FORM 2
THE PATENT ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
PROVISIONAL SPECIFICATION
(See section 10 and rulc!3)
] TITLE OF THE INVENTION: "Azlactone-based Quaternary Polymeric Conditioners"
2. APPLICANT
(a) NAME: GALAXY SURFACTANTS LTD.
(b)NATlONALITY: Indian Company incorporated under the Indian
Companies ACT, 1956 (c) ADDRESS: C-49/2, TTC Industrial Area, Pawne,
Navi Mumbai - 400703
Maharashtra, India
3.PREAMBLE TO THE DESCRIPTION
The following specification describes the invention.



TECHNICAL FIELD OF THE INVENTION:
The present invention relates to novel quaternary polymers useful in softening, caring and conditioning synthetic and natural fibers (e.g. hair, cotton, etc.). More particularly, the present invention relates to stable^ wide pH ranged^ azlactotie-based quaternary polymers and to processes for the preparation thereof.
BACKGROUD AND PRIOR ART:
Monomeric and polymeric azlactones (also known as oxazolones) are well known and have been described in numerous patents and other publications.
Copolymers of 2-alkenyl azlactones and olefinically unsaturated monomers are disclosed in U.S. Pat. No. 3,488,327. U.S. Pat. No. 3,598,790 and U.S. Pat. No. 3,583.950 (all three to Rohm & Haas). The use of these copolymers in the manufacture of superior coating materials are disclosed.
U.S. Pat. NO. 4,378.411 (Minnesota Mining & Manufacturing Company) has disclosed energy sensitive polymers having pendent ethenically unsaturated peptide groups. These energy-sensitive polymers were prepared by the reaction of an ethylenically unsaturated nucleophilic compounds with certain groups of polymer having pendant azlactone groups. Such polymers are useful in the field of graphic arts.
SwwilMty, U.S. Pat. Mo. 4,777.217 (MuvaesoVd Mu\u\g <£c M&wdtacturing, Company) has disclosed polymers comprising the reaction product of at least one hydroxy! functional polymer with at least one isopropenyl azlactone in the presence of an acidic catalyst- These polymers find utility in coatings, films, binders, printing inks, adhesives, and the graphic arts.
U.S. Pat. No- 5,714,632 (Minnesota Mining & Manufacturing Company) has claimed certain azlactone-based surfactants useful in stabilizing dispersions of hydrophobic materials (e.g. pigments, ferromagnetic materials, abrasive particulates, and the like) in liquid dispersion, especially aqueous dispersions. These surfactants

arc the reaction products of N-substituted amino acid compounds and alkenyl azlactones.
EP-A-0392735 (Minnesota Mining & Manufacturing Company) has claimed certain azlactone-functional polymeric solid supports which are useful as complexing agents, catalysts, reagents, adsorbents, chromatographic supports and as biologically active supports for reaction with functional materials, one example of which is a protein, for example in protein synthesis.
U.S. Pat. No. 5,200,471 (Minnesota Minning & Manufacturing Co.) has disclosed a biologically active adduct support, prepared from an azlactone-functional polymeric support and biomolecules covalently immobilized thereon. These supports may be crosslinked azlactone-functional polymeric beads or they may be solid substrates coated on at least one surface with a layer of an azlactone-functional polymer. A copolymer bead of vinydimethyl aziactone and methylene-bis-acrylamide is disclosed as a polymeric bead.
EP-0463520 (Polaroid Corp.) has disclosed 2-(4-alkenylphenyl)-5-oxazolones useful in the production of homopolymers and copolymers having pendant function groups obtained by ring-opening addition to aziactone (oxazolone) groups. Similarly, U.S. Pat. No. 4.981,933 (Polaroid Corp.) has disclosed copolymers of aziactone with vinyl benzyl halides which can be used in various biological and immunoassay methods used for the detection and measurement of proteins and others.
As a relevant prior art to the present invention there may be mentioned U.S. Pat. No. 5.656,265 (Chesebrough-Pond's) which has disclosed a hair styling process comprising the steps of contacting the reduced hair with a hydrophobic aziactone compound which makes a chemical bond with the hair.
WO 94/26237 (Unilever) has disclosed an azlactone-functionalised cosmetic agent for providing one or more cosmetic benefits, wherein molecules of the cosmetic agent have chemically bonded thereto at least one aziactone substituenl moiety capable of reaction with a nucleophilic reactive site of the substrate (e.g. hair). It claims the silicone copolymerized aziactone polymer.

Thus, the azlactone functionalised compounds have been variedly used in different technological fields but it has been used in hair care and personal care in a very rare fashion. Although there are very few patents on the use of azlactonc-functionalized compounds in hair products but those are not satisfactorily fit into the demand and criteria of good polymeric conditioners. Moreover, these relevant patents are associated with the following additional problems:
1. Azlactone ring is very faciie for the attack in aqueous medium. Hence, stabilization of the pendant azlactone group in aqueous formulations or compositions is very difficult. Thus, the use of azlactone ring as such in aqueous compositions is extremely difficult.
2. As far as conditioning of hair is concerned, chcmisorption of azlactone group onto the keratin of hair is not recommended for the long run as it would be very difficult to remove the compound which is chemically strongly bonded to the hair and it would lead to heavy deposition of the conditioning polymer e.g. in WO 94/26237 (Unilever) which leads to heavy deposition of silicone polymer on hair even after drastic washing of hair. Moreover, the chemisorption may occur on the skin protein of the scalp and head and hence may prove potent skin irritant to the user.
Thus, there was a need of a good polymeric conditioner without the above mentioned disadvantages. Under these circumstances, wc have assiduously conducted investigations, and have consequently found that the above-mentioned object can be achieved by certain novel azlactone-based quaternary polymers. This finding has led to the completion of the present invention.
SUMMARY OF THE INVENTION:
As we have seen, hairs carry negative charges. The negative charges attract the positively charged molecules and these deposit on the hair, especially on areas where there is a degree of weathering. The immediate effect is that positive and negative charges cancel each other out, so reducing static electricity on the hair -and. of course, the 'fly away' that is associated with it.

Shampoos with anionic surfactants leave hair difficult to comb while wet and it fly¬away when comb after drying. Addition of cationic conditioners increases the wet and dry combability and decrease the static charge. Also, these conditioners are compatible with anionic surfactants. Hence, the cationic conditioners are best opted one but with superior quality.
Surprisingly, we have found that the abovementioned object is achieved by the azlactone-based cationic polymers of the present invention. They cling to the hair, smoothing out any roughness on the surface and protecting the cuticle. These polymers exert a caring, softening and lustrous effect on synthetic and natural fibers (e.g. hair, cotton, etc.) and exhibit high affinity to the said fibers.
Accordingly, a first aspect of the present invention provides azlactone-based quaternary polymers of formula (I):

Formula (I)
wherein, R is a radical R2 or a fatty alkyl radical having 8 to 22 carbon atoms. R2 - -A - Z+ X"
with the proviso that in the average molecule, at least one radical R is a radical R2, wherein Z" is a radical of formula (la)


R3 and R.3' are identical or different and arc in each case hydrogen or lower alkyl radical having 1 to 6 carbon atoms,
R/i is selected from an alkyl or aryl radical stem from a suitable quaterni/ing agent such as epichlorohydrin. glycerol monochloro hydrin, C1-C22 fatty alkyl halidcs, dialkyl sulfates, alkyl tosylates, aryl halidcs, aryl-alkyl halidcs.
A is a lower alkyl radical having 1 to 6 carbon atoms.
X is an inorganic or organic anion which stems from the quatcrni/.ing agents as
defined hereinbefore.
n has a value of from 0 to 10, preferably 0 lo 3.
V and 'b' represents the mole percent of the corresponding monomer wherein 'a: has a value from 1 mole% to 100 mole% whereas, 'b' has a value from 0 mole % to 99 molc%.
R" and R|" arc the radicals selected from alkyl groups having 1 to 6 carbon atoms or are the aryl radicals.
W is a radical of formula (lb). (Ic) or (Id):
N R3" formula (lb)
wherein R3 and R^' has same meaning as defined hereinbefore.
-0 R5 formula (le)
Wherein, R5 A Y'X A is same as hereinbefore defined.
Y' is a radical ■ N' Re,
wherein, R3 and Ry' arc same as defined hereinbefore
Rf, is aryl radical or a lower alkyl radical having 1 to 6 carbon atoms.
X ' is an inorganic or organic anion which stem from alky groups as defined
for R,,.

~-N-R5

formula (Id)

Rg wherein, R8 is R3 or R3" R5 is same as defined hereinbefore.
Ri and R\' are lower alkyl radical having 1 to 6 carbo11 atoms.
The second aspect of present invention provides a method of preparing Ihe compounds of Formula (1) according to the invention.
DETAILED DESCRIPTION OF THE INVENTICrN:
As indicated previously, the present invention is directec* towards novel azlactone-based quaternary polymers which can be used as a cafing and conditioning agent for

I Formula (I)
R
wherein. R is a radical R2 or a fatty alkyl radical having 8 t0 22 carbon atoms-R2 = -A - 7_: X"
with the proviso that in the average molecule, at leas1 one radical R is a radical R2, wherein Z+ is a radical of formula (la)


R.3 and R{ arc identical or different and are in each case hydrogen or lower alkyl radical having 1 to 6 carbon atoms.
R4 is selected from an alkyl or aryl radical stem from a suitable quaterni/.ing agent such as cpichlorohydrin, glycerol monochloro hydrin, C1-C22 fatly alkyl halidcs, dialkyl sulfates, alkyl tosylates, aryl halidcs. aryl-alkyl halidcs.
A is a lower alkyl radical having I to 6 carbon atoms.
X is an inorganic or organic anion which stems from the quaterni/.ing agents as
defined hereinbefore.
n has a value of from 0 to 10. preferably 0 to 3.
'a' and 'b* represents the mole percent of the corresponding monomer wherein 'a' has a value from 1 molc% to 100 molc% whereas, 'b" has a value from 0 mole % to 99 mole%.
R" and Rf' arc the radicals selected from alkyl groups having 1 to 6 carbon atoms or are the aryl radicals.
R7 is a radical of formula (Jb). (Ic) or (Id) :
N- R3; formula (lb)
wherein R3 and R;,' has same meaning as dcJmcd hereinbefore.
O R5 formula (Ic)
Wherein. R5 A Y"X A is same as hereinbefore defined. R3
Y' is a radical N"! Rfl
R3" wherein. R3 and R3' arc same as defined hereinbefore Rf, is aryl radical or a lower alkyl radical having 1 u> 6 carbon atoms.
X is an inorganic or organic anion which stem from alky groups as defined for Rf,

N-R5 formula (Id)
Rs wherein. Rs is R3 or R3' R5 is same as defined hereinbefore.
Ri and R\' are lower alkyl radical having 1 to 6 carbon atoms.
The formula (I) polymers of the present invention can be prepared by a reaction scheme which, for example, involves
(a) Copolymerizing of alkenyl aziactone monomer shown by formula (II) with an ethylenically-unsaturated monomer shown by formula (III) followed by
(b) Ring-opening of aziactone moiety of the copoiymerized polymer with an amine of formula (IV) then
(c) Quaternizing the product of Step (b) with a suitable quaternizing agent such as epichlorohydrin. glycerol monochloro hydrin, C1-C22 fatly alkyl halides, dialkyl sulfates, alkyl tosylate halides and aryl halides.



Formula (IV)
(CH2)n

HN
l7ormula(])

The formula (1) copolymers can be prepared by copolymerization of the formula (11) and (III) monomers using a variety of polymerization methods, such as solution, bulk, suspension and emulsion polymerization methods. The polymerization can be initiated chemically, e.g. by suitable free-radical or redox initiation or by other means, such as heat or incident radiation. As examples of chemical initiators, mention may be made of 2,2'-azobisisobuityronitrile, potassium persulfate, sodium bisulfite, benzoyl peroxide and diacetyl peroxide. It will be appreciated that the chosen means of initiation should be substantially incapable of degrading or otherwise adversely reacting with either reactanls or products of the reaction. Generally, the polymerization should proceed satisfactorily by carrying out the reaction at a temperature between 30°C to 100°C and using less than 5% by weight of initiator, based on the starting weight of the polymerizable monomer or monomers.
The proportions of formula (II) and (III) conomomers can vary widely, for example, in a molar range of from 1:99 to 99:1. In general, the azlactone repeating units will be of primary importance for their versatility as derivatizable units and will be present in the copolymers such that the ratio of "a" and "b" repeating units is in the rage of from 1:9 to 9:1. and especially, from 1:4 to 4:1. Particular ratios can vary depending upon the desired derivatizations to be performed on the respective and different reactive sites.
Useful azlactone monomers and their syntheses are described in U.S. Pat. No. 4.378411, U.S. Pat No. 4695608 and in "Polyazlactones", Encyclopedia of Polymer Science and Engineering. Vol.11, Second Edition. Wiley, N.Y., 1988, pp. 558-571, both of which are incorporated herein by reference.
The present invention can be best understood by the following examples. The following examples are given for purpose of illustration and arc not to be considered as limiting the invention to the embodiments of the invention. Modification will be apparent to those skilled in the art without departing from the spirit or scope of the invention.
Following acronyms are used for the corresponding chemicals for the sake of
convenience.
DMA PA : Dimethylaminopropylamine

GMCH
AIBN
MAPTAC

Glycerol monochloro hydrin 2,2'-azobisisobiiityronitrile Methacrylamidopropyltriammoniumchloride

EXAMPLE 1
Preparation of a novel quaternary polymer of the general formula (V):


18n37
Formula (V)

The quaternary polymer of formula (V) can be prepared by the following steps:
Step I - Preparation of copolymer of vinyl aziactone and acryiamide with 10%
solids.
A 250 ml four-necked flask provided with stirrer, thermometer, reflux condenser and
nitrogen inlet was charged with 9 g (0.0647 mole) of Vinyl Aziactone of the general
formula (Va):

H,C
H,C
CH, ° Formula (Va)

together with 4.6 g (0.0647 mole) of acryiamide. 0.14 g of AIBN and 123.6 g of tertiary butanol. The resulting solution was heated at 75°C for 8 hrs under nitrogen atmosphere. The progress of the reaction was monitored by iodine value titration. After completion of the reaction Step II was followed.

Step II - Ring Opening of Azlactone with Amine.
To the copolymerized reaction mass of step I was added 5.02 g (0.0492 mole) of DMAPA and 3.31 g (0.0123 mole) of stearyl amine and the reaction mass was stirred for another 30 mins to 1 hr at same temperature of 75°C till the estimated theoretical amine value was achieved.
Step 111 - Quaternization
To the reaction mass of step II was added 5.44 g (0. 0492 mole) of GMCH and continued heating at 75°C for another 6-8 hrs. The reaction progress was monitored by analyzing the chlorine content of the reaction mass.
EXAMPLE 2
Preparation of a novel quaternary polymer of the general formula (V) but with 40% solids during copolymerization step. The method of preparation is same as explained in Example I.
EXAMPLE 3
Preparation of a novel quaternary polymer of the general formula (VI):

The method of preparation is same as explained in Example 1 except the mole ratio of vinyl azlactone : acrylamide in the copolymerization step is 1:3.

EXAMPLE 4
Preparation of a novel quaternary polymer of the general formula (VII):
The method of preparation is same as explained in Example I except the amine used
jn the Step II of Example 1 is only DM A PA (no stearyl amine).


Formula (VII)

EXAMPLE 5
Preparation of a novel quaternary polymer of the general formula (VIII):
The method of preparation is same as explained in Example I but instead of
acrvlamide here MAPTAC is used.