CA2158072A1 - Method of production of copolymers of polyamino acids - Google Patents
Method of production of copolymers of polyamino acidsInfo
- Publication number
- CA2158072A1 CA2158072A1 CA002158072A CA2158072A CA2158072A1 CA 2158072 A1 CA2158072 A1 CA 2158072A1 CA 002158072 A CA002158072 A CA 002158072A CA 2158072 A CA2158072 A CA 2158072A CA 2158072 A1 CA2158072 A1 CA 2158072A1
- Authority
- CA
- Canada
- Prior art keywords
- carbons
- alcohol
- agents
- solution
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Copolymers of polyamino acids formed by reaction of an alcohol with maleic anhydride to form the half ester followed by addition of ammonia, ammonia and an amine, or ammonia and a polyamine. The mixture is then heated to 120 - 350 °C to form polysuccinimide or a derivative thereof. The resulting polysuccinimide may be hydrolyzed to form a derivative of polyaspartic acid or its salt.
Description
215~072 -METHOD ~F PRODUCTION OF COPOLYMERS OF POLYAMINO ACIDS
FIELD OF THE INVENTION
This invention relates to a method of synthesis of copolymers of polyamino acids and their salts.
DESCRIPTION OF RE~ATED ART
U.S. Pat.3,846,380 discleses the preparation and col"position of copolymers of polyamino acids by the reaction of polysucc;.,' Il' le with primary or secondary aliphatic amines, followed by alkaline hydrolysis to provide surface active agents. The polysuccinimide is formed by high temperature reaction in tetralin and further reacted with amines in the soivent dimethyi~ur,,,arr,'de. Emphasis is placed on long chain ali<ylamines having eight to twenty carbon atoms. The products formed are sald to have good solubilizing ability, emulsifying and dispersing propellies, as well as good foaming properties.
They are useful as foaming agents, solubilizing agents, dispersing agents, emulsifying agents, rust-proofing agents, fiber-treating agents, level dyelng agents and r~ta,Ji"g agents.
U.S. Pat. 3,351,520 i~closes the prep&rd~lon wet strength agents from maleic acid esters with amines followed by reaction with ep'ch'Qroi-,ydrin. i-xcess alcohol can function as a solvent for the reaction with the amine.
Summary ot the l,~,ntlGn We have discovered that polypeptWe n~ar;al~ that have a general formula of /R' -CH-CO-N and-CH-CO-NH-¦ R~ ¦ /R' C~-CO-NH- Ci~-CO-i~
R~
wherein R' is a hydrogen or an alkyi, an alkenyi or an amide group having 1 to 36 carbons and Rr is a hydrogen, an ali~yl, an alkenyi or an amide group having 1 to 36 carbons, together with at least one of the groups -CH-COOZ and -CH-CO-NH-Ci~-CO-NH- Ci~-COOZ
wherein Z represents a hydrogen atom, an a",r"or,ià l~~'ecu'~, an alkall metal or an alkaline earth metal, as a repeating unit, can be prepar~d by reacting maleic anhydride with an alcohol conldin Iq 1 to 36 carbons, preferably 1 to 20 carbons, and more pl~erdbly 1 to 5 carbons, to form the half ester followed by the addition of an equivalent of a"""onia, or arrlr"onià and an amine or a polyamine, containlng one to~6 carbons, preferably 8-20 carbons, and heatlng to 120~50C, pr~r~ldbly 14o-22socand more preferably 150-180C, until one equivalent of alcohol Is distilled away and hydrolyzing the copolymer of polysuccinimide formed with a hydroxlde.
Illustrative of the the suitable alcohols one can mention are methyi alcohol, ethyi alcohol, n-propyi alcohol, isopropyi alcohol, n-butyi alcohol, sec-butyi alcohol, n-hexyi alcohol, n-heptyi alcohol, n-octyi alcohol, lauryi alcohol, nonyi alcohol, oleyi alcohol, stearyi alcohoi, allyi alcohol, crotyi alcohol.
cyclopentanol, cyclohexanol, ethyiene glycol, propyiene glycoi, trimethyiene glycol, tetramethylene 2l~3n72 WO 94/21710 PCT/llS94/02218 glycol, pentamethyiene glycol, h~xd")etl,yiene glycol, glycerol, trimethylol propane, pentaerythritol, arabitol, sorbitol, mannitoi and the like.
The object of this invention Is to provide a method for production of polymers and copolymers of amino acids.
Polysuccinimide is the imlde form of polyaspartic acid and is also known as anhydropolyaspartic acid.
The counterion, ~Z~ above Includes hydrogen, a" ,l "on1urn ion, the aikali and alkaline earth metals examples of which as their cations are, i~, Na~ , Mg~ , and Ca~, Zn~, Ba~, Co~, Fe~, Fe~t, and NH4~. 10 Detalled D~sc~ tion of the Embodiments.
iVlethods of pr~pa,dlion of poiyamino acld derivathes based upon reaction of primary or secondary amines with poiysuccinlmlde are known as dlsclosed In U.S. Pat 3,846,380, incorporated hereln by reier~nce. The polysucclnlmlde Is formed by hlgh temperature reaction In tetralin and further reacted with amines In the solvent dimethyilur,,,ar,,' 'e These ",dterials were observed to have useful 15 properties as surface active agents havlng no cloud polnt and good solllhlll7lng~ emulsifying and dispersing abllities. Thus, thelr use as foamlng agents, solubllking agents, dlspersil lg agents. emulsifying agents, rust-proofing agents, fiber treating agents, level dyelng agents and retarding agents was disclosed.
The use of these agents as inhlbitors of tartar depositlon has been dlsclosed in U.S. Pat. Appl. ' Ser. No. 07/968,506 Filed Oct. 29, 1992, Wood, et al., Copolymers of Polyamino Aclds as Tartar Barrier Agents and Is incorporated hereln by relerence. Polyamlno acld derivatives are excellent inhibitors o~
the fon,ldlion of hydroxyiapatite In vitro, whlch has previously been shown to correlate closely with In vivo inhlbition of tanar deposition. 5 The use of these poiyamino acid derivatives as Inhibitors of scale deposition has been disclosed in U.S. Pat. Appl. Ser. No. 07/968,319 FUed Oct. 29,1992, Wood, et al., Copolymers of Polyamino Acids as Scale Inhlbltion Agents, and Is Incorporated hereln by ~lerence. Poiyamlno acld derivatives are exce'lEnt inhibitors of the fo.,.,dtion of scale depositlon. In particular, the types of scale in which deposition is inhlbited are those ~er"~ I;lied by hard water, boiler water, cooling water. oil well waters, agricultural sprays and i"lgatlon water. These scales typically consist of the salts of the bivalent metal ions.
That polyamino acld derivatives that have a general fommula of /R' -CH-CO-N and -CH-CO-NH-¦ R" ¦ R' R~
FIELD OF THE INVENTION
This invention relates to a method of synthesis of copolymers of polyamino acids and their salts.
DESCRIPTION OF RE~ATED ART
U.S. Pat.3,846,380 discleses the preparation and col"position of copolymers of polyamino acids by the reaction of polysucc;.,' Il' le with primary or secondary aliphatic amines, followed by alkaline hydrolysis to provide surface active agents. The polysuccinimide is formed by high temperature reaction in tetralin and further reacted with amines in the soivent dimethyi~ur,,,arr,'de. Emphasis is placed on long chain ali<ylamines having eight to twenty carbon atoms. The products formed are sald to have good solubilizing ability, emulsifying and dispersing propellies, as well as good foaming properties.
They are useful as foaming agents, solubilizing agents, dispersing agents, emulsifying agents, rust-proofing agents, fiber-treating agents, level dyelng agents and r~ta,Ji"g agents.
U.S. Pat. 3,351,520 i~closes the prep&rd~lon wet strength agents from maleic acid esters with amines followed by reaction with ep'ch'Qroi-,ydrin. i-xcess alcohol can function as a solvent for the reaction with the amine.
Summary ot the l,~,ntlGn We have discovered that polypeptWe n~ar;al~ that have a general formula of /R' -CH-CO-N and-CH-CO-NH-¦ R~ ¦ /R' C~-CO-NH- Ci~-CO-i~
R~
wherein R' is a hydrogen or an alkyi, an alkenyi or an amide group having 1 to 36 carbons and Rr is a hydrogen, an ali~yl, an alkenyi or an amide group having 1 to 36 carbons, together with at least one of the groups -CH-COOZ and -CH-CO-NH-Ci~-CO-NH- Ci~-COOZ
wherein Z represents a hydrogen atom, an a",r"or,ià l~~'ecu'~, an alkall metal or an alkaline earth metal, as a repeating unit, can be prepar~d by reacting maleic anhydride with an alcohol conldin Iq 1 to 36 carbons, preferably 1 to 20 carbons, and more pl~erdbly 1 to 5 carbons, to form the half ester followed by the addition of an equivalent of a"""onia, or arrlr"onià and an amine or a polyamine, containlng one to~6 carbons, preferably 8-20 carbons, and heatlng to 120~50C, pr~r~ldbly 14o-22socand more preferably 150-180C, until one equivalent of alcohol Is distilled away and hydrolyzing the copolymer of polysuccinimide formed with a hydroxlde.
Illustrative of the the suitable alcohols one can mention are methyi alcohol, ethyi alcohol, n-propyi alcohol, isopropyi alcohol, n-butyi alcohol, sec-butyi alcohol, n-hexyi alcohol, n-heptyi alcohol, n-octyi alcohol, lauryi alcohol, nonyi alcohol, oleyi alcohol, stearyi alcohoi, allyi alcohol, crotyi alcohol.
cyclopentanol, cyclohexanol, ethyiene glycol, propyiene glycoi, trimethyiene glycol, tetramethylene 2l~3n72 WO 94/21710 PCT/llS94/02218 glycol, pentamethyiene glycol, h~xd")etl,yiene glycol, glycerol, trimethylol propane, pentaerythritol, arabitol, sorbitol, mannitoi and the like.
The object of this invention Is to provide a method for production of polymers and copolymers of amino acids.
Polysuccinimide is the imlde form of polyaspartic acid and is also known as anhydropolyaspartic acid.
The counterion, ~Z~ above Includes hydrogen, a" ,l "on1urn ion, the aikali and alkaline earth metals examples of which as their cations are, i~, Na~ , Mg~ , and Ca~, Zn~, Ba~, Co~, Fe~, Fe~t, and NH4~. 10 Detalled D~sc~ tion of the Embodiments.
iVlethods of pr~pa,dlion of poiyamino acld derivathes based upon reaction of primary or secondary amines with poiysuccinlmlde are known as dlsclosed In U.S. Pat 3,846,380, incorporated hereln by reier~nce. The polysucclnlmlde Is formed by hlgh temperature reaction In tetralin and further reacted with amines In the solvent dimethyilur,,,ar,,' 'e These ",dterials were observed to have useful 15 properties as surface active agents havlng no cloud polnt and good solllhlll7lng~ emulsifying and dispersing abllities. Thus, thelr use as foamlng agents, solubllking agents, dlspersil lg agents. emulsifying agents, rust-proofing agents, fiber treating agents, level dyelng agents and retarding agents was disclosed.
The use of these agents as inhlbitors of tartar depositlon has been dlsclosed in U.S. Pat. Appl. ' Ser. No. 07/968,506 Filed Oct. 29, 1992, Wood, et al., Copolymers of Polyamino Aclds as Tartar Barrier Agents and Is incorporated hereln by relerence. Polyamlno acld derivatives are excellent inhibitors o~
the fon,ldlion of hydroxyiapatite In vitro, whlch has previously been shown to correlate closely with In vivo inhlbition of tanar deposition. 5 The use of these poiyamino acid derivatives as Inhibitors of scale deposition has been disclosed in U.S. Pat. Appl. Ser. No. 07/968,319 FUed Oct. 29,1992, Wood, et al., Copolymers of Polyamino Acids as Scale Inhlbltion Agents, and Is Incorporated hereln by ~lerence. Poiyamlno acld derivatives are exce'lEnt inhibitors of the fo.,.,dtion of scale depositlon. In particular, the types of scale in which deposition is inhlbited are those ~er"~ I;lied by hard water, boiler water, cooling water. oil well waters, agricultural sprays and i"lgatlon water. These scales typically consist of the salts of the bivalent metal ions.
That polyamino acld derivatives that have a general fommula of /R' -CH-CO-N and -CH-CO-NH-¦ R" ¦ R' R~
2~5~07ff~
wherein R is a hydroger~ or an alkyl an alkenyi or an amide group ~aving 1 to 36 carbons and R is a hydrogen an alkyl an a,Kenyi or an amide group having 1 to 36 carbons together with at least one of the groups -7H-COOZ and -CH-CO-NH-Ci~-CO-NH- Ci~-COOZ
wherein Z is defined above as a repeating unit. The polyamino acid derivatives are prepared by reacting maleic anhydride with an alcohol con~dl-, ,9 1 to 36 carbons preferably 1 to 20 carbons and more preferably 1 to 5 carbons to form the half ester followed by ths addition of an equivalent of ammonia or a",r"onla and an amine or a polyamine containing one to 36 carbons preferably 8-20 10 carbons and heating to 120~00C preferably 140-225Cand more preferably 150-180C until one equivalent of alcohol Is dlstllled away. The resultlng polymer or copolymer of polysuccinimide may be hydrolyzed with an alkallne earth or alkall metal hydroxlde or ar"r"or-lrn hydroxlde forming the polyamlno acld derivatives. Aikallne earth and alkali metal hydloxldes Inciude magneslum calclum strontlum barlum lithlum sodlum, and ~ ssillrn hydroxldes. They may be used In their solid form or 15 as their aqueous or organlc solutlons Fle~e..ed groups for R and R~ are hydrogen methyi oleyi stearyi and lauryl.
i-:XAMPi- F 1 Poly",eri~dlion of monomethyi,nonod..""or:llrn maleate with oieyi amine.
To 40 9 of ",etl,ar,ol was added 39.2 9 (0.4 moles) of maleic anhydride. The resultant solution was stlrred at 40 to 50 C for 2 hrs and ~hen allowed to stand at 25 C for 12 hrs. To the resultant solution of, - ,ono" l~hyimaleate In " I~I ,anoi was added 10.8 9 (0.04 moles) of oleyi amine. This solutlon was stirred at 40 to 50 C for 3 hrs and allowed to stand at 25 C for 12 hrs. To this solution was then added 6.0 9 (0.35 moles) of gaseous al"-"onla. The resultant solution was then bolled at 60 to 100 C
for one hour to remove the soivent alcohoi. The residuai oll was ralsed to 150 C and then slowiy ralsed ~5 to 230 C over a four hour period. The resultant 49.5 9 of brown gummy solid was heated to 240-245 C for an adclitiondl 20 mlnutes yleidlng 48.1 9 of brown solids.
These solids were slurried In 80 9 of water and treated with 16 9 of NaOH In 24 9 of water to give a dark red-brown solution. Thls solution was stirred at 50 C whlle a totai of 6 9 of 30% H2 02 was addedoveraperiodofthreehourstodec:'cri~etheproduct. Continuedstirringat25Cfor12hours gave a clear orange solution estimated to contaln 40% soilds consl~ling of a copolymer of oleyl a,l3-polyaspartate amide and ~ ~polyaspartlc acld as an aqueous solution of its sodium salt.
EXAMPI_E 2 Polymerization of ",ononl~ "onod,.""on:u m maleate.
To 20 9 of ...~-anol was added 1Q6 9 (0.2 moles) of malelc anhydride. The resultant solution was stirred at 40 to 50 C for 1.5 hrs while allowing it to cooi to room ternperdlure. To this solution wa added 3.7 9 (0.22 moles) of gaseous a-"-"onla. The resultant solution evaporated to a melt at 110C.
The melt was heated at 145-150 C for 15 minutes and then heated at 150-180 C for thitty minutes to give 20.0 9 of red solids.
A 10 9 portion of these solids were slurrled In 20 9 of water and treated with 4 9 of NaOH in 6 21~8~72 g of water to give a ciear red solution. This soiution was stirred at 50 C while a total of 1.5 9 of 30%
H2 2 was added over a period of two hours to decolorke the product resulting in a clear yellow solution estimated to contain 40% soiids consi~li"g of a poiymer of B-polyaspartic acid as an aqueous solution of its sodium salt.
-:XAMPLE 3 Polymerization of ",ol1oisopropyimonoammonium maleate with oleyl amine.
To 75 9 of isoprupanoi was added 3g.2 9 (0.4 moles) of maleic anhydride. The resultant solution was stirred at 25 to 70 C for 3 hrs while cooling to 25 C. To this solution was added 5.2 9 (0.02 moles) of oleyi amine. The soiution was stirred for 30 min at 25 C and 6.5 9 (0.38 moles) of gaseous a"""onia was added. The resultant solution was placed in a pear shaped flask on a rotary evaporator and the solution was heated a~ 150~ C for 30 minutes and then heated at 200-220 C for fifteen mlnutes to give a red-brown soiid. The soild was cooled to 2S C and pulverked. The solids were then heated with rotation at 235-245 C for ten min. After pulverizing further heating of these solids at 240-250 C for 15 min gave 44.1 9 red-brown solld.
These solids were slurried In 60 9 of water and treated with 16 9 of NaOH in 24 9 of water to give a clear red-brown solutlon. A total of 5.5 9 ot 30% iH2O2 was added to decoiorize the product giving a clear orange solution after 24 hrs contalning 38% solids conslsting of a copolymer of oleyl~ B-poiyaspartic acid as an aqueous solution of its sodium salt. When shaken the solution gave a stable foam.
i~~ .h~t;on assay for calclum sulfate.
The material to be tested as an Inhlbitor of scale formation was added in appropriate quantities to a solutlon of 10 mi of caicium chlorlde solutions (21.6 g/L of CaCI2 dihydrate and 41.4 g/L of NaCI) and 10 ml of sulfate solution (20.9 g/L of Na2SO4 and 41.4 9 NaCI). The mlxture was then placed in an oven at 16a F for 12 hours. Flnaily the mixture was flltereci through Whatman #2 paper and dried at 16aFfor8hours afterwhlchthewelghtofp,.cl~~ wasdetermlned.
In the CaSO4 preclpitation assay the biank gave 82 mg of pr~ te. while at 2.5 ppm of the above copoiymer 67 mg was obt~l"ed and at 5.0 ppm 36 mg was obtalned.
Pol~,.,e,i~at;ûn of monobutyl~"onoa"""on-lm maleate with oleyl amine.
In an Wentlcal fashlon to that of i~xdlll~,le 3 92.5 9 of n-butanol was added 39.2 9 (0.4 moies) of maleic anhydride and treated as In i~xampie 3 resulting In 48.1 9 red-brown solld.
These sdids were treated as In i Xd"~i e 3 to ghe a llght orange solution containing 399~ soiids conskli"g of a copoiymer of oieyi~ ~poiyaspartic acid as an e~lueous solution of its sodium salt. When shaken the soiution gave a stabie foam. In the CaSO4 preclp~tatlon assay ghen In i ~ 'e 3 the blank gave 82 mg of precipitate while at 2.5 ppm of the above copoiymer 78 mg was obtained and at 5.0 ppm 50 mg was obl~i~,ed.
Poiy",eruation of monocyclohexyimonoammonium maleate with oleyl amine.
In an identlcai fashion to that of Example 3 125 9 of cyclohexanoi was added 39.2 9 (0.4 2158~37~
moles) of maleic anhydride and treated as in i_xample 3 resulting In 63 9 red-brown solid. The solid was washed with two 25 ml portions of Isoprupanol to remove 1.8 9 of brown gum.
These solids were then hydrolyzed as In i~d,-~'a 3 to give a dark red-brown aqueous solution and 15 9 of a coloriess phase consi~li"g of cyclohexanol. When shaken the aqueous solution gave a 5 stable foam. In the CaSO4 preclpitation assay of i xample 3 the blank gave 82 mg of precipitate while at 2.5 ppm of the above copolymer, 85 mg was obtai-~ed and at 5.0 ppm 54 mg was obtained.
i-:XAMPi~E 6 Copolymer of Oleyiamlde-diethyien~lr,dinine and monomethyimonoammonium maleate Diethyiene triamine (4 0 9 0.039 moles) was added to tall oll fatty aclds (over 95O~ oleic acid) 110 (2.25 9) and heated for 10 min with stirrin~ at 190-20aC and the mixturc was dissolved in 40 9 of methanol. Malelc anhydrlde (39.2 9 0.4 moies) was added to thls mixture and the reaction exothermed to 60 C. The reaction mix was cooied to 25 C and ar ~- - .onia (6.8 9) was added over a period of 20 min.
The solution was heated with stlrring at 175-19S Cfor 20 min resulting in an orange syrup. The reaction was then heated for 8 mtn at 195-22S C and the resulting foam was broken up. The mixture was then headed for 10 mln at 225-245C broken up and heated for 10 min at 235-245C resulting in 41.3 go of a tan powder.
The powder was mixed with 60 ~ of water and NaOH (15 9 In 24 9 water) was slowiy added.
Addition of 120 ml of water gave a fluld soiution whlch was very sudsy. In the CaSO4 pr, ~ icn assay of i xa" r~e 3, the biank gave 81 mg of preclpitate, while at 2.5 ppm of the above copolymer 51 mg was ob~i"eci and at 5.0 ppm 3 mg was obtained.
Drift Assay for CaCO3 The sodium poiyaspartate was tested for Inhibition of calcium carbonate precipit~tion by the calcium drffl assay. In this assay a supersaturated solution of calcium c~ri ondle Is formed by adding 29.1 ml of 0.55 M NaCI and 0.01 M KCi to 0.3 mi of 1.0 M CaCi2. The compound to be tested is then added at 1.7 ppm (flnai concent,dllon). The reactlon Is Initiated by the additlon of 0.6 ml of 0.5 M
NaHCO3 and i"""edlately adJusting the pH to 7.5-8.0 by titration with 1 N NaOH. At three minutes 10 mg of CaCO3 Is added and the pH Is .~cor.led. The dec,~ase In pH Is dlrectly correlated to the amount of CaCO3 that preclpitates. The effectiveness of the Inhlbitlon Is co""~ar~d to that of sodium polyacryiate used collllll~rl;ldlly for the purpose of preventing scale fommation. The blank had a change In pH of 0.90 and 1.00 at 10 and 20 min respectively whereas the above copoiymer had a change of 0.56 and 0.58 respectively. The 2500 moi wt sodlum poiyacrylate had a change of 0.34 at both times.
It will be appar~nt to those skilled In the art that the examples and embodiments described herein are by way of illustration and not of limitation and that other examples may be utilized without departing from the spirit and scope of the present invention as set forth In the appended claims.
wherein R is a hydroger~ or an alkyl an alkenyi or an amide group ~aving 1 to 36 carbons and R is a hydrogen an alkyl an a,Kenyi or an amide group having 1 to 36 carbons together with at least one of the groups -7H-COOZ and -CH-CO-NH-Ci~-CO-NH- Ci~-COOZ
wherein Z is defined above as a repeating unit. The polyamino acid derivatives are prepared by reacting maleic anhydride with an alcohol con~dl-, ,9 1 to 36 carbons preferably 1 to 20 carbons and more preferably 1 to 5 carbons to form the half ester followed by ths addition of an equivalent of ammonia or a",r"onla and an amine or a polyamine containing one to 36 carbons preferably 8-20 10 carbons and heating to 120~00C preferably 140-225Cand more preferably 150-180C until one equivalent of alcohol Is dlstllled away. The resultlng polymer or copolymer of polysuccinimide may be hydrolyzed with an alkallne earth or alkall metal hydroxlde or ar"r"or-lrn hydroxlde forming the polyamlno acld derivatives. Aikallne earth and alkali metal hydloxldes Inciude magneslum calclum strontlum barlum lithlum sodlum, and ~ ssillrn hydroxldes. They may be used In their solid form or 15 as their aqueous or organlc solutlons Fle~e..ed groups for R and R~ are hydrogen methyi oleyi stearyi and lauryl.
i-:XAMPi- F 1 Poly",eri~dlion of monomethyi,nonod..""or:llrn maleate with oieyi amine.
To 40 9 of ",etl,ar,ol was added 39.2 9 (0.4 moles) of maleic anhydride. The resultant solution was stlrred at 40 to 50 C for 2 hrs and ~hen allowed to stand at 25 C for 12 hrs. To the resultant solution of, - ,ono" l~hyimaleate In " I~I ,anoi was added 10.8 9 (0.04 moles) of oleyi amine. This solutlon was stirred at 40 to 50 C for 3 hrs and allowed to stand at 25 C for 12 hrs. To this solution was then added 6.0 9 (0.35 moles) of gaseous al"-"onla. The resultant solution was then bolled at 60 to 100 C
for one hour to remove the soivent alcohoi. The residuai oll was ralsed to 150 C and then slowiy ralsed ~5 to 230 C over a four hour period. The resultant 49.5 9 of brown gummy solid was heated to 240-245 C for an adclitiondl 20 mlnutes yleidlng 48.1 9 of brown solids.
These solids were slurried In 80 9 of water and treated with 16 9 of NaOH In 24 9 of water to give a dark red-brown solution. Thls solution was stirred at 50 C whlle a totai of 6 9 of 30% H2 02 was addedoveraperiodofthreehourstodec:'cri~etheproduct. Continuedstirringat25Cfor12hours gave a clear orange solution estimated to contaln 40% soilds consl~ling of a copolymer of oleyl a,l3-polyaspartate amide and ~ ~polyaspartlc acld as an aqueous solution of its sodium salt.
EXAMPI_E 2 Polymerization of ",ononl~ "onod,.""on:u m maleate.
To 20 9 of ...~-anol was added 1Q6 9 (0.2 moles) of malelc anhydride. The resultant solution was stirred at 40 to 50 C for 1.5 hrs while allowing it to cooi to room ternperdlure. To this solution wa added 3.7 9 (0.22 moles) of gaseous a-"-"onla. The resultant solution evaporated to a melt at 110C.
The melt was heated at 145-150 C for 15 minutes and then heated at 150-180 C for thitty minutes to give 20.0 9 of red solids.
A 10 9 portion of these solids were slurrled In 20 9 of water and treated with 4 9 of NaOH in 6 21~8~72 g of water to give a ciear red solution. This soiution was stirred at 50 C while a total of 1.5 9 of 30%
H2 2 was added over a period of two hours to decolorke the product resulting in a clear yellow solution estimated to contain 40% soiids consi~li"g of a poiymer of B-polyaspartic acid as an aqueous solution of its sodium salt.
-:XAMPLE 3 Polymerization of ",ol1oisopropyimonoammonium maleate with oleyl amine.
To 75 9 of isoprupanoi was added 3g.2 9 (0.4 moles) of maleic anhydride. The resultant solution was stirred at 25 to 70 C for 3 hrs while cooling to 25 C. To this solution was added 5.2 9 (0.02 moles) of oleyi amine. The soiution was stirred for 30 min at 25 C and 6.5 9 (0.38 moles) of gaseous a"""onia was added. The resultant solution was placed in a pear shaped flask on a rotary evaporator and the solution was heated a~ 150~ C for 30 minutes and then heated at 200-220 C for fifteen mlnutes to give a red-brown soiid. The soild was cooled to 2S C and pulverked. The solids were then heated with rotation at 235-245 C for ten min. After pulverizing further heating of these solids at 240-250 C for 15 min gave 44.1 9 red-brown solld.
These solids were slurried In 60 9 of water and treated with 16 9 of NaOH in 24 9 of water to give a clear red-brown solutlon. A total of 5.5 9 ot 30% iH2O2 was added to decoiorize the product giving a clear orange solution after 24 hrs contalning 38% solids conslsting of a copolymer of oleyl~ B-poiyaspartic acid as an aqueous solution of its sodium salt. When shaken the solution gave a stable foam.
i~~ .h~t;on assay for calclum sulfate.
The material to be tested as an Inhlbitor of scale formation was added in appropriate quantities to a solutlon of 10 mi of caicium chlorlde solutions (21.6 g/L of CaCI2 dihydrate and 41.4 g/L of NaCI) and 10 ml of sulfate solution (20.9 g/L of Na2SO4 and 41.4 9 NaCI). The mlxture was then placed in an oven at 16a F for 12 hours. Flnaily the mixture was flltereci through Whatman #2 paper and dried at 16aFfor8hours afterwhlchthewelghtofp,.cl~~ wasdetermlned.
In the CaSO4 preclpitation assay the biank gave 82 mg of pr~ te. while at 2.5 ppm of the above copoiymer 67 mg was obt~l"ed and at 5.0 ppm 36 mg was obtalned.
Pol~,.,e,i~at;ûn of monobutyl~"onoa"""on-lm maleate with oleyl amine.
In an Wentlcal fashlon to that of i~xdlll~,le 3 92.5 9 of n-butanol was added 39.2 9 (0.4 moies) of maleic anhydride and treated as In i~xampie 3 resulting In 48.1 9 red-brown solld.
These sdids were treated as In i Xd"~i e 3 to ghe a llght orange solution containing 399~ soiids conskli"g of a copoiymer of oieyi~ ~poiyaspartic acid as an e~lueous solution of its sodium salt. When shaken the soiution gave a stabie foam. In the CaSO4 preclp~tatlon assay ghen In i ~ 'e 3 the blank gave 82 mg of precipitate while at 2.5 ppm of the above copoiymer 78 mg was obtained and at 5.0 ppm 50 mg was obl~i~,ed.
Poiy",eruation of monocyclohexyimonoammonium maleate with oleyl amine.
In an identlcai fashion to that of Example 3 125 9 of cyclohexanoi was added 39.2 9 (0.4 2158~37~
moles) of maleic anhydride and treated as in i_xample 3 resulting In 63 9 red-brown solid. The solid was washed with two 25 ml portions of Isoprupanol to remove 1.8 9 of brown gum.
These solids were then hydrolyzed as In i~d,-~'a 3 to give a dark red-brown aqueous solution and 15 9 of a coloriess phase consi~li"g of cyclohexanol. When shaken the aqueous solution gave a 5 stable foam. In the CaSO4 preclpitation assay of i xample 3 the blank gave 82 mg of precipitate while at 2.5 ppm of the above copolymer, 85 mg was obtai-~ed and at 5.0 ppm 54 mg was obtained.
i-:XAMPi~E 6 Copolymer of Oleyiamlde-diethyien~lr,dinine and monomethyimonoammonium maleate Diethyiene triamine (4 0 9 0.039 moles) was added to tall oll fatty aclds (over 95O~ oleic acid) 110 (2.25 9) and heated for 10 min with stirrin~ at 190-20aC and the mixturc was dissolved in 40 9 of methanol. Malelc anhydrlde (39.2 9 0.4 moies) was added to thls mixture and the reaction exothermed to 60 C. The reaction mix was cooied to 25 C and ar ~- - .onia (6.8 9) was added over a period of 20 min.
The solution was heated with stlrring at 175-19S Cfor 20 min resulting in an orange syrup. The reaction was then heated for 8 mtn at 195-22S C and the resulting foam was broken up. The mixture was then headed for 10 mln at 225-245C broken up and heated for 10 min at 235-245C resulting in 41.3 go of a tan powder.
The powder was mixed with 60 ~ of water and NaOH (15 9 In 24 9 water) was slowiy added.
Addition of 120 ml of water gave a fluld soiution whlch was very sudsy. In the CaSO4 pr, ~ icn assay of i xa" r~e 3, the biank gave 81 mg of preclpitate, while at 2.5 ppm of the above copolymer 51 mg was ob~i"eci and at 5.0 ppm 3 mg was obtained.
Drift Assay for CaCO3 The sodium poiyaspartate was tested for Inhibition of calcium carbonate precipit~tion by the calcium drffl assay. In this assay a supersaturated solution of calcium c~ri ondle Is formed by adding 29.1 ml of 0.55 M NaCI and 0.01 M KCi to 0.3 mi of 1.0 M CaCi2. The compound to be tested is then added at 1.7 ppm (flnai concent,dllon). The reactlon Is Initiated by the additlon of 0.6 ml of 0.5 M
NaHCO3 and i"""edlately adJusting the pH to 7.5-8.0 by titration with 1 N NaOH. At three minutes 10 mg of CaCO3 Is added and the pH Is .~cor.led. The dec,~ase In pH Is dlrectly correlated to the amount of CaCO3 that preclpitates. The effectiveness of the Inhlbitlon Is co""~ar~d to that of sodium polyacryiate used collllll~rl;ldlly for the purpose of preventing scale fommation. The blank had a change In pH of 0.90 and 1.00 at 10 and 20 min respectively whereas the above copoiymer had a change of 0.56 and 0.58 respectively. The 2500 moi wt sodlum poiyacrylate had a change of 0.34 at both times.
It will be appar~nt to those skilled In the art that the examples and embodiments described herein are by way of illustration and not of limitation and that other examples may be utilized without departing from the spirit and scope of the present invention as set forth In the appended claims.
Claims (8)
1. A method of synthesis of a polyamide that has a general formula of and wherein R' is a hydrogen or an alkyl, an alkenyl or an amide group having 1 to 36 carbons and R" is a hydrogen or an alkyl, an alkenyl or an amide group having 1 to 36 carbons, together with at least one of the groups and wherein Z represents a hydrogen atom, an alkali metal or an alkaline earth metal, as a repeating unit, the method comprising reacting maleic anhydride with an alcohol containing 1 to 36 carbons, to form the half ester followed by the addition of an equivalent of ammonia, or ammonia and an amine or a polyamine, containing one to 36 carbons, and heating to 120-350°C, until one equivalent of alcohol is distilled away and hydrolyzing the copolymer of polysuccinimide formed with an alkaline earth or alkali metal hydroxide or ammonium hydroxide.
2. The method of claim 1 in which the alcohol contains 1 to 20 carbons.
3. The method of claim 1 in which the alcohol contains 1 to 10 carbons.
4. The method of claim 1 in which the alcohol is methanol, ethanol, n-propanol, isopropanol, or n-butanol.
5. The method of claim 1 in which the amine or polyamine contains 8-20 carbons.
4. The method of claim 1 in which the temperature is 140-285 ° C.
7. The method of claim 1 in which the temperature is 150-245°C.
8. The method of claim 1 in which the hydroxide is sodium, potassium or ammonium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/031,856 US5292858A (en) | 1993-03-16 | 1993-03-16 | Method of production of copolymers of polyamino acids |
| US031,856 | 1993-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2158072A1 true CA2158072A1 (en) | 1994-09-17 |
Family
ID=21861767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002158072A Abandoned CA2158072A1 (en) | 1993-03-16 | 1994-03-01 | Method of production of copolymers of polyamino acids |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5292858A (en) |
| EP (1) | EP0690885A1 (en) |
| JP (1) | JPH08507822A (en) |
| KR (1) | KR960701126A (en) |
| AU (1) | AU689470B2 (en) |
| CA (1) | CA2158072A1 (en) |
| WO (1) | WO1994021710A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466760A (en) * | 1992-08-07 | 1995-11-14 | Srchem, Inc. | Copolymers of polyaspartic acid |
| US5410017A (en) * | 1993-05-21 | 1995-04-25 | Rohm And Haas Company | Continuous thermal polycondensation process for preparing polypeptide polymers |
| US5457176A (en) * | 1993-09-21 | 1995-10-10 | Rohm And Haas Company | Acid catalyzed process for preparing amino acid polymers |
| EP0650995B1 (en) * | 1993-11-02 | 2000-01-05 | Bayer Ag | Process for preparing aspartic acid polymers |
| US5491213A (en) * | 1994-01-28 | 1996-02-13 | Donlar Corporation | Production of polysuccinimide |
| US5552516A (en) * | 1994-06-22 | 1996-09-03 | Donlar Corporation | Soluble, crosslinked polyaspartates |
| US5681920A (en) * | 1994-06-28 | 1997-10-28 | Donlar Corporation | Process for production of a polysuccinimide and derivatives thereof |
| DE4425952A1 (en) * | 1994-07-21 | 1996-01-25 | Bayer Ag | Process for the preparation of polysuccinimide or maleic acid |
| US5478919A (en) * | 1994-07-29 | 1995-12-26 | Donlar Corporation | Aspartic acid copolymers and their preparation |
| DE19545678A1 (en) * | 1995-12-07 | 1997-06-12 | Goldschmidt Ag Th | Copolymers of polyamino acid esters |
| US5869027A (en) * | 1996-04-22 | 1999-02-09 | Wood; Louis L. | Method for odor reduction |
| US5872285A (en) * | 1996-06-10 | 1999-02-16 | Donlar Corporation | Production of D,L-aspartic acid |
| US5981691A (en) * | 1997-04-23 | 1999-11-09 | University Of South Alabama | Imide-free and mixed amide/imide thermal synthesis of polyaspartate |
| DE19822599C2 (en) * | 1998-05-20 | 2003-02-06 | Goldschmidt Ag Th | Copolymers hydrophobically modified polyaspartic esters and their use |
| US6365706B1 (en) | 2000-06-21 | 2002-04-02 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
| DE10342926A1 (en) * | 2003-09-17 | 2005-04-14 | Bayer Chemicals Ag | Polyether-modified polymers as leather auxiliaries |
| US7888297B2 (en) * | 2005-01-06 | 2011-02-15 | Halliburton Energy Services, Inc. | Compositions for reducing the viscosity of treatment fluids |
| KR100764933B1 (en) * | 2006-09-25 | 2007-10-09 | 애경유화 주식회사 | Manufacturing method of polyaspartic acid using maleic anhydride |
| KR102273808B1 (en) * | 2015-06-11 | 2021-07-06 | 주식회사 케이씨씨 | Polyamide curing agent with ring-opening product of acid anhydride by alcohol |
| CN107328929B (en) * | 2017-06-24 | 2019-06-04 | 安徽师范大学 | A kind of quantitative detecting method of PSI-OAm-NAPI amphiphilic polymer/nanometer material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2306918A (en) * | 1940-02-15 | 1942-12-29 | Research Corp | Amine reaction product |
| US3052655A (en) * | 1958-08-01 | 1962-09-04 | Sidney W Fox | Thermal polymerization of amino acid mixtures containing aspartic acid or a thermal precursor of aspartic acid |
| US3351520A (en) * | 1964-11-13 | 1967-11-07 | Union Carbide Corp | Poly-beta-asparaginepolyalkylenepoly-amine halohydrin resins and application thereof in production of wet strength paper and flocculation of solids |
| US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
| US4169924A (en) * | 1977-06-09 | 1979-10-02 | Gaf Corporation | Preparation of linear cyclic polyimides from latices |
| DE3626672A1 (en) * | 1986-08-07 | 1988-02-11 | Bayer Ag | POLYASPARAGINAMID ACID |
| US5057597A (en) * | 1990-07-03 | 1991-10-15 | Koskan Larry P | Process for the manufacture of anhydro polyamino acids and polyamino acids |
-
1993
- 1993-03-16 US US08/031,856 patent/US5292858A/en not_active Expired - Fee Related
-
1994
- 1994-03-01 AU AU64428/94A patent/AU689470B2/en not_active Ceased
- 1994-03-01 CA CA002158072A patent/CA2158072A1/en not_active Abandoned
- 1994-03-01 WO PCT/US1994/002218 patent/WO1994021710A1/en not_active Application Discontinuation
- 1994-03-01 KR KR1019950703904A patent/KR960701126A/en not_active Application Discontinuation
- 1994-03-01 JP JP6521056A patent/JPH08507822A/en active Pending
- 1994-03-01 EP EP94912170A patent/EP0690885A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| AU689470B2 (en) | 1998-04-02 |
| EP0690885A4 (en) | 1995-11-15 |
| KR960701126A (en) | 1996-02-24 |
| EP0690885A1 (en) | 1996-01-10 |
| WO1994021710A1 (en) | 1994-09-29 |
| JPH08507822A (en) | 1996-08-20 |
| AU6442894A (en) | 1994-10-11 |
| US5292858A (en) | 1994-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2158072A1 (en) | Method of production of copolymers of polyamino acids | |
| EP1085033B1 (en) | Salts of polyaspartic acid by high temperature reaction | |
| US5519110A (en) | Polymers of maleic acid with amines | |
| US5357004A (en) | Copolymers of polyaspartic acid | |
| US5708126A (en) | Process for the preparation of copolymers of polysuccinimides | |
| AU689812B2 (en) | Amino acid copolymers of maleic acid | |
| JP2006124719A (en) | Biodegradable poly(amino acid) | |
| WO1998047964A1 (en) | Imide-free and mixed amide/imide thermal synthesis of polyaspartate | |
| JP3528000B2 (en) | Polyaspartic acid and copolymers of polycarboxylic acids and polyamines | |
| US3890291A (en) | Alpha-hydroxyacrylic acid/acrylic acid-copolymers and a process for making them | |
| DE4427630A1 (en) | Process for the preparation of polymers containing hydroxamic acid, hydroxamic acid ether and / or hydrazide groups in the side chain and their use | |
| US5610267A (en) | Process for preparing polysuccinimide by high temperature reaction | |
| US3592830A (en) | Alkylenediamine derivatives containing carbohydrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |