DE1468931A1 - Acrylic compounds containing hydroxyl and quaternary ammonium groups and processes for their preparation - Google Patents

Description

D ;. Walt-r hatchet

Dr Hans Joid in WoIK M,

Dr. Hari3 Chr. Hatchet T-

Lawyers

Frankfurt α M.-Hft'.lnt

Te.elor. M do 24

Our no. 11 926

Rohm & Haas Company Philadelphia, Pa., V.St.A,

Acrylic compounds containing hydroxyl and quaternary ammonium groups and methods of making them

The invention relates to hydroxyl and quaternary ammonium groups containing acrylic compounds of the general formula

OH

CH ₂ = C-CH-COCH ₂ CH ₂ N

wherein R is hydrogen or an alkyl radical with 1 to 3 carbon atoms, R ₁ , R ₂ and R, alkyl radicals with 1 to 18 carbon atoms, a phenyl radical, aralkyl radicals or hydrocarbon-substituted aralkyl radicals with 7 to 24 carbon atoms and χ is an anion, and method zua? their manufacture.

In the general formula, R ₁ , R ₂ and R, also hydrocarbon- or alkyl-substituted aralkyl radicals with 1 to 18 carbon atoms in substituents and X can be an anion such as a halo

809901/0861

New documents (Art. 7, Paragraph 1, Paragraph 2, No. 1, Clause S of the Amendment Act of September 4, 1967).

genide anion (i.e. «chloride, bromide, iodide or fluoride anion), Sulfate, methyl sulfate, acetate, phosphate, citrate, tartrate, bicarbonate anion, etc. mean. Of course, others can too Anions are present.

Preferred compounds according to the invention are compounds of general formula

R OH

IT I ₊

CH ₂ = C-OCH ₂ CH-CH ₂ N

in which R. H or a methyl, R _K and R a: "7f thyl or ethyl, R ₇ a methyl, ethyl, phenyl or a ^ n benzyl radical and X an anion, preferably a halide anion in particular chloride anion.

The process according to the invention is characterized in that an alkali salt of an acrylic acid is reacted with chlorohydroxypropyl quaternary ammonium chloride or edine acrylic acid directly with an epihalohydrin and a tertiary amine. The acrylic compounds of the present invention can be satisfactorily produced in various ways. For example, you can get a Chlorhydroxyl- (O propyl-quart.ammoniumhalogenid with an alkali salt of acrylic or methacrylic acid _o implement. Below is given an example of this general reaction scheme, wherein for explanation

ο as alkali metal potassium and as quaternary ammonium reaction cd Participants called chlorohydroxypropyltrimethylammonium chloride Ξ? are:

OH,

OH ₀ = C-COK

0 ^

^0H ei "

₂₂ (CH ₃ ),? ^H 3 OH Cl "

¹ S 1 ⁺

CH ₉ = CC-OCH ₉ CH-CH ₀ N (CH,),

* ^{ά ά} * * + KCl

(3-methacryloxy-2-hydroxypropyltrimethylammonium chloride)

A suitable solvent is used for the reactants, for example acetonitrile or ethanol, is used and the reaction is generally carried out at temperatures above room temperature and preferably carried out under reflux conditions · The reactants can the reaction mixture in equivalents Quantities can be added, or any one may if desired Reactants are used in weak or strong excess.

The chlorohydroxypropyl quaternary ammonium chloride used as a reactant or intermediate can be used according to the Method of Slobodin et al. Zhur. Obshchei Khim. 26, 694-9 (1956), reported in Chemical Abstracts Volume 50, 14510 i, or can be made by other known methods.

The inventive acrylic compounds can also by direct Reaction of acrylic or methacrylic acid with an epihalohydrin and a tertiary amine without a required separation of intermediates such as chlorohydroxypropyltrimethylammonium chloride getting produced. The reactants can the reaction mixture in equivalent proportions or desired tenfall be supplied in weak or strong excess. The order of addition of the reactants is not critical; however, in order to minimize the formation of the bis-quaternary ammonium compound, it will preferred to bring the reactants together such that a pre-reaction between the epihalohydrin and the tertiary Amine is avoided. By way of illustration, using epichlorihydrin as epihalohydrin, trimethylamine is used below the course of the reaction is indicated as tertiary amine and methacrylic acid, the order of addition of the reactants (1a) addition of epichlorohydrin first to the methacrylic acid and then (1b) addition of the trimethylamine to the reaction product of (1a).

(1a) CH ₀ = C-CO ₀ H + CH ₀ CHCH ₀ Cl ψ CH ₀ = C-CO ₀ CH ₀ CHCH ₀ Ci

2 | 2 v22 2 j 2 2, 2

CH ₃ ^N 0 CH ₃ OH

809SC 1/0861

_i A -

CH ₃ OH

The reaction proceeds according to the reaction scheme given below, when the addition is the reactant; (2a) Addition of the ^ rimethylamine to methacrylic acid and then (2b) Addition of the epichlorohydrin to the reaction product of (2a):

(2a) CH ₀ = C-CO ₀ H + (CH,), N ^ (CH,), Ν O ₀ CC = CH ₀

^v 2 I 2 YY Y YY * - ι ά

CH,

+
(2b) (CH ₃ ) ₃ NO ₂ CC = CH ₂ + CH ₂ CHCH ₂ Cl

H CH, θ '

CH ₀ = C-CO ₀ CH ₀ CHCH ₀ N (Ch,)

I I ei

CH ₃ OH

The acrylic compounds containing the hydroxyl and the quaternary ammonium group according to the invention can be used in a wide variety of ways Use and deploy wisely. They are generally pale colored solid materials with useful bacteriostatic properties and bactericidal effectiveness.

The acrylic compounds of the invention can be used to produce polymers and copolymers which are water-soluble or ^{dispersible in VVas} ser, have antistatic properties, form flakes and can be treated in water, and have other desirable properties. Because of their reactive hydroxyl groups, the acrylic compounds according to the invention can be used in crosslinking reactions.

The acrylic monomers according to the invention are also suitable for modification tion of cellulosic materials such as starch, paper, Cotton, textiles, etc. ιϊΤοργ a v> p> - "pnr < ^ he implementation taking place Polymerization and i-iischpolycerir-ation suitable,.) Ie

8G9SÜ 1/086 1

° ^To ORIGINAL.

modified products formed in the process show an improved Affinity for dyes and optical brighteners, improved binding power for pigments, and other desirable properties. The above-mentioned in situ polymerization can be carried out, for example, by immersing the cellulose-containing material in any form into an aqueous or non-aqueous solution or dispersion of the polymerizable quaternary ammonium acrylic monomer be carried out, the solution using a conventional free radical polymerization catalyst or initiator such as azodiisobutyronitrile and at the appropriate polymerization temperature must be held until the polymerization has occurred. Then the surface polymer H. removed from the cellulosic material. The modified in this way cellulosic material contains internally precipitated quaternary ammonium acrylic polymers.

In addition to the homopolymers of the acrylic quaternary according to the invention Ammonium monomers can also make useful interpolymers by copolymerizing the ammonium-containing monomer, usually with 5096 or more of one or more other polymerizable Compounds containing a single ethylenically unsaturated group can be obtained. Others suitable for this awakening polymerizable compounds include, for example, the esters of acrylic or methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl Benzyl, phenylethyl alcohol and the like, diesters of itaconic acid with the aforementioned "alcohols, ^ ster of Walein- • and fumaric acid with the aforementioned alcohols, vinyl esters of carboxylic acids such as ssigaäure, propionic acid, butyric acid and the like. Vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, methacrylonitrile or acrylonitrile, acrylamide or methacrylamide and N-alkyl-substituted amides of this type, Vinyl toluene, vinyl naphthalenes, vinyl chloride, styrene and others.

The invention is illustrated in the following examples. The parts given are parts by weight, unless otherwise specified is specified.

809901/0861

- ο -

example 1

Preparation of 3-Methacryloxy_2-hydroxyP ^ ° Pyl ' ^fcr i ⁿⁱ e'thylammoniumchlorid

(a) 188 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 12.4 parts of potassium methacrylate, 200 .mu. The reaction mixture was refluxed for 2 1/2 hours and then left to stand at room temperature overnight. The reaction mixture was then filtered in order to remove 7.72 parts of potassium chloride. The acetonitrile was distilled off under reduced pressure from the filtrate and as the residue ^ 22.0 parts 3-methacryloxy-2-hydroxypropyl as a tan powder obtained, melting at 173- 180 ⁰ C under clearly polymerization "A sample was prepared by recrystallization from a 1: 1 mixture of isopropanol and ethyl acetate and gave the following analytical values:

Calculated for C ₁₀ H ₂₀ NO ₃ Cl: C 50.76 % \ H 8.42%; N 5.89 #;

Chloride ion $ 14.93> \ bromine number 67.3. Found: C, 50.31 #; H 8.49 $ ', N 6.03 i> \ chloride ion 15.23 ⁰ M

Bromine number 63.3.

(b) By repeating the above process steps (a), but instead of Laliummethacrylat 10.8 Parts of sodium methacrylate were used, the same product, 3-methacryloxy-2-hydroxypropyltrimethylammonium chloride, manufactured.

(c) By repeating process steps (a) above, but using 9.2 parts of lithium ^{methacrylate instead of potassium methacrylate, the same product, 3-1} " ⁱ ethacryloxy-2-hydroxypropyltrimethylammonium chloride, was prepared.

The table below shows other possible procedures.

809901/0861

Explained that can be used for the preparation of the compounds according to the invention. In these examples
As in Example 1, 0.01 'weight of the monomethyl ether of hydroquinone was used as a polymerization inhibitor. The reaction mixture was refluxed for about 4 to 5 hours, after which the inorganic salt (e.g. KCl, KBr, etc.) was filtered off to obtain the desired acrylic products as residue.

Table A.

Example reaction mixture

(CHPTMAcI, 18.8 parts (KA, 11.0 parts

Solvent medium

Acetonitrile,
ecm

(BHPTMAbr, 27.7 parts acetonitrile, (KMA, 12.4 parts 200 ecm

(CHPTBAcI, 31.4 parts of ethanol, (KMA, 12.4 parts 150 ecm

(CHPTOAcI, 48.3 parts of ethanol, (KMA, 12.4 parts 150 ecm

(CHPCDAcI, 39.8 parts of ethanol, (KMA, 12.4 parts 150 ecm

(CHPTODAcI, 90.2 parts of ethanol, (KMA, 12.4 parts of 150 ecm

(CHPDMBAcI, 22.9 parts of ethanol, (KMA, 12.4 parts of 150 ecm product

3-acryloxy-2-hydroxypropyl trimethylammonium chloride

3-methacrylic

oxy-2-hydroxy

propyltrime-

thylammonium

chloride

3-methacrylic

oxy-2-hydroxy

propyltri-

butylammonium

chloride

3-methacrylic

oxy-2-hydroxy

propyltri-

octylammonium

chloride

3-methacrylic acid

oxy-2-hydroxy

propylcetyl

dimethylammo-

nium chloride

3-methacrylic

oxy-2-hydroxy

propyl-tri-

n-octadecyl-

ammonium-

chloride

3-methacrylic

oxy-2-hydroxy

propyldime-

th3'lbenzyl-

ammonium-

chloride

Table A (continued)

Example reaction mixture solvent product

medium

(CHPDMPAc1,21.7 parts of ethanol, (KMA, 12.4 parts 150 ecm

9 (CHPDMPAc1,21.7 parts of ethanol, 3-methaeryloxy-

2-hydroxypropyldimethylphenylammonium-chloric

The following is an explanation of the abbreviations above:

CHPTMAcI = 3-chloro-2-hydroxypropyltrimethylammonium chloride KA = potassium acrylate
KMA = potassium methacrylate

BHPTMAbr = 3-bromo-2-hydroxypropyltrimethylammonium-bromide CHPTBAcI = 3-chloro-2-hydroxypropyltributylammonium chloride CHPTOAcI = 3 ~ chloro-2-hydroxypropyltrioctylammonium chloride CHPCDAcI = 3 ~ chloro-2-hydroxypropylcetyldimethylammonium chloride CHPTODAcI = 3-chloro-2-hydroxypropyltri-n-octadecylammonium chloride CHPDMBAcI = 3-chloro-2-hydroxypropyldimethylbenzylammonium chloride CHPDMPAcI = 3-chloro-2-hydroxypropyldimethylphenylammonium chloride

Example 10

Production of other salts through ion exchange.

In a glass column with a capacity of 150 ecm, which was closed at one end by a glass frit washer, 100 ecm of an ion exchange resin of the Stj'rol-divinylbenzene type with a content of quaternary ammonium groups in chloride form and with a capacity of 3.6 meq ./ccm given. A 10% solution of sodium sulfate was slowly poured through the column until the outflow was relatively free of chloride ions. The column was ater with ^vV washed to remove excess sodium sulfate solution to remove "Sine ^ robe of 23.8 parts of 3-i ^'i ethacryloxy-2-hydroxypropyl water was dissolved in 238 parts and" slowly through the columns then 250 cc of water were poured through the column to displace the solution of the product, - ^ he effluent is p.ue an aqueous solution of 3-Methacryloxy_2_h_vr'ro-x "Dro-n ^ l" ^tr i ⁿⁱ ethylamriioniumsul fat.

8 C 9 9 G 1 / O 8 6 1

With reference to Example 10, it should be noted that numerous known anion-exchanging resins for converting the halide-containing acrylic compounds according to the invention into any other desired anion form are suitable. An insoluble, crosslinked styrene-divinylbenzene copolymer is preferably used as the anion exchanger quaternary ammonium salt in its sulfate, phosphate or similar form used to make the halide-containing To convert the acrylic compound into another desired form, such as the sulfate, phosphate or the like. That Styrene-divinylbenzene type ion exchange resin is preferred prepared by the process described in U.S. Patent 2,591,573.

Example 11

Polymerization of methacryloxyhydroxypropyltrimethylammonium chloride

5 3/10 parts of 3 ~ ^M ethacryloxy-2-hydroxypropyltrimethylammonium chloride, 150 ecm dimethylformamide and 0.01 part azodiisobutyronitrile were placed in a 20 ecm three-neck bottle, which was equipped with a stirrer, thermometer, nitrogen, wiper, reflux condenser and an automatic temperature controller. The suspension was stirred and heated to 58.degree. A clear solution was obtained at this point. After about 4-0 minutes at 58-65 ° C, a precipitate began to form. The temperature was maintained at 65 N _ac ht ° C. The reaction mixture was then filtered off and the residue was washed with ether. 4.6 g of a white polymer powder were obtained. This powder is soluble in water. The nuclear magnetic resonance spectrum in D ₂ O shows the absence of peaks for unsaturated methylene hydrogen, and the infrared spectrum is characteristic of a polymethacrylate.

809901/0861

Claims (4)

PATENT CLAIMS: 1. Acrylic compounds containing hydroxyl and quaternary ammonium groups indications of the general formula R Ο OH I I I CH ₂ = C-COCH ₂ CH-CH ₂ N. where R is hydrogen or an alkyl radical with 1 "to 3 carbon atoms, R ₁ , Rp and R * are alkyl radicals with 1 to 18 carbon atoms, a phenyl radical, aralkyl radicals or hydrocarbon-substituted aralkyl radicals with 7 to 24 carbon atoms and χ is an anion _e 2. Process for the production of hydroxyl and quaternary ammonium groups containing acrylic compounds of the general formula RO OH Il in which R is hydrogen or an alkyl radical with 1 to 3 carbon atoms, R ₁ , R ₂ and R, alkyl radicals with 1 to 18 carbon atoms, a phenyl radical, aralkyl or hydrocarbon-substituted aralkyl radicals with 7 to 24 carbon atoms and X is an anion, in particular a halide, sulfate, ^ivi ethylsulfat-, Acetat_ _f phosphate, citrate, tartrate or bicarbonate anion, characterized in that an alkali salt of an acrylic acid with chlorohydroxypropyl-quaterbärem-anionium chloride or an acrylic acid directly with an epihalohydrin and a tertiary amine. New documents (Art. 7, Paragraph 1, Paragraph 2, No. 1, Sate 3 of the Amendment Act of 4 September 19:57). 809SC1 / 0861 " 3. The method according to claim 1, characterized in that the potassium salt of methacrylic acid is used. 4. The method according to claim 1, characterized in that one Acrylic acid or methacrylic acid with an epichlorohydrin and a tertiary amine. For Rohm & Haas Company Philadelphia, Pa., VStA. Lawyer 80Saü1 / Ü861