Note: Descriptions are shown in the official language in which they were submitted.
~ 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.
16
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.
24
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).
26
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.
14
The particular amine may be used in excess based on
16 the hydroxy- or alkoxy-amide.
17
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.
23
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.
16
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.
21
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
27
28 `N - C~z - c-c~ -NH~
7~'7
3-diethylamino-2,2~dimethylpropylamine
c 2H5, f~I 3
/ f
C2H5 CH3
3~dibutylamino-2,2-dimethylpropylamine
C4Hg\ CIH3
N - CH ~ f ~ CH2 ~ NH2
C4Hg CH3
4-dimethylamino-3,3-dimethylbutylamine-1
CH3 \ fH3
N - CH2 - C - CH2 - CH2 - NH2
CH3 CH3
5-dimethylamino-4,4-dimethylpentylamine-1
CH3 \ CIH3
/ 2 I CH2 - CH2 - CH2 - NH2
CH3 CH3
5-diethylamino-4,4~dimethylpentylamine-1
C2H5 f 3
/ 2 Cl ~ CH2 ~ CH2 ~ CH2 ~ NH2
C2H5 CH3
3-dimethylamino-2-ethyl-2-methylpropylamine
CH3 \ fH3
N - CH - C - CH -NH2
CH3 C2H5
X
. : l . ::
7~
3-dimethylamino-2-methyl~2-phenylpropylamine
CH3 \ 1 3
N - CH2 I C 2 2
CH3 C6H5
and
3-dimethylamino-2-ethyl-2-butylpropylamine
CH3 \ f2H5
N - CH2 - C - CH -NH2
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.
23
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.
21
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.
14
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.
29
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.
22
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
27
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.
-14-
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)
13
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.)
23
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.
21
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.
17
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.
29
~ 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.
12
13 10. N~3-dibutylamino-2,2-dimethylpropyl)me~hacrylamide
14 Boiling point, 125 C/0.032 millibar
NMR: See accompanying Fig. 8.
16
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.
24
13. ~-(4-dimethylamino-3,3-dimethylbutyl)methacrylamide
26 Boiling point, 113 C/0.14 millibar
27 NMR: See accompanying Fig. 11.
28
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.
12
13 18. N-(5-diethylamino-4,4~dimethylpentyl)acrylamide
14 Boiling point, 130 C/0.06 millibar
NMR: See accompanying Fig. 16.
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.
24
21. N-(3-dimethylamino-2-ethyl-2-methylpropyl)methacrylamide
26 Boiling point, 98 C/0.06 millibar
27 ~MR: See accompanying Fig. 19.
28
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.
17
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.
26
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.
24
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.
27
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.
12
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
11
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.
21
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.
18
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
BP ENERTHENE 1269
6 with additive 6.763 2.353~168 100%
(Product accord-
7 ing to Example 31)
8 BP ENERTHENE 1269
with additive 6.985 2.403-168 100%
9 (Product accord-
ing to Example 32)
11
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).
22
26
28
29
: I - 28 -
