CA1176797A - PREPARATION OF .alpha.,.beta.-UNSATURATED CARBOXYLIC ACID N- SUBSTITUTED-AMIDES, AND POLYMERS THEREOF - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The invention relates to the preparation of ?, .beta.-un-saturated carboxylic acid N-substituted-amides, polymers thereof and the use of these polymers as sedimentation, flocculating, dewatering and retention aids, as additives for mineral oils, and as ion exchangers, The ?, .beta.-unsaturated carboxylic acid N-substituted-amides are prepared by transamidation of .beta.-hydroxy or .beta.-alkoxy-carboxylic acid amides with primary amines and heating of the resulting .beta.-hydroxy- or .beta.-alkoxy-carboxylic acid N-substituted-amides in the vapor phase in the presence of catalysts. Primary amines are preferably used for the trans-amidation which have no hydrogen beta to the amino group. These ?, .beta.-unsaturated carboxylic acid amides nay be neutralized and/or quaternized and polymerized alone or with other comonomers, and preferably acrylic or methacrylic acid derivatives such as acrylamide, to give cationic polymers. These polymers are suited for use as flocculating and sedimentation aids, as dewatering and retention aids in paper-making, as additives for mineral oils, and as ion exchangers.

Description

~ 3 ~

This application is directed to homo- and copolymers of certain novelC~ unsaturated carboxylic acid N-substituted amides while parent application 342,641 filed 27 December 1979 is directed to the novel amides and a process for preparing the novel amides and other such amides.
N-substi~uted alkylacrylamides have been known ~or some time They may be prepared by reaction of acrylonitrile with l-olefins (JACS 73, 1951, 4076) and by reaction of primary and secondary amines with an addition compound o~
maleic anhydride and triphenylphosphiTIe (Japanese Patent 6~9~0,083). According to British Pa~ent 746,747, N-substituted acrylamides can be obtained by dehydrohalogenation o~ ~-chloro-propionic acid amides, and according to German Patent ~)pli-cation DOS 2,344,070 by pyrolysis of ~-methoxypropionic acid amides. They can also be prepared by the process employing the Schotten-Baumann reaction by reaction of acrylic acid chloride with appropriate diamines (U. S. Patent 2,951,907~, by catalytic addition of functionalized amines to acetylene under a CO atmosphere (U. S. Patent 2,773,063), by reductive amination of diacetone acrylamide (J. Pol~m. Sci. 10 [1972~, 595), and by pyrolysis of norbornene derivatives (German Patent Application DOS 2,354,602). Finally, these compounds can be obtained also by the process according to German Patent Applications DOS 2,5~2,247 and 2,656,682 and U. S.
Patent 3,878,247, wherein amines are added to acrylic or methacrylic acid esters with concurrent aminolysis, N-sub-stituted ~-aminopropionic acid amides being so obtained which are pyrolytically decomposed to the corresponding ~,~-unsatur-ated carboxylic acid N-substituted amides. In our Canadian Patent 1,104,5~6 processes are described for the preparation ofC~
unsaturated acid N-substituted amides by transamidation of s-hydroxy or ~l-- .

~ J

l ¦ or ~-alkoxy-carboxylic acid amides with amines to eliminate

2 ¦ ammonia and conversion of the N-substituted hydroxy- or

3 alkoxy-carboxylic acid N-substituted amides formed by de-

4 hydration or by dealcoholysis to the corresponding a,~-un-saturated carboxylic acid N-substituted amides by heating in 6 the liquid phase in the presence of catalysts.

8 It has now been found that ~ unsaturated carboxylic 9 acid N-substituted amides can also be prepared, in techni-cally simple manner and in high yields, by dehydration or ll dealcoholysis of the ~-hydroxy- or ~-alkoxy carboxylic acid 12 N-substituted amides,obtained by transamidation of ~-hydroxy-13 or ~-alkoxy carboxylic acid amides with amines, in vapor 14 phase to the desired ~,~-unsaturated carboxylic acid N-sub-stituted amides.

17 The invention thus has as its object a process for the 18 preparation of ~,~-unsaturated carboxylic acid amides of the 19 general formula 22 ¦ R 1 \~ NH ( Y ) ~X) (I) 24 wherein Rl and R2 each independently is hydrogen or methyl, 26 Y is a divalent straight- or branched-chain organic moiety 27 with from 2 to 30, and preferably 2 to 18, carbon atoms, 28 and preferably a group of the formula ~(Yl)m-(Y2)n-(Y3)t-, 29 Yl, Y2 and Y3 each represents an alkylene group or the moiety of a cyclic ring system with 5 or 6 carbon atoms, ~ ~ '7~7 1 m + n -~ t is 2 or 3, 2 X is hydrogen or the radical of an amine of the formula 3 -N(R4)(R5), and 4 R4 and R5 each independently is an alkyl radical having 1 to 4 carbon atoms, 6 by transamidation of ~-substituted carboxylic acid amides 7 with primary amines of the general formu].a 8 H2N-~Y)-(X) (II) 9 with elimination of ammonia and conversion of the carboxylic acid N-substituted amides formed to ~,~-unsaturated acid 11 N-substituted amides, said process being characterized in 12 that the starting materials used are ~-substituted carboxylic 13 aci.d amides of the general formula 14`

5 ¦ 1 T2 NH2 (III) 18 wherein 19 Z is a hydroxy group or an alkyl radical having 1 to 4 carbon atoms, and that the conversion of the resulting ~-hydroxy- or 21 ~-alkoxy-carboxylic acid amides to the a,~-unsaturated car-22 boxylic acid N-substituted amides is effected by heating in 23 vapor phase in the presence of catalysts.

The conversion of the ~ydroxy- or ~-alkoxy-carboxylic 26 acid N-substituted amides to ~,~-unsaturated carboxylic acid 27 N-substituted amides by dehydration or dealcoholysis thus is 28 no longer carried out in the liquid phase; rather, ~-hydroxy-29 or ~-alkoxy-carboxylic acid amide is evaporated ~or the pur-pose of splitting off water or alcohol, respectively, prefer--~I ~ '7~7 1 ¦ ably in a gentle manner, i. e., ~mder mild conditions, and 2 ¦ the vapors are conducted over a solid catalyst which is ad-3 ¦ vantageously disposed in a heatable reaction tube. E'or gentle 4 ¦ evaporation, a vacuum aspirator is preferably used. For still 5 ¦ gentler treatment, the evaporation may optionally be carried

6 ¦ out under vacuum. In contrast to pyrolysis in liquid phase,

7 ¦ in which the sump is thermally stressed for a prolonged time,

8 ¦ the retention time in the hot reaction tube in the instant

9 ¦ process is very short, and the risk of side reactions such as

10 ¦ polymerization or condensation of the ~-hydroxy-carboxylic

11 ¦ acid N-substituted amide to polyester, attended by spl-Ltting

12 ¦ off of amine, which cannot be avoided when operating in

13 ¦ liquid phase at elevated temperature, therefore is minimized.

14 I

15 ¦ The transamidation is advantageously effected at. a

16 ¦ temperature ranging from about 100 to 200 C, optionally

17 ¦ with addition of catalytic amounts of acid. It has been

18 found that especially when ~-alkoxy-carboxylic acid amides

19 are used, about 0.5 to 1.0 mole percent of acetic acid is particularly well suited for use as catalyst. Acid amide and 21 amine can be caused to react simply by heating, withou-t the 22 addition of a solvent, the ammonia formed being driven off 23 to shift the reaction equilibrium in the direction of the 24 desired products (~-hydroxy- or ~-alkoxy-carboxylic acid N-substituted amide).

27 The transamidation can also be effected under normal 28~ pressure without the addition of a catalyst, amines having 29 boiling points above about 110 C being used in order to limit the reaction time to about 6 hours.

1 Preferred are amines which in addition form a homo-2 geneous phase with the molten acid amide or which are par-3 tially soluble in the molten acid amide or which themselves 4 dissolve part of the acid amide.

6 Reduced reciprocal solvency may retard the reaction 7 initially; however, as the conversion proceeds the reaction 8 rate increases since the ~-hydroxy- or ~-alkoxy-acid N-sub-9 stituted amide formed serves as a solubilizing aid and a homogeneous phase begins to form. Of advantage is the addi-11 tion of about 5 to 10~/o of the particular ~-hydroxy~ or ~-12 alkoxy-carboxylic acid N-substituted amide in order to 13 bridge over over this initial induction period.

The particular amine may be used in excess based on 16 the hydroxy- or alkoxy-amide.

18 The hydration or dealcoholysis is preferably carried 19 out at a temperature ranging from about 200 to 400 C. In the case of ~-hydroxy- or ~-alkoxy-carboxylic acid amides 21 containing amino groups, temperatures up to about 250 C
22 have proved sufficient.

24 Suitable for use as dehydration catalysts are, in particular, metal oxides such as aluminum oxide. Mixtures 26 of oxides, such as aluminum oxide/silicon dioxide, or im-27 pregnated carriers, for example, acidic aluminum oxide or 28 pumice impregnated with phosphoric acid, are also suitable, 29 as are salts such as aluminum phosphate or boron phosphate.
Suitable solid catalysts for the dealcoholysis are, in parti-~ r~ 7~

l cular, mineral oxides of acidic or basic character, such as 2 aluminum oxide, silicon dioxide or barium oxide, which option-3 ally may be impregnated with acids such as phosphoric acid or 4 with bases such as sodium hydroxide.

6 For the purposes of the invention, the preferred 7 ~-hydroxy-carboxylic acid amides are ~-hydroxy-propionic 8 acid amide or ~-hydroxy-butyric acid amide.
Examples of suitable amines of the general formula ll H2N-~Y)-(X) (II) 12 are ~-dimethylaminoethylamine, 2-diethylaminoethylamine, 13 3-dimethylaminopropylamine, benzylamine, cyclohexylamine, 14 dodecylamine and stearylamine.
16 Amines are preferably used which have the general 17 formula 1~

H2~-~CH2)n-~-Cl~2 ~x) (II') 22 wherein R6 and R7 may be alkyl groups, and preferably lower 23 alkyl groups having l to 4 carbon atoms and in particular 24 methyl, or aryl groups, or together form an aliphatic ring, and in particular the cyclohexyl or cyclopentyl moiety; n is 26 a number from 0 to lO; and X is the radical of an amine of 27 the formula -N(R4)(R5), R4 and R5 representing alkyl radicals 28 having l to 4 carbon atoms, or cycloalkyl radicals having 29 3 to 8 carbon atoms.

i 1 The divalent organic radical Y may be a straight- or 2 branched-chain alkylene radical, optionally substituted.
3 When Y represents a group of the formula ~(Yl)m-(y2)n-(y3)t 4 then each of the moieties Yl, Y2 and Y3 may be a straight-or branched-chain alkylene radical, optionally substituted, 6 or the radical of a cylic organic ring system having 5 or 6 7 carbon atoms. The cycloalkyl radical may optionally likewise 8 be substituted, for example, by alkyl.
When X stands for the radical of an amine of the 11 formula -N(R4)(R5), the radicals R4 and R5, which may be the 12 same or different, may represent straight- or branched-chain 13 alkyl radicals, for example, methyl, ethyl, propyl, iso-14 propyl or n-butyl, or cycloalkyl radicals such as cyclo-propyl, cyclobutyl, cyclopentyl or cyclohexyl.

17 Similarly, Z in formula (III) represents the moiety 18 of an alcohol of the formula R80~ where R8 is a straight- or 13 branched-chain alkyl radical such as methyl, ethyl, propyl, isopropyl or n-butyl.

22 Examples of such preferred amines are amines of the 23 N',N',2,2-tetramethylpropylenediamine-1,3 (dimethylamino 2~ neopentylamine) type (formula II', n=l, R6=R7=CH3), and more particularly:
26 3-dimethylamino-2,2-dimethylpropylamine 28 `N - C~z - c-c~ -NH~

7~'7 3-diethylamino-2,2~dimethylpropylamine c 2H5, f~I 3 / f 3~dibutylamino-2,2-dimethylpropylamine C4Hg\ CIH3 N - CH ~ f ~ CH2 ~ NH2 C4Hg CH3 4-dimethylamino-3,3-dimethylbutylamine-1 CH3 \ fH3 5-dimethylamino-4,4-dimethylpentylamine-1 CH3 \ CIH3 5-diethylamino-4,4~dimethylpentylamine-1 C2H5 f 3 / 2 Cl ~ CH2 ~ CH2 ~ CH2 ~ NH2 3-dimethylamino-2-ethyl-2-methylpropylamine CH3 \ fH3 X

. : l . ::

7~

3-dimethylamino-2-methyl~2-phenylpropylamine CH3 \ 1 3 and 3-dimethylamino-2-ethyl-2-butylpropylamine CH3 \ f2H5 CH3 C4Hg as well as l-taminomethylene)~l-(dimethylamirlomethylene)cyclohexene-3 CH \ C ~ 2 NH

ll ¦ CH2 ~ N / 3 CE ~ CH~ ~ CH3 CH
In these amines, the carbon atom which is beta to the tertiary amino group does not carry a hydrogen but instead is alkyl-substituted or cycloalkenyl-substituted. These amines of the general formula ~II), which do not carry hydrogen atoms on the nitrogen beta to the tertiary nitrogen, are preferred in accordance with the invention because in the reaction products obtained by the use of these amines no heat-induced beta elimina-tion of amine can occur. This splitting off of amine, which with monomeric ~,~ -unsaturated, N-substituted acid amides would result in a further terminal double bond in addition to the ~,~
double bond, is highly undesirable when using the monomeric acid amides in the preparation of water-soluble polymers since that double bond would be available for unwanted cross-linking.

_ g _ ~ ~t~j`7~

1 Moreover, by proper choice of the beta substituents, 2 the hydrophilic or hydrophobic properties of the monomers and 3 of the polymers produced therefrom can be modified in accor-4 dance with the end use.
6 The invention further has as its object novel ~ un-7 saturated carboxylic acid N-substituted amides of the general ~6~

12 ~ R \\~-N11- ~CH2 ) n 1- C 12 14 wherein Rl and R2 each is hydrogen or methyl, R6 and R7 are lS alkyl groups, and preEerably lower alkyl groups having 1 to 4 16 carbon atoms, and in particular methyl or aryl groups, or 17 R6 and R7 together are a constituent of an aliphatic ring, 18 and in particular of the cyclopentyl or cyclohexyl ring, 19 n is an integer from O to 10, and X is the radical of an amine of the formula -N~R4)(R5), R4 and R5 representing alkyl 21 radicals having 1 to 4 carbon atoms, or cycloalkyl radicals 22 having 3 to 8 carbon atoms.

24 The a,~-unsaturated carboxylic acid N-substituted amides in accordance with the invention can readily be poly-26 merized, either alone or with other polymerizable monomers, 27 by known processes, to homopolymers, copolymers and other 28 subpolymers. These polymers are excellent ~locculants and 29 dewatering aids for use in waste-water treatment, and they are further adapted to improve the dry and wet strengths of ~ ~ 7~

l paper and are also suited ~or use as retention aids. The 2 elimination of amine in these polymers would reduce their 3 specific activity and, in extreme cases, render them com-4 pletely inef~ective.

6 The invention thus has as a further object a process 7 for the production of polymers of compounds prepared in 8 accordance with the foregoing disclosure which contain re-peating units of the formula 11 ~

14 \~H- ( CH;~ ) n~ ~ H2 16 wherein Rl, R2, R~, R7, X and n have the meaning given in 17 formula (I), said process being characterized in that the 18 unsaturated st~rting compound is polymerized alone or with l9 other polymerizable monomers by processes which are known per se, as well as the polymers obtained by such process.

22 The polymerization is conducted con~entionally. It 23 may be initiated thermally, photochemically, by radiation, or 24 with the usual radical initiators. It may be carried out in solution, suspension or emulsion. Suitable initiators are, 26 ~or example, inorganic peroxides such as hydrogen peroxide;
27 organic hydroperoxides and peroxides such as tert-butyl 28 hydroperoxide, cumene hydroperoxide or dibenzoyl peroxide;
29 aliphatic azo compounds decomposing into radicals, such as 2,2'-azobisisobutyronitrile; redox catalyst systems such as -~ ~ 7~'7 1 persulfate or chlorate with disulfite or iron(III) salts; and 2` transition-metal chelates which are known radical fonmers.
3 The initiators are generally used in an amount of from O.OOl 4 to 1 wei~ht percent, based on the amount of monomer. The optimum amount and the most effective initiator can readily 6 be determined by experimentation.
8 The polymerization is advantageously conducted in the 9 presence of a solvent or diluent. The suspension, solution or emulsion polymerization processes used with other monomers 11 may be used also for the polymers in accordance with the in-12 vention. Optionally such auxiliaries as buffers, dispersants, 13 protective colloids and the like may be used.

Suitable comonomers are compounds containing a poly-16 merizable double bond, and in particular:
17 vinyl aromatics such as styrene, ~-methylstyrene, and vinyl-18 pyridine;
19 acrylonitriles such as acrylonitrile and methacrylonitrile;
acrylamides such as acrylamide, methacrylamide and N-mono-21 and N-disubstituted acrylamides and methacrylamides;
22 acrylic and methacrylic acid esters;
23 acrylic and methacrylic acids;
24 vinyl esters and vinyl ethers;
fumaric and maleic acids and their derivatives; and 26 compounds containing more than one polymerizable double bond, 27 for example, divinylbenzene, methylenebisacrylamide and 28 allyl acrylate.

Particularly preferred is acrylamide.

~ ~ Li'ti7~t7 1 The composition oE the copolymers in accordance with 2 the invention may vary widely. Copolymers in accordance with 3 the invention may contain relatively small amo~mts of monomers 4 in accordance with the invention, for example, 5 weight per-cent, while the remaining 95 weight percent, for example, is 6 made up of other comonomers.
8 However, the invention also includes copolymers with 9 a high proportion, for example, 50 to 95 weight percent, of monomers in accordance with the invention and 50 to 5 weight 11 percent of other comonomers. Homopolymers of the monomers 12 in accordance with the invention of course also fall within 13 the scope of ~he invention. Preferred copolymers consist to 14 the extent of 5 to 60 weight percent, and more particularly 10 to 50 weight percent, of monomers in accordance with the 16 invention, that is to say, of unsaturated carboxylic acid 17 amides of formula (I'), and to the extent of 95 to 40 weight 18 percent, and more particularly 90 to 50 weight percent, of 19 other comonomers, the preferred comonomers being acrylic or ~ethacrylic acid derivatives such as acrylamide and meth-21 acrylamide, or acrylic or methacrylic acid esters.

23 The invention has as a further object provision of 2~ polymers of a,~-unsaturated carboxylic acid N-substituted amides in accordance with the foregoing disclosure which are 26 characterized by the smallest repeating units of the formula 29 ¦ J~H- (CH2 ~ n-~7C1~2 3'7 wherein Rl, R2, R6 and R7 have the meanings given in connection with formula ~I').
The monomeric products in accordance with the invention can be neutralized and~or quaternized, and the polymers produced fxom these cationic monomers are not only excellent flocculating and dewatering aids for u~e in waste water trea~ment and as aids in improving the dry and wet strengths of paper and also as retention aids but, because of their high-temperature stability, can also be used to advantage as ~iscosity regulat~rs and dispersants in lubricant~.
Moreover, anion exchanger resins may be obtained by conducting the polymerization in the pre~ence of deined amounts of crosslink-ing agents.
For use as 10cculating and dewatering aids, the polymers in accordance with the invention pre~erably have molecular weights on the order o~ 5 to 10 million; for use as aids in papermaking, preferably from about 1 to 5 million; and for use in the other applications mentioned, preferably under 1 million.
In the drawin~s Fig. 1 is the NMR spectrum o~ N-(N',N',2',2'-tetramethylaminopropyl)acrylamide in CDC13.
Fig. 2 is the NMR spectrum of N-(N 3 ~ 2~2-tetramethyl-3-amino propyl)methacrylamide in CC14.
Fig. 3 is the NMR spectrum of N-(N',N',2',2'-tetramethylamino~
propyl)-crotonic acid amide in CDC13.
Fig. 4 is the NMR spectrum of N-~3-diethylamino-2,2-dimethyl-propyl~acrylamide in CC14.
Fig. 5 is the NMR spectrum of N-(3 diethylamino-2,2-dimethyl-propyl)methacrylamide in CC14.
Fig. 6 is the NMR spectrum of N-(3-diethylamino-2,2-dimethyl-propyl)crotonamide in CDC13.
Fig. 7 is the NMR spectrum of N-~3-dibutylamino-2~2-dimethyl-propyl)acrylamide in CC14.

Fig. 8 is the N~R spectrum of N-(3~dibuty}amino-2,2-dimethyl-propyl~methacrylamide in CC14.
Fig. 9 is the NMR spectrum of N-(3-dibutylamino-2,2-dimethyl~
propyl)crotonamide in CC14.
Fig. 10 is ~he NMR spectrum of N-(4-dimethylamino-3,3-di-methylbutyllacrylamide in CC14.
Fig. 11 is the NMR spectrum of N-(4-dimethylamino-3,3-di-methylbutyl~methacrylamide in CC14.
Fig. 12 is the NMR spectrum of N-(4-dimethylamino-3,3-di-methylbutyl)crotonamide in CC14.
Fig. 13 is the NMR spectrum of N-(5-dimethylamino-4,4-di-methylpentyl~acrylamide in CC14.
Fig. 14 is the NMR spectrum of N-~5-dimethylamino-4,4-di-methylpentyl)methacrylamide in CC14.
Fig. 15 is the NMR spectrum of N-(5-dimethylamino-4,9~di-methylpentyl)crotonamide in CC14.
Fig. 16 is the NM~ spectrum of N-(5-diethylamino-4,4-di-methylpentyl)acrylamide in CC14.
Fig. 17 is the NMR spectrum of ~-(5-diethylamino-4,4-di-methylpentyl)methacrylamide in CC14.
Fig. 18 is the NMR spectrum of N-~3-dimethylamino-2-ethyl-2-methylpropyl~acrylamide in CC14.
Fig. 19 is the NMR spectrum of N-(3--dimethylamino-2-ethyl-2-methylpropyl)methacrylamide in CC14.
Fig. 20 is the NMR spectxum of N~3-dime~hylamino-2-methyl-2-phenylpropyl)acrylamide in CC14.
Fig. 21 is the NMR spectrum of a homopolymer of N-~N',N',2',2' -tetramethylaminopropyl)acrylamide~l/2 HZSO4 in DzO.
Fig. 22 i5 the IR spectrum of the homopolymer to which Fig. 21 relates.
Fig. 23 is the NMR spectrum in DzO of a copolymer of acryl -14a-$7 amide and N-(N',NI,2',2'-tetramethylaminopropyl~ac~ylamide'l/2 HzS04.
Fig. 24 is the IR spectrum of the copolymer to which Fig. 23 relates.
Fig. 25 is the NMR spectrum in DzO of a homopolymer of N-~3-dimethy}amino-2,2-dimethylpropyl)methacrylamide l/2 HzS04.
E~ig. 26 is the NMR spectrum in DzO of a copolymer of acryl-amide and N-~3-dimethylamino-2,2-dimethylpropyl)methacrylamide 1/~ HzS04.
Fig. 27 is the NMR spectrum of l-~Acrylamidomethylene)-l-di-methylaminomethylene-cyclohexene-3 in CCl~.
Fig. 28 is the NMR spectrum of l~~Methacrylami~omethylene)-l-dimethylaminomethylene-cyclohexene-3 in CC14~
The examples which follow will serve to illustrate the invention.

- 14b -"`

l Example 1 3 N-(N'N',2',2'-tetramethylaminopropyl)acrylamide (TEMAPA) 4 471 g ~-hydroxypropionamide and 722 g N,N,2,2-tetra-methylpropylenediamine-1,3 were heated for 7 hours over a 6 temperature range from 140 to 160 C until ~he liberation of 7 ammonia ceased. The evaporation by means of a thin-layer ~8 evaporator which followed yielded 1058 g ~-hydroxy-N-(~',N', 9 2',2'-tetramethylaminopropyl)propionic acid amide, boiling point 206 C/10 mm Hg.
11 NMR (CDC13): ~ = 0.9 (s,6); 2.25 (s,2); 2.3 (s,6); 2.45 (t,2);
12 3.2 (d,2); 3.9 (t,2) 14 917 g of the hydroxy product was then successively evaporated in the thin-layer evaporator (230 C evaporator 16 temperature, vacuum lO millibars) and the vapors were con-17 ducted through a reaction tube which had been filled with 18 700 g alumina and heated to 220D C. During the 3.5-hour l9 process, 727 g N-(N',N',2',2'-tetramethylaminopropyl)acryl-amide was obtained. Boiling point, 137 C/10 millibars.
21 NMR (CDC13): ~ = O.9 (s,6); 2.3 (m,8); 3.25 (d,2); 5.4 to 22 6.2 (m,3) (See accompanying Fig. 1.) 24 Example 2 N-(N',N',2,2-tetrameth~l-3-aminopropyl)-3-methoxypropionamide 26 412.5 g (4.0 moles) 3 methoxypropionamide was heated 27 with 547 g (4.2 moles) N,N,2,2-tetramethylpropanediamine-1,3 28 and 4 ml glacial acetic acid for 8 hours over a temperature 29 range from 145 to 170 C until the liberation of ammonia ceased. The high-vacuum distillation which followed yielded ~ r~ ~;t;j~ ~ ~

l 820 g (3.8 moles = 95% o theory) of a colorless liquid with 2 a boiling point of 105 to 108~ C.
3 0.2 4 NMR (in CC14): ~ = 0.9 ~s,6); 2.0 to 2.5 (m,10); 3.05 (d,2);
3.3 (s,3); 3.55 (t,2); 7.40 (m,l) 7 N-(N',N',2,2-tetramethyl- -aminopropyl)acrylamide 8 A total of 820 g (3.8 moles) N-(Ni,N',2,2-tetramethyl-9 3-aminopropyl)-3-methoxypropionamide was fed continuously to an evaporator flask heated to 170 to 180 C, and the vapors 11 were conducted under a vacuum of 14 millibars to a reaction 12 tube l mèter long and 3 cm in diameter which was heated ex-13 ternally, by means of a strip hea~er, to 300 C and was filled 14 with alumina beads impregnated with 10% sodium hydroxide.
lS With a head temperature ranging from 150 to 220 C, about 16 475 g of a yellow oil was collected over a period of 2 hours, 17 which for further purification was distilled once more in a 18 high vacuum. 383 g (2.1 moles = 52V/o of theory, based on l9 3-methoxypropionamide) of a product having a boiling pointO 2 of 98 to 102 C was obtained.

22 NMR (in CC14): ~ = 0.9 (s,6); 2.1 (s,2); 2.3 (s,6); 3.15 (d,2);
23 5.3 to 6.5 (m,3); 8.0 ~m,l).
24 (See accompanying Fig. 1.) 26 Example 3 27 N-(N'N' 2,2-tetramethyl-3-aminopropyl)-2-methyl-3-methoxy-28 ~opionamide 29 By the procedure of Example 2, there was obtained from 468.6 g (4.0 moles) 2-methyl-3-methoxypropionamide 857 g ~ '7~3 ~

l (3.7 moles = 93% of theory) of a colorless liquid having a 2 boiling point o 2 of 102 to 106 C.
3 NMR (in CC14): ~ = 0.9 (s,6); 1.05 (d,3); 2.0 to 2.7 (m,9);
4 3.05 (d,2); 3.2 to 3.6 (m,5); 7.3 (m,l).

6 N-(N' N',2,2-tetrameth 1-3-aminopropyl)methacrylamide (TEMAPA) ~ .. .., Y .. .
7 Analogously to Example 2, 510 g of product was obtained 8 from 857 g (3.7 moles) of starting product. High-vacuum dis-9 tillation yielded 420 g (2.1 moles = 53% of theory, based on 2-methyl-3-methoxypropionamide) with a boiling point Q 2 of 11 92 to ~ C.
12 MNR (in CC14): ~ = 0.9 (s,6); 1.9 (d,3); 2.2 (s,2); 2.3 (s,6);
13 3.1 (d,2); 5.1 to 5.7 (m,2); 8.0 (m,l).
14 (See accompanyin~ Fig. 2.) 16 Example 4 17 N-(N',N',2',2'-tetramethylaminopropyl)-crotonic acid a~ide 18 412 g ~-hydroxybutyric acid amide and 546 g N,N,2,2-l9 tetramethylpropylenediamine-1,3 were heated for 16 hours over a temperature range of 148 to 160 C. 829 g of ~he reaction 21 product was ~ed successively, by means of a thin-layer .
22 evaporator (250 C/10 millibars), as vapor to a reaction tube 23 which had been heated to 220 C and filled with 70Q g alumina.
24 During the 4-hour process, 543 g N-(N',N',2',2'-tetramethyl-aminopropyl)-crotonic acid amide was obtained. Li 26 point, 102 C/0.035 millibars.
27 MNR (CDC13): ~ = 0.9 (s,6); 1.9 (dd,3); 2.15 to 2.6 (m,8);
28 3.35 (m,2); 5.6 to 7.0 (m,2).
29 (See accompanying Fig. 3.) .. ~ ~ '7~ 7 1 Example 5 2 N-(N',N' 3 2,2-tetramethyl-3-aminopropyl)-3-methoxybutyric acid 3 amide 4 By the procedure of Example 2, there is obtained from 468.6 g (4.0 moles) 3-methoxybutyric aci.d ami.de 80a g (3.5 6 moles = 87% of theory) of a pale-yellow liquid having a boil-ing point o 2 of 112 to 114 C.
8 NMR (in CDC13): ~ = 0.9 (s,6); 1.15 (d,3); 2.0 to 2.5 (m,10);
3.1 (d,2); 3 35 (s,3); 3.7 (q,l); 7.7 (m,l) ll N-(N',N',2,2-tetramethyl-3-aminopropyl2-crotonic acid amide 12 Analogously to Examp]e 2, there is obtained from 800 g 13 (3.5 moles) of starting product 587 g of product which after 14 high-vacuum distillation yields 516 g (2.6 moles = 65% of theory, based on 3-methoxybutyric acid amide~ of a pale-16 yellow, viscous oil having a boiling point o 2 of 104 to 108 C.

18 NMR (in CC14): ~ = 0.9 (s,6); 1.8 (ddt3~; 2,1 (sl2); 2 3 (s,6);
l9 5.6 to 7.0 (m,2); 7~6 (m~
21 Analogously to Examples 1 to 5, there are o~tained by 22 reaction of the appropriate amines with the corresponding 23 ~-hydroxy- or ~-methoxy-carboxylic acid amides in molar-24 equivalent amounts:
26 6. N-(3-diethylamino-2,2-dimethylpropyl)acrylamide 27 Boiling point, 110 C/0.1 millibar 28 NMR: See accompanying Fig. 4.

~ 7 1 7. N-(3-diethylaminQ-2,2-dimethy~lpropyl)methacrylamide 2 Boiling point, 117 C?0.1 millibar 3 N~IP~: See accompanying Fig. 5.
5 8. N-(3~diethyIamino-2,2-dimethylpropyl)crotonamide 6 Boiling poi.nt, 113 C/0.035 millibar 7 NMR: See accompanying Fig. 6.
9 9. N-(3-dibutylamino-2,2-dimethylpropyl)acrylamide Boiling point, 155 C/0.09 millibar 11 NMR: See accompanying Fig. 7.

13 10. N~3-dibutylamino-2,2-dimethylpropyl)me~hacrylamide 14 Boiling point, 125 C/0.032 millibar NMR: See accompanying Fig. 8.

17 11. N-(3-dibutylamino-2,2-dimethylpropyl)crotonamide 18 Boiling point, 129 C¦0.03 millibar 19 NMR: See accompanying Fig. 9.
21 12. N-t4-dimethylamino-3,3-dimethylbutyl)acrylamide 22 Boiling point, 107 C/0,08 millibar 23 NMR: See accompanying Fig. 10.

13. ~-(4-dimethylamino-3,3-dimethylbutyl)methacrylamide 26 Boiling point, 113 C/0.14 millibar 27 NMR: See accompanying Fig. 11.

29 14. N-(4-dimethylamino-3,3-dimethylbutyl)crotonamide Boiling point, 120 C/0.03 millibar 31 NMR: See accompanying Fig. 12.

¢-3~7 l 15~ N (5-dimcthylamino-4,4-dimethylpentyl)acrylami.de 2 Boiling point, 127 C/0.03 millibar 3 NMR: See accompanying Fig. 13.
5 16. N-(5-dimethylamino-4,4-dimethylpentyl)methacrylamide 6 Boiling point, 127 C/0.04 millibar 7 N~: See accompanying Fig. 14.
9 17. N-(5-dimethylamino-4,4-dimethylpent~l)crotonamide Boiling point, 134 C/0.03 millibar 11 NMR: See accompanying Fig. 15.

13 18. N-(5-diethylamino-4,4~dimethylpentyl)acrylamide 14 Boiling point, 130 C/0.06 millibar NMR: See accompanying Fig. 16.

17 19. N-(5-diethylamino-4,4-dime~hylpentyl)methacrylamide 18 Boiling point, 132 G/0.035 millibar 19 NMR: See accompanying Fig. 17 21 20. ~-(3-dime-thylamino-2-ethyl-2-methylpropyl)acrylamide 22 ~oiling point, 98 C/0.03 millibar 23 NMR: See accompanying Fig. 18.

21. N-(3-dimethylamino-2-ethyl-2-methylpropyl)methacrylamide 26 Boiling point, 98 C/0.06 millibar 27 ~MR: See accompanying Fig. 19.

29 22. N-(3-dimethylamino-2-methyl-2-phenylpropyl)acrylamide Boiling point, 128 C/0.06 millibar 31 NMR: See accompanying Fig. 20.

1~'7~

22A. l-~Acrylamidomethylene?-l-dimethylaminomethylene--cyclohexene-3 Boiling point, 122 C/0.04 millibar NMR (CC14): See accompanying Fig. 27 22B. l-(Methacrylamidomethylene?-l-dimethylaminometh~lene-cyclohexene-3 ~oiling point, 122C/0.05 millibar NMR (CC14~: See accompanying Fig. 28 - 20a --~ '7 1 The amino compounds prepared in the manner described 2 above may be converted to the corresponding amine salts by 3 reaction with an appropriate acid (for example, sulfuric acid~
4 or may be quaternized with an appropriate alkyl halide or alkyl sulfate. Th:is will be illustrated by the examples 6 which follow.
8 Example 23 9 Trimethyl-3-(1-acrylamido-2,2-dimethylpropyl)-ammonium metho-sulfate ll To a solution of 289.5 g N-(N',N',2',2'-tetramethyl-12 aminopropyl)-acrylamide in 317 g water, there was added drop-13 wise, with stirring and cooling with ice, 185.4 g dimethyl-14 sulfate over a period of 2.5 hours. After further reaction for 3 hours, a 60% solution of the quaternary product was 16 obtained.

18 Example 24 l9 (3 acrylamido-2,2-dimethylpropyl)-trimethylammonium chloride Into a vigorously stirred 80 C solution of 376 g 21 N-(3-dimethylamino-2,2-dimethylpropyl)-acrylamide (TEMAPA of 22 Example 1) in 320 g water, there was introduced over a period 23 of 3,5 hours under a working pressure of 0.4 bar 103 g methyl 24 chloride. An aqueous solution of the quaternary product was obtained.

27 The acrylamido compounds of the invention may be 28 polymerized either alone or with other polymerizable monomers 29 to give copolymers or other subpolymers, as will be shown in the following examples.

~ t7 1 ¦ Example 25 2 1 Homopolymer TE~PA I H2SO4 l - 2 3 ¦ 160 g N-(N',N',2',2'-tetramethylaminopropyl)-acrylamide 4 ¦ was dissolved in 85 g water and acidified with 199.5 g 20%
5 ¦ sulfuric acid. The solution was heated to 55 C and polymer-6 ¦ ization was initiated by the addition of gO mg azobisiso-7 ¦ butyronitirile. After being allowed to s~and for 2 hours, 8 ¦ the gel-like polymerization product was comminuted, dried and 9 ¦ ground to a white powder. Residual monomer content: 0.72%.
10 ¦ Viscosity (1% aqueous solution): 184 mPa/s. ~R and IR: See 11 ¦ accompanying Figs. 21 and 22.
12 l 13 ¦ Egample 26 14 ¦ Copolymer TEMAPA ~ H2SO4/acr~lamide 15 ¦ 80 g N-(N',N',2',2'-tetramethylaminopropyl)-acrylamide 16 was dissolved in 386 g water and acidified with 100 g 20%
17 sulfuric acid. After addition of 100 g acrylamide, the solu-18 tion was heated to 55 C and polymerization was initiated 19 with 80 mg azobisisobutyronitrile. After being allowed to stand for 3 hours J the gel-like copolymeriza~ion product 21 was comminuted, dried and ground to give a white powder.
22 Residual monomer content: 0.7%.
23 Viscosity (1% aqueous solution): 1200 mPa/s.

Example 27 26 ~lomopolymer of TEMAPA CH3Cl 27 200 g TE~APA CH3Cl was dissolved in 380 g water and 28 adjusted to pH 4. AEter purging with nitrogen, polymerization 29 was initiated by addition of 3 mg potassium persulfate~ 2 mg sodium disulfite, 0.2 mg iron(II) sulfate and 30 mg 2,2'-~ ~ ~'7~

1 ¦ azobis-(2-amidinopropane) dihydrochloride (~IBA~. The gel 2 ¦ obtained was dried to a residual water content of 10% and 3 ¦ ground. Limiting viscosity (10% sodium chloride solution):
4 ¦ 387.5 ml/g.
S l 6 ¦ Example 28 7 ¦ ~E~olymer of acrylamide (78 wt. %) and TEMAPA 2 H2 ~ (22 wt. ~/O) 8 ¦ 234 g acrylamide and 66 g TE~PA 12 H2S0~ were mixed 9 ¦ in 700 g water with 30 mg AIBA and, after nitrogen had been 10 ¦ passed through the solut~on, exposed for 30 minutes to the 11 ¦ light from a la~p (OSRAM HWL 250 watts). The gel obta:ined 12 was dried to a residual water content of 11% and ground.
13 Limiting viscosity (10% sodium chloride solution): 1640 ml/g.
14 NMR: See accompanying Figs. 23 and 24.
16 Example 29 17 Homopolymer of N-~3-dimethylamino-2,2~dimethylpropyl)-18 methacrylamide 2--H2S04 (TEMAP 2 2 4 19 80 g TEMAPMA was dispersed in 40 g water and neutral-ized with 100 g 20% sulfuric acid, purged of oxygen and, 21 after addition of 100 mg AIBA, exposed for 1 hour to light 22 (OSR~ HWL 250 watts).
23 Brookfield viscosity of the dried polymer (1% aqueous solu-24 tion): 240 mPa/s. NMR: See accompanying Fig. 25.
26 Example 30 27 Copolymer of acrylamide (75 wt. %) and TEMAPMA 12 H2S04(25 wt.V/o) 28 150 g acrylamide was dissolved in 470 g water, 40 g 29 TE~PMA was added and the solution was neutralized with 50 g

20% sulfuric acid. After ~he addition of 25 mg AIBA, the ~ T ~ Ma~ - 23 -~ '7~'~

1 solution was purged of oxygen and exposed to light for 30 2 minutes (OSRAM ~WL 250 watts). The gel obtained was dried 3 ancl ground.
4 Brookfield viscosity (1% aqueous solution): 3800 mPa/s. .
NMR: See accompanying Fig. 26.

7 ¦ Example 31 8 ¦ The products obtained by the process of the invention 9 ¦ were tested as sedimentation aids in flocculating tests. The 10 ¦ flocculating behavior of copolymers according to Examples 26 11 ¦ and 28 was tested by determining the rate of sedimentation 12 ¦ in an aqueous solution after their addition to aqueous clay 13 ¦ suspensions prepared in the usual way by slurrying kaolin 14 ¦ in water and adjusting with A12(S04~3 solution to a pH value 15 ¦ of about 4.8. The results are presented in Table I.
16 l 17 ¦ TABLE I
18 ¦ Flocculating effect on a clay suspension with 20 g/l I solids content with the addition of A12(S04)3, 19 ~ product in 0.1% solution, concentration 2 ppm 20 ¦ Product Time (sec) I

21 ¦ None 180

22 ¦ According to Example 26 2.5

23 ¦ According to Example 28 4.3

24 l With regard to the conduct of the test, see H, Akyel 26 and M. Neven, Chemie-lngenieur-Technik 39 (1967), 172.

28 Moreover, the products described may also be used to 29 dewater sewage sludges.

~'76'~'r3~

1 Dewa-tering test with sewage sludge; solids content, 3.7%.
2 . Amount Solids in Supernatant Dewaterlng used effluent Appearance Extinction (xlO0) 3 aid (g/cm~) (%) 4 Product accord- 190 26.4 l~hite 20 S ing ~o Example 26 6 Product accord- 200 25.8 White 20 7 ing to Example 28 8 Fxample 32 9 The copolymers produced in accordance with Examples 26 and 28 were then tested for their sui~ability for use as de-11 watering aids and retention aids in papermaking.

13 ~a) Dewatering 14 Testing apparatus and method The Schopper-Riegler degree-o~-fineness tester ("SR
16 apparatus"~ was used as testing apparatus. To measure 17 the time required to dewater a solids suspension, the 18 overflow is introduced into the measuring cylinder of the 19 apparatus together with the nozzle effluent and the dewatering time tE is determined in seconds for 600 ml 21 of the screen water. ~enever possible, the degree of 22 fineness of the solids should not be under 55 SR. As 23 under the standard conditions for SR measurements, the 24 solids suspension contains 2 g atro/l.

26 Fibrous-material suspension 27 In this case, 4Q0 g of rotogravure paper was broken up 28 into 20 1 of water and ground for 2 hours in a Valley 29 hollander at a low load to 55 to 57 SR.

1 Test results 2 0 sample (without additive): tE = 44 sec 3 Dosage (%) Product tE (sec?

4 0 4 According to Example 26 2123 6 0 4 According to ~xample 28 l4 8 (b) Retention 9 Tes~in~ me:thod Filler retention: In the RK sheet former In the SR apparatus 12 The test sheets for the sheet former were standardized 13 at a basic weight of 100 gfm2 and the amount of pulp in 14 the SR apparatus at 2.0 g atro~
16 The retention efect in the sheet former was evaluated 17 on the basis o the residual ash, referred to the filler 18 addition. For testing of the retention in the SR appara-19 tus, the degree of turbidity was measured in 60~ ml of the effluent water with a Lange colorimeter.

22 3. Test results 23 3.1 Retention in sheet former 24 Dosage: 0,02% retention aid/pulp

25 Filler RETENTION (%~
26add tion ControlExample 26 Example 28 27 10 30.~87.0 85.2 28 20 35.285.1 83.2 29 30 33.083.4 73.8 33.3 82.3 79.8 1 3.2 Retention in SR apparatus 2~osage: 0.02% retention aid/pulp ABSORPTION (%) 3 Filler addition Product Product 4 % ControlExample 26 Example 28 27.0 0.5 ~.0 6 40 . 65.5 10.0 14.0 7 60 80.0 25.0 30.0 9 Example 33 Copolymer TEMAPA/dodecylmethacrylate (90:10 wt. %) 11 23.33 g TEMAPA and 210 g dodecylmethacrylate were 12 heated ~o 80 C with 0.1167 g dodecylmercaptan in 116.67 g 13 neutral oil (BP ENERTHENE 1269) and polymerized by the m.etered 14 addition of a total of 1.2 g AIBN over a period o 5 hours.
Two parts of -the resulting highly viscous reaction product 16 were mixed with another 98 parts of BP ENERTHENE 1269 and 17 used in -the tests described below.

19 Example 34 Copolymer TEMAPMA/dodecylmethacrylate (10:~0 wt, %~
21 Analogously to Example 31, a mixture of a copolymer of 22 TE~PMA/dodecylmethacrylate in neutral oil ~as prepared.
23 The effect of the above copolymers on the viscosity of 24 the neutral oil was determined by determining the Viscosity index in conformity with ASTM D 2270-77. Moreover, the dis-

26 persing properties of the above copolymers were tested on the

27 basis of the sedimentation behavior of a coal-dust suspension

28 in neutral oil.

29 ~ rr~ k ~ t3~ r~

l Viscosity (cSt) VIE Percent coal 2 40 C 100 C for 4 days 4 BP ENERTHENE 1269 4 29 1 48 79 50%
without additive 6 with additive 6.763 2.353~168 100%
(Product accord-7 ing to Example 31) with additive 6.985 2.403-168 100%
9 (Product accord-ing to Example 32) 12 Example 35 13 Homopolymer of 1,3-propylene-bis[(3-acrylamido-2,2-dimethyl)-14 prop~dimethylammonium] dibromide 73.7 g TEMAPA and 40.4 g 1,3-dibromopropane were 16 stirred in S0 g water for 6 hours at 90 C and then cooled to 17 40 C, and polymerization was then initiated by addition o~
18 0.5 g potassium persulfate. The crosslinked polymer obtained 19 was dried to a residual water content of 10%, comminuted, and tested for its ion-exchange properties. Ion-exchanger capa-21 city: 3.1 mVal/g (Br form).

: I - 28 -

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AM EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A homopolymer or copolymer of an .alpha.,.beta.-unsaturated carboxylic acid N-substituted-amide comprising repeating units of the formula wherein R1 and R2 each independently is hydrogen or methyl, R6 and R7 each independently is an alkyl radical having 1 to 4 carbon atoms, or aryl, or together complete a cyclopentyl, cyclohexyl or cyclohexenyl ring, n is 0 to 10, X is the radical of an amine of the formula -N(R4)(R5), R4 and R5 each independently is an alkyl radical having 1 to 4 carbon atoms, or a cycloalkyl radical having 3 to 8 carbon atoms, or an ammonium group of the formula R3 is hydrogen or an alkyl radical with 1 to 4 carbon atoms, and A is a salt-forming anion.

2. A homopolymer of repeating units according to claim 1.

3. A copolymer comprising repeating units according to claim 1, and comonomeric units of styrene, .alpha.-methylstyrene, vinylpiridine, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-monosubstituted acrylamide or methacrylamide, N-disubstituted acrylic or methacrylic acid amide, acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, vinyl esters, vinyl ethers, fumaric acid, maleic acid, divinylbenzene, methylenebisacrylamide or allyl acrylate.

4. A copolymer according to claim 3, wherein the comonomeric units comprise 40 to 95% by weight.

5. A flocculating and sedimentation aid comprising the polymer of claim 1, 2 or 3.

6. A dewatering aid for sewage sludge comprising the polymer of claim 1, 2 or 3.

7. A dewatering and retention aid in papermaking, comprising the polymer of claim 1, 2 or 3.

8. An additive for mineral oils, comprising the polymer of claim 1, 2 or 3.

9. An ion exchanger comprising the polymer of claim 1, 2 or 3.