AU479215B2 - Nove-3-amimoalkyl amides, polymers thereof and method for their preparation - Google Patents

Description

421/72 This invention relates to new compositions of mattei both monomeric and polymeric, and methods for their preparati( M'ore particularly, it relates to compounds of the formula Y R2 R4 0 R'-CH-C R

.herein each of R24 i Re 4.3,z1b:-A !;dlrbon

-C=CH 2 or -CHCH 2 OR"; R 7 is hycrogen or a lower alkyl radica'

RI is a 'hYdrocarbon r 2 *cal; Y is or -N-_Z X X i,

sa't-fo- g4nanion; Z' is hydrogen o hydrocarbon radical and Z2 is hydrogen or an alkyl or cycloalky adical, or

is a heterocyclic radical; and Z3 is hydrogen or a low alky.

As used herein, the term "hydrocarbon radical"' incli alkyl, cycloalktyl, aryl, aralkyl and alkaryl radicals. It al: includes substantially hydrocarbon radicals; that is, radicalg vwhich contain substituents such as ether, ester, nitro or hal, provided such substituents do not materially alter the charac, or reactivity of the radicals. The term "lower alkyl radical' t (denotes alkyl x adicals containing no more than abo 10 carboi atom~s. In the ppeferrcd emzizt f tho compounds of th.: invention, each of R1_1 is a hydrogen, lower alkyl, or C 151

arom-ntic ralical; each of R4 and Rs is a lower alkyl, C 3 8 7 eyelally! or Ce t, ;ic :rmtcraia;R hydr-eor. er methy'- 4 7 92

221.72 6 aromatic radical; R is -C=CH 2 or cycloalkyl or C6-1s 17 R

a 'lower alkyl -CHCH2zO, R7 is hydrogen or methyl; Re is

Z X or C6 -15 aromatic radical; Y is -N ,Zor

~'and Z2 are hydrogen

47 92l15

40. 4 /72

lowr 1~ylor C3 -6 cycloal1-y1 radicals, or4-N"Zl is a hete cyclic ra dical such as pyrrolidino, piperidino or morpholino; and X (if present) is any typical salt-forming anion such as

chloride, brominde, iodide :'sulfate, bisulfate, acetate, carbo

bicarbonate or the like. More desirably, each of R 1 3 is 4 5 h iro:-en or low..er alkyl, each of R and R is lower alkyl, R 7 is hycdrogen, RI is lower alkyl, Z' and Z 2 are lower alkyl, an 3 Z prsent) is methyl.

The following are illustrative of the compounds or

i.nventi on. N-(l 1 -ethy -3-d 2e thylaminopropy1)ac rylamide

CH3 0 (CH3 )2N1CH2CiHCN-C-CH=CH 2

CH3 H

l- 4'ehyl-3-direthylaminobutyl)acrylamide

IJ(CH3 2 CHs 0 -I3C CH- 2 C-N-C-CH=CH 2 CH3 H

Di-neth':l1-3-(1 acrvlamido-l, l-dtnmethylpropyl)armnium chloride

CH3 0 ClG( CH-3 2NkIAC 2 CH 2 CI-d- CCCH2 CH3 H

Trrehl3(-ciaido11dmtybtlarinu iodide

CH3 O0 CF2C-Ii-C-CH=CH 2

CH 3 H. 41 ~Z 1

40.42172

il(C 2 H5s) 2

2 C;-V-C-C=CH 2

CH3 H CH3

,3-(p-chlorophenyl) -3-pyrrolid inoarony 1]-acry lamide

CN- CH3 O0

Cl

1- :L-et'hyl-3-dime thylam~inobu ty 1) -3-me thoxy-propionamide

CH3 0 CH3 C:=-UC 2 C-N-C-CH2 CH 2OCH 3 CH3 H

-dLethy'L-3-m-ethylanilinobutyl)-3-ethoxypropionamide CSHS-!N-CH 3 CR3 0 CH3 -CH-CHt2 C-N-C-CH 2 CH2 OC2H CH 3 H

lu-(1, 1-ji~eh"y1-3-Direridinopropyl) -3-nhenoxy-2-m-ethylpropiorna-flide CH3 0 ICH2 CH2 C-!H-C-CHCH 2 0C8 0 I I CH3 H CH3

Tri-vetuhy1--3-L l-(3-methoxypropionamido) -1-methyl-1,3-di-phenyl- pro ::Iiaznoniun iodide ~CKL;(- 3 X CeHs 0 C8 H5-C-- CC- N-C-CH2 CF2OCH3 I I CH3 H 47 92

40.421/72 o-.i x) 1 cyelelhey! 3 (p nitrphen:

N(CH 3 2 H- N 0 CP2 C NO -N03

Compounds of the present invention wherein Rs is -CH( R7 (hereinafter sometimes referred to as "oxy compounds") may be prepared by reacting an oxypropionamide of the formula 0 R2 R' 0

R'-C-C-C-N-C-CHCH0OR 8 RR H R Z* with an amine of the formula HN" in the presence of a 'Z2

reducing agent. Oxypropionamides of the above formula may be obtained by the reaction of a hydroxy compound (alcohol or phe preferably an alcohol) with an N-3-oxohydrocarbon-substituted acrylamide of the type disclosed in U.S. Patents 3,277,056 and 3,425,942. The reaction leading to the oxypropionamide is dis U.S. i'kn( i 3454 66 9. closed in aprinnr g a 1i-atin,Scr. Ne. 659,66'4, filed Ag"i't 7. '197 The disclosures of these patents and applica- tion are hereby incorporated by reference in the present speci cation. The reaction of the oxypropionamide with the amine i of the type generally identified as "reductive aination". A typical example of such a reaction is the Leuckart reaction, ii which an oxo compound is reacted with an amine in the presence for..iz acid, or with an amine formate, with the result that th

47 92

04 21 72 is aminated and carbon carbon atoz formerly part of the oxo group

dioxide and water are evolved as by-products. oxy- A preferred method for reductive amination of the the amine in the presence proplonamide involves its reaction with as platinum/platinum of hydrogen and a hydrogenation catalyst such Of these oxide, palladium, copper chromite or Raney nickel. is preferred. catalysts, platinum/platinum oxide (Adams' catalyst) because it is (It is referred to as "platinum/platinum oxide" reduced to usually introduced as the oxide, but.is immediately

elemental platinum upon contact with hydrogen.) Typically, the

a small amount of the oxypropio.'-ide and the amine are mixed and is then pressurized hydrogenation catalyst is added; the mixture typically with hydrogen to at least about 50 psi. and agitated, 0 with periodic at a temperature of about 25-100 C. and usually hydrogen uptake has replenishment of the hydrogen pressure, until in the presence ceased. 'The reductive amination may be effected the like, but of a suitable solvent such as an alcohol, ether or also been found such solvent is frequently unnecessary. It has 0.1-5.03 by that the presence of a small amount (usually about increases the reaction weight of the reaction mixture) of an acid sulfonic rate. Typical acids which may be used are aromatic thereof, and acids, mineral acids, perchloric acid and amine salts

the like. in the The molar ratio of amine to oxypropionamide is generally greater reaction mixture should be at least 1:1, and

(up to about Ratios between about 1.25:1 and 3:1 are

preferred. reaction, Following completion of the reductive amination in the customary ways. the product may be isolated and purified 7 1 47 9215

40.4 21/72 The following examples illustrate the preparation of

ox'y compounds of the present invention. All parts, percentage

and proportions are by weight unless otherwise stated.

E::a-.le 1

To a mixture of 201 parts (1 mole) of N-(l,l-dimethy

3-oxobutyl)-3-methoxypropionamide and 91 parts (2 moles) of

di.ethyla.ine are added 0.5 part of platinum oxide and 3 parts

of p-tol-enesulfonic acid. The liquid mixture is poured into

hydrogenation bottle, flushed with hydrogen and pressurized wi e-

hydrogen on a Parr hydrogenation apparatus at 69 psi. and hydr

genated for about 12 hours, with hydrogen pressure being reple

ished to 70 psi. vwhen it has dropped to 27 psi. The mixture i

then stripped on a rotary evaporator and the residue, a yellow

liquid, is dissolved in 165 aqueous hydrochloric acid and

extracted with four 10-_ll portions of chloroform. The aqueou

solution is then made alkaline by the addition of a solution c

parts of sodium hydroxide in 75 parts of water, the alkalin solution is again extracted with four 100-ml. portions of chic

form and the chloroform extracts are stripped and distilled.

desired product, l-dim-ethyl-3-dimethylaminobutyl)-3-methc

propionamide, is obtained boiling at 87-95 0 C./0.5 mm. It con

tains 12.1i nitrogen, as compared with 12.2S theoretical.

Example 2 Following the procedure of Example 1, 263 parts (1

of N-(l,l-d rethyl-3-oxobuty )-3-phenoxypropionamide is reacte with 95 parts (2.11 moles) of dimethylamine in the presence of

1.75 parts of 70G aqueous perchloric acid and 0.5 part of plat oxide. The product is l;-(l,l-dimethyl-3-dimethylaminobutyl)-3

phenoxypropiona.ide.

4 21 7 Exa..?le 3

The procedure of Example 2 is repeated, except that the

phern.c-:xropiona.nide used therein is replaced by 216 parts (1 mole)

of N-(l,l-di-ethyl-3-oxobutyl)-3-methoxy-l-methylpropionamide.

The product is :i-(l,l5-imethyl-3-d-iTethylamninobutyl) me t hoxy-l-

methylpropionamide.

Exe-ple 4 A one-gallon autoclave, fitted with a stirrer, is charged with 1684 parts (8.38 moles) of N-(l,l-dimethyl-3-oxobutyl)-3- methoxypropioneamide, 762 parts (16.9 moles) df dimethylamine,

parts.of platinum oxide and 15 parts of dimethylammonium perchlorate. The autoclave is pressurized with hydrogen to 750 psi., and stirring is begun. Hydrogen pressure is periodically restored to 850-900 psi. and stirring is continued until hydrogen untake has ceased. Sodium bicarbonate, 10 parts, is added to the mixture which is then stripped, acidified, extracted with chloro- form, made alkaline and again extracted with chloroform as in Example 1. The chloroform extract from the alkaline solution is stripped and distilled, and the product, N-(l,l-dimethyl-3- dimethylaminobutyl)-3-methoxypropionamide, is obtained boiling at 108 0C./0.9 mm. The yield is 1418.6 parts, or 73.6% of the

theoretical amount.

Example The procedure of Example 4 is repeated, except that the methoxypropionamide used therein is replaced by 325 parts (1 mole) of N-(1,3-diphenyl-l-methyl-3-oxopropy )-3-methoxypropionamide.

The product is N-(1,3-diphenyl-l-methyl-3-dimethylaminobutyl)-3- me thoxypropionamide. 47 9.2

421172. Exam-le 6

To a solution of 20.1 grams (0.1 mole) of N-(l,l-di-

.methyl-3-oxobutyl)-3-metho-.ypropionamide and 10 grams (0.137 r of diethylamine in 100 ml. of methanol is added 0.25 gram of Raney nickel. The mixture is placed in a hydrogenation bottl

and charged with hydrogen to 260 psi. It is then placed on a Parr hydrogenation apparatus and hydrogenated at 50°C. until

hydrogen uptake is complete. The product, isolated as descril

in Example 1, is N-(l,l-dimethyl-3-diethylaminobutyl)-3-metho)

propionamide.

Exa::.ple 7 Following the procedure of Example 4, a mixture of parts (1 mole) of N-(l,l-dimethyl-3-oxobutyl)-3-methoxypropio amide, 170 parts (2 moles) of piperidine, 0.5 part of platinu oxide and 1 part of dimethylarmmonium perchlorate is hydrogenal in the Parr apparatus, starting at a pressure of 70 psi. and recharging when the pressure has reached 39 psi. After worku] described in Example 4, the desired product, N-(l,l-dimethyl- piperidinobutyl)-3-methoxypropionanide, is obtained boiling al 0 112-115 C./0.25 mm,

Exa-.ole 8 Following the procedure of Example 1, 20.1 grams (0. mole) of N-(l,l-dimethyl-3-oxobutyl)-3-methoxypropionamide is reacted with 10 grams (0.14 mole) of pyrrolidine in the preser of 0.3 gram of platinum oxide and 100 ml. of methanol. When hydrogen uptake has ceased, the methanol is stripped and the product, N-(l,1-dimethyl-3-pyrrolidybutyltyl)-3-methoxypropionar is isolated as described in Example 1. 47 92

40,421 /72

Exam le 9 Following the procedure of Example 1, N-(l,l-dimethyl- by the 3-mrorpholirnoutyl)-3-methoxypropiona.-ide is prepared reaction of 2C1 parts (1 role) of i-(l,l-dimethyl-3-oxobutyl)-3- of morpholine in the methoxypropionamide with 174 parts (2 moles) part of dimethyl- presence of 0.5 part of platinum oxide and 1 ammoniu-. perchlorate.

Exa-mple The procedure of Example 4 is repeated, except that the dimethyla.ine is replaced by 1810 parts (16.9 moles) of methylaniline.

The product is N-(1,1-dime thyl-3-methylanilinobutyl)-3-methoxy- propionazide. e is -C=CHa The compounds of this invention wherein R R7

compounds") (hereinafter sometimes referred to as "acrylamido above by elimina- may be obtained from the oxy compounds described are known per se. tion of ReOH by any of several methods which a recent review: Typical methods are described briefly in 35, 39 (1966). P. F. Butskus et al., Russian Chemical Reviews, presence of a basic The preferred method is pyrolysis in the solid sodium hydroxide, reagent, ordinarily a strong base such as carried out at at about 70-150°C. This reaction is conveniently reduced pressure. compounds Another method for preparation of acrylamido nitrile of the formula of this invention is by the reaction of a the formula CH2 =C-CIH with an a,8-unsaturated amine of R

47 9.2 1

40,4 21 /72

1 21

N R2

R -CH-C=C" I \R R3

in the presence of sulfuric acid. Unsaturated amines of this

type may be prepared by the reaction of a compound of the ZI formula HN with a 1,3-diene, usually in the presence of

a strongly alkaline catalyst such as metallic sodium. This is

typical 1,4-addition reaction, known in the art.

For the reaction of the unsaturated amine with the

nitrile, it is usually preferred to use at least about 1.5 mole

typically about 1.9-3.0 moles, of the nitrile per mole of

unsaturated amine. The sulfuric acid should be at least about

and preferably 96-98', in strength and the molar ratio of

sulfuric acid to amine should be at least about 1:1, and pre-

ferably between about 1.1:1 and 2:1. Solvents are usually

unnecessary, but it may be advantageous to add a small amount

a polymerization inhibitor such as hydroquinone, a hindered pht

or the like. When the reaction is complete, the product may bE

isolated by diluting and neutralizing the mixture and separatil

the unsaturated amide by traditional techniques.

The preparation of acrylamido compounds of this invei

tion is illustrated by the following examples.

Example 11 A mixture of 144.7 parts (0.63 mole) of N-(l,l-dimet]

3-di.-ethyla:inobutyl)-3-methoxypropionamide, 1 part of solid

sodium hydroxide and 1 part of hydroquinone is charged to a

reaction flask fitted with a condenser with a Dry Ice-cooled

12 47 9.21

42 1 71

The pressure receiver, a stirrer and temperature control means." is in the flask is reduced to less than 5 rr-. and the flask

heated to 83°C. Vigorous reaction begins and liquid condenses

in the receiver. After about one-half hour, the temperature is 0 for 3 hours. increased to 90 C. and this temperature is maintained

The product is distilled and the desired N-(l,l-dimethyl-3-

di-:.ethylainobutyl)acrylamide is obtained at 80-91°C./0 .5-0.4 mm.

The yield is 109.1 parts, or 87.4- of the theoretical amount, and the nitrogen percentage is the calculated 14.1%. e-

Exa.-les 12-14

The procedure of Example 11 is repeated starting with,

respectively, -diphenyl-l-methyl-3-dimethylaminopropyl)-

3-methoxypropionaifide, N-(1,l-diJmethyl-3-piperidinobutyl)-3-

methoxypropionamide, and The corresponding acrylamides are obtained. 3-methoxypropionamide.

Example To a mixture of 273 parts (4 moles) of isoprene and 2

parts (0.337 mole) of sodium metal, at is added 180 parts

(4 moles) of dimethylamine over one hour. The temperature is 0 maintained below 12 C. by cooling with a Dry Ice-isopropanol-

filled cooling coil. After the di-methylamine addition is complete, 3-1/2 hours. the mixture is stirred and cooled for an additional the sodium and the Methanol, 6 parts, is then added to decompose

mixture is distilled. The fraction boiling at 117.5-119.5*C. is

the desired 1-dimethylamino-3-methyl-2-butene. A resin flask is cooled to 0°C. and 450 grams (8.5 moles) acid and of acrylonitrile, 1020 grams (10 moles) of sulfuric

37 gra-s of water are added. To this mixture are then added 475 1 47 921

4 21/72 grams (4.2 moles) of the l-dimethylamino-3-methyl-2-butene pre pared as described above, and 8.5 grams of 2,6-di-t-butyl-p-cr

The mixture is stirred at 680 C. for about one hour and is ther neutralized with about 30 sodium hydroxide. The organic laye is separated, diluted with 2050 ml. of methanol and neutralize with ar-onia. An additional 1000 ml. of methanol is added and the solution is filtered. The methanol is stripped from the filtrate and the residue is distilled. There is obtained 400 grams (64.5 of the theoretical amount) of the desired N-(1,1- di.ethyl-3-dimethylaminopropyl)acrylamide boiling at 75-92°C./ 0.25-0.9 rm. The nitrogen analysis is 15.41, as compared with a theoretical value of 15.22. The amino compounds prepared as described above may converted into amine salts by reaction with a suitable acid, o into quaternary ammonium salts by reaction with an alkyl halid sulfate or the like. This is illustrated in the following exa

Example 16 Nethyl iodide, 2.8 grams (0.0197 mole), is added to solution of 3.6 grams (0.0182 mole) of N-(l,l-dimethyl-3-dimet] aminobut.yl)acrylamide in 10 ml. of benzene. An exothermic reai takes place and the temperature of the mixture is held at 25-3( by external cooling. Upon stirring overnight, a gummy solid precipitates; this solid is separated and recrystalized from a mixture of methanol and benzene. There is obtained 4.7 grams the desired trimethyl-3-(l-acrylamido-l,l-dimethylbutyl)ammonit iodide.

Examn-.le 17 Hydrogen chloride is bubbled through a solution of

14 14 47921

404 21 grams of l,l-dir.ethyl-3-dime thylaminopropyl)acrylamide in benzene. The desired dim-ethyl-3-(l-acylamido-, ,l-dimethyl-

propyl)a.-oniu- chloride precipitates and is separated by fil-

tration.

The oxy compounds of this invention are useful

primarily as chemical intermediates for the preparation of

acrylamido compounds, as described hereinabove.

The acrylamido compounds of this invention are readily

either alone or with other monomers. The term polymerized,

"polymer", as used herein, includes homopolymers, copolymers,

terpolysers and other interpolymers.

The free-radical method is generally the most convenient Poly- one for polymerization of the compounds of this invention.

merization by this method may be effected in bulk, solution, or monomers suspension or emulsion, by contacting-the monomer or presence with a polymerization initiator either in the absence 0 Suitable free- of a diluent at a temperature.of about 0-200 C.

radical initiators include benzoyl peroxide, tertiary butyl peroxide, azobisiso- hydroperoxide, acetyl peroxide, hydrogen persulfate-sodium butyronitrile, sodium persulfate, ammonium Solution polymeri- metabisulfite, chlorate-sulfite and the like. as benzene, zation may be effected in an organic solvent such mineral toluene, cyclohexane, n-hexane, naphtha, tetrahydrofuran,

oil or the like; emulsion and suspension polymerization are of water with a conveniently effected in water or a mixture

hydroxylated organic solvent.

Free-radical polymerization of the monomers of this

techniques invention may also be effected by photoinitiation 47 9215

4 21/72 using ultraviolet, visible or infrared radiation. For these

methods, the presence of suitable initiators and sensitizers, which are known in the art, is required. Suitable emulsifiers for use in the preparation of emulsion polymers of this invention include cationic materials such as stearyl dimethyl benzyl a-.monium chloride; non-ionic materials such as .alkyl aryl polyether alcohols and sorbitan mono-oleate; anionic materials such as sodium decylbenzene sul- fonate, dioctyl sodium sulfosuccinate, sodium salts of alkyl aryl polyether sulfates, and sodium lauryl Sulfate; alkali metal salts of lignosulfonic acids, silicic acids and the like; and colloidal materials such as casein, sodium polyacrylate, carboxymethylcellulose, hydroxyethylcellulose, gum tragacanth, sodium alginate, gelatin, methylcellulose, gum arabic, dextrinE or polyvinyl alcohol. A large variety of monomers can be used to form intei polymers with the compounds of this invention. For the most

part, these monomers are polymerizable vinyl compounds. They

include esters of unsaturated alcohols, esters of un-

saturated acids, esters of unsaturated polyhydric alcohols

butenediol), vinyl cyclic compounds, unsaturate(

ethers, unsaturated ketones, unsaturated amides, (8)

unsaturated aliphatic hydrocarbons, vinyl halides, (10) un

saturated acids, (11) unsaturated acid anhydrides, (12) un- saturated acid chlorides, and (13) unsaturated nitriles. Spec:

illustrations of such compounds are: 1. Esters of unsaturated alcohols: Allyl, methally

crotyl, 1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methyl- vinyl, 1-phenallyl, butenyl esters of saturated acids such

16 47 9.2 caproic and stearic; as acet~-c, propionic, butyric, valeric, acrylic unsaturated acids such as acrylic, al-oha-substituted (incl-..d'rz* a) ,ylacrylic, methacrylic, ethylacrylic, pro-IrlC etc., and arylacrylic such as ohenylacrylic), oleic, linoleic nd linolenic; polybasic acids croto'nic adipic, pimelic, such as ox:alic, malonic, succinic, glutaric, suberic, azelaic and sebacic; unsaturated polybasic acids methyl- such as rlc, fumaric, citraconic, mesacolic, itaconic, aconitic; aromatic ene~ralcrJ_:, ace tylened icarboxylic and and acids, benzoic, phenylacetic, phthalid, terephthalic benzoy--z:*tna'ic acids. 2. Esters of saturated alcohols, such as methyl, tert- ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, alcohols, with un- butyl, 2-ethylhexyl, cyclohexyl or behenyl acids, examples of~ saturated aliphatic monobasic and polybasic which are illustrated above. e.g., 3. Esters of unsaturated polyhydric alcohols, and aromatic, butenedAol, with saturated and unsaturated aliphatic examples of which monobasic and polybasic acids,'illustrati.2ve a~ear atove. monovinyl 4i. Vinyl cyclic compounds including allylbelzee, styrene, in-, p- aromatic hyd,-rocarbonS, -iethylstyrenes, chloro~t'renes, -broinostyrenes, -fluorostyrefleS, and tetra-, etc., -ethylstyrefles, -cyanostyrenes; di-, tri-, -methyl- -chlorostyreles, -brompostyrenes, -fluorostyrenes, vinylnaphthalene, styrenesC, -ethylstyrenes, -cyanostyrenes; as vin~l-..-'ohexane; corresponding pojijlcompounds such and vinyl heterocycles divin::l-__nzne and trivinylbenzene; N-vinyl- such as vinylfuran, vinylpyridine, vinylbenzofuran, 1 47 92

4 2 1,'72 Carl-azole, !:-vin ylpyrrolif.done, i.-vinylthiopyrrolidone and

-vinvlo.-zciidone.

Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, cycl&'exyl vinyl ether, octyl vinyl ether,

dfall.'l ether, ethyl meth-alyl ether and allyl ethyl ether.

6. Unsaturated ketones, methyl vinyl ketone

and ethy2 vinyl ketone.

7. Unsaturaze3d a--des, such as acrylamide, methacry-

a-mmethy acrylamiu~e, Npihenylacrylamide, N-allylacrylarn-

-ethioicri.-amide, N-allycanrolac tam, diacetone acrylamide and i, l-dL-_e etiyl-3-v8ro'oxybnutyl)acrylamide.

8. Unsaturated aliphatic hydrocarbons, for instance,

ethylene, propylene, butenes, butadiene, isoprene, 2-chloro-

butadiene arnd azha-olefins in general. 9. Vinyl halides, vinyl fluoride, vinyl chlor:

vinyl bromide, vInylidene chloride, vinylidene bromide, allyl

chloride and allyl bromide.

Unsaturated acids (for example, acrylic, methac

ic, prp-placryic), examplnes of which appear above.

11. Unsaturated acid anhydrides, maleic, citri

conic, itaconic, cis-4-cyclohexene-,2-dicarboxylic and bi-

cyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydrides.

12. Unsaturated acid halides such as cinnamoyl,

acrylyl, methacrylyl, crotonyl, oleyl and fumaryl chlorides or

bromides.

13. Unsaturated nitriles, acrylonitrile, meth.

acrylontrile and other substituted acrylonitriles.

The preferred comonomers are vinyl esters of carboxy'

acids, illustrated by vinyl acetate; alkyl esters of unsaturatf

47 9.215

4 0 .42i

carboxylic acids, illustrated by ethyl acrylate, 2-ethylhexyl

acrylate and methyl methacrylate; unsaturated nitriles such as

acrylonitrile; and unsaturated amides such as acrylamide, N-

methylacrylamide and methacrylamide.

The relative proportions of the compounds of this

invention and the comonomers to be used in interpolymerization

depend upon the reactivity of these monomers as well as the

properties desired for the interpolymers being formed. To

illustrate, interpolymers in which rigidity is desired are

obtained by polymerization of a mixture of monomers having a

few substitutions or substitutions of relatively short chain

length. If a still higher degree of rigidity is desired, a

monomer.mixture may be used in which a small amount of a bi-

functional monomer is included such as divinylbenzene which

will crosslink the polymer.

The polymers of this invention can also be prepared

from polymers of N-3-oxohydrocarbon-substituted acrylamides

such as N-(1,1-dimethyl-3-oxobutyl)acrylamide (diacetone

acrylamide) by reductive amination, using techniques and con-

ditions similar to those described herein for the preparation

of oxy compounds of this invention.

Polymers of this invention wherein Y is an amino group

can be converted to salts, including quaternary ammonium salts,

by the same methods described herein for monomers; or polymeric

salts may be obtained from monomeric salts by ordinary poly-

merization means.

The preparation of polymers of this invention is

illustrated by the following examples.

47 92!

40421/72 Example 18

A solution of 10 parts of N-(l,l-dimethyl-3-dimethyl aminobutyl)acrylamide in 40 parts of benzene is flushed with nitrogen for 10 minutes, and 0.05 part of benzoyl peroxide is added. The solution is heated at 60-65°C. for 16 hours, after which an additional 0.05 part of benzoyl peroxide is added.

Heating is continued for 16 hours, after which the benzene is

removed by evaporation, leaving a viscous oil. This oil is dissolved in methanol and the solution is poured into water.

The desired homopolymer of N-(l,l-dimethyl-3-dimethylaminobuty

acryla-ide precipitates and is air dried.

Exa.ple 19

Four grams (0.202 mole, based on monomer) of the pol, mer of Example 18 is dissolved in 25 ml. of methanol and 2.85

grams (0.202 mole) of methyl iodide is added. The solution is 0 heated at 50-60 C. for 1-1/2 hours, during which time a white

precipitate forms. The liquid is removed by decantation and t] precipitate, which is the desired poly-[trimethyl-3-(l-acrylam:

l,l-di--ethylbutyl)ammonium iodide], is washed with acetone and

air dried.

Example

A mixture of 20 parts of N-(l,l-dimethyl-3-'dimethyl- aminobutyl)acrylamide, 80 parts of water and 0.1 part of sodiur lauryl sulfate is purged with nitrogen for one-half hour, and

then a solution of 0.1 part of ammonium persulfate in one part

of water is added. The solution is stirred as polymerization takes place. The mixture is allowed to stand overnight and is then filtered. The desired suspension homopolymer is air dried

47 9.215

421! 7 Example 21 A solution of 20 parts (0.109 mole) of N-(l,l-dimethyl-

3-dizethylazinopropyl)acrylamide in 8.5 parts of water is purged The with nitrogen and 0.5 part of ammonium persulfate is added. mixture is stirred for about. 1-1/2 hours, during which time

Water, 175 parts, is then added polymerization takes place. followed by 13.7 parts (0.109 mole) of dimethyl sulfate. An exothermic reaction takes place as stirring is continued over- night. There is obtained an aqueous solution of the quaternized homopolymer from which water is removed by evaporation and vacuum drying.

Example 22 The procedure of Example 18 is repeated, except that

the monomer is replaced on an equal weight basis with N-(1,3- A similar diphenyl-l-=ethyl-3-dimethylaminopropyl)acrylamide. homopolymer is obtained.

Example 23 The procedure of Example 18 is repeated, except that the monomer is replaced on an equal weight basis by N-(1,1- dimethyl-3-methylanilinobutyl)acrylamide. A similar homopolymer is obtained.

ExaT.ple 24 To a solution of one part of N-(l,l-dimethyl-3-di- 0.1 methylaminobutyl)acrylamide in 5 parts of water is added triethanol- part of methylene blue and a solution of 0.2 part of amine in 1C parts of water. The solution is exposed to an infrarei heat lamp, and polymerization begins after about 3 seconds as evidenced by the dissipation of blue color in the 21 47 9.2 1

4 21 I solution and the formation of a hazy precipitate.

Examples 25-27

Copolyners of acrylonitrile with N-(l,l-dimethyl-3-

dime thylainobutyl)acrya-.i-e are prepared, respectively, from

49.5 parts of acrylonitrile and 0.5 parts of the acrylamide, 47.5 parts of acrvlonitrile and 2.5 parts of the acrylamide, a

parts of acrylonitrile and 5 parts of the acrylamide. In e

case, the polymerization is effected by dissolving the monomer

in 600 parts of water, flushing with nitrogen and adding a sol

tion of 0.25 part of amonium persulfate in 1 part of water. When precipitation of the copolymer is complete, it is removed

by filtration, washed with water and dried in a vacuum oven.

Example 28 Dinethyl sulfate, 2.03 parts, is added to a solution

of 2.97 parts of N-(1,1-d-ethyl-3-dimethylaminopropyl)acryla

in 225 parts of water, with stirring. An exothermic reaction

takes place over about one-half hour. Acrylamide, 15 parts, i

then added and the solution is purged with nitrogen, after whi

time about 0.5 gram of ammonium persulfate is added. Polymeri tion takes place over 4 hours, and after this time 200 parts c

water is added and stirring is continued. A homogenous mixtur

is obtained which is diluted with water to a 1% solution of tI

desired quaternized copolyzer.

Example 29 A mi)ture of 40 parts of vinyl acetate, 10 parts of

N-(l,l-di.methyl-3-dimethyla.inobutyl)acrylamide, 0.5 part of sodiu~ lauryl sulfate and 45 parts of distilled water is flus

47 92

421/7 with nitrogen, and a solution of 0.25 part of ammonium persulfate in 1 part of ater is added. The mixture is heated to 55 0 C.,

with stirring, and is held at this temperature for one hour. The

Droduct is an emulsion of the desired copolymer.

Example Follo.ing the procedure of Examphs 25-27, a copolymer is prepared from 33 parts of ethyl acrylate, 20 parts of

N-(l,l-diimethyl-3-dimethylaminobutyl)acrylamide, 450 parts of water, 0.5 part of sodium lauryl sulfate and a solution of 0.25 part of ammoniuz persulfate in 1 part of water. The polymer which

is obtained by coagulation is filtered and dried in a vacuum oven. Incorporation of the acrylamido compounds of this inven- tion in acrylonitrile polymers improves their dyeability. This is: shown by a test in which films of the copolymers of Examples 27 are compared with a polyacrylonitrile film in reaction to Orange II dye. The films are suspended for 1-1/2 hours in a 0 0.05' aqueous solution of Orange II at 80-98 washed with distilled water and dried. Following this procedure, the poly- acrylonitrile film is uncolored while the color in the films of Examples 25-27 increases in proportion to the amount of N-(1,1- dimethyl-3-di.methylaminobutyl)acrylamide incorporated therein. The dyeability of polypropylene is also improved by treatment with the polymers of this invention. This is shown by a test in which 2.5 grams, 5.0 grams and 7.5 grams, respec-

tively, of an N-(l,l-dimethyl-3-dimethylaminobutyl)acrylamide homopolyr.er sirilar to that of Example 20 are added to samples of polypropylene. Sufficient methanol is added to cover the polypropylene and the mixtures are shaken for one minute and allo.ed to stand in closed bottles for 40 minutes. The

23 47 9215

40,4 21 /72 bottles are then opened and the methanol is removed by evapora-

tion at room temperature and finally in a vacuum oven at 48-50*

Films of the resulting modified polypropylene samples are sus-

pended in the Orange II dye solution described above at 60-90*C

for 2-1/4 hours. The strips are then removed, rinsed with dis-

tilled water and dried. Each of the strips is noticeably color

by the dye.

The polymers of this invention are useful to improve

both dry strength and wet strength of paper. Their utility as

dry strength improvers is shown by a test in fhich strips of

filter paper are saturated with a 53 solution in methanol of tt

polymer of Example 20 and dried by suspension for 2 hours at

room temperature. The average tensile strength of the treated

strips, as measured on an Instron tester using a crosshead spee

of 0.2 inch per minute at a temperature of 72*F., was 21.6 pour

per inch width, as compared with 13.8 pounds per inch width fox

untreated specimens.

Quaternized polymers of this invention are useful as

flocculants for precipitation of many substances from water. I effectiveness of these polymers as flocculants for the precipit

tion of kaolin is shown by a test in which one part of kaolin 1

suspended in 100 parts of water and about 0.1 part of a 20Z aqu

solution of the polymer of Example 19 is added. The suspensior

shaken for about 1/2 minute and allowed to. stand. A flocculent precipitate forms immediately. By contrast, the kaolin in a

control sample which is not treated with homopolymer of Example

remains suspended. The effectiveness of the quaternized polymers of this invention as flocculants for raw sewage is shown by a test in

24 47 9.

421/t

and an aqueous which 600 ml. of sewage is placed in a beaker stirring. solution of the quaternized polymer is .added, with rapid

The razid stirring is continued for 3 minutes, followed by 12

A minutes of slow stirring and 15 minutes of settling. mixture aliouot is then removed from the top half inch of the

and its turbidity is measured on a Boyce-Phoenix light scattering

photometer. The results are shown in the follo-ing table.

Flocculant Concentration, pp". Turbidity

Homopolyer of Ex. 21 2.57 2.03 0.931 0.400 0.152 0.112 0.090

Copolymer of Ex. 28 1.39 0.570 0.306 0.136 0.067

sus- The monomers of this invention, by virtue of their useful in photo- ceptibility to photoinitiated polymerization, are

engraving and photographic techniques. They may also be copoly-

in the merized with crosslinking agents such as divinylbenzene, to form cationic presence of suspending agents such as bentonite,

ion exchange resins.

47 9215

40,42 1 The claims defining the invention are as follows 1A compound of the formula Y R2 R4 0 RI I I 1 11 R 3R H wherein each of R1 to R3 is a hydrogen, lower alkyl or h'f-d wa$41V C 6 -Is aromati-clradical; each of R4 and R5 is a lower alkyl, C 3 8 cycloalkyl or C -is aromatic/radical; 6 6 R is -C=CHz or -CH-CH 2 -0Re; R is hydrogen or methyl; 7 Re is a R? R7 lower alkyl or C 6 -25 aromatichradical; Y is -N\,2or Z.1 -N-Z2 X 0 Z2, Z2 afd-" are hydrogen, lower alkyl or

C3 8 cycloalkyl radicals,Lor -N'Z2is a pyrrolidino, piperidino or morpholino radical; and X (if present) is a. salt forming anion.

4 7 92

Claims (1)

1. 40. 4 21 JI

   2. A compound according to claim 1 wherein R5 is 8 2 OR' -CHCH- A 7 is hydrogen or methyl and R is a lower alkyl

   radical.

   3. A compound according to claim 2 wherein Y is Z1. "%Z2

   41. A co=7pound according to claim 3 wherein each of R' 4 R2 And R3 is hydrogen or a lower alkyl radical, each of' R and 1 2 R5 is a lower alkyl radical, R is hydrogen, and Z and Z are 7

   lower alkyl radicals.

   '21 2447 9.2

   4 21 !/7 A compound according to claim 4 wherein R' is hydrogen or methyl; R2 R 3 and R7 are hydrogen; R4 R 5 and R8 are methyl; and Y is N(CH3 2

   6. A compound according to claim 2 wherein Y is GZ- 2

   NZ x 13 z

   7. A compound according to claim 6 wherein each of 4 R,.R2 and R 3 is hydrogen or a lower alkyl radical, each of R 7 2 and R 5 is a lower alkyl radical, R is hydrogen, and Z* and Z are lo..-er alkyl radicals.

   8. A compound according to claim 7 wherein R* is hydrogen or methyl; R2 R 3 and R7 are hydrogen; R4 R5 and R8 are methyl; and Y is N(CH3 3X

   9. A compound according to claim 1 wherein R6 is -C=CHa and R7 is hydrogen or methyl. R7

   A compound according to claim 9 wherein Y is Z 1 Z -N NZ2

   11. A compound according to claim 10 wherein each o: 4 R1 R 2 and R3 is hydrogen or a lower alkyl radical, each of R and R 5 is a lower alkyl radical, R7 is hydrogen, and each of Z and Z2 is a lower alkyl radical.

   12. A compound according to claim 11 wherein R1 is hydrogen or methyl; R2 R3 and R7 are hydrogen; R4 and R 5 are '29 47 9215

   40,4 21/ 72

   methyl; and Y is N(CH 3 )2.

   Y is 13. A compound according to claim 9 wherein

   13

   of 14. A compound according to claim 13 wherein each 4 radical, each of R R 1, R2 and R3 is hydrogen or a lower alkyl 7 hydrogen, and each of ZI and R is a lower alkyl radical, R is 5

   and Z is a lower alkyl radical. 2

   R' is A compound according to claim 14 wherein 4 R3 and R are hydrogen; R and R5 are 2 7 hydrogen or methyl; R

   methyl; and Y is (CHA3)3

   16. A method for the preparation of a compound according of the formula to claim 3 which comprises reacting a compound 4 0 0 ReR

   R3 R5 H R7 Z.1 with an amine of the formula HN in the presence of a reducing

   agent.

   the reducing 17. A method according to claim 16 wherein oxide. agent is hydrogen in the presence of platinum

   each of 18. A method according to claim 17 wherein 4 s each of R and R 5 is Ri, R2 and R3 is hydrogen or lower alkyl, 2 7 of Z 1 and Z is lower alkyl. lower alkyl, R is hydrogen and each 29 47 92

   19. A method for the preparation of a compound ace

   ing to claim 10 which comprises eliminating RsOH from a compc

   of the formula ZI Z2

   R2R4 0 1 R -CH-C-C-N-C-CHCH 2 OR8

   R3R5H R7

   A method according to claim 19 wherein said R8 is cli-ir..-ned by pyrolysis in the presence of a strong base,

   21. A method according to claim 20 wherein each of 1 2 R R and R 3 is hydrogen or lower alkyl, each of R 4 and R 5 i

   lower alkyl, R 7 is hydrogen and each of Z 1 and Z2 is lower al

   22. A polymer of a compound according to claim 9.

   23. A polymer of a compound according to claim 12.

   24. A polymer of a compound according to claim

   An interpolymer of a compound according to claim 9.with a polymerizable vinyl monomer.

   26. An interpolymer of a compound according to cla:

   12 with a polyr.erizable vinyl monomer.

   27. An interpolymer of a compound according to cla: with a polymerizable vinyl monomer.

   47 9.

   404 21 7 28. A method for the preparation of a co.pound according to claim 10 which comprises'reacting a nitrile. of the formula CHa=C-CN with an unsaturated amine of the formula R7 Z Z

   I I R R R CH-C=C

   R3

   in the presence of sulfuric acid.

   1 29. A method according to claim 2'8 wherein each of R 4 R2 and R3 is hydrogen or a lo..er alkyl radical, each of R and 7 R5 is a lower alkyl radical, R is hydrogen, and each of Z' and Z2 is a lower alkyl radical.

   A method according to claim 29 wherein R 1 R2 R3

   and R 7 are hydrogen, and R 4 R5 Z 1 and Z2 are methyl.

   31. A method according to claim 29 wherein at least :abwh 1.5 moles of nitrile are used per mole "of amine.

   32. A method according to claim 31 wherein the molar ratio of sulfuric acid to amine is at least a eu 1:1, and the

   sulfuric acid is at least be.ut 90Z in strength.

   47 9215

   4 21/72 33. A compound according to claim 1 substantially

   as described with reference to the examples. 34. A method according to claim 16 substantially

   as described with reference to the examples.

   DATED this 21 day of March 1972

   THE LUBRIZOL CORPORATION

   32 A7 92