Method of preparing cosmetological polymers

Novel organic polymers have a chain carrying active groups, a hydroxyl, alkoxy, halogen, thiol or sulphide group or a second active group being attached as a substituent to a carbon which is in the alpha position with respect to that carrying the first active group. The preparation of these polymers is advantageously effected using polymers carrying epoxide bridges, which are opened by the action of an active cosmetological or other active compound. These polymers are particularly suitable for the protection of the skin against solar radiation, as creams or gels for the skin and for the hair and/or as pigments.

BACKGROUND 
The invention relates to organic polymers carrying active groups chemically 
fixed to the polymer chain, these groups having specific properties, 
particular examples being chromophoric, tensio-active, ion exchange, 
cosmetological, rheological, chelating or other groups. The invention 
includes the uses of polymers provided with such groups, in particular for 
the preparation of pigments, varnishes, paints, ion exchange resins, 
cosmetic products, chromatographic supports and so on. 
In order to provide simplification, the following part of the present 
description relates mainly to cosmetic agents which illustrate the 
invention, but it is to be understood however that the invention is 
applicable to other areas of use, because the active cosmetological groups 
can be replaced in analogous fashion by other active groups. 
For several years, there has been a tendency in cosmetology to utilize 
various active substances, not only as such, in an appropriate excipient, 
but also by fixing them to macromolecules. The main reason for this is 
that the skin tends to absorb various monomeric active compounds, which 
gives the disadvantage of removing a part of these compounds from the 
surface of the skin where their action should occur. On the other hand, 
penetration into the organism can be prejudicial to health in many cases. 
This penetration can be considerably diminished or even totally prevented, 
if the active substance is in the form of a polymer of sufficiently large 
molecular dimensions. Various polymers have thus been employed for this 
purpose, particularly polyacrylates, polymethacrylates and their 
copolymers, especially those with vinyl-pyrrolidone, the polyoxyalkylenes 
and so on. The important point of this technique is the manner in which 
the active cosmetological groups are attached to the polymer chain. This 
has been realised previously through the intermediary of two conjugated 
carboxylic groups: 
##STR1## 
according to French Patent Specification No. 73 23704, or by means of an 
imide group: 
##STR2## 
as described in French Patent Application No. 76 23174. However, this 
technique still needs to be perfected. It is necessary for the activity of 
the groups concerned not to undergo too great a reduction by reason of 
their combination with the polymer and that the product can exhibit the 
requisite solubility for its intended use. 
SUMMARY 
The present invention relates to an improvement in the products indicated 
above. In fact, it allows the formation of a chemical bond between the 
active groups and the macromolecule, whilst conserving good activity of 
the active groups. Moreover, the products according to the invention can 
be made soluble or insoluble, as required, in water or in organic 
solvents. The preferred process of preparation of the products according 
to the invention allows the utilization, as starting materials, of 
products which are easily and economically available. This process renders 
possible the ready fixation of the desired active molecules on the polymer 
chains. It also allows the convenient elimination of undesirable groups, 
contrary to what has occurred in processes of the prior art, particularly 
those which utilize anhydrides. 
The invention can be applied to various types of substances, particularly 
to those whose role is the treatment of the hair or the protection of the 
skin, in particular creams, gels and ultraviolet absorbants, whether or 
not they are products having a decorative or hygienic character. Thus the 
invention is highly utilizable, for example, for the fixation of U.V. 
absorbants or of colourants on various polymers, the latter also 
comprising copolymers. 
One of the important applications of the present invention concerns 
polymers carrying mercaptan groups. It relates more particularly to the 
production of mercaptan polymers, in which the --SH function is located in 
a chain adjacent a carboxylic group, the latter being fixed to the 
macromolecule of a polymer. 
DESCRIPTION OF THE INVENTION 
Polymercaptans are industrial products utilized in various areas, 
particularly for the complexing of heavy metals, with a view to their 
elimination in the form of mercaptides, as cross-linking agents for epoxy 
resins, in sealing joints, for adhesive composition, for treatment of the 
hair or fibres, as ion exchange resins and so on. In view of the utility 
of these polymers, industry has contemplated various processes of 
preparation, but the question of a process which is both economic and 
leads to interesting products still remains unanswered. In particular, a 
method is known which consists in reacting an aliphatic mercapto-acid with 
an acrylic or methacrylic copolymer carrying epoxy groups on the side 
chains attached to the chain of the macromolecule. However, this 
technique, described in U.S. Pat. No. 2,992,210, generally leads to 
partially cross-linked products having a very high content of thiol 
groups. It has also been proposed to introduce --SH groups into vinyl 
chains by the action of sodium hydro-sulphide on polyvinyl chloride (IWATE 
University, Japan), but this reaction is difficult to conduct and must be 
carried out in liquid ammonia. 
The present invention relates to an economical process, which is easily 
carried out and leads to products which can readily be prevented from 
undergoing spontaneous cross-linking and in which the number of mercapto 
groups per macromolecule can be regulated as desired. 
The novel products according to the invention are organic polymers, having 
a chain which carries one or more specific active groups fixed to the 
chain by chemical bonds, characterized in that each of these bonds is 
connected to a carbon atom adjacent to another carbon which carries a 
hydroxyl, alkoxy, halogen, thiol or sulphide substituent or a second 
active group similar to the first. Stated otherwise, the polymers 
according to the invention are characterized by pairs of the 
above-indicated substituents in the alpha position with respect to one 
another, one at least being a specific active group. 
In a preferred form of the invention, the polymer also carries pairs of 
substituents in the alpha position with respect to one another, 
constituted by hydroxyls, halogens and/or thiols alone, i.e. without 
active groups. 
The configuration of the polymers according to the invention can be 
illustrated diagrammatically by a chain: 
##STR3## 
where A designates the recurrent unit of the polymer, the groups R and R' 
being the substituents, defined above, attached to two adjacent carbon 
atoms. It will be understood that the chain can be that of a copolymer: 
##STR4## 
where B and C are other units, which can if required also carry the 
radicals RR'. 
In the products according to the invention, the two adjacent carbon atoms 
carrying the groups RR' can be part of the polymer backbone chain itself 
or they can be located in its side chains. The first case corresponds to 
the configuration: 
##STR5## 
while the second can be represented by the diagram: 
##STR6## 
The polymer chain of a product according to the invention can be that of a 
polyolefin, a polyvinyl compound, a polyoxyalkylene, a polydiene, a 
polysaccharide and so on, if required containing a copolymer. Particularly 
suitable are polyacrylates, polymethacrylates, polypropylenes, 
polyisobutenes and so on, including copolymers, for example 
polyvinyl-pyrrolidone. Unsaturated oligomers derived from the propene or 
isobutene chain are particularly useful. 
In the particular case of active cosmetological groups, these include, for 
example, compounds such as alicyclic dienones, cinnamic derivatives, 
galloyl oleates, p-amino-benzoates, benzophenone, urocanic acid, 
benzylidene-camphor, cyano-acrylic derivatives, salicylic compounds, 
various colourants and so on. As cosmetic agents are particularly well 
known in the art, it is not necessary to give here the formulae of these 
various compounds. A polymer according to the invention can also carry 
several active cosmetological groups of different kinds. 
By way of illustration, the structure is given below of a fragment of a 
polyacrylic ester representing an example of a compound in which two 
adjacent carbon atoms are substituted in accordance with the invention, 
being located in the ester residue of the polymer: 
##STR7## 
As can be seen, in the first and third side chains, of the two carbon 
atoms indicated by asterisks, one carries an OH (R in the formula given 
above), while the second carries the radical of p-methoxy cinnamic acid: 
##STR8## 
which is a specifically active cosmetological compound, in particular for 
the absorption of U.V. This group constitutes the radical R' of the 
formula indicated above. It can also be seen that, in the second side 
chain, the two carbons in the alpha position to one another both carry 
hydroxyl groups which tend to confer solubility on the macromolecule. This 
non-limitative example makes it understandable how, according to the 
invention, a more or less large proportion of the substitutions in the 
alpha position can be made with active cosmetological groups, while 
another part, carrying OH, halogen, alkoxy or SH groups, renders possible 
modification of certain other properties of the molecule and, in 
particular, its solubility. It will be understood that the ratio of 2 
p-methoxy-cinnamic groups per 4 OH groups, in the example of the above 
formula, is in no way limitative. By varying this ratio, products of the 
desired properties can be obtained, particularly insoluble solids or 
polymers soluble in water, alcohol, glycerol and/or other solvents. 
A particularly practical process of preparation of the polymers according 
to the invention consists in utilizing polymers carrying epoxy bridges 
which are opened by reaction with an active compound. The epoxide groups 
can be located within the actual chain of the polymer or at the ends of 
the chain, as is the case for example with epoxided polyisoprene or an 
epoxy resin oligomer. They can be located in a side chain, as is the case 
with glycidyl polymethacrylates or those of other alkyl groups having an 
epoxy function. In one case as in the other, a compound which is active, 
for example cosmetologically, containing reactive hydrogen atoms, is 
reacted with the selected epoxided polymer. 
The reaction in question can be expressed as follows: 
##STR9## 
where Q represents the active cosmetological group. 
This reaction according to the invention is preferably conducted in a 
liquid in which the polymer to be treated has been dissolved. Best yields 
are obtained when operating in the presence of an organic base, 
particularly a triamine, if the active compound is an acid. Depending upon 
the reactivity of the compounds present, operation is effected at a more 
or less elevated temperature, e.g. ranging from 20.degree. to 150.degree. 
C. and particularly from 40.degree. to 80.degree. C. It generally takes a 
time of the order of 1 to 30 hours. 
As can be seen from the above, the properties of the polymer can be 
modified by the nature and proportion of the R and R' radicals introduced 
by opening the epoxy bridges. Thus, if it is possible to replace all the 
epoxy groups by residues of an active compound, by utilizing an 
appropriate proportion of the latter in the reaction with the epoxided 
polymer, it is preferable in general to attach groups only to part of the 
epoxy groups. According to a preferred form of the invention, the 
remaining epoxides are then opened in known manner, for instance by 
hydrolysis, alcoholysis or some other reaction, in order to introduce in 
their place OH radicals and, for example, SH, alkoxy, sulphide, amine, 
second OH, halogen or other groups. Thus, in the particular case of 
opening of the expoxided bridge with HCl, the bridges become: 
##STR10## 
The specific active groups of the agents employed according to the 
invention, in the above reaction, can have one or more reactive hydrogens. 
When it is desired to obtain soluble polymers, it is preferable to use 
groups only having a single reactive hydrogen, because the presence of a 
second can give rise to cross-linking with a second chain of the polymer 
and thus yield an insoluble compound. Nevertheless, such cross-linking can 
be desired in certain cases and then the use of cosmetological or other 
agents with several reactive hydrogens becomes useful. 
The case of groups with several reactive hydrogens is often met with 
colourants which are to be attached to the polymer, within the scope of 
the present invention. Such a case is constituted by colourants carrying 
2--SO.sub.3 H groups, such as are present for example in various diazoic 
colourants derived from naphthalene. In these cases, it is desirable to 
block one of these sulphonic groups in known manner, in order to react 
only one of them with epoxy groups. 
In the examples given above, the reactive hydrogen of the active 
cosmetological group to be attached to the polymer is derived from an acid 
function. This hydrogen can also be that of an amine. For this, the 
NH.sub.2 function of the desired compound can react with the halogenated 
derivative (3) indicated above. A product is then obtained in which the 
part of the molecule indicated with the asterisks in formula (1) takes the 
form: 
##STR11## 
where Q represents the active group of the amine substance utilized. Thus, 
polymers are obtained in which the chain carries both amine groups and 
other active groups, as for example the p-methoxy-cinnamic groups 
illustrated by formula (1) above. 
In the application of the invention to polymercaptans, one process consists 
of eliminating an electropositive or electronegative atom or group of a 
polymer by reaction with, respectively, an electronegative or 
electropositive atom or group of a compound carrying the thiol function, 
and is characterized in that an electropositive atom or group to be 
eliminated is located in the form of a carboxylate. 
Stated otherwise, the process according to the invention makes use of a 
reaction which can be represented, in a general manner, as follows: 
##STR12## 
where X is an electropositive or electronegative atom or group, Y is 
respectively negative or positive, R is an organic group, particularly a 
carboxylic group, which cannot exist when X is electronegative, while Q 
represents another organic group which includes a carboxyl when Y is 
electropositive. As will be understood, the chain: 
##STR13## 
diagrammatically represents a macromolecule, without attempting to 
indicate its particular structure nor the number of lateral RX groups. 
To illustrate this definition, two non-limitative examples are given of 
reactions according to the invention. 
##STR14## 
The reaction (6) corresponds in particular to the attachment of 
mercapto-propionic groups on the chain of a polyvinyl chloride. 
##STR15## 
The latter reaction can correspond, for example, to the attachment of 
1-mercapto-4-butyric groups on the chain of an acrylic or methacrylic 
polymer. This is also the case with polymers or copolymers of acrylic or 
methacrylic acid combined with an alkaline base. 
Thus the invention allows the preparation of novel polymercaptans which can 
include the groups: 
##STR16## 
where n can range from 1 to 30, on the chain of a polymer. 
In a particular embodiment of the invention, the process is carried out in 
such a manner that the group carrying the mercapto function is attached to 
a carbon atom in the alpha position to another carbon atom carrying a 
hydroxyl substituent. The presence of the --OH, thus located in the alpha 
position to the group carrying the --SH, can affect the solubility of the 
product in water and in organic solvents. At the same time, it also makes 
possible modifications of the hydrophilic-lipophilic balance of the 
product in the desired manner. 
This embodiment can be carried out with polymers containing epoxy groups 
which are first opened by means of a reactant capable of attaching an 
electronegative atom or group, for example halogen, sulpho, 
dithiophosphoric or other, to the polymer and then treating the derivative 
obtained by a mercaptocarboxylate of a mineral or organic cation. Polymers 
which are particularly suitable for such a reaction are alkyl 
polyacrylates or polymethacrylates with epoxy groups. In practice, it is 
advantageous to employ copolymers of methyl, ethyl or other alkyl 
acrylates or methacrylates with glycidyl acrylates or methacrylates or 
glycidyl homologues. 
By way of example, the formula (8) is given of a unit of a 50/50 copolymer 
of methyl methacrylate with glycidyl methacrylate: 
##STR17## 
By the action of an appropriate reactant, particularly aqueous HCl, the 
epoxide bridge is opened to give the group: 
##STR18## 
In accordance with the invention, the polymer thus treated is then reacted 
with the mercaptocarboxylate of an organic or inorganic base, for example 
sodium mercaptopropionate, SH--CH.sub.2 CH.sub.2 COONa, which leads to the 
elimination of NaCl and the transformation of the groups (9) into: 
##STR19## 
The process according to the invention can be carried out at variable 
temperatures, preferably ranging from 20.degree. to 100.degree. C., in an 
appropriate solvent. The duration of the reaction naturally depends upon 
the nature of the reactants and the temperature; it is usually in the 
range from 5 to 30 hours. During preparation and storage of the product, 
precautions are taken to avoid all contact with the air, because thiol 
polymers are very sensitive to the action of oxygen. 
In the example of the formulae (8) to (10) above, a copolymer with one mole 
of methyl methacrylate, which does not take part in the reaction, has 
reacted with one mole of glycidyl methacrylate, the epoxy group of which 
reacts with the mercaptocarboxylate utilized. However, depending upon the 
properties sought, in particular according to the number of --SH functions 
which are desired to introduce into the macromolecule, copolymers 
containing variable proportions of glycidyl methacrylate with respect to 
the methyl methacrylate are employed. On the other hand, for a given 
copolymer, the proportion of the epoxide bridges opened can be varied and 
also the proportion of mercaptocarboxylate correspondingly utilized.

The invention is illustrated by the non-limitative Examples which follow. 
EXAMPLE 1 
Attachment of cinnamic groups to the copolymer of methyl methacrylate with 
glycidyl methacrylate. 
The polymer utilized results from the copolymerization of one mole of 
methyl methacrylate with one mole of glycidyl methacrylate. Its molecular 
weight is 50,000 and its epoxy group content is 3.7 milli-equivalents per 
gram. 
15 g of this copolymer was dissolved in 150 ml of distilled 
dimethyl-formamide containing 1.17 g water (130 m.eq.). To this solution, 
10.2 g (0.0688 mole) of cinnamic acid, C.sub.6 H.sub.5 CH.dbd.CH--COOH, 
and 6.9 g (0.0681 mole) of triethylamine were added and the temperature 
was taken up to 80.degree. C. The mixture was maintained at this 
temperature for 20 hours. 
The reaction for opening the epoxide bridges of the polymer by cinnamic 
acid was monitored during the operation by ultraviolet spectrography. This 
confirmed with time a chage in the maximum absorption from the value of 
267 nm to 276 nm, the latter value corresponding to that of the cinnamic 
ester formed. 
When the reaction was completed, the product was slowly poured with 
agitation into 750 ml of sulphuric ether which gave rise to precipitation. 
The product was taken up in a minimum of dimethyl formamide and the 
solution obtained was again precipitated with ether. A very fine white 
powder was thus obtained, which is soluble in methanol and hot ethanol, 
but insoluble in water, glycerol, olive oil and soya oil. 
Measurement of the epoxide residues indicated that the rate of opening of 
the latter exceeded 80%. U.V. analysis of the cinnamic ester, using methyl 
cinnamate as a reference, gave 48% for the proportion of epoxides opened 
by the cinnamic acid. It is thus possible to attribute the opening of 
80-48=32% of the bridges to the hydrolysis reaction. 
In order to open the remaining 20% of the epoxy groups, 10 g of the product 
obtained was dissolved in 50 ml of tetrahydrofuran (THF), to which was 
added 1.5 ml of aqueous HCl containing 0.457 g HCl (12.5 m.eq.). The 
mixture was allowed to stand at ambient temperature for 30 minutes, after 
which precipitation from ether was carried out. This purification was 
repeated by redissolving the precipitate in a minimum of THF, followed by 
a new addition of ether. The powder obtained, after drying, is soluble in 
methanol and in ethanol. It is insoluble in water and in glycerol. 
EXAMPLE 2 
Preparation of a powder insoluble in alcohol. 
5 g of the very fine powder obtained in Example 1, still containing 20% of 
epoxides, that is to say not treated with HCl, was placed in 20 ml of 
sulphuric ether and 5 ml of 1,4-diaminobutane was added. The whole was 
heated under reflux with vigorous agitation for 3 hours. At the end of 
this reaction, the powder was washed several times with distilled water at 
60.degree. C. After drying, the powder, the grain size of which was of the 
order of microns, proved to be insoluble in ether, ethanol, water and 
glycerol. It is suitable for the preparation of anti-solar compositions 
based on solid particles. 
EXAMPLE 3 
The operations were the same as in Example 1, but the polymer solution 
contained a larger quantity of water. 20 g of glycidyl polymethacrylate of 
molecular weight 48,500 was dissolved in 190 ml of distilled dimethyl 
formamide containing 1.43 g water (160 m.eq.). 19.4 g of cinnamic acid and 
13.2 g of trimethylamine were added to the solution. After 20 hours at 
80.degree. C., the solution was poured into 900 ml of ether. The polymer 
precipitated in a thick form which, after drying, yielded a fine powder. 
The remaining epoxide content of this powder was 17%, while 40% of the 
initial epoxide had been opened by the cinnamic acid, as indicated by U.V. 
measurement with, as a reference coefficient, methyl cinnamate. It can 
thus be seen that the remainder, that is to say 100-(17+40)=43% of the 
initial bridges have been opened by hydrolysis. It can be seen that the 
increase in the water content of the diemthyl formamide used, with respect 
to Example 1, caused an increase in hydrolysis such that the product 
obtained became soluble in methanol, THF and hot ethanol. In glycerol, it 
is soluble at 70.degree. C. at the rate of 80 g/l of glycerol. The latter 
solution does not precipitate when it returns to ambient temperature and 
the solution accepts unlimited quantities of water. 
EXAMPLE 4 
Stabilization of the product of Example 3. 
10 g of the product prepared according to Example 3 was put into solution 
in 60 ml of THF and 1.46 g HCl or 40 m.eq. acid in the form of 38% aqueous 
HCl was then added. The reaction for opening 17% of the remaining epoxy 
bridges, in the product, was completed after 2 hours at ambient 
temperature. The polymer was then precipitated by the introduction of its 
solution into 300 ml of ether. After drying, the precipitate had the form 
of an extremely fine white powder. 
It was confirmed that there were no longer any epoxy groups in this powder 
and that the 17% of residues, opened by the action of the HCl, were in the 
form of macromolecular chlorhydrins. The powder is soluble in the same 
solvents as the product of Example 3. 
After two months of storage at ordinary temperature, this powder remained 
soluble and gave no sign of cross-linking commencing, in contrast to the 
product of Example 3, which was not sufficiently stable to be stored. 
The efficacy of the powder of the present Example, from the standpoint of 
absorption of ultraviolet, was determined comparative with that of methyl 
cinnamate. In the 275-278 nm band, for a 27 mg/l methanolic solution of 
the powder, the same absorption was found as with a solution of 8.6 mg of 
methyl cinnamate per liter of methanol. 
Measurement of the stability of the U.V. filter, effected comparatively 
with that of methyl cinnamate, showed that the two products evolve in the 
same fashion with time. 
EXAMPLE 5 
Fixation of cinnamic acid on a polymer in an anhydrous medium. 
20 g of glycidyl polymethacrylate of molecular weight 48,500, having a 
polydispersity of 2.4, were dissolved in 190 g of anhydrous THF. To the 
solution so obtained, 19.4 g of cinnamic acid and 12.1 g of triethylamine 
were added, namely 93 moles of the acid and 85 moles of the amine per 100 
moles of glycidyl methacrylate. The mixture was maintained for 20 hours at 
60.degree. C. 
After precipitation of the polymer with ether and drying of the product, it 
was found in the latter that 84% of the epoxides had reacted. The content 
of cinnamic groups in the product, in solution in methanol, by U.V. at 
.lambda.=278 nm, with the coefficient of absorption of methyl cinnamate as 
reference, indicated a rate of 70% for epoxides having cinnamic groups 
attached. The product is soluble in THF and in methanol, but insoluble in 
ether, water and glycerol. 
EXAMPLE 6 
Suppression of the epoxides of the product of Example 5. 
This operation was effected in two different ways on two separate portions 
of the product. 
(1) 10 g of the product obtained according to Example 5 was dissolved in 
100 ml of anhydrous THF and 50 m.eq. of HCl were added to the solution, in 
the form of the concentrated acid. The solution as allowed to stand for 30 
minutes at about 30.degree. to 40.degree. C., after which the polymer was 
precipitated with ether and washed with the latter. At the end of this 
treatment, the epoxy bridges which subsist in the product of Example 5 
were integrally transformed to chlorhydrins. The final product so obtained 
was soluble in THF and in methanol, but insoluble in ethanol. 
(2) Another 10 g portion of the product of Example 5 was dissolved in 100 
ml of dimethyl formamide and 18 ml of 0.73 N H.sub.2 SO.sub.4 (or 13.2 
m.eq. of acid) was added. The solution was heated to 80.degree. C. for 15 
hours. After cooling, the polymer was precipitated by the addition of 
ether. 
By this operation, all the bridges which were not opened in Example 5 had 
undergone hydrolysis and replacement of the groups: 
##STR20## 
The resultant product, washed with ether and dried, is soluble in THF and 
methanol. It is insoluble in water and glycerol. It can be seen that 
hydrolysis (2), in place of chlorhydrination (1), rendered the product 
soluble in ethanol. 
EXAMPLE 7 
The preparation of Example 5 was repeated, but without the addition of 
triethylamine. 
This confirmed that only 16% of the epoxide of the glycidyl 
polymethacrylate used had reacted. After measurement by U.V. at 
.lambda.=278 nm of the reaction product, 9% of the initial epoxides had 
retained cinnamic groups. 
When treated with HCl, as in Example 6(1), to transform all the remaining 
epoxy bridges to chlorhydrin groups, the product became soluble in 
ethanol. 
On the other hand, hydrolysis with 0.73 N H.sub.2 SO.sub.4, with 6 H.sup.+ 
ions per 10 epoxy bridges, as in Example 6(2), led to a product soluble in 
water. 
It can thus be seen that with more than 80% of the initial epoxides 
transformed into the groups: 
##STR21## 
solubility in ethanol is obtained, while the same proportion of 
##STR22## 
groups provides solubility in water. 
EXAMPLE 8 
Attachment of cinnamic groups to polyisobutene. 
A polyisobutene of molecular weight 800 determined by tonometry, in the 
form of an oil having 2.1 unsaturated groups per 1000 g, was subjected to 
epoxidation with peracetic acid in well known manner. 
The epoxided oil contained 1.15 epoxy groups per 1000 g. 5.3 g of 
trans-methoxycinnamic acid, CH.sub.3 OC.sub.6 H.sub.4 CH.dbd.CHCOOH, and 
1.61 g of triethylamine were added to 20 g of this oil dissolved in 200 ml 
THF and then the mixture was maintained at 60.degree. C. for 15 hours. 
Then, the solvent was removed under vacuum. After taking up the product in 
chloroform and washing with a solution of sodium bicarbonate and then with 
water to neutrality, the solution was dried and then the solvent was 
evaporated to separate the oily product formed. This showed that 80% of 
the epoxy bridges of the polyisobutene had been opened. 
After treatment with 38% HCl in THF solution, as in the preceding examples, 
the product contained 1 methoxycinnamic group per 1200 g, viz about 15% by 
weight, or 1 group per 18 isobutene units. 
The maximum absorption of light, determined for the product in a mixture of 
75 parts hexane and 25 parts ethanol, was obtained with wavelengths of 
around 306 to 308 nm. 
EXAMPLE 9 
Attachment of trans-paramethoxy cinnamic acid to the polymer. 
20 g of the same glycidyl polymethacrylate as in Example 5 were dissolved 
in 200 ml of anhydrous THF. To the solution obtained, which thus contained 
130 m.eq. of epoxides, 130 m.eq. of trans-paramethoxycinnamic acid and 52 
m.eq. of triethylamine were added. The mixture was maintained at 
60.degree. C. for 20 hours, after which the polymer was precipitated with 
ether and then dried. Analysis of the dried product indicated the 
attachment of methoxycinnamic acid to 90% of the initial epoxy groups of 
the polymethacrylate employed. This product is insoluble in water and in 
cold methanol, but dissolves in the latter in the hot. 
In the manner described under (2) in Example 6, the product obtained was 
hydrolysed with aqueous H.sub.2 SO.sub.4 in dimethylformamide. After this 
hydrolysis, the product became soluble in cold ethanol, but remained 
insoluble in water. It can thus be seen that attachment of 90% of 
p-methoxycinnamic acid groups to the polymer is too high for the formation 
of --OH groups, in place of the remaining epoxy groups, to be able to 
yield solubility in water. 
EXAMPLE 10 
The operations were the same as in Example 9, except that the proportion of 
catalyst, triethylamine, was reduced to a quarter, that is to say, it was 
reduced from 52 to 13 m.eq. 
It was then found, after precipitation from ether and drying, that there 
was attachment of p-methoxycinnamic acid to 24% of the initial epoxy 
groups. The maximum absorption was located at 312 nm. The product was 
insoluble in water, but became soluble after sulphuric hydrolysis in 
aqueous medium, effected as in Example 9. Thus, solubility in water can be 
obtained by the creation of a larger number of hydroxyl groups than in 
Example 9. 
EXAMPLE 11 
Mercaptan modification of a polymer carrying methoxycinnamic groups. 
In the manner described in Examples 9 and 10, a glycidyl polymethacrylate 
was prepared, having 22% of its epoxy groups opened by 
trans-paramethoxycinnamic acid. 20 g of this product of 86 m.eq. of 
epoxides was put into solution in 200 ml of tetrahydrofuran. 6.84 g, that 
is to say 90 m.eq., of propylmercaptan and 5.6 m.eq. of KOH dissolved in 7 
ml of butanol were added. The mixture was heated to 60.degree. C. for 1/2 
hour. After cooling, 50 m.eq. of 38% aqueous HCl were added and, after 1/2 
hour, the medium was neutralized with potash. The KCl formed was separated 
by filtration. 
After precipitation of the polymer with ether, it was confirmed that 
virtually all the epoxide groups previously present adjacent the 
methoxycinnamic groups had been opened by the propylmercaptan. The 
sulphide functions thus attached can be transformed into sulphonium, 
sulphoxide or other sulphur-containing groups. They permit regulation of 
the solubility in water and other properties of the products. 
EXAMPLE 12 
Attachment of salicylic groups to a polymer. 
In order to obtain an ultraviolet filter, salicylic acid was attached to 
glycidyl polymethacrylate, as in Example 5. 
In order to avoid the action of the OH of the salicylic acid on the epoxy 
groups of the polymer and not to allow cross-linking to occur, operation 
was carried out so as to attach only a minor proportion of this acid. For 
this, HO--C.sub.6 H.sub.4 --COOH was reacted with the polymer in the 
absence of a catalyst. 
130 m.eq. of salicylic acid was reacted in 200 ml of tetrahydrofuran with 
130 m.eq. of the epoxide in the form of glycidyl polymethacrylate. After 
44 hours at 60.degree. C., the mixture was treated with 1000 ml of 
sulphuric ether, which dissolved the remaining salicylic acid, while also 
precipitating the modified polymer. Washed and dried, the product still 
contained 75% of its initial epoxides, while 25% of them had attached 
salicylic acid to give groups: 
##STR23## 
In a 50/50 chloroform/methanol mixture, this product had a maximum 
absorption of light at a wavelength of 306 nm. 
Hydrolysis. 
Hydrolysis of 6.6 g of the modified polymer, obtained as indicated above, 
was effected with aqueous sulphuric acid in 60 ml of THF, with the 
molecular ratios: H+/epoxy=0.9 and H.sub.2 O/epoxy=73. The solution was 
heated to 60.degree. C. for 40 hours. Precipitated with ether and dried, 
the hydrolysed product was soluble in water, methanol, ethanol and 
glycerol. 
EXAMPLE 13 
Attachment of a colourant material on a copolymer of vinyl-pyrrolidone with 
glycidyl methacrylate. 
The copolymer utilized contained 95% weight of polyvinyl pyrrolidone. It 
was dissolved in dimethyl formamide. The colourant was Naphthol Yellow: 
##STR24## 
3 moles of this colourant were employed per mole of methacrylate, that is 
to say per epoxy group present in the polymer. The mixture was heated to 
70.degree. C. for 5 hours, after which the polymer was precipitated by 
introduction of the solution into heptane. The precipitate was yellow. It 
was suitable as a pigment for cosmetological utilization and had no 
toxicity. 
Similar properties were obtained with eosinic and azinic colourants. 
EXAMPLE 14 
Attachment of a diazoic colourant. 
To 6 g of the copolymer comprising 44 mole percent of methyl methacrylate 
and 56 mole percent of glycidyl methacrylate, molecular weight 50,000, 
dissolved in 100 ml of dimethyl formamide, 4.63 g of colourant 491/CB/I 
(commercial denomination) of the formula: 
##STR25## 
was added. The mixture was heated to 70.degree. C. for 9 hours. After 
cooling, 2.9 ml of a 38% aqueous solution of HCl was added and the mixture 
was allowed to stand at ambient temperature for 1/2 hour. By precipitation 
from water, a very fine reddish-violet powder was obtained. The excess of 
the colourant was extracted by soxhlet apparatus by means of water. The 
polymer so obtained contained 9.6% of the initial colourant. In methanol, 
this product has an absorption of light at .lambda.=525 nm, as against 500 
nm for the initial colourant. The polymer thus coloured is insoluble in 
water. In acetone, it gives an excellent nail varnish. 
EXAMPLE 15 
Attachment of a colourant to a copolymer. 
The copolymer is that of methyl methacrylate with glycidyl methacrylate, as 
mentioned in Example 14. 5 g (or 18.6 m.eq. of epoxide) was dissolved in 
30 ml of dimethyl formamide. Also, 50 ml of a solution in the same solvent 
of 4.29 g of Sulphacide Yellow 5 R.L. light, of the formula: 
##STR26## 
was prepared. The two solutions were combined and the mixture was heated 
without agitation for 24 hours at 70.degree. C. 
The final product was isolated by precipitation from water. A series of 
washings with distilled water eliminated the greater part of the colourant 
which was not combined with the polymer. These washings were each effected 
at 70.degree. C. for 45 minutes. After purification completed by 
methanolic soxhlet extraction, 12 9 g of the colourant was found to be 
fixed per 100 g of product. Measurement was effected at 370 nm. 
EXAMPLE 16 
The polymer employed was a copolymer of 1 mole of methyl methacrylate with 
1 mole of glycidyl methacrylate. Its molecular weight was 60,000 and its 
content of epoxide groups was 3.8 m.eq. per gram of product. 
In a reactor, 35 g of this copolymer, that is 133 m.eq. of epoxide, was 
dissolved in 300 ml of distilled nitrogen-degassed dimethyl formamide. 1.5 
times the stoichiometric proportion of concentrated HCl, viz. 13.4 g of a 
38% aqueous solution of HCl, was added. The mixture was allowed to stand 
at ambient temperature for 1 hour. The epoxides were thus transformed into 
chlorhydrins. 
A solution of 31 g of mercaptopropionic acid neutralized with caustic soda 
(292 m.eq. of this acid with 292 m.eq. of NaOH) in 50 ml of 
doubly-distilled nitrogen-degassed waer was then poured into the reactor. 
The temperature of this mixture in the reactor was taken to 75.degree. C. 
and maintained at this value for 24 hours, with an energetic input of 
nitrogen. 
At the end of the reaction, the product was poured into degassed water, 
well deprived of oxygen, which had the effect of precipitating the 
polymercaptan formed. This precipitate was washed with water to effect 
elimination of the excess carboxylate and the NaCl formed. Drying of the 
precipitate was effected at 45.degree. C. under 1 mm of Hg for 24 hours. 
The product so obtained was totally soluble in tetrahydrofuran, which 
proved that it is free from cross-linking. Its structure by statistical 
distribution corresponds to the formula: 
##STR27## 
in which y, i.e. the thiol function units, constitutes 24 molar percent of 
the whole. The product is stored under nitrogen, preferably in the cold 
and in the absence of light. 
EXAMPLE 17 
As in Example 16, 35 g of the same copolymer dissolved in 300 ml of 
tetrahydrofuran was used. 160 m.eq. of chloracetic acid and 100 m.eq. of 
triethylamine were added to it and then the mixture was heated to 
60.degree. C. for 30 hours. The solution was then cooled to 20.degree. C. 
and 200 m.eq. of HCl were added in the form of a 38% aqueous solution. 
After 1/2 hour, the mixture was poured into water, where it precipitated 
and was then washed and dried. The precipitate of the polymer was 
redissolved in 300 ml of distilled nitrogen-degassed dimethyl formamide. 
To the solution obtained, 50 ml of doubly-distilled water containing 292 
m.eq. of sodium mercaptopropionate were added. The whole was heated to 
75.degree. C. for 24 hours. The product was then treated as in Example 1. 
In addition to the monomeric units of Example 16, the unit below was then 
found in the polymer: 
##STR28## 
The sum of the units carrying an --SH function, i.e. the sum of y+q, is 34 
molar percent, while the sum of the unreacted chlorinated units was 12 
molar percent. 
EXAMPLE 18 
The starting polymer was polyvinyl chloride. 2 g of this polymer was 
dissolved in 50 ml of deoxygenated dimethyl formamide. To this solution 
1.34 g of sodium mercaptopropionate dissolved in 15 ml of deoxygenated 
absolute methanol was added, the mixture being maintained at 70.degree. C. 
for 22 hours. 
At the end of this time, the modified polymer was recovered by 
precipitation from water under nitrogen atmosphere. It was purified by 
washing with water and then with methanol. The product obtained contained 
0.7 m.eq. SH per gram. 
A 50 g/l solution of this polymer in tetrahydrofuran gelled when oxygenated 
water was added. This confirmation was carried out by adding 1 ml of 
2-vol. oxygenated water to 5 ml of the solution. 
Gelification can also be produced by the addition of a solution of iodine 
in dimethyl formamide. 
EXAMPLES 19 TO 23 
Polymers were prepared in the manner described in Example 16, but with 
variable proportions of sodium mercaptopropionate at different 
temperatures and durations. The table below indicates the final 
compositions in the units x, y and z of the formula (11), as a function of 
the factors indicated. The second column gives the number of millimoles of 
units of chlorinated monomeric groups z, while the third column gives the 
corresponding number of millimoles of mercaptopropionate used. 
TABLE 
______________________________________ 
m. moles mer- Final Composition 
Ex. m. moles captopropio- Time molar % 
No. z nate .degree.C. 
h x z y 
______________________________________ 
19 3.5 3.5 40 20 51.8 44.1 4.0 
20 3.5 7.0 " " 51.9 40.8 7.3 
21 7.0 " 60 " 51.8 42.0 6.2 
22 3.6 3.6 80 22 " 29.6 18.6 
23 7.2 " " 24 51.9 37.0 11.1 
______________________________________ 
It can be seen that the process according to the invention allows 
regulation as desired of the proportion of units with --SH groups in the 
final polymer. 
EXAMPLE 24 
Application of the product obtained according to Example 16 to the 
elimination of heavy metals. 
To an aqueous solution containing 1 mg of each of the cations of Cu.sup.++, 
Ni.sup.++ and Cr.sup.+++ per liter, there was adder per liter 10 mg of the 
polymercaptan prepared according to Example 1, in the form of a 10% 
solution in tetrahydrofuran. After 2 hours of contact in the solution, 
filtered using active carbon, the remaining traces of these cations were 
measured by atomic absorption spectrophotometry. 
There were then found: Cu.sup.++ : less than 0.01 mg/l, Ni.sup.++ : 0.02 
mg/l and Cr.sup.+++ : less than 0.01 mg/l. 
It is thus seen that the complexing of the three heavy metals by the 
polymercaptan according to the invention allows elimination of more than 
99% of the copper and the chromium, as well as 98% of the nickel.