CA1057746A - Propylene glycol alginic acid esters - Google Patents
Propylene glycol alginic acid estersInfo
- Publication number
- CA1057746A CA1057746A CA260,371A CA260371A CA1057746A CA 1057746 A CA1057746 A CA 1057746A CA 260371 A CA260371 A CA 260371A CA 1057746 A CA1057746 A CA 1057746A
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- alginic acid
- reaction
- propylene glycol
- equivalent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Alginic acid which has been neutralized to the ex-tent of about 0.2 - 17 mole percent, preferably about 3 - 12 mole percent, and has a solids content of from about 20 to about 80 weight percent, is reacted with propylene oxide at a temperature of from about 60°C. to about 140°C., at a pressure sufficient to maintain the propylene glycol in liquid phase. The reaction is complete when a 2 percent (weight) solution of the propylene glycol alginate has a pH
of from about 3.4 to about 4.9. The reaction is conducted in the substantial absence of any gas other than that present due to the vapor pressure of the reactants.
Alginic acid which has been neutralized to the ex-tent of about 0.2 - 17 mole percent, preferably about 3 - 12 mole percent, and has a solids content of from about 20 to about 80 weight percent, is reacted with propylene oxide at a temperature of from about 60°C. to about 140°C., at a pressure sufficient to maintain the propylene glycol in liquid phase. The reaction is complete when a 2 percent (weight) solution of the propylene glycol alginate has a pH
of from about 3.4 to about 4.9. The reaction is conducted in the substantial absence of any gas other than that present due to the vapor pressure of the reactants.
Description
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This invention relates to a process for the prepara-tion of propylene glycol alginate. More specifically, alginic acid which has been neutralized to the extent of about 0.2 -17 mole percent, preferably about 3 - 12 mole percent, and has a solids content of from about 20 to about 80 weight percent, is reacted with propylene oxide at a temperature of from about 60C to about 140C, at a pressure sufficient to main-tain the propylene ylycol in liquid phase. The reaction is complete when a 2 percent (weight) solution of the propylene glycol alginate has a pH of from about 3.4 to about 4.9. The reaction is conducted ir, the substantial absence of any gas other than that present due to the vapor pressure of the reactants.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of our process, partially neutra-lized alginic acid is employed as a reactant. This reactant material may be prepared by partially neutralizing alginic acid by reaction with a base or basic salt or other material which when combined with the alginic acid will form a salt of the alginic acid, desirably a water soluble product salt.
Typical of such reactants are ammonium hydroxide, the lower alkyl amines, alkali and alkaline earth hydroxides and car-bonates and basic salts. Examples of such bases and basic salts are sodium hydroxide, sodium bicarbonate, sodium car-bonate, trisodium phosphate, potassium carbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, ammonia (NH3) and magnesium carbonate. The alginic acid _ '~
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This invention relates to a process for the prepara-tion of propylene glycol alginate. More specifically, alginic acid which has been neutralized to the extent of about 0.2 -17 mole percent, preferably about 3 - 12 mole percent, and has a solids content of from about 20 to about 80 weight percent, is reacted with propylene oxide at a temperature of from about 60C to about 140C, at a pressure sufficient to main-tain the propylene ylycol in liquid phase. The reaction is complete when a 2 percent (weight) solution of the propylene glycol alginate has a pH of from about 3.4 to about 4.9. The reaction is conducted ir, the substantial absence of any gas other than that present due to the vapor pressure of the reactants.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of our process, partially neutra-lized alginic acid is employed as a reactant. This reactant material may be prepared by partially neutralizing alginic acid by reaction with a base or basic salt or other material which when combined with the alginic acid will form a salt of the alginic acid, desirably a water soluble product salt.
Typical of such reactants are ammonium hydroxide, the lower alkyl amines, alkali and alkaline earth hydroxides and car-bonates and basic salts. Examples of such bases and basic salts are sodium hydroxide, sodium bicarbonate, sodium car-bonate, trisodium phosphate, potassium carbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, ammonia (NH3) and magnesium carbonate. The alginic acid _ '~
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1 employed in our process is partially neutralized to the
2 extent that about 0.2 to 17 mole percent, and preferably
3 about 3 - 12 mole percent of the carboxyl groups in the
4 alginic acid are neutralized.
Following tha partial neutralization of the 6 alginic acid, the solids content of the partially neutra-7 lized acid is adjusted to about 20 to 80~ by weight, i.e., 8 a liquid content on the order of about 80 to 20 percent 9 by weight. The liquid present in the partially neutralized acid is normally water but may be an admixture with a 11 water miscible solvent, such as a lower alcohol, e.g., 12 isopropyl alcohol.
13 The moisture content of the partially neutralized 14 alginic acid may be reduced by gentle drying or by extrac-tion with an alcohol or ketone.
16 The reaction time is increased (esterification 17 rate decreases) considerably when the solids content of 18 the partially neutralized alginic acid reactant is more 19 than about 80% by weight.
It has been discovered that substantial benefits 21 are obtained if the reaction is carried out with liquid 22 propylene oxide in contact with the deined alginic acid.
23 The invention is further described by the 24 following examples.
~-1923 15~S7746 2 Into a stainless steel bomb reactor fitted with 3 a pressure gauge, an evacuation port and thermometer well 4 was placed twenty-five grams of 30 percent solids alginic acid containing residual calcium at 2.2 equivalent percent 6 and which had been further neutralized with NaOH for a 7 total of 15.2 equivalent percent. The alginic acid fibers 8 were covered by li~uid propylene oxide, which was accom-9 plished by using 130 gms. of li~uid. The air over the liguid was removed by using a water aspirator. The bomb 11 was then sealed and brought to temperature by partial 12 immer5ion in a hot water bath at 89C. The temperature 13 ro5e to 79C. within S minutes and was maintained at 80C.
14 for 25 minutes. The pressure was at 50 psig. During this lS time no mechanical agitation was provided, because the 16 fibers were being buffeted by the boiling liquid within the 17 partially immersed bomb. Ater a total of 30 minutes of 18 reaction, the bomb was removed from the bath and placed 19 into a stream of cold water. The reaction temperature and presRure were reduced to ambient values within two mi~utes.
21 The bomb was then opened and the contents placed on a vacuum 22 filtor where the fiber~ were washed with acetone.
23 The analysis was as follows: Ester (COOR where O
24 R - C~2-C~C~3 84%, Na 13%, Ca 2.2~, and free acid (COOH) 0.8~; No product pH was obtained. (Owing to the nature 26 of the analytical procedures, the ~l~" given do not 27 alway~ add to 100%.) 1~57 7~
2 Into the stainless steel bomb was placed about 3 50 grams of 47 percent solids alginic acid that contained 4 2.1 equivalent percent sodium and 14.7 equivalent percent calcium. The average temperature was 76C. After 50 6 minutes the reactor was rapidly cooled and opened. After 7 filtration, the product when dissolved in water, gave a 8 1.6 percent solution viscosity of 18 cps. The solution 9 wàs clear with only trace sediment or haze, and the pH
was 3.9. Subsequent beer foam stability tests showed it 11 to be the equal of the standard propylene glycol beer foam 12 stabilizer. Free acidity and percent ester content were 13 not obtained.
Glycol production was measured for a liquid 16 propylene oxide reaction. Into the bomb reactor was 17 placed 10.7 g. of alginic acid containing 4.4 equivalent 18 percent of residual calcium and was then further neutra-19 lized to a total of 17.6 equivalent percent using NaOH;
percent solids not available. The fibers were covered 21 with an excess of propylene oxide liquid and the bomb 22 evacuated and sealed. The reaction took place at 80C.
23 The average pressure was 50 psig. and the time was 2 hours.
24 The resultant product had an analysis as follows: pH 4.3, ester 72%, acid 10.6%, Na 13.4%, calcium 4.4 equivalent 26 percent. There was produced 0.15 grams of propylene glycol 27 per gram of anhydrous weight starting alginic acid.
l~S7746 _ 2 As a comparison to Example 2 another alginic 3 acid with high neutralization was used. This acid was 4 70 percent solids and contained 15 equivalent percent sodium and 2.4 equivalent percent calcium. The alginic 6 acid was placed into the stainless steel bomb and reacted 7 at 80C. for 2 hours, at 50 psig. The reaction was 8 terminated by rapid cooling. The filtered product has 9 a l percent in water viscosity of 19 cps; equivalent to 35 cps at 1.6% solution; and a pH 4.2. The analysis ll showed it to contain 8.2 percent free acid and 74.4 percent 12 ester. This product was not acceptably clear and free 13 of sediment for some uses, and, thus, the 17.4 equivalent 14 percent neutralization appears to be near the upper limit for this reaction.
17 Into the stainless steel bomb was placed 12.2 g.
18 of 74 percent solids alginic acid, i.e., 9.0 grams of l9 anhydrous weight algin and 3.2 grams of water. One hundred thirty grams of liquid propylene oxide was added 21 to this. The bomb was sealed and the reaction was run at a 22 temperature to 85C. After reactio~ termination the 23 product had the following characteristics: Free acid 27.8 24 equivalent percent, ester 71.8 equivalent percent, sodium 0.2 equivalent percent, calcium 0.2 equivalent percent and 26 glycol by product l.S grams.
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2 Into a large stainless steel pressure vessel 3 fitted with a stirrer a propylene oxide inlet port and 4 a pressure guage was added through the inlet port 20.6
Following tha partial neutralization of the 6 alginic acid, the solids content of the partially neutra-7 lized acid is adjusted to about 20 to 80~ by weight, i.e., 8 a liquid content on the order of about 80 to 20 percent 9 by weight. The liquid present in the partially neutralized acid is normally water but may be an admixture with a 11 water miscible solvent, such as a lower alcohol, e.g., 12 isopropyl alcohol.
13 The moisture content of the partially neutralized 14 alginic acid may be reduced by gentle drying or by extrac-tion with an alcohol or ketone.
16 The reaction time is increased (esterification 17 rate decreases) considerably when the solids content of 18 the partially neutralized alginic acid reactant is more 19 than about 80% by weight.
It has been discovered that substantial benefits 21 are obtained if the reaction is carried out with liquid 22 propylene oxide in contact with the deined alginic acid.
23 The invention is further described by the 24 following examples.
~-1923 15~S7746 2 Into a stainless steel bomb reactor fitted with 3 a pressure gauge, an evacuation port and thermometer well 4 was placed twenty-five grams of 30 percent solids alginic acid containing residual calcium at 2.2 equivalent percent 6 and which had been further neutralized with NaOH for a 7 total of 15.2 equivalent percent. The alginic acid fibers 8 were covered by li~uid propylene oxide, which was accom-9 plished by using 130 gms. of li~uid. The air over the liguid was removed by using a water aspirator. The bomb 11 was then sealed and brought to temperature by partial 12 immer5ion in a hot water bath at 89C. The temperature 13 ro5e to 79C. within S minutes and was maintained at 80C.
14 for 25 minutes. The pressure was at 50 psig. During this lS time no mechanical agitation was provided, because the 16 fibers were being buffeted by the boiling liquid within the 17 partially immersed bomb. Ater a total of 30 minutes of 18 reaction, the bomb was removed from the bath and placed 19 into a stream of cold water. The reaction temperature and presRure were reduced to ambient values within two mi~utes.
21 The bomb was then opened and the contents placed on a vacuum 22 filtor where the fiber~ were washed with acetone.
23 The analysis was as follows: Ester (COOR where O
24 R - C~2-C~C~3 84%, Na 13%, Ca 2.2~, and free acid (COOH) 0.8~; No product pH was obtained. (Owing to the nature 26 of the analytical procedures, the ~l~" given do not 27 alway~ add to 100%.) 1~57 7~
2 Into the stainless steel bomb was placed about 3 50 grams of 47 percent solids alginic acid that contained 4 2.1 equivalent percent sodium and 14.7 equivalent percent calcium. The average temperature was 76C. After 50 6 minutes the reactor was rapidly cooled and opened. After 7 filtration, the product when dissolved in water, gave a 8 1.6 percent solution viscosity of 18 cps. The solution 9 wàs clear with only trace sediment or haze, and the pH
was 3.9. Subsequent beer foam stability tests showed it 11 to be the equal of the standard propylene glycol beer foam 12 stabilizer. Free acidity and percent ester content were 13 not obtained.
Glycol production was measured for a liquid 16 propylene oxide reaction. Into the bomb reactor was 17 placed 10.7 g. of alginic acid containing 4.4 equivalent 18 percent of residual calcium and was then further neutra-19 lized to a total of 17.6 equivalent percent using NaOH;
percent solids not available. The fibers were covered 21 with an excess of propylene oxide liquid and the bomb 22 evacuated and sealed. The reaction took place at 80C.
23 The average pressure was 50 psig. and the time was 2 hours.
24 The resultant product had an analysis as follows: pH 4.3, ester 72%, acid 10.6%, Na 13.4%, calcium 4.4 equivalent 26 percent. There was produced 0.15 grams of propylene glycol 27 per gram of anhydrous weight starting alginic acid.
l~S7746 _ 2 As a comparison to Example 2 another alginic 3 acid with high neutralization was used. This acid was 4 70 percent solids and contained 15 equivalent percent sodium and 2.4 equivalent percent calcium. The alginic 6 acid was placed into the stainless steel bomb and reacted 7 at 80C. for 2 hours, at 50 psig. The reaction was 8 terminated by rapid cooling. The filtered product has 9 a l percent in water viscosity of 19 cps; equivalent to 35 cps at 1.6% solution; and a pH 4.2. The analysis ll showed it to contain 8.2 percent free acid and 74.4 percent 12 ester. This product was not acceptably clear and free 13 of sediment for some uses, and, thus, the 17.4 equivalent 14 percent neutralization appears to be near the upper limit for this reaction.
17 Into the stainless steel bomb was placed 12.2 g.
18 of 74 percent solids alginic acid, i.e., 9.0 grams of l9 anhydrous weight algin and 3.2 grams of water. One hundred thirty grams of liquid propylene oxide was added 21 to this. The bomb was sealed and the reaction was run at a 22 temperature to 85C. After reactio~ termination the 23 product had the following characteristics: Free acid 27.8 24 equivalent percent, ester 71.8 equivalent percent, sodium 0.2 equivalent percent, calcium 0.2 equivalent percent and 26 glycol by product l.S grams.
1t)577~f~
2 Into a large stainless steel pressure vessel 3 fitted with a stirrer a propylene oxide inlet port and 4 a pressure guage was added through the inlet port 20.6
5 lbs. of propylene oxide liquid. Agitation was begun and
6 the temperature was raised until the internal pressure
7 reached 40 psig. No temperature could be taken but the
8 boiling point of the liquid propylene oxide at 40 pcig.
9 is about 75C. The reaction was run under these conditions for 2 hours and 10 minutes. The product was washed with 11 isopropyl alcohol and centrifuged to remove liquid. The 12 product was then dried in a circulating air oven.
13 The analysis of the product was as follows:
14 Free acid 4.25%, ester 88.0%, Na 0.4%, Ca 7.5% and pH
4.3.
16 Glycol production based on both what was found -17 in the product and in the wash solvent amounted to 0.16 18 lbs./lb. of anhydrous alginic acid.
Into the stainless steel bomb was placed 100 gms.
21 of 34 percent solids alginic acid that contained as a resi-22 due 0.7 equivalent percent sodium and 0.3 equivalent percent 23 calcium. The reaction was run with the temperature main-24 tained at 71C. for 2 hours. The product had the following characteristics: pH 3.4, free acid 9.2 equivalent percent, 26 ester 89.8 equtvalent percent, sodium 0.7 equivalent percent 27 and calcium 0.3 equivalent percent.
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.
2 Into the stainless steel bomb was placed 100 3 gms. of 34 percent solids alginic acid. This was the same 4 acid as in Example 7. The reaction was run as in Example 7 except that the temperature was raised to 80C. for the 6 two hour reaction period.
7 The product had the following characteristics:
8 pH 3.8, free acid 2.7 equivalent percent, ester 96.3 equi-9 valent percent, sodium 0.7 equivalent percent and calcium 0.3 equivalent percent.
12 Into a stainless steel bomb was placed 30 gms.
13 of 34 percent solids alginic acid that contained an addi-14 tional 20 gms. of isopropYl alcohol. The alginic acid had 0.3 equivalent percent sodium and 0.2 equivalent 16 percent calcium as residual partial neutralization. The 17 reaction was run for two hours attaining a temperature 18 of 85C. and a pressure of 47 psig. The product had the 19 following characteristics: 3.6 pH, 3.6 equivalent percent free acid, 95.9 equivalent percent ester, 0.3 equivalent 21 percent sodium and 0.2 equivalent percent calcium. The 22 product was readily soluble and formed a clear solution 23 in water.
Into the bomb reactor was placed 50 grams of 26 alginic acid at 34 percent solids. This acid had been 27 washed three times with a 5 percent HCl solution to remove 1~7'7~
1 more of the residual sodium and calcium from the precipita-2 tion process. There still remained 0.3 equivalent percent 3 sodium and 0.1 equivalent percent calcium. The reaction 4 was made to proceed as that in Example 1. The average temperature of reaction was 85C. and the average 6 pressure was 51 psig. The reaction proceeded for 2 hrs.
7 and produced a product of pH 3.8.
8 This product was for low viscosity applications 9 and had a 1 percent viscosity in water of 9.0 cps. equi-valent to 20 cps. at 1.6%. The solution was clear and the 11 product had the following analysis: Free acid 2.2 equi-12 valent percent, ester 9?.4 equivalent percent, sodium 0.3 13 equivalent percent, calcium 01. equivalent percent. There 14 was produced 1.53 lbs. of glycol per pound of anhydrous alginic acid.
16 Comparative Examples 11-14 were carried out using 17 gaseous propylene oxide reaction conditions.
18 ExAMæLE 11 19 As a comparison to the liquid reactions of Examples 1-11, the following gaseous propylene oxide reaction 21 was carried out to reveal the added time required to run a 22 gaseous reaction versus a liquid reaction.
23 Into a glass tum~ler reactor of 5 liters capacity 24 and fitted with lifting vanes for agitation was placed 227 grams of 73.5 percent solids alginic acid. This acid con-26 tained 2.2 equivalent percent residual calcium and was 27 further neutralized to 11.7 total equivalent percent with 28 NaOH. The reactor was evacuated of air using a water ia~5774~
1 aspirator, then when the evacuation was terminated, after 2 about 3 minutes, there was introduced from an adjacent 3 propylene oxide boiler, propylene oxide gas at about 4 3 psig. This proylene oxide pressure remained throughout the reaction. The tumbler was set in motion in a hot water 6 bath and the fibers were lifted and dropped through the 7 propylene oxide atmosphere. The reaction reached 81C.
8 in 10 minutes and averaged 80C. for a total reaction time g of 2 hours and 5 minutes. At the end of this time the vessel was re-evacuated using a water aspirator, thus, 11 terminating the reaction. The results of this reaction 12 are listed below: 3.9 equivalent percent free acid; 85.2 13 equivalent percent ester; 9.5 equivalent percent Na;
14 2.2 equivalent percent Ca. pH is not available.
16 One hundred grams of 70 percent solids alginic 17 acid containing 9.6 equivalent percent calcium and 1.5 18 equivalent percent sodium was placed into a glass tumbler 19 reactor as described in Example 12. The reaction proceeded at a temperature of 70C. and a pressure of about 2 psig.
21 for 3-1/2 hours. The product had a pH of 3.7 and an 22 analysis as follows: Free acid 5.5%, ester 84.4%, sodium 23 1.5~, and calcium 8.6 equivalent percent.
24 The amount of glycol produced was 0.65 lbs./lb.
of anhydrous alginic acid.
27 As a speed of reaction comparicon to Example 10, 28 a low neutralized alginic acid was used in a gaseous 29 propylene oxide reaction. Into the sarne S liter tumbler _ 9 _ lV5774~;i 1 reactor used in Example 11 was placed 240 grams of 71 2 percent solids alginic acid containing 0.5 equivalent 3 percent residual Na and 2.6 equivalent percent residual 4 Ca. The reaction was run in a like manner as Example 11 for 7 hours at 81C. at about 2 psig. The product reached 6 a pH of 3.1 and had the following analysis in equivalent 7 percent: Free acid 9.1 percent, ester 87.8 percent, 8 sodium 0.5 percent and calcium 2.6 percent. This product 9 is under reacted after 7 hours time.
11 The data for Example 14,which is summarized 12 in the Table below, is taken from Example 1 of U.S.
13 Patent 3,772,266.
TABLE
The results of the above examples are more 16 easily grasped and the benefit of the process of the 17 instant invention more vividly displayed when set forth 18 in tabular form. In the table, the percent metal content 19 of the preneutralized alginic acid charge, the percent solids content of said acid charge, the temperature C.
21 at which the reaction was carried out, the time in minutes 22 of the reaction period, the percent free acid (nonreacted 23 COOH groups); the total COOH groups reacted as percent 24 reacted and the pH of a water solution of the ester product of the example. Where information was not recorded, a NA
26 (not available) i~ noted.
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13 The analysis of the product was as follows:
14 Free acid 4.25%, ester 88.0%, Na 0.4%, Ca 7.5% and pH
4.3.
16 Glycol production based on both what was found -17 in the product and in the wash solvent amounted to 0.16 18 lbs./lb. of anhydrous alginic acid.
Into the stainless steel bomb was placed 100 gms.
21 of 34 percent solids alginic acid that contained as a resi-22 due 0.7 equivalent percent sodium and 0.3 equivalent percent 23 calcium. The reaction was run with the temperature main-24 tained at 71C. for 2 hours. The product had the following characteristics: pH 3.4, free acid 9.2 equivalent percent, 26 ester 89.8 equtvalent percent, sodium 0.7 equivalent percent 27 and calcium 0.3 equivalent percent.
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2 Into the stainless steel bomb was placed 100 3 gms. of 34 percent solids alginic acid. This was the same 4 acid as in Example 7. The reaction was run as in Example 7 except that the temperature was raised to 80C. for the 6 two hour reaction period.
7 The product had the following characteristics:
8 pH 3.8, free acid 2.7 equivalent percent, ester 96.3 equi-9 valent percent, sodium 0.7 equivalent percent and calcium 0.3 equivalent percent.
12 Into a stainless steel bomb was placed 30 gms.
13 of 34 percent solids alginic acid that contained an addi-14 tional 20 gms. of isopropYl alcohol. The alginic acid had 0.3 equivalent percent sodium and 0.2 equivalent 16 percent calcium as residual partial neutralization. The 17 reaction was run for two hours attaining a temperature 18 of 85C. and a pressure of 47 psig. The product had the 19 following characteristics: 3.6 pH, 3.6 equivalent percent free acid, 95.9 equivalent percent ester, 0.3 equivalent 21 percent sodium and 0.2 equivalent percent calcium. The 22 product was readily soluble and formed a clear solution 23 in water.
Into the bomb reactor was placed 50 grams of 26 alginic acid at 34 percent solids. This acid had been 27 washed three times with a 5 percent HCl solution to remove 1~7'7~
1 more of the residual sodium and calcium from the precipita-2 tion process. There still remained 0.3 equivalent percent 3 sodium and 0.1 equivalent percent calcium. The reaction 4 was made to proceed as that in Example 1. The average temperature of reaction was 85C. and the average 6 pressure was 51 psig. The reaction proceeded for 2 hrs.
7 and produced a product of pH 3.8.
8 This product was for low viscosity applications 9 and had a 1 percent viscosity in water of 9.0 cps. equi-valent to 20 cps. at 1.6%. The solution was clear and the 11 product had the following analysis: Free acid 2.2 equi-12 valent percent, ester 9?.4 equivalent percent, sodium 0.3 13 equivalent percent, calcium 01. equivalent percent. There 14 was produced 1.53 lbs. of glycol per pound of anhydrous alginic acid.
16 Comparative Examples 11-14 were carried out using 17 gaseous propylene oxide reaction conditions.
18 ExAMæLE 11 19 As a comparison to the liquid reactions of Examples 1-11, the following gaseous propylene oxide reaction 21 was carried out to reveal the added time required to run a 22 gaseous reaction versus a liquid reaction.
23 Into a glass tum~ler reactor of 5 liters capacity 24 and fitted with lifting vanes for agitation was placed 227 grams of 73.5 percent solids alginic acid. This acid con-26 tained 2.2 equivalent percent residual calcium and was 27 further neutralized to 11.7 total equivalent percent with 28 NaOH. The reactor was evacuated of air using a water ia~5774~
1 aspirator, then when the evacuation was terminated, after 2 about 3 minutes, there was introduced from an adjacent 3 propylene oxide boiler, propylene oxide gas at about 4 3 psig. This proylene oxide pressure remained throughout the reaction. The tumbler was set in motion in a hot water 6 bath and the fibers were lifted and dropped through the 7 propylene oxide atmosphere. The reaction reached 81C.
8 in 10 minutes and averaged 80C. for a total reaction time g of 2 hours and 5 minutes. At the end of this time the vessel was re-evacuated using a water aspirator, thus, 11 terminating the reaction. The results of this reaction 12 are listed below: 3.9 equivalent percent free acid; 85.2 13 equivalent percent ester; 9.5 equivalent percent Na;
14 2.2 equivalent percent Ca. pH is not available.
16 One hundred grams of 70 percent solids alginic 17 acid containing 9.6 equivalent percent calcium and 1.5 18 equivalent percent sodium was placed into a glass tumbler 19 reactor as described in Example 12. The reaction proceeded at a temperature of 70C. and a pressure of about 2 psig.
21 for 3-1/2 hours. The product had a pH of 3.7 and an 22 analysis as follows: Free acid 5.5%, ester 84.4%, sodium 23 1.5~, and calcium 8.6 equivalent percent.
24 The amount of glycol produced was 0.65 lbs./lb.
of anhydrous alginic acid.
27 As a speed of reaction comparicon to Example 10, 28 a low neutralized alginic acid was used in a gaseous 29 propylene oxide reaction. Into the sarne S liter tumbler _ 9 _ lV5774~;i 1 reactor used in Example 11 was placed 240 grams of 71 2 percent solids alginic acid containing 0.5 equivalent 3 percent residual Na and 2.6 equivalent percent residual 4 Ca. The reaction was run in a like manner as Example 11 for 7 hours at 81C. at about 2 psig. The product reached 6 a pH of 3.1 and had the following analysis in equivalent 7 percent: Free acid 9.1 percent, ester 87.8 percent, 8 sodium 0.5 percent and calcium 2.6 percent. This product 9 is under reacted after 7 hours time.
11 The data for Example 14,which is summarized 12 in the Table below, is taken from Example 1 of U.S.
13 Patent 3,772,266.
TABLE
The results of the above examples are more 16 easily grasped and the benefit of the process of the 17 instant invention more vividly displayed when set forth 18 in tabular form. In the table, the percent metal content 19 of the preneutralized alginic acid charge, the percent solids content of said acid charge, the temperature C.
21 at which the reaction was carried out, the time in minutes 22 of the reaction period, the percent free acid (nonreacted 23 COOH groups); the total COOH groups reacted as percent 24 reacted and the pH of a water solution of the ester product of the example. Where information was not recorded, a NA
26 (not available) i~ noted.
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Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of propylene glycol alginate which process comprises:
(1) reacting (a) an alginic acid which is neutralized to the extent of from about 0.2 mole % to about 17 mole %; and (b) has a solids content of from about 20 to about 80 weight percent;
(2) and propylene oxide;
(3) at a temperature from about 60°C. to about 140°C.; and (4) at a pressure sufficient to maintain the propylene oxide in liquid phase.
(1) reacting (a) an alginic acid which is neutralized to the extent of from about 0.2 mole % to about 17 mole %; and (b) has a solids content of from about 20 to about 80 weight percent;
(2) and propylene oxide;
(3) at a temperature from about 60°C. to about 140°C.; and (4) at a pressure sufficient to maintain the propylene oxide in liquid phase.
2. The process of Claim 1 wherein said alginic acid is partially neutralized by an ion from the class consisting of alkali metals, alkaline earth metals, ammonium, lower alkylamines and mixtures thereof.
3. The process of Claim 2 wherein said propylene glycol alginate produced has a pH, in a 2 weight percent solu-tion of said alginate in distilled water, of from about 3.4 to about 4.9.
4. The process of Claim 3 wherein about 3 mole percent to about 12 mole percent of the carboxyl groups of said alginic acid are neutralized.
5. The process of Claim 1 wherein said alginic acid reactant and said reaction conditions are coordinated to produce a propylene glycol alginate product having a pH, in a 2 weight percent solution of said alginate in distilled water, of about 3.8 - 4.5, in a reaction time of not more than about 2 hours.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61377575A | 1975-09-16 | 1975-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057746A true CA1057746A (en) | 1979-07-03 |
Family
ID=24458628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA260,371A Expired CA1057746A (en) | 1975-09-16 | 1976-09-01 | Propylene glycol alginic acid esters |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5236177A (en) |
| CA (1) | CA1057746A (en) |
| DE (1) | DE2641303A1 (en) |
| FR (1) | FR2324645A1 (en) |
| GB (1) | GB1563019A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264422A (en) * | 1986-06-30 | 1993-11-23 | Fidia S.P.A. | Esters of alginic acid with steroidal alcohols |
| IT1203814B (en) * | 1986-06-30 | 1989-02-23 | Fidia Farmaceutici | ESTERS OF ALGINIC ACID |
| PE20060468A1 (en) * | 2004-04-26 | 2006-07-06 | Cp Kelco Aps | DERMOPROTECTIVE COMPOSITION TO CONTROL SKIN ALKALINITY, INCLUDING CARBOXYLIC ACID POLYSACCHARIDS |
| JP4180023B2 (en) * | 2004-06-30 | 2008-11-12 | 株式会社資生堂 | Hair cosmetics |
| CN101168572B (en) * | 2007-11-08 | 2010-06-02 | 青岛明月海藻集团有限公司 | Method for producing propylene glycol alginate specially used for yoghourt |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426125A (en) * | 1944-04-03 | 1947-08-19 | Kelco Co | Manufacture of glycol alginates |
| GB676618A (en) * | 1947-09-12 | 1952-07-30 | Kelco Co | Alkylene glycol esters of alginic acid |
| CA942744A (en) * | 1970-12-11 | 1974-02-26 | David J. Pettitt | Method for preparing propylene glycol esters of alginic acid |
| CA1019326A (en) * | 1974-07-16 | 1977-10-18 | Uniroyal Ltd. | Process for the production of alkylene glycol alginates |
-
1976
- 1976-09-01 CA CA260,371A patent/CA1057746A/en not_active Expired
- 1976-09-08 GB GB3724476A patent/GB1563019A/en not_active Expired
- 1976-09-13 FR FR7627483A patent/FR2324645A1/en active Granted
- 1976-09-14 DE DE19762641303 patent/DE2641303A1/en not_active Withdrawn
- 1976-09-16 JP JP11127476A patent/JPS5236177A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5236177A (en) | 1977-03-19 |
| GB1563019A (en) | 1980-03-19 |
| FR2324645A1 (en) | 1977-04-15 |
| DE2641303A1 (en) | 1977-03-31 |
| FR2324645B1 (en) | 1980-04-30 |
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