.0 cm ^3, 0.12 mol) and the mixture was heated at about 353 K for one hour, resulting in fosfinometylowanie amo31 niaku, as confirmed by ³¹ P NMR spectrum, showing major signals at 10-11 ppm [N-CH2-P (O) (OH) H]; and the ¹ H NMR spectrum which shows the signals at 8.03 and 6.20 ppm (PH) and at

3.35 / 3.32 ppm (N-CH ₂ -P). After this time the mixture was cooled to a temperature of about 300-310 C, added ₃ drops of a second portion of 37% formalin (9.0 cm ^3, 0.12 mol) and continued heating for hours at a temperature of about 353 K, so that there is cross-linking product and partial precipitation of a gel-like polyampholyte. ³¹ P NMR spectrum constructed from the soluble portion comprises primarily poliamfolitu signals at approximately 16 ppm, which originate from a fragment of the N-CH ₂ -P-CH ₂ -N. Followed by ₃ again cooling the mixture to about 300-310 C, is added a third portion of 37% formalin (9.0 cm, 0.12 mol) and then heated at about 353 K for 4 h, which hardens by po31 liamfolitu dosieciowanie polymer, as confirmed by the P NMR spectrum (made from a solution above the insoluble resin), which shows only the residual signals from the substrates and products, with a very low signal-to-noise ratio, indicating that all components have been incorporated into the resin. The formed product is cooled to room temperature and the volatile components are distilled off under a reduced pressure of 20 hPa from a bath with a final temperature of 373 K. After these operations, the product is additionally dried in a Petri dish on an electric heating plate with a temperature of about 333-353 K and obtained in the result was a product which contains 6.6 mmol / g of amino groups and 9.9 mmol / g

Of the phosphine groups, and the molecular weight and the sum formula of the smallest possible number to write is M = 304.1 for C ₆ H ₁₅ N ₂ O ₆ P ₃ .

P r z k ł a d 23

The procedure is as in Example 22, except that no hydrochloric acid is added, the polyampholyte is obtained in the form of a colorless, water-soluble viscous mass.

P r z k ł a d 24

The procedure is as in example 22 with the difference that instead of a 50% solution of phosphinic acid, a solution made of monohydrate sodium hypophosphite (15.9 g, 0.15 mol), water (15 g) ₃ and 12M hydrochloric acid (12, 5 cm ³ , 0.15 mol), a polyampholyte with properties similar to the polyampholyte obtained in Example 22 was obtained.

P r z l a d 25

The procedure is analogous to that of Example 22, with the difference that instead of formalin, trioxane is used (in three portions of 3.6 g, 0.12 mol each), a polyampholyte with properties similar to the polyampholyte obtained in Ex. 22.

P r z l a d 26

The procedure is analogous to that in Example 22, with the difference that paraform (in three portions of 3.6 g, 0.12 mol) is used instead of formalin, a polyampholyte is obtained with properties similar to the polyampholyte obtained in Ex. 22.

Example 27 ₃

A 14M aqueous ammonia solution (14.2 cm ³ , 0.20 mol) is added to water (20 g), then ₃ is carefully added dropwise, at a temperature of about 300-310 K, 12M hydrochloric acid (15.0 cm ³ , 0.180 mol), then 50% phosphinic acid (31.2 cm ³ , 0.30 mol) and 37% formalin (18.0 cm ³ , 0.24 mol), then the mixture was heated at about 353 K for one hour . After this time the reaction mixture spends Ochla ₃ to a temperature of about 300-310 C, is added dropwise a second portion of 37% formalin (18.0 cm ^3, 0.24 mol) and continued heating for 2 hours at a temperature of about 353 K, so that cross-linking of the product takes place. The ³¹ P NMR spectrum shows mainly the extended signal at 17.5-18.7 ppm coming from the N-CH2-PH fragment, the broadened signal at 23.1-23.6 ppm coming from the N-CH ₂ -P-CH ₂ fragment -N and broad signal at 35.7-35.9 ppm from the fragment

N-CH ₂ -P-CH ₂ -OH. The mixture is cooled once more to about 300-310 K, a third portion of 37% ₃ formalin (18.0 cm ³ , 0.24 mol) is added and reheated at about 353 K for 6 hours. The mixture is cooled to a temperature of about 298 K and volatile components are distilled off under a reduced pressure of 20 hPa from a bath with an initial temperature of 293 K and a final temperature of 373 K, resulting in about 36 g of polyamphol in the form of a white semicrystalline residue, the structure of which is confirmed by the spectra NMR [WG11872C]: ³¹ P ^{1 H} NMR (D 2 O, δ [ppm]) extended at 17,2-19,5 ppm signal derived from a portion of the polymeric N-P-CH2-CH2-N signal, and expanded at 30 -35 ppm derived from the polymeric fragment N-CH2-P-CH2-OH, in addition, the spectrum shows traces of phosphonic acid (<1%), traces of HO-CH2-P (O) OH-CH2OH (<2%) and about 5% HOCH2-P (O) HOH. ¹ H NMR (D 2 O, δ [ppm]): 2.95 (bs) (from CH 3 N-products), 3,1-4,2 ppm broad signal with superimposed thereon doublet 3: 3.60 (d, J = 5.4 Hz), 3.62 (d, J = 5.4 Hz), 3.70 (d, J = 5.2 Hz) derived from CH2P, 6.78 ppm (dt, _HB-CH2, J = 552, J = 2.3 Hz), 7.0 ppm (bdt, _HB-CH2, J = 567 Hz, J = nieozn.).

Claims (1)

Polyampholyte, which is a derivative of dimethylphosphinic acid and ammonia of the formula 1, PL 220 887 B1