CA1236639A - Quaternary nitrogen containing polyvinyl alcohol polymers for use in skin conditioning, cosmetic and pharmaceutical formulations - Google Patents
Quaternary nitrogen containing polyvinyl alcohol polymers for use in skin conditioning, cosmetic and pharmaceutical formulationsInfo
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- CA1236639A CA1236639A CA000463380A CA463380A CA1236639A CA 1236639 A CA1236639 A CA 1236639A CA 000463380 A CA000463380 A CA 000463380A CA 463380 A CA463380 A CA 463380A CA 1236639 A CA1236639 A CA 1236639A
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- polyvinyl alcohol
- weight
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Abstract
Abstract Polyvinyl alcohol polymers having pendant cationic quaternary nitrogen containing groups provide for a film forming moisture barrier in skin conditioning lotions, ointments, cosmetic conditioning treatments and pharmaceutical formulations.
Description
foe ~UATEPllARY NITROGEN CONTINUITY
POLYVINYL ALCOHOL PYRES FOR USE III SKIN
CONDITION lug, COSMETIC AND PHA~IACEUTICAL FEALTIES
The present invention is directed to skin conditioning 5 polymers which when applied to skin form thin films which aid in reducing moisture loss. The invention relates on general to film forming polyvinyl alcohol polymer derivatives end specifically to those having certain cat ionic qua ternary nitrogen containing pendant groups. Of particular interest are polymers having a 10 polyvinyl alcohol backbone or base chain with pendant substituent qua ternary ammonium groups attached through oxygen linkages to the chain and spaced at random along the base chain. As a result of the presence of these qua ternary amm~nium groups in the polymer, thin film coatings on animal skin penetrate the outer layers of 15 the skin to provide sufficient adhesive properties while remaining sufficiently elastomeric to avoid discomfort after drying. While the thin films act as a partially impenetrable barrier to prevent loss of moisture by evaporation they also behave as moisture retainers through the possible formation of hydrates at the 20 qua ternary anl~onium sites and by inclusion of water molecules through hydrogen bonding on the hydrophilic polymer matrix. In general the compositions are made by treating readily available polyvinyl alcohol polymers with hydroxy reactive compounds containing quaternized anonym groups linked thereto.
It is an object of the invention to provide for a quarter nary nitrogen containing polyvinyl alcohol polymer base chain (having a number average molecular weight of at least 2,00Q
and preferably up to about 200,000 and higher when unmodified) and a random distribution of a multiplicity of oxy-linked pendant 30 groups having the general formula:
:: :
-R-N+RlR2R3A
::
, `, , .: . Jo .
.
~36~39 wherein R is alkaline, substituted alkaline preferably hydroxyalkylene, or acylene of formula weight- ranging from 14 to about 3,000, Al, R2, R3 are alkyd or arylalkyl radicals having 1-20 carbon atoms which may be the same or difîerer.t, ' A is an anion, such that the total nitrogen content in the resin polymer ranges from 0.012-7.0% by weight. Another object is to provide for a 10 preferred process for the synthesis of such compositions. It is still another object to provide for aqueous solutions containing 0.1-307~ by weight of these polymers which are useful in skin conditioning lotions, ointments, cosmetic and pharmaceutical formulations for application to hair, skin and nails. Another 15 object is to provide for a film forming polymer which also performs as a dispersant for particulate in such formulations.
R in the above formula may be selected from alkyd groups such as ethylene, ethylene, propylene, battalion, pentylene, hexylene, ethylhexylene, dodecylene, tetradecylene, hexadecylene, 20 octadecylene, and substituted alkyd groups such as hydroxy-propylene, hydroxybutylene, acutely, propionyl, bitterly, octal decanoyl, and octadecenoyl and their equivalents.
Al, R2, and Pi may be selected from the alkyd groups such as methyl, ethyl, propel, bottle, ponytail, Huxley, octal, decal, 25 dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, phonology and bouncily and their equivalents.
may be selected from a large number of anions such as chloride, bromide, iodide hydroxide lower alkylsulfate (1-6 carbon atoms), tetrafluoroborate, nitrate and per chlorate to name 30~s~few.
The qua ternary nitrogen containing polyvinyl alcohol I; polymer compositions of the invention may be represented by a typical polymer segment having the following idealized structural formula ::
:
- -:
' ~2~63~
POLYVINYL ALCOHOL PYRES FOR USE III SKIN
CONDITION lug, COSMETIC AND PHA~IACEUTICAL FEALTIES
The present invention is directed to skin conditioning 5 polymers which when applied to skin form thin films which aid in reducing moisture loss. The invention relates on general to film forming polyvinyl alcohol polymer derivatives end specifically to those having certain cat ionic qua ternary nitrogen containing pendant groups. Of particular interest are polymers having a 10 polyvinyl alcohol backbone or base chain with pendant substituent qua ternary ammonium groups attached through oxygen linkages to the chain and spaced at random along the base chain. As a result of the presence of these qua ternary amm~nium groups in the polymer, thin film coatings on animal skin penetrate the outer layers of 15 the skin to provide sufficient adhesive properties while remaining sufficiently elastomeric to avoid discomfort after drying. While the thin films act as a partially impenetrable barrier to prevent loss of moisture by evaporation they also behave as moisture retainers through the possible formation of hydrates at the 20 qua ternary anl~onium sites and by inclusion of water molecules through hydrogen bonding on the hydrophilic polymer matrix. In general the compositions are made by treating readily available polyvinyl alcohol polymers with hydroxy reactive compounds containing quaternized anonym groups linked thereto.
It is an object of the invention to provide for a quarter nary nitrogen containing polyvinyl alcohol polymer base chain (having a number average molecular weight of at least 2,00Q
and preferably up to about 200,000 and higher when unmodified) and a random distribution of a multiplicity of oxy-linked pendant 30 groups having the general formula:
:: :
-R-N+RlR2R3A
::
, `, , .: . Jo .
.
~36~39 wherein R is alkaline, substituted alkaline preferably hydroxyalkylene, or acylene of formula weight- ranging from 14 to about 3,000, Al, R2, R3 are alkyd or arylalkyl radicals having 1-20 carbon atoms which may be the same or difîerer.t, ' A is an anion, such that the total nitrogen content in the resin polymer ranges from 0.012-7.0% by weight. Another object is to provide for a 10 preferred process for the synthesis of such compositions. It is still another object to provide for aqueous solutions containing 0.1-307~ by weight of these polymers which are useful in skin conditioning lotions, ointments, cosmetic and pharmaceutical formulations for application to hair, skin and nails. Another 15 object is to provide for a film forming polymer which also performs as a dispersant for particulate in such formulations.
R in the above formula may be selected from alkyd groups such as ethylene, ethylene, propylene, battalion, pentylene, hexylene, ethylhexylene, dodecylene, tetradecylene, hexadecylene, 20 octadecylene, and substituted alkyd groups such as hydroxy-propylene, hydroxybutylene, acutely, propionyl, bitterly, octal decanoyl, and octadecenoyl and their equivalents.
Al, R2, and Pi may be selected from the alkyd groups such as methyl, ethyl, propel, bottle, ponytail, Huxley, octal, decal, 25 dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, phonology and bouncily and their equivalents.
may be selected from a large number of anions such as chloride, bromide, iodide hydroxide lower alkylsulfate (1-6 carbon atoms), tetrafluoroborate, nitrate and per chlorate to name 30~s~few.
The qua ternary nitrogen containing polyvinyl alcohol I; polymer compositions of the invention may be represented by a typical polymer segment having the following idealized structural formula ::
:
- -:
' ~2~63~
2 1R2R3A Jo CH2CHOH-)m(CH2CHORN+RlR2R3A-)] -where n = 20-3000, and m = 0-600, and ' R, Al, R2, R3, and A- are the same as described above.
' Illustrative of the types of numerous pendant qu~ternary groups linked by oxygen as randomly distributed units in the polyvinyl alcohol base chain may be given as follows:
(l) -CH2CH(OH)CH2N (C~3)3 ( 2 [SHEA (C~3)3Cl ]O)nCH2CH(OH)CH2N+(C~3)3Cl-n = 1-20
' Illustrative of the types of numerous pendant qu~ternary groups linked by oxygen as randomly distributed units in the polyvinyl alcohol base chain may be given as follows:
(l) -CH2CH(OH)CH2N (C~3)3 ( 2 [SHEA (C~3)3Cl ]O)nCH2CH(OH)CH2N+(C~3)3Cl-n = 1-20
(3) -(COUCH (CH2CH3)3Br
4) -CH2CH(OH)C~2ll (CH3)2(CH2P ) ( ) CH2CH2~l (cH3)(cH2c~3)(cH2ph)cH3so4 where Pi = phenol.
While the above structures serve to illustrate the types 15 of pendant qua ternary ammonium groups which can be added to the polyvinyl alcohol base chain it is apparent to one skilled in the art that many other arrangements of similar chemical structure can be easily incorporated. It has been found that each of the above types of groups used alone or in combination with one or more of Thea others as a substituent on the polyvinyl alcohol base chain yields the desired combination of products having useful moisture barrier properties especially whorl the nitrogen content of the final product ranges from 0.01%-7% and preferably .01-3~ by White Depending on the type of radical attached to the nitrogen.
2~5 of~the~quaternary group the effective range of the nitrogen content could be even more specific It has been found for ' ~L236~
example what when the Al, I R3, in the above general formulas are all methyl radicals the effective nitrogen content may range from 0.1-3~ by weight.
While many techniques have been employed in the art to add 'substituent qua ternary groups to vary polymer charge four preferred methods for attaching the substituent groups to polyvinyl alcohol im701ve the reaction of the hydroxy groups Or polyvinyl alcohol with an epoxy (oxirane) group or a halohydrin group in aqueous solution, or a low molecular weight alkyd alcohol 10 ester of the sllbstituent in a bipolar aprotic solution or an acid halide in either a bipolar aprotic solvent or a two phase system in the presence of base catalyst or acid catalyst when appropriate.
While a number of methods may be utilized for the 15 preparation of the PEA derivatives described in this invention, the use of non-aqueous solvents such as dim ethyl formamide or similar polar materials is possible, but generally these solvents must be thoroughly removed from the final product. The use Or aqueous solvents or mixed aqueous systems is preferable but, in 20 this case, yields must be optimized because of competitive reactions of the qua ternary ammonium compound with water as well as PEA hydroxyls in the presence of catalyst. Improved yields can be obtained by increasing the PEA concentration in water, adding the oxirane compound as a concentrate and reducing to a minimum 25 the amount of base used to catalyze the addition reaction. Salt formed during the reaction is preferentially removed from the final product, since it may have a deleterious effect on the skin moisture barrier properties and its formulation. It has also been found that the pi of the derivatized PEA may affect the skin 30 moisture barrier properties as well as the substantivity to skin..
It is generally desirable to work in a pi range between 2-10 preferably from 5-9.
The product can be obtained in a dry form by precipitation, filtering, drying and grinding. The precipitation 35 is accomplished by adding the reaction mixture to a nonsolvent such as acetone, methanol, ethanol and the like. The product also finds use in the form of the aqueous solution or suspension which :,...
:
, ~236~39 can preferably be obtained by dwelling the reaction mass to free it from salts and low molecular weight unrequited intermediates.
To obtain a better understanding of the preparative techniques found to be most satis~aetory attention is dray to the following
While the above structures serve to illustrate the types 15 of pendant qua ternary ammonium groups which can be added to the polyvinyl alcohol base chain it is apparent to one skilled in the art that many other arrangements of similar chemical structure can be easily incorporated. It has been found that each of the above types of groups used alone or in combination with one or more of Thea others as a substituent on the polyvinyl alcohol base chain yields the desired combination of products having useful moisture barrier properties especially whorl the nitrogen content of the final product ranges from 0.01%-7% and preferably .01-3~ by White Depending on the type of radical attached to the nitrogen.
2~5 of~the~quaternary group the effective range of the nitrogen content could be even more specific It has been found for ' ~L236~
example what when the Al, I R3, in the above general formulas are all methyl radicals the effective nitrogen content may range from 0.1-3~ by weight.
While many techniques have been employed in the art to add 'substituent qua ternary groups to vary polymer charge four preferred methods for attaching the substituent groups to polyvinyl alcohol im701ve the reaction of the hydroxy groups Or polyvinyl alcohol with an epoxy (oxirane) group or a halohydrin group in aqueous solution, or a low molecular weight alkyd alcohol 10 ester of the sllbstituent in a bipolar aprotic solution or an acid halide in either a bipolar aprotic solvent or a two phase system in the presence of base catalyst or acid catalyst when appropriate.
While a number of methods may be utilized for the 15 preparation of the PEA derivatives described in this invention, the use of non-aqueous solvents such as dim ethyl formamide or similar polar materials is possible, but generally these solvents must be thoroughly removed from the final product. The use Or aqueous solvents or mixed aqueous systems is preferable but, in 20 this case, yields must be optimized because of competitive reactions of the qua ternary ammonium compound with water as well as PEA hydroxyls in the presence of catalyst. Improved yields can be obtained by increasing the PEA concentration in water, adding the oxirane compound as a concentrate and reducing to a minimum 25 the amount of base used to catalyze the addition reaction. Salt formed during the reaction is preferentially removed from the final product, since it may have a deleterious effect on the skin moisture barrier properties and its formulation. It has also been found that the pi of the derivatized PEA may affect the skin 30 moisture barrier properties as well as the substantivity to skin..
It is generally desirable to work in a pi range between 2-10 preferably from 5-9.
The product can be obtained in a dry form by precipitation, filtering, drying and grinding. The precipitation 35 is accomplished by adding the reaction mixture to a nonsolvent such as acetone, methanol, ethanol and the like. The product also finds use in the form of the aqueous solution or suspension which :,...
:
, ~236~39 can preferably be obtained by dwelling the reaction mass to free it from salts and low molecular weight unrequited intermediates.
To obtain a better understanding of the preparative techniques found to be most satis~aetory attention is dray to the following
5 generalized and specific preparations which are intended to illustrate but not limit the invention and wherein all proportions mentioned are based on weight unless otherwise specified.
General Preparation I
A flask equipped with a water cooled condenser, lo mechanical stirrer and thermometer is charged with polyvinyl alcohol and distilled water. The polyvinyl alcohol (POW) which is generally a commercially available product prepared by hydrolysis of polyvinyl acetate may have from 0 to 25% residual acetate groups, preferably from 2 to 15% and the number average molecular 15 weight may range from 2,000 to 200,000 and higher and preferably from 25,000 to 150,000. In addition, and for the purpose of this invention, a polyvinyl alcohol base chain may include up to I by weight of another comonomer such as vinyl pyrolid~ne, acrylic and methacrylic acids and esters thereof. The aqueous slurry is 20 heated to 80-90C and held for 1 hour or until the polyvinyl alcohol is completely dispersed or salivated. A catalytic amount of aqueous base such as alkali hydroxide such as sodium or potassium hydroxide is then added and the solution cooled to 40-90C. At this point 2,3-epoxypropyltrialkylammonium halide, 25 either in aqueous solution or crystalline form, may be added incrementally or all at once. This reagent is typically used in 0.003-l.0 mow ratio preferably from 0.10-0.3 mow per mow of hydroxyl group on the polyvinyl alcohol base chain. The entire solution is then stirred for an additional period typically 4 30 hours at 60C after which the solid product may be recovered.
Recovery is accomplished by one of two general techniques. The solution can be poured into a polymer non-solvent to precipitate solid product from aqueous solution. Alternatively I, 3L236~
the solution may be dialyzed through a simpers membrane and the purified aqueous polymer used as obtained or precipitated out.
The precipitation is preferably accomplished either if.
acetone or in methanol affording yields up to I or better by weight after drying. Depending on reaction conditions the precipitated products have a nitrogen content in the range of 0.01-7~.
In the purification by dialysis the reaction mixture is freed from all species below a certain molecular weight. Two lo methods may be used one a static and one dynamic. In the static method the reaction mixture is placed inside a commercial semi-porous dialysis tube and the tubes are submerged in distilled water typically for periods of I to 48 hours. The contents of the tubes are then recovered and the product may be used as is.
15 In the dynamic system a pressure pump is used to Jove water iron.
the reaction mixture through a simpers membrane. The water carries out any inorganic and lo- molecular weight organic. The resulting concentrated product stream is then collected.
General Preparation II
A flask equipped as described in General Preparation 1 is charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80-90C and held for one hour or until the polymer is completely salivated. A catalytic amount of aqueous alkaline hydroxide such as sodium or potassium hydroxide is added 25 and the pot cooled to 60-65C. At this point, (chlorohydroxy-propyl)trimeth~lammonium halide, either in aqueous solution or crystalline form, is added either incrementally or all at once.
This reagent is typically used in Lowe mole ratio preferably from OWE mole per mole of hydroxyl group on the polyvinyl 30 alcohol base chain. The entire solution is then stirred at 40-~90C for an additional period, typically four hours. The product ; is then recovered by one of the methods described in GeneralPr~eparatioD I.
::
.
General Preparation III
In preparing qua ternary ammonium groups linked to the polyvinyl alcohol base chain through ester linkages it is preferred to prepare thrill using a transesterification technique.
In a typical reaction a four-neck one liter round bottom flask equipped with a thermometer, mechanical stirrer, water cooled condenser and a nitrogen sparser is charged with polyvinyl alcohol as described in the above General Preparation I, dim ethyl-formamide, a trialkylalkoxycarbonyl ammonîum halide, and a small 10 amount of a transition metal salt as catalyst as manganese acetate for example. The entire dispersion is then heated to a temperature of Luke for 2 to 24 hours preferably 3 to 6 hours. Nitrogen is used as a carrier gas to remove the alcohol formed during the esterification reaction. The solution is then 15 cooled to ambient temperature and poured into a polymer nonsolvent such as for example methanol, ethanol or acetone. The resulting precipitate is collected by filtration, washed, shredded mechanically and dried under vacuum to afford a nearly white product with a desired nitrogen content.
Jo ..
20 General Preparation IV
A flask equipped as described in General Preparation I
is charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80-90C and held for one hour or until the polymer is completely dispersed or salivated. A catalytic 25 amount of an acid such as sulfuric acid or aluminum hydrosilicate or any proton acid or Lewis acid is added and the pot cooled to 40-90C. At this point 2,3-epoxypropyltrialkyla~r~onium halide may be added incrementally or all at once. This reagent is typically used in 0.003-1.0 mole ratio preferably from 0.1-0.3 mow per mow of 30 hydroxyl group on the polyvinyl alcohol base chain. The entire solution lo then stirred for an additional period typically 4 ::
~L23~t';39 hours at 60C aster itch thy solid product may be recovered by one of the methods described in General Preparation I.
The following examples and preparations serve to illustrate but not limit the invention. All proportions used 5 Rafferty parts by weight unless otherwise specified.
r Preparation A
(Chlorohydroxypropyl)trimethylammonium chloride A one-liter flask equipped with dropping funnel, mechanical stirrer, thermometer a condenser was charged with 10 epichlorohydrin (95 grams, 1.0~ molt and placed in an isothermal bath at 18C. Aqueous trimethylamine (238.7 grams, 25% by weight, 1.01 molt was then added drops over a 3 hour period maintaining the temperature below 25CC when the addition was complete the solution was allowed to stir overnight at ambient temperature.
Example 1 RN RlR2R3A = -CH2-CH(OH)CH2N(CH3)3Cl A flask equipped as described in General Preparation I
was charged with 44 grams polyvinyl alcohol (commercially available) having a molecular weight of 126,000 (98~ hydrolyzed -20 2% acetate) and 400 milliliters of distilled water. The resulting slurry was heated to 85C and held for 1 hour. The polymer dissolved completely to afford a pale yellow transparent solution.
Potassium hydroxide (3.0 gram, 0.11 molt in water (30 milliliters) was then added and the solution cooled to 60C. Aqueous (sheller-25~hydroxypropyljtrimethylammdnium chloride (78 milliliters of 4~7~ boutiques solution prepared according to Preparation A), was then added all at once and the entire solution was heated to 6Q-65C~for 4 additional hours. The warm solution was poured with ::: :` : :
:
~;~36639 g stirring into acetone (2.0 liters) and allowed to stand. 63.5 grams OX colorless solid precipitate was collected by filtration shredded mechanically and dried under vacuum.. The nitrogen content of the product was 2.15% by weight wherein the value for (m) -in the above general formula segment is approximately 21.
Preparation B
Crystalline 2,3-epoxypropyltrimethylammonium chloride A one-liter flask equipped with gas sparser, Messianic stirrer, thermometer and an aqueous acid trap was charged with 10 epichlorohydrin (55.2 grams, 6.0 molt and placed in an isothermal bath at 19C. Tri~ethylamine gas (119.5 grams, 2.0 molt was then sparred into the epichlorohydrin over a period of 3 hours. The temperature was mairltained below 23C. The solution was stirred for an additional 30 minutes and the precipitate collected by 15 filtration. The crystalline product was washed with diethylether and vacuum dried to afford 262.2 grams of 2,3-epoxypropyltri-methylammonium chloride.
Example 2 -Rl~+RlR2R3A - -(H2cH(oH)cH2N(cH3)3cl The procedure of Example 1 was repeated exactly except that pure crystalline 2,3-epoxypropyltrimethylammonium chloride (15.2 grams, 0.10 molt was added in place of the aqueous solution.
The mixture was then stirred for an additional 5.5 hours at 60C
Jo and recovered from acetone as described. The nitrogen content of 5~the~fina~1 product was 1.12% by weight wherein the value for (m) is approximately 28.
: :
,,~., : :
Jo :
::
:' ' ` ' ` ''' ` ~%36~39 example 3 -RN+RlR2R3A = -CH2cH(O~)CH2N(cH3)3cl ' The procedure of Example was reproduced except that the amount of aqueous 2,3-epoxypropyltrimethyla~monium chloride 5 was 56.2 milliliters of 48% solution and the warm aqueous polymer was recovered by precipitation in methanol (2.0 liters). The solid collected was shredded mechanically dried under vacuum and ruled to a fine powder. The yield was 49.9 grams and the nitrogen content was 0.22% by weight wherein the value for (I) in lo the general formula segment is approximately 282.
Example 4 -RN+RlR2R3A = -CH2CH(OH)CH2N(CH3)3Cl The procedure of Example 3 was reproduced with the exception that the aqueous reaction mixture was cooled to ambient 15 temperature and placed in a commercially available dialysis tube.
The simpers membrane in the dialysis tube retains all molecules with molecular weights greater than 8,000. The tubs were placed in water (4 liters) and allowed to stand. The bath water was changed ever 6-8 hours over a 36 hour period. The tubes 20 were then recovered and the aqueous polymer solution inside was tested for moisture barrier properties.
Example 5 RN RlR2R3A = -C~2cH(OH)c~2~(cH3)3cl The procedure of Example 3 was reproduced with the I; 25 exception that recover was accomplished by precipitation from acetone lo liters). The scale was slightly reduced to 38.0 grams polyvinyl alcohol and 49 mill lens of 48% aqueous epoxide :: : : : :
:
: , I: : :
: : ' :
:
,, 63~
solution. The yield was 63.5 trams and the nitrogen content was 2.63% by weight wherein the flu for em) in the general formula segment is approximately 15.
Preparation C
Preparation of 2,3-epoxypropyltr nethylammonium bromide A flask equipped with a sparser, mechanical stirrer, thermometer and efficiency condenser was charged with acetone (500 milliliters) at ambient temperature. Trimethylamine (58 grams, 0.98 molt was charged into the solution. The pot was cooled to 10 10C and epibromohydrin (137 grams, 1.0 molt was added drops over a l hour period. The resultant cloudy solution was allowed to slowly rise to ambient temperature and stand for 60 hours.
Precipitate was collected by filtration washed with acetone (60 milliliters) and dried yielding a colorless crystalline product 15 tl79.4 grams, 94~).
sample 6 RlR2P~3A -c~2cH(oH)cH2N(cH3)3Br A flask equipped as described m General Preparation I
was charged with polyvinyl alcohol (44.0 groans), (98% hydrolyzed, 20 number average molecular weight equals 125,000) and 500 milliliters water. The slurry was warmed to 70C and potassium hydroxide (3.0 grams) was added. The pot was stirred an additional 30 minutes and 2,3-epoxypropyltrimethylammonium bromide (49~.0 grams, 0.25 Poles) was added through a powder funnel. This solution stirred for 16 hours at 80C. The solution was then poured into acetone (1500 milliliters) and the precipitate was collectedly filtration, shredded, washed and dried. The pale brown solid powder which resulted had a nitrogen content of 2.10%
.., :
;
.
. . . .
~3~639 by weight wherein the value for (m) in the general formula segment is approximately 19.
Example 7 -RlR2R3A = -CH2CH(O~)CH2N+(CH3)3Cl A flask equipped as described in General Preparation I
woes charged with polyvinyl alcohol (44~0 grams), (100% hydrolyzed, number average molecular weight equals 86,000), 200 milliliters distilled water and 3 grams potassium hydroxide. The pot was heated to 60C an aqueous (chlorohydroxypropyl)trimethylammoniu~
lo chloride (320 milliliters, 48% aqueous solution as prepared in Preparation A) was added. Heating was continued for an additional 24 hours and recovery was accomplished by precipitation, from acetone. After collection joshing and drying the nitrogen content was 0.72% wherein the value for (m) in the general formula segment lo is approximately 80.
Example 8 RlR2R3A = -cH2cH(oH~cH2N+(cH3)3cl A flask equipped as described in General Preparation 1 was charged with polyvinyl alcohol t88.0 grams), (98.5~
20 hydrolyzed, having a molecular weight of 25,000) and 800 milliliters of water. The reaction was carried out exactly as d~escr~ibed~in~Example 2 using crystalline I;
2,3-epoxypropyltrimethylammonium chloride (79.6 grams). Recovery was accomplished by precipitation yin acetone. The nitrogen continuity was 1~.01% by weight wherein the value for (m) in the general formula segment is approximately 84.
:
:, Example 9 -RN+RlR2R3A = -Cohesion (SHEA 2 A flask equipped as described in general Preparation TO
was charged with polyvinyl alcohol (44.0 grams), (100% hydrolyzed, molecular weight 86,000), 500 milliliters dimethylformamide, 5.5 grams manganese acetate, and benzyldimethylethoxycarbonylmethyl ammonium chloride (51.0 grams, 0.25 mole). A nitrogen stream was passed through the solution as was heated to 125C and held for 6 hours. The resulting solution was poured into acetone (1500 10 milliliters) while hot. The precipitate was collected by filtration, shredded mechanically, washed again with polymer nor.-; solvent and dried. The product was found to have a chloride content of 4.10~ by weight and a calculated nitrogen content of 1.62% wherein the value for (m) in the general formula segment is 15 approximately 28.
Example _ 1~`2~`3' -COHESION (CH3)2(CH2Ph)Cl The process of Example 9 was repeated with polyvinyl alcohol (98% hydrolyzed having molecular weight of ]26,000). The 20 chloride content of the product was 4.41% by weight and the calculated nitrogen content was 1.72% wherein the value for (m) in the general formula segment is approximately 25.
Example 11 ROY -C~2CH(OH)CH2N (Shekel 25~ Polyvinyl alcohol (44.0 g, MY = 12~,000, 98% hydrolyzed) was~stirred`in water (400 ml) and warmed to 85-90CC. The solution was cooled to 80C and aqueous potassium hydroxide (5.6 g in 30 ml : "' '' '' :
, , .........
~236~39 HO) was added. This solution was cooled over 30 minutes to 60$C
and I chloro-2-hydroxypropyl)trimethyla~monium chloride (18.8 g, 0.10 molt was added all at once. The pi at this time was 7.3.
The product was recovered by dialysis through a semi-porous 5 membrane as previously described. The nitrogen content was 0.15 which corresponds Jo idealized formula with m = 415.
-Example I
-RN+RlR2R3A = -CH2CH(OH)CH2~ (Shekel Polyvinyl alcohol (22.0 g), Jo = 126,000, 98~
lo hydrolyzed) was stirred in water (210 ml) and warmed to 85C over 45 minutes. Potassium hydroxide (1.5 g in 10 ml HO) was then added and the solution cooled to 60C. Crystalline 2,3-epoxy-propyltrimethylammonium chloride (75.8 g, 0.50 molt was added and the entire solution held at 60C for 4 hours. The product was 15 then recovered by precipitation from acetone, filtration and drying to afford 102 trams of white powder. The nitrogen content was 5.96% or 88~ of theoretical, and wherein (m) has a value of approximately 2Ø
Example 13 RlR2R3A -cH2cH(oH)cH2N~(cH3) Polyvinyl alcohol (44.0 g), (MET = 126,000, 98%
hydrolyzed wag stirred in water (400 ml) and warmed to 85C over ~30 minutes. The solution was cooled to 80C and Potassium hydroxide g in 20 ml HO) was added. The entire solution way ;~25 cooled to 60C over 45 minutes and~2,3-epoxypropyltrimethyl- -ammonium~chlor~ide (37.9 g in 100 ml HO) was added drops over ~30 minutes. The solution was stirred at 60C for 3 additional hours and the product recovered by precipitation from acetone.
The reaction afforded 50.4 grays of white solid with a nitrogen , , : - ' '' :
I..
~236~3~
content of 2.92~ or 71% of theoretical, and wherein (m) has a value of approximately 13.
Moisture Barrier Test On per While the modified polyvinyl alcohol polymers of the invention are best tested for retentivity, substantivity and moisture barrier film forming properties on living animal spin an indication of their effectiveness as a moisture barrier eon be obtained by testing on filter paper. In the test results listed in the following Table 1 a 2.5 inch circle of number 1 Whitman 10 filter p&per was treated with aqueous solutions containing from 5-10/o by weight of the modified polymer as described if. the examples to obtain a polymer film deposit amounting to about 0.1 gram when dried at room temperature. The test is carried out by taking about 2 grams of aqueous solution of the modified polymer 15 and dropping it over a water wet circle of filter paper from one side. The saturated paper is permitted to dry overnight at room temperature and weighed. Depending on the concentration of solution the procedure may be repeated until the weight pickup is about 0.1 gram so that each filter paper is treated with 20 substantially an equal amount of polymer. The dry paper is sealed over the opening of a test cell containing 100 grams of water arid permitted to stand or 1~0 hours in a constant humidity and typewriter room at 70F at 40% relative humidity. The weight of water passing through the paper under these conditions is measured 25 by weighing the amount of water remaining in the test cell. Each test employs a control cell containing the identical paper having no polymer treatment. Considering the weight loss through untreated paper as lC0 thy test results which are listed as percentage reduction in evaporation of water are calculated from Thea water remaining in the cell. The paper test results provide a rough indication of effectiveness as a moisture barrier for further testing on animal skin.
I: I: :: : :
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:::: : : : ::
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.
~3~639 Table 1
General Preparation I
A flask equipped with a water cooled condenser, lo mechanical stirrer and thermometer is charged with polyvinyl alcohol and distilled water. The polyvinyl alcohol (POW) which is generally a commercially available product prepared by hydrolysis of polyvinyl acetate may have from 0 to 25% residual acetate groups, preferably from 2 to 15% and the number average molecular 15 weight may range from 2,000 to 200,000 and higher and preferably from 25,000 to 150,000. In addition, and for the purpose of this invention, a polyvinyl alcohol base chain may include up to I by weight of another comonomer such as vinyl pyrolid~ne, acrylic and methacrylic acids and esters thereof. The aqueous slurry is 20 heated to 80-90C and held for 1 hour or until the polyvinyl alcohol is completely dispersed or salivated. A catalytic amount of aqueous base such as alkali hydroxide such as sodium or potassium hydroxide is then added and the solution cooled to 40-90C. At this point 2,3-epoxypropyltrialkylammonium halide, 25 either in aqueous solution or crystalline form, may be added incrementally or all at once. This reagent is typically used in 0.003-l.0 mow ratio preferably from 0.10-0.3 mow per mow of hydroxyl group on the polyvinyl alcohol base chain. The entire solution is then stirred for an additional period typically 4 30 hours at 60C after which the solid product may be recovered.
Recovery is accomplished by one of two general techniques. The solution can be poured into a polymer non-solvent to precipitate solid product from aqueous solution. Alternatively I, 3L236~
the solution may be dialyzed through a simpers membrane and the purified aqueous polymer used as obtained or precipitated out.
The precipitation is preferably accomplished either if.
acetone or in methanol affording yields up to I or better by weight after drying. Depending on reaction conditions the precipitated products have a nitrogen content in the range of 0.01-7~.
In the purification by dialysis the reaction mixture is freed from all species below a certain molecular weight. Two lo methods may be used one a static and one dynamic. In the static method the reaction mixture is placed inside a commercial semi-porous dialysis tube and the tubes are submerged in distilled water typically for periods of I to 48 hours. The contents of the tubes are then recovered and the product may be used as is.
15 In the dynamic system a pressure pump is used to Jove water iron.
the reaction mixture through a simpers membrane. The water carries out any inorganic and lo- molecular weight organic. The resulting concentrated product stream is then collected.
General Preparation II
A flask equipped as described in General Preparation 1 is charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80-90C and held for one hour or until the polymer is completely salivated. A catalytic amount of aqueous alkaline hydroxide such as sodium or potassium hydroxide is added 25 and the pot cooled to 60-65C. At this point, (chlorohydroxy-propyl)trimeth~lammonium halide, either in aqueous solution or crystalline form, is added either incrementally or all at once.
This reagent is typically used in Lowe mole ratio preferably from OWE mole per mole of hydroxyl group on the polyvinyl 30 alcohol base chain. The entire solution is then stirred at 40-~90C for an additional period, typically four hours. The product ; is then recovered by one of the methods described in GeneralPr~eparatioD I.
::
.
General Preparation III
In preparing qua ternary ammonium groups linked to the polyvinyl alcohol base chain through ester linkages it is preferred to prepare thrill using a transesterification technique.
In a typical reaction a four-neck one liter round bottom flask equipped with a thermometer, mechanical stirrer, water cooled condenser and a nitrogen sparser is charged with polyvinyl alcohol as described in the above General Preparation I, dim ethyl-formamide, a trialkylalkoxycarbonyl ammonîum halide, and a small 10 amount of a transition metal salt as catalyst as manganese acetate for example. The entire dispersion is then heated to a temperature of Luke for 2 to 24 hours preferably 3 to 6 hours. Nitrogen is used as a carrier gas to remove the alcohol formed during the esterification reaction. The solution is then 15 cooled to ambient temperature and poured into a polymer nonsolvent such as for example methanol, ethanol or acetone. The resulting precipitate is collected by filtration, washed, shredded mechanically and dried under vacuum to afford a nearly white product with a desired nitrogen content.
Jo ..
20 General Preparation IV
A flask equipped as described in General Preparation I
is charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80-90C and held for one hour or until the polymer is completely dispersed or salivated. A catalytic 25 amount of an acid such as sulfuric acid or aluminum hydrosilicate or any proton acid or Lewis acid is added and the pot cooled to 40-90C. At this point 2,3-epoxypropyltrialkyla~r~onium halide may be added incrementally or all at once. This reagent is typically used in 0.003-1.0 mole ratio preferably from 0.1-0.3 mow per mow of 30 hydroxyl group on the polyvinyl alcohol base chain. The entire solution lo then stirred for an additional period typically 4 ::
~L23~t';39 hours at 60C aster itch thy solid product may be recovered by one of the methods described in General Preparation I.
The following examples and preparations serve to illustrate but not limit the invention. All proportions used 5 Rafferty parts by weight unless otherwise specified.
r Preparation A
(Chlorohydroxypropyl)trimethylammonium chloride A one-liter flask equipped with dropping funnel, mechanical stirrer, thermometer a condenser was charged with 10 epichlorohydrin (95 grams, 1.0~ molt and placed in an isothermal bath at 18C. Aqueous trimethylamine (238.7 grams, 25% by weight, 1.01 molt was then added drops over a 3 hour period maintaining the temperature below 25CC when the addition was complete the solution was allowed to stir overnight at ambient temperature.
Example 1 RN RlR2R3A = -CH2-CH(OH)CH2N(CH3)3Cl A flask equipped as described in General Preparation I
was charged with 44 grams polyvinyl alcohol (commercially available) having a molecular weight of 126,000 (98~ hydrolyzed -20 2% acetate) and 400 milliliters of distilled water. The resulting slurry was heated to 85C and held for 1 hour. The polymer dissolved completely to afford a pale yellow transparent solution.
Potassium hydroxide (3.0 gram, 0.11 molt in water (30 milliliters) was then added and the solution cooled to 60C. Aqueous (sheller-25~hydroxypropyljtrimethylammdnium chloride (78 milliliters of 4~7~ boutiques solution prepared according to Preparation A), was then added all at once and the entire solution was heated to 6Q-65C~for 4 additional hours. The warm solution was poured with ::: :` : :
:
~;~36639 g stirring into acetone (2.0 liters) and allowed to stand. 63.5 grams OX colorless solid precipitate was collected by filtration shredded mechanically and dried under vacuum.. The nitrogen content of the product was 2.15% by weight wherein the value for (m) -in the above general formula segment is approximately 21.
Preparation B
Crystalline 2,3-epoxypropyltrimethylammonium chloride A one-liter flask equipped with gas sparser, Messianic stirrer, thermometer and an aqueous acid trap was charged with 10 epichlorohydrin (55.2 grams, 6.0 molt and placed in an isothermal bath at 19C. Tri~ethylamine gas (119.5 grams, 2.0 molt was then sparred into the epichlorohydrin over a period of 3 hours. The temperature was mairltained below 23C. The solution was stirred for an additional 30 minutes and the precipitate collected by 15 filtration. The crystalline product was washed with diethylether and vacuum dried to afford 262.2 grams of 2,3-epoxypropyltri-methylammonium chloride.
Example 2 -Rl~+RlR2R3A - -(H2cH(oH)cH2N(cH3)3cl The procedure of Example 1 was repeated exactly except that pure crystalline 2,3-epoxypropyltrimethylammonium chloride (15.2 grams, 0.10 molt was added in place of the aqueous solution.
The mixture was then stirred for an additional 5.5 hours at 60C
Jo and recovered from acetone as described. The nitrogen content of 5~the~fina~1 product was 1.12% by weight wherein the value for (m) is approximately 28.
: :
,,~., : :
Jo :
::
:' ' ` ' ` ''' ` ~%36~39 example 3 -RN+RlR2R3A = -CH2cH(O~)CH2N(cH3)3cl ' The procedure of Example was reproduced except that the amount of aqueous 2,3-epoxypropyltrimethyla~monium chloride 5 was 56.2 milliliters of 48% solution and the warm aqueous polymer was recovered by precipitation in methanol (2.0 liters). The solid collected was shredded mechanically dried under vacuum and ruled to a fine powder. The yield was 49.9 grams and the nitrogen content was 0.22% by weight wherein the value for (I) in lo the general formula segment is approximately 282.
Example 4 -RN+RlR2R3A = -CH2CH(OH)CH2N(CH3)3Cl The procedure of Example 3 was reproduced with the exception that the aqueous reaction mixture was cooled to ambient 15 temperature and placed in a commercially available dialysis tube.
The simpers membrane in the dialysis tube retains all molecules with molecular weights greater than 8,000. The tubs were placed in water (4 liters) and allowed to stand. The bath water was changed ever 6-8 hours over a 36 hour period. The tubes 20 were then recovered and the aqueous polymer solution inside was tested for moisture barrier properties.
Example 5 RN RlR2R3A = -C~2cH(OH)c~2~(cH3)3cl The procedure of Example 3 was reproduced with the I; 25 exception that recover was accomplished by precipitation from acetone lo liters). The scale was slightly reduced to 38.0 grams polyvinyl alcohol and 49 mill lens of 48% aqueous epoxide :: : : : :
:
: , I: : :
: : ' :
:
,, 63~
solution. The yield was 63.5 trams and the nitrogen content was 2.63% by weight wherein the flu for em) in the general formula segment is approximately 15.
Preparation C
Preparation of 2,3-epoxypropyltr nethylammonium bromide A flask equipped with a sparser, mechanical stirrer, thermometer and efficiency condenser was charged with acetone (500 milliliters) at ambient temperature. Trimethylamine (58 grams, 0.98 molt was charged into the solution. The pot was cooled to 10 10C and epibromohydrin (137 grams, 1.0 molt was added drops over a l hour period. The resultant cloudy solution was allowed to slowly rise to ambient temperature and stand for 60 hours.
Precipitate was collected by filtration washed with acetone (60 milliliters) and dried yielding a colorless crystalline product 15 tl79.4 grams, 94~).
sample 6 RlR2P~3A -c~2cH(oH)cH2N(cH3)3Br A flask equipped as described m General Preparation I
was charged with polyvinyl alcohol (44.0 groans), (98% hydrolyzed, 20 number average molecular weight equals 125,000) and 500 milliliters water. The slurry was warmed to 70C and potassium hydroxide (3.0 grams) was added. The pot was stirred an additional 30 minutes and 2,3-epoxypropyltrimethylammonium bromide (49~.0 grams, 0.25 Poles) was added through a powder funnel. This solution stirred for 16 hours at 80C. The solution was then poured into acetone (1500 milliliters) and the precipitate was collectedly filtration, shredded, washed and dried. The pale brown solid powder which resulted had a nitrogen content of 2.10%
.., :
;
.
. . . .
~3~639 by weight wherein the value for (m) in the general formula segment is approximately 19.
Example 7 -RlR2R3A = -CH2CH(O~)CH2N+(CH3)3Cl A flask equipped as described in General Preparation I
woes charged with polyvinyl alcohol (44~0 grams), (100% hydrolyzed, number average molecular weight equals 86,000), 200 milliliters distilled water and 3 grams potassium hydroxide. The pot was heated to 60C an aqueous (chlorohydroxypropyl)trimethylammoniu~
lo chloride (320 milliliters, 48% aqueous solution as prepared in Preparation A) was added. Heating was continued for an additional 24 hours and recovery was accomplished by precipitation, from acetone. After collection joshing and drying the nitrogen content was 0.72% wherein the value for (m) in the general formula segment lo is approximately 80.
Example 8 RlR2R3A = -cH2cH(oH~cH2N+(cH3)3cl A flask equipped as described in General Preparation 1 was charged with polyvinyl alcohol t88.0 grams), (98.5~
20 hydrolyzed, having a molecular weight of 25,000) and 800 milliliters of water. The reaction was carried out exactly as d~escr~ibed~in~Example 2 using crystalline I;
2,3-epoxypropyltrimethylammonium chloride (79.6 grams). Recovery was accomplished by precipitation yin acetone. The nitrogen continuity was 1~.01% by weight wherein the value for (m) in the general formula segment is approximately 84.
:
:, Example 9 -RN+RlR2R3A = -Cohesion (SHEA 2 A flask equipped as described in general Preparation TO
was charged with polyvinyl alcohol (44.0 grams), (100% hydrolyzed, molecular weight 86,000), 500 milliliters dimethylformamide, 5.5 grams manganese acetate, and benzyldimethylethoxycarbonylmethyl ammonium chloride (51.0 grams, 0.25 mole). A nitrogen stream was passed through the solution as was heated to 125C and held for 6 hours. The resulting solution was poured into acetone (1500 10 milliliters) while hot. The precipitate was collected by filtration, shredded mechanically, washed again with polymer nor.-; solvent and dried. The product was found to have a chloride content of 4.10~ by weight and a calculated nitrogen content of 1.62% wherein the value for (m) in the general formula segment is 15 approximately 28.
Example _ 1~`2~`3' -COHESION (CH3)2(CH2Ph)Cl The process of Example 9 was repeated with polyvinyl alcohol (98% hydrolyzed having molecular weight of ]26,000). The 20 chloride content of the product was 4.41% by weight and the calculated nitrogen content was 1.72% wherein the value for (m) in the general formula segment is approximately 25.
Example 11 ROY -C~2CH(OH)CH2N (Shekel 25~ Polyvinyl alcohol (44.0 g, MY = 12~,000, 98% hydrolyzed) was~stirred`in water (400 ml) and warmed to 85-90CC. The solution was cooled to 80C and aqueous potassium hydroxide (5.6 g in 30 ml : "' '' '' :
, , .........
~236~39 HO) was added. This solution was cooled over 30 minutes to 60$C
and I chloro-2-hydroxypropyl)trimethyla~monium chloride (18.8 g, 0.10 molt was added all at once. The pi at this time was 7.3.
The product was recovered by dialysis through a semi-porous 5 membrane as previously described. The nitrogen content was 0.15 which corresponds Jo idealized formula with m = 415.
-Example I
-RN+RlR2R3A = -CH2CH(OH)CH2~ (Shekel Polyvinyl alcohol (22.0 g), Jo = 126,000, 98~
lo hydrolyzed) was stirred in water (210 ml) and warmed to 85C over 45 minutes. Potassium hydroxide (1.5 g in 10 ml HO) was then added and the solution cooled to 60C. Crystalline 2,3-epoxy-propyltrimethylammonium chloride (75.8 g, 0.50 molt was added and the entire solution held at 60C for 4 hours. The product was 15 then recovered by precipitation from acetone, filtration and drying to afford 102 trams of white powder. The nitrogen content was 5.96% or 88~ of theoretical, and wherein (m) has a value of approximately 2Ø
Example 13 RlR2R3A -cH2cH(oH)cH2N~(cH3) Polyvinyl alcohol (44.0 g), (MET = 126,000, 98%
hydrolyzed wag stirred in water (400 ml) and warmed to 85C over ~30 minutes. The solution was cooled to 80C and Potassium hydroxide g in 20 ml HO) was added. The entire solution way ;~25 cooled to 60C over 45 minutes and~2,3-epoxypropyltrimethyl- -ammonium~chlor~ide (37.9 g in 100 ml HO) was added drops over ~30 minutes. The solution was stirred at 60C for 3 additional hours and the product recovered by precipitation from acetone.
The reaction afforded 50.4 grays of white solid with a nitrogen , , : - ' '' :
I..
~236~3~
content of 2.92~ or 71% of theoretical, and wherein (m) has a value of approximately 13.
Moisture Barrier Test On per While the modified polyvinyl alcohol polymers of the invention are best tested for retentivity, substantivity and moisture barrier film forming properties on living animal spin an indication of their effectiveness as a moisture barrier eon be obtained by testing on filter paper. In the test results listed in the following Table 1 a 2.5 inch circle of number 1 Whitman 10 filter p&per was treated with aqueous solutions containing from 5-10/o by weight of the modified polymer as described if. the examples to obtain a polymer film deposit amounting to about 0.1 gram when dried at room temperature. The test is carried out by taking about 2 grams of aqueous solution of the modified polymer 15 and dropping it over a water wet circle of filter paper from one side. The saturated paper is permitted to dry overnight at room temperature and weighed. Depending on the concentration of solution the procedure may be repeated until the weight pickup is about 0.1 gram so that each filter paper is treated with 20 substantially an equal amount of polymer. The dry paper is sealed over the opening of a test cell containing 100 grams of water arid permitted to stand or 1~0 hours in a constant humidity and typewriter room at 70F at 40% relative humidity. The weight of water passing through the paper under these conditions is measured 25 by weighing the amount of water remaining in the test cell. Each test employs a control cell containing the identical paper having no polymer treatment. Considering the weight loss through untreated paper as lC0 thy test results which are listed as percentage reduction in evaporation of water are calculated from Thea water remaining in the cell. The paper test results provide a rough indication of effectiveness as a moisture barrier for further testing on animal skin.
I: I: :: : :
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:::: : : : ::
:: :
.
~3~639 Table 1
6 Reduction Example in Evaporation Control (unmodified PEA 40-50 ' l 55 c 4 58
7 46 : 15 In-vitro tests on animal skins having 1, 3 and 5 weight percent of the modified polyvinyl alcohol polymers of this : invention indicate comparable results with regard to water vapor transmission on Neonatal Rat Stratum Corneum as shown in the results listed in Table 2.
Table 2 Water Vapor Transmission I polymer solution on neonatal rat stratum corneum) Sample : % Reduction 25 Control 66.7 Example 1 55.6 Example 7 77.8 example 55.6 I: The effect of polymer coatings having 5% modified POW
Jo polymers on the elasticity of pi skin is shown in Table 3.
Table :3 Elasticity of pigskin treated:
with 5% polymer solution.
Elasticity :35~ Control Expel 1~:8.~8'2.0 Example .11.4i2.0 Example l.6~0.8 ,: : . :
- -. :
Compares skin elasticity (petroleum jelly produces maximum elasticity - approximately 28 units) The use of unmodified polyvinyl alcohol polymer- in film forming ointment bases and barrier creams for use in protecting the skin against the action of Paternal irritants has met with only limited success (JOB. Ward and G. J. Spurned, "American Perfumer and Cosmetics" Volume 79, pages 53-55 (1964)). Film forming creams are difficult to produce with polyvinyl alcohol because they are either very difficult to formulate because of 10 their poor mixing characteristics or whey form poor fullers.
Lotions and creams made with polyvinyl alcohol in general lack elegance, that is, the in-vitro films made from ointments and lotions containing about 15% polyvinyl alcohol are either slow drying, become greasy and tacky and eventually leave a film which 15 is hard and leathery. Furthermore, Good PEA moisture barrier films usually are very hard to remove from the skin because whey are difficult to remove with soap and water.
The problems associated with employing unmodified PEA in film forming bases are substantially overcome by the compositions 20 of this invention in that they are easily dispersible in water are compatible with typical lotion formulations, and when applied to the surface of the skin, they dry quickly to form an elastic, smooth pellicle which retains its integrity over long periods of time and is easily removed with soap and water. Tests for 25 pharmaceutical elegance is accomplished by applying typical moisture barrier lotion formulas to the back of the hand and making observations with respect to ease of application, feel on the skin, time of drying, durability of the film, ease of removal and a host of subjective factors. In most instances, the 30 formulations evaluated do not adversely effect the film forming characteristics of the modified polyvinyl alcohol compositions of this invention. The aqueous moisture barrier compositions of the invention generally have a lotion consistency and may be in the form of oil-in-water or water-in-oil emulsions with the former 35 being preferred because of their more pleasing cosmetic ' .
properties. The lotions are preferably Audi by first preparing the oil phase then preparing the water phase and thereafter adding the water phase to the oil phase. Usually the aqueous phase to heated to a temperature of about 70 to about 80~C and then added sly with stirring to the oil phase which is heated to about the same temperature.
The oil phase components may contain a variety of materials including emulsifiers, emollients, oils, waxes, perfumes, lanolin, polyalkylenes, strolls and the like.
Water phase components may contain many different materials josh include humectants, modified POW moisture barrier components of the invention, proteins and polypeptides, preservatives, alkaline agents, thickening agents, perfuses, stabilizers and antiseptics.
The lotions and ointments of the invention contain as an essential ingredient from n. 1-15~ by weight and preferably from .5-5% by weight of the above described modified polyvinyl alcohol polymers of the invention. They may be added as aqueous dispersions containing 0,1-30~ by weight of modified PEA or as dry 20 powder.
The lotions may contain an emulsifier in an amount of from about 0.05 to about I and preferably from about 0,25 to about 5% to emulsify the oil components. Typical emulsifiers are selected from the group consisting of polyethoxylated fatty acids 25 having less than about 30 mows of ethylene oxide per mow of fatty acid, ethyoxylated esters, unethoxylated sugar esters, polyoxy-ethylene fatty ether phosphates, fatty acid asides, phospholipids, polypropoxylated fatty ethers, acyllactates, polyethoxylated polyp oxypropylene glycols, polypropoxylated polyoxyethylene glycols, 30 polyoxyethylene, polyoxypropylene ethylene dominoes, soaps and mixtures thereof.
Examples of such emulsifiers include polyoxyethylene (~) Stewart, myristyl ethics (3) myristate, myristyl ethics (3) palpitate, methyl glucose sesquistearate, sucrose distrait, 35 sucrose laureate, certain monolaurate, polyoxyethylene (3) oilily :: :
~2~S3~
ether phosphate, polyoxyethylene (10) oilily ether phosphate, Laurie diethenyl aside, Starkey monthly aside, lecithin, lanolin alcohol propoxylates, sodium stearoyl-2-lactate r calcium stearoyl-2-lactate, and the Pluoronics~ offered by BASS Wyandotte Soars such as alkaline metal or triethanolamine salts of long chain; fatty acids which include sodium Stewart, triethanolamine stout and similar salts of lanolin fatty acids. A preferred emulsifier is polyoxyethylene ( 1) stroll ether.
The lotion formulations may contain an emollient 10 material in an amount ranging from 0.2 to 25% and more often 1 to
Table 2 Water Vapor Transmission I polymer solution on neonatal rat stratum corneum) Sample : % Reduction 25 Control 66.7 Example 1 55.6 Example 7 77.8 example 55.6 I: The effect of polymer coatings having 5% modified POW
Jo polymers on the elasticity of pi skin is shown in Table 3.
Table :3 Elasticity of pigskin treated:
with 5% polymer solution.
Elasticity :35~ Control Expel 1~:8.~8'2.0 Example .11.4i2.0 Example l.6~0.8 ,: : . :
- -. :
Compares skin elasticity (petroleum jelly produces maximum elasticity - approximately 28 units) The use of unmodified polyvinyl alcohol polymer- in film forming ointment bases and barrier creams for use in protecting the skin against the action of Paternal irritants has met with only limited success (JOB. Ward and G. J. Spurned, "American Perfumer and Cosmetics" Volume 79, pages 53-55 (1964)). Film forming creams are difficult to produce with polyvinyl alcohol because they are either very difficult to formulate because of 10 their poor mixing characteristics or whey form poor fullers.
Lotions and creams made with polyvinyl alcohol in general lack elegance, that is, the in-vitro films made from ointments and lotions containing about 15% polyvinyl alcohol are either slow drying, become greasy and tacky and eventually leave a film which 15 is hard and leathery. Furthermore, Good PEA moisture barrier films usually are very hard to remove from the skin because whey are difficult to remove with soap and water.
The problems associated with employing unmodified PEA in film forming bases are substantially overcome by the compositions 20 of this invention in that they are easily dispersible in water are compatible with typical lotion formulations, and when applied to the surface of the skin, they dry quickly to form an elastic, smooth pellicle which retains its integrity over long periods of time and is easily removed with soap and water. Tests for 25 pharmaceutical elegance is accomplished by applying typical moisture barrier lotion formulas to the back of the hand and making observations with respect to ease of application, feel on the skin, time of drying, durability of the film, ease of removal and a host of subjective factors. In most instances, the 30 formulations evaluated do not adversely effect the film forming characteristics of the modified polyvinyl alcohol compositions of this invention. The aqueous moisture barrier compositions of the invention generally have a lotion consistency and may be in the form of oil-in-water or water-in-oil emulsions with the former 35 being preferred because of their more pleasing cosmetic ' .
properties. The lotions are preferably Audi by first preparing the oil phase then preparing the water phase and thereafter adding the water phase to the oil phase. Usually the aqueous phase to heated to a temperature of about 70 to about 80~C and then added sly with stirring to the oil phase which is heated to about the same temperature.
The oil phase components may contain a variety of materials including emulsifiers, emollients, oils, waxes, perfumes, lanolin, polyalkylenes, strolls and the like.
Water phase components may contain many different materials josh include humectants, modified POW moisture barrier components of the invention, proteins and polypeptides, preservatives, alkaline agents, thickening agents, perfuses, stabilizers and antiseptics.
The lotions and ointments of the invention contain as an essential ingredient from n. 1-15~ by weight and preferably from .5-5% by weight of the above described modified polyvinyl alcohol polymers of the invention. They may be added as aqueous dispersions containing 0,1-30~ by weight of modified PEA or as dry 20 powder.
The lotions may contain an emulsifier in an amount of from about 0.05 to about I and preferably from about 0,25 to about 5% to emulsify the oil components. Typical emulsifiers are selected from the group consisting of polyethoxylated fatty acids 25 having less than about 30 mows of ethylene oxide per mow of fatty acid, ethyoxylated esters, unethoxylated sugar esters, polyoxy-ethylene fatty ether phosphates, fatty acid asides, phospholipids, polypropoxylated fatty ethers, acyllactates, polyethoxylated polyp oxypropylene glycols, polypropoxylated polyoxyethylene glycols, 30 polyoxyethylene, polyoxypropylene ethylene dominoes, soaps and mixtures thereof.
Examples of such emulsifiers include polyoxyethylene (~) Stewart, myristyl ethics (3) myristate, myristyl ethics (3) palpitate, methyl glucose sesquistearate, sucrose distrait, 35 sucrose laureate, certain monolaurate, polyoxyethylene (3) oilily :: :
~2~S3~
ether phosphate, polyoxyethylene (10) oilily ether phosphate, Laurie diethenyl aside, Starkey monthly aside, lecithin, lanolin alcohol propoxylates, sodium stearoyl-2-lactate r calcium stearoyl-2-lactate, and the Pluoronics~ offered by BASS Wyandotte Soars such as alkaline metal or triethanolamine salts of long chain; fatty acids which include sodium Stewart, triethanolamine stout and similar salts of lanolin fatty acids. A preferred emulsifier is polyoxyethylene ( 1) stroll ether.
The lotion formulations may contain an emollient 10 material in an amount ranging from 0.2 to 25% and more often 1 to
8% by weight. One function of the emollient is to ensure that the modified polyvinyl alcohol polymer is classified sufficiently to allow it to be in a film-like state on the surface of the skin..
Typical emollients are selected from the group consisting of fatty 15 alcohols, esters having fewer than about 24 carbon atoms (for example, isopropylpalmitate), branch chain esters having greater than about 24 total carbon atoms (for example, cetearyl octonate), skyline, liquid or solid paraffins, mixtures of fatty acids and skyline, mixtures ox fatty acids and liquid or solid paraffins 20 and mixtures thereof. Typical alcohols and fatty acids which are useful include those having from 12 to 22 carbon atoms such as Seattle alcohol, myristyl alcohol, stroll alcohol, Starkey acid and palmitic acid. Paraffins include, for example, mineral oil, petrolatum and paraffin wax.
The lotions and ointments are particularly stable and effective when adjusted to a pi of I
The following formulations will serve to demonstrate but not limit the formulations containing the modified polyvinyl alcohol film forming moisture barrier polymer of the invention.
30 Typical lotions contain 0.1-5.0% of the above described modified PEA polymers, 2-5% of a fatty alcohol, and 2-5% emulsifier in an aqueous emulsion.
':..
, foe Exhume A portion of the aqueous solution- prepared according to Example 4 containing 0.5 grams of modified PEA polymer was dilute with water and added to an aqueous solution containing 2.4 grays 5 Seattle alcohol, 1.6 grams stroll alcohol and 3.0 grams of polyethylene (21) stroll ether (Baja 721 surfactant by ICY
Americas Inc.). Additional water was added to bring the water concentration to 92.5%. After stirring for about five minutes at 75C the emulsion to per lied to cool to room temperature and stored. The lotion Was tested subjectively for cosmetic elegance lo by applying the product to the back of the hand and arm. It was determined to have smooth, silky feel, drying time of less thaw 15 minutes and a film durability in excess of two days. Residual films and lotions are easily removed from the skin with soap and water.
As mentioned above the polymers of the invention had advantageous cosmetic properties that permit them to be used in preparing cosmetic formulations either as ready to use compositions or concentrates which have to be diluted before use.
Therefore, the cosmetic formula may contain the modified polyvinyl 20 alcohol polymers in concentrations ranging from 0.01-15% by weight. The solution of these polymers are particularly useful when they are applied to hflir, either alone or with other active substances during a treatment such as shampooing, dyeing, setting, blow drying, permanent waving, etc. They may improve notably the I quality of the hair. Zen employed in hair treatment they facilitate untangling of wet hair and do not remain on dry hair as a sticky residue. In some instances they are expected to give dry hair additional life, a soft feel, a glossy appearance and resistance to tangling.
pair treating formulations containing dilute aqueous, alcohol or dilute alcohol solutions of the modified polyvinyl alcohol polymer can be cr,lployed. Furthermore, they may be employed as creams, lotions, gels or as aerosol sprays. Thyme ~3~i~3~
be used in combination with perfumes, dyes, preserving agents, sequestering agents, thickening agents, emulsifying agents, etc.
Example B
A typical hair rinse formulation containing 5 grams of 5 the modified polymer of Example 8, 7 grams Swahili alcohol, 3 grams of a linear polyoxyethylenated C10-Cl8 fatty alcohol, 2 grams of a cozen derivative, 0.5 grams tetradecyltri~,ethyla~monium chloride and 82.5 grams of water and a minor amount of hair dye can be used to treat hair having improved looks and anti-static properties.
Example C
A typical oxidation hair dye solution containing a 2.5 gram of the modified polymer of Example 9, 10 trams bouncily alcohol, 20 grams oleic acid, 3 grams polyoxyethylene (30), Leo Seattle alcohol, 7 grams Olin diethanolamide, 7.5 grams 2 octyldo-15 decanol, 2.5 grams triethanolamine Laurie sulfate, 10 grams ethanol, 18 milliliters aqueous ammonium, 1 gram n,n-bis(2-hydroxy-ethanol)parapherlylenediamine, 0.4 grams resorcin, 0.15 grams m-aminophenol, .4 grams alphanaphthol, 0.1 grams hydra-quinine, 0 24 grams ethylene Damon tetracetic acid, 1 milliliter 20 sodium bisulfite, and water sufficient to make 100 grams is a typical ammo a oil composition for use as an oxidation hair dye when 130 grams of the solution is mixed with 30 grams of hydrogen peroxide bleach. After hair is treated with the material and allowed to stand for 30-40 minutes and thereafter rerinsed the us hair is expected to untangle easily and Dave a spiky touch.
The modified polyvinyl alcohol compositions ox the invention may be explored to improve the elegance and stability of personal care products such as liquid and bar soaps, shaving creams, bath products, antiperspirants, sunscreens, cleansing 30 creams and as a suspending agents for insoluble pigments and pharmaceutical active. Improvement is generally realized when so ~66;~9 from 0.5-5~ by weight of the compositions of this invention are employed in conventional formulations as hereinafter exemplified.
-- Roll-On Antiperspirant e :5 Ingredient % WOW
Example 3 4.0 polyoxyethylene (21) stearylether 0.76 polyoxyehtylene (2) stearylether 3.24 water (deionized) 34.76 : 10 Dozily 200~, Dow Chemical 0.
: Al Or tetrachlorohydrex-Gly, : Russell 36G, Rehems 57.14 : Example E
Aerosol Shave Cream Ingredient % W/W
Example 3 5.0 Seattle alcohol 4.3 polyoxyethylene (21) stearylether 2.2 sorbic acid .17 20 water 74.9 : : fragrance .08 : water 13.35 :
Example F
Oil-in-Water sun are en Lotion us ln~redien~ W/W :
monorail : :18.~ :
c~tyl:alcohol 5.0 :
Aurelius emulsifier 2.5 Tween:60~:emulsifier:: : : 7.5 30 Amy para~-dimethylaminobenzoic acid 1~.2 Employ 2 0 Jo rreser-ative~ us ,,,,.~ ,. .. . .
. , : ; Jo .: ' ' .
, `::
~23~63~
Example G
Water-in-Oil Pigmented Makeup - Ingredient W/W %
Mineral Oil 10 5 Beeswax 1.5 Cevesin wax 1.0 Arlacel 186P emulsifier 3.2 Sorb sorbitol 28.8 Two and other pigments 20.0 10 water 33.5 Example 6 2.C
Example H
Calamine Lotion Calamine 80 gyms Zinc Oxide 80 gyms glycerine 20 mls bentonite magma 250 mls calcium hydroxide 950 mls (concentrated aqueous sol.) Example 1 50 gyms :: :
::
, ``
:
:, I`
Typical emollients are selected from the group consisting of fatty 15 alcohols, esters having fewer than about 24 carbon atoms (for example, isopropylpalmitate), branch chain esters having greater than about 24 total carbon atoms (for example, cetearyl octonate), skyline, liquid or solid paraffins, mixtures of fatty acids and skyline, mixtures ox fatty acids and liquid or solid paraffins 20 and mixtures thereof. Typical alcohols and fatty acids which are useful include those having from 12 to 22 carbon atoms such as Seattle alcohol, myristyl alcohol, stroll alcohol, Starkey acid and palmitic acid. Paraffins include, for example, mineral oil, petrolatum and paraffin wax.
The lotions and ointments are particularly stable and effective when adjusted to a pi of I
The following formulations will serve to demonstrate but not limit the formulations containing the modified polyvinyl alcohol film forming moisture barrier polymer of the invention.
30 Typical lotions contain 0.1-5.0% of the above described modified PEA polymers, 2-5% of a fatty alcohol, and 2-5% emulsifier in an aqueous emulsion.
':..
, foe Exhume A portion of the aqueous solution- prepared according to Example 4 containing 0.5 grams of modified PEA polymer was dilute with water and added to an aqueous solution containing 2.4 grays 5 Seattle alcohol, 1.6 grams stroll alcohol and 3.0 grams of polyethylene (21) stroll ether (Baja 721 surfactant by ICY
Americas Inc.). Additional water was added to bring the water concentration to 92.5%. After stirring for about five minutes at 75C the emulsion to per lied to cool to room temperature and stored. The lotion Was tested subjectively for cosmetic elegance lo by applying the product to the back of the hand and arm. It was determined to have smooth, silky feel, drying time of less thaw 15 minutes and a film durability in excess of two days. Residual films and lotions are easily removed from the skin with soap and water.
As mentioned above the polymers of the invention had advantageous cosmetic properties that permit them to be used in preparing cosmetic formulations either as ready to use compositions or concentrates which have to be diluted before use.
Therefore, the cosmetic formula may contain the modified polyvinyl 20 alcohol polymers in concentrations ranging from 0.01-15% by weight. The solution of these polymers are particularly useful when they are applied to hflir, either alone or with other active substances during a treatment such as shampooing, dyeing, setting, blow drying, permanent waving, etc. They may improve notably the I quality of the hair. Zen employed in hair treatment they facilitate untangling of wet hair and do not remain on dry hair as a sticky residue. In some instances they are expected to give dry hair additional life, a soft feel, a glossy appearance and resistance to tangling.
pair treating formulations containing dilute aqueous, alcohol or dilute alcohol solutions of the modified polyvinyl alcohol polymer can be cr,lployed. Furthermore, they may be employed as creams, lotions, gels or as aerosol sprays. Thyme ~3~i~3~
be used in combination with perfumes, dyes, preserving agents, sequestering agents, thickening agents, emulsifying agents, etc.
Example B
A typical hair rinse formulation containing 5 grams of 5 the modified polymer of Example 8, 7 grams Swahili alcohol, 3 grams of a linear polyoxyethylenated C10-Cl8 fatty alcohol, 2 grams of a cozen derivative, 0.5 grams tetradecyltri~,ethyla~monium chloride and 82.5 grams of water and a minor amount of hair dye can be used to treat hair having improved looks and anti-static properties.
Example C
A typical oxidation hair dye solution containing a 2.5 gram of the modified polymer of Example 9, 10 trams bouncily alcohol, 20 grams oleic acid, 3 grams polyoxyethylene (30), Leo Seattle alcohol, 7 grams Olin diethanolamide, 7.5 grams 2 octyldo-15 decanol, 2.5 grams triethanolamine Laurie sulfate, 10 grams ethanol, 18 milliliters aqueous ammonium, 1 gram n,n-bis(2-hydroxy-ethanol)parapherlylenediamine, 0.4 grams resorcin, 0.15 grams m-aminophenol, .4 grams alphanaphthol, 0.1 grams hydra-quinine, 0 24 grams ethylene Damon tetracetic acid, 1 milliliter 20 sodium bisulfite, and water sufficient to make 100 grams is a typical ammo a oil composition for use as an oxidation hair dye when 130 grams of the solution is mixed with 30 grams of hydrogen peroxide bleach. After hair is treated with the material and allowed to stand for 30-40 minutes and thereafter rerinsed the us hair is expected to untangle easily and Dave a spiky touch.
The modified polyvinyl alcohol compositions ox the invention may be explored to improve the elegance and stability of personal care products such as liquid and bar soaps, shaving creams, bath products, antiperspirants, sunscreens, cleansing 30 creams and as a suspending agents for insoluble pigments and pharmaceutical active. Improvement is generally realized when so ~66;~9 from 0.5-5~ by weight of the compositions of this invention are employed in conventional formulations as hereinafter exemplified.
-- Roll-On Antiperspirant e :5 Ingredient % WOW
Example 3 4.0 polyoxyethylene (21) stearylether 0.76 polyoxyehtylene (2) stearylether 3.24 water (deionized) 34.76 : 10 Dozily 200~, Dow Chemical 0.
: Al Or tetrachlorohydrex-Gly, : Russell 36G, Rehems 57.14 : Example E
Aerosol Shave Cream Ingredient % W/W
Example 3 5.0 Seattle alcohol 4.3 polyoxyethylene (21) stearylether 2.2 sorbic acid .17 20 water 74.9 : : fragrance .08 : water 13.35 :
Example F
Oil-in-Water sun are en Lotion us ln~redien~ W/W :
monorail : :18.~ :
c~tyl:alcohol 5.0 :
Aurelius emulsifier 2.5 Tween:60~:emulsifier:: : : 7.5 30 Amy para~-dimethylaminobenzoic acid 1~.2 Employ 2 0 Jo rreser-ative~ us ,,,,.~ ,. .. . .
. , : ; Jo .: ' ' .
, `::
~23~63~
Example G
Water-in-Oil Pigmented Makeup - Ingredient W/W %
Mineral Oil 10 5 Beeswax 1.5 Cevesin wax 1.0 Arlacel 186P emulsifier 3.2 Sorb sorbitol 28.8 Two and other pigments 20.0 10 water 33.5 Example 6 2.C
Example H
Calamine Lotion Calamine 80 gyms Zinc Oxide 80 gyms glycerine 20 mls bentonite magma 250 mls calcium hydroxide 950 mls (concentrated aqueous sol.) Example 1 50 gyms :: :
::
, ``
:
:, I`
Claims (22)
1. A quaternary nitrogen modified polyvinyl alcohol polymer useful in skin conditioning, cosmetic, and pharmaceutical formulations which comprises a polyvinyl alcohol base chain having oxygen linked pendant groups of the general formula:
-R-N+R1R2R3A-whewein R is selected from the group consisting of an alkylene, 2 hydroxy alkylene, or acylene radical, R1, R2 and R3 are selected from the group consisting of alkyl or arylalkyl radicals having 1-20 carbon atoms, A- , is an anion, said polymers having a total nitrogen content ranging from 0.01%-7% by weight.
-R-N+R1R2R3A-whewein R is selected from the group consisting of an alkylene, 2 hydroxy alkylene, or acylene radical, R1, R2 and R3 are selected from the group consisting of alkyl or arylalkyl radicals having 1-20 carbon atoms, A- , is an anion, said polymers having a total nitrogen content ranging from 0.01%-7% by weight.
2. A composition of Claim 1 wherein said polyvinyl alcohol base chain has a number average molecular weight of at least 2,000.
3. A composition of Claim 1 wherein R is a radical selected from the group consisting of -CH2-CHOH-CH2- and -[(CH2CH(CH2N+R1R2R3A-)O]nCH2CH(OH)CH2-wherein R1, R2 and R3 are alkyl and arylalkyl radicals having 1-70 carbon atoms and A- is halide or lower alkylsulfate ion and n =
1-20.
1-20.
4. A composition of Claim 3 wherein said pendant group is -COCH2N+R1R2R3A-.
5. A composition of Claim 3 wherein R1, R2 and R3 are selected from the group consisting of -CH3, -CH2CH3, -CH2CH2CH3, , and -CH2Ph where Ph is phenyl.
6. A composition of Claim 4 wherein R1, R2 and R3 are selected from the group consisting of -CH3, -CH2-CH3, -CH2CH2CH3, , and -CH2Ph where Ph is phenyl.
7. A composition of Claim 3 wherein R1, R2 and R3 are methyl groups and the nitrogen content ranges from 0.01-3% by weight.
8. A composition of Claim 4 wherein R1, R2 and R3 are methyl groups and the nitrogen content ranges from 0.1 to 3% by weight.
9. A composition of Claim 1 prepared by the steps of (a) reacting equimolar quantities of epichlorohydrin with aqueous trimethylamine at temperatures below 25°C and (b) reacting at 40-90°C the aqueous product of step (a) with an aqueous dispersion of polyvinyl alcohol having a number average molecular weight of at least 2,000 containing catalytic quantities of base.
10. A composition of Claim 1 when made by reacting (chlorohydroxypropyl)trialkylammonium chloride in aqueous solution or crystalline form with an aqueous solution of polyvinyl alcohol having a number average molecular weight of at least 2,000, said solution containing catalytic quantities of potassium hydroxide, and maintaining the resulting reaction mixture at 40-90°C.
11. A composition of Claim 1 when made by reacting an aqueous dispersion of polyvinyl alcohol polymer having a number average molecular weight of at least 2,000 with an aqueous solution of 2,3-epoxypropyl trialkylammonium halide, said reaction being carried out at a temperature of 40-90°C in the presence of a catalytic amount of base in amounts wherein the mol ratio of said ammonium halide to each mol of hydroxyl group on the polyvinyl alcohol polymer ranges from 0.003-1.
12. A composition of Claim 1 when made by reacting an aqueous dispersion of polyvinyl alcohol polymer having a number average molecular weight of at least 2,000 with an aqueous solution of 2,3-epoxypropyltrialkylammomium halide at a temperature of 40-90°C in the presence of a catalytic amount of acid in amounts wherein the mol ratio of said ammonium halide to each mol of hydroxyl group on the polyvinyl alcohol polymer ranges from 0.003-1.
13. A composition of Claim 1 when made by reacting 2,3-epoxypropyltrimethylammonium chloride in aqueous solution or crystalline form with an aqueous dispersion of polyvinyl alcohol having number average molecular weight ranging from 2,000-200,000 and a random distribution of oxygen linked pendant groups having a general formula:
-R-N+R1R2R3A-wherein R is selected from the groups consisting of alkylene, a hydroxy alkylene, or acylene radical.
-R-N+R1R2R3A-wherein R is selected from the groups consisting of alkylene, a hydroxy alkylene, or acylene radical.
14. A composition of Claim 1 when made by reacting 2,3-epoxypropyltrimethylammomium chloride in aqueous solution with an aqueous dispersion of polyvinyl alcohol having a number average molecular weight of at least 2,000, said reaction being carried out at a temperature of 40-90°C in the presence of a catalytic amount of base in amounts wherein the mol radio of said ammonium halide to each mol of hydroxyl group on the polyvinyl alcohol polymer ranges from 0.003-1.
15. A composition of Claim 1 when prepared by reacting polyvinyl alcohol, having a number average molecular weight of at least 2,000 with trimethylethoxycarbonylmethylammonium halide in dipolar aprotic solution to which catalytic quantities of manganese acetate are added, said reaction being carried out at a temperature of 100-150°C for about 5-8 hours.
16. A composition of Claim 1 made by a process wherein benzyldimethylethoxycarbonylmethylammonium halide in aqueous solution or crystalline form is added to an aqueous dispersion of polyvinyl alcohol containing catalytic quantities of potassium hydroxide and maintaining said resulting mixture at 40-90°C until reaction is complete.
17. A composition of Claim 1 which is separated from an aqueous reaction mixture by precipitation through the addition of a nonsolvent selected from the group consisting of acetone and methanol.
18. A composition of Claim 1 which is purified by dialysis or ultrafiltration.
19. An aqueous dispersion comprising from 0.1-30% by weight of a composition of Claim 1.
20. An aqueous skin conditioning composition comprising, 0.1-10.0% by weight of a composition of Claim 1, 2-5%
by weight of an emulsifier, and 2-5% by weight of an emollient.
by weight of an emulsifier, and 2-5% by weight of an emollient.
21. An aqueous hair conditioning composition comprising 0.1-10% by weight of a composition of Claim 1.
22. A composition of Claim 1 wherein said polyvinyl alcohol is a copolymer having 1% to 25% by weight of polyvinyl acetate, polyvinylacrylate, polyvinylmethacrylate and polyvinyl-pyrolidone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54004183A | 1983-10-07 | 1983-10-07 | |
| US06/540,041 | 1983-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1236639A true CA1236639A (en) | 1988-05-10 |
Family
ID=24153730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000463380A Expired CA1236639A (en) | 1983-10-07 | 1984-09-17 | Quaternary nitrogen containing polyvinyl alcohol polymers for use in skin conditioning, cosmetic and pharmaceutical formulations |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS60133008A (en) |
| AU (1) | AU564745B2 (en) |
| CA (1) | CA1236639A (en) |
| MX (1) | MX202910A (en) |
| NZ (1) | NZ209699A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0627205B2 (en) * | 1986-12-27 | 1994-04-13 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for packaging alkaline substances |
| CN114040745A (en) * | 2019-07-03 | 2022-02-11 | 株式会社资生堂 | Cosmetic method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523689A (en) * | 1975-06-27 | 1977-01-12 | Yotsukaichi Gosei Kk | Process for preparing cationic high polymers |
| JPS5811046A (en) * | 1981-07-13 | 1983-01-21 | Mitsubishi Chem Ind Ltd | Porous anion exchange resin and production thereof |
-
1984
- 1984-09-17 CA CA000463380A patent/CA1236639A/en not_active Expired
- 1984-09-25 AU AU33479/84A patent/AU564745B2/en not_active Ceased
- 1984-09-27 NZ NZ20969984A patent/NZ209699A/en unknown
- 1984-10-01 MX MX20291084A patent/MX202910A/en unknown
- 1984-10-08 JP JP21120584A patent/JPS60133008A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| MX202910A (en) | 1994-02-28 |
| JPS60133008A (en) | 1985-07-16 |
| NZ209699A (en) | 1987-11-27 |
| AU3347984A (en) | 1985-04-18 |
| AU564745B2 (en) | 1987-08-27 |
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