|Publication number||US3904685 A|
|Publication date||Sep 9, 1975|
|Filing date||Jul 20, 1973|
|Priority date||Jul 20, 1973|
|Publication number||US 3904685 A, US 3904685A, US-A-3904685, US3904685 A, US3904685A|
|Inventors||Blay Jorge Alberto, Shahidi Iraj Khatib|
|Original Assignee||Celanese Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (1), Referenced by (46), Classifications (16)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent [191 Shahidi et a1.
[451 Sept. 9, 1975 POLYACRYLIC ACID HAVING HIGH CHELATION VALUE AND ITS PRODUCTION  Inventors: Iraj Khatib Shahidi, Florham Park,
N.J.; Jorge Alberto Blay, Corpus Christi, Tex.
 Assignee: Celanese Corporation, New York,
 Filed: July 20, 1973  Appl. No.: 381,190
 US. Cl 260/537 N; 252/109; 252/133;
252/135; 252/184; 260/526 N  Int. Cl. C07C 55/24  Field of Search 260/526 N, 537 N  References Cited UNITED STATES PATENTS 2,833,745 5/1958 Fikentscher 260/80 FOREIGN PATENTS OR APPLICATIONS 695,097 8/1940 Germany ..260/537 167,857 10/1953 Australia ..260/537 OTHER PUBLICATIONS Jacobson Chem. Abstracts, V. 57( 1962), V. 1037. Sakaguchi et a1. Chem. Abstracts, V. 64(1966), p. 12822.
Salutsky Chem. Abstracts, V. 70(1969), p. 248.
l-lwa et al. Chem. Abstracts, V. 7l( 1969), p. 216.
Primary Examiner.lames A. Patten Attorney, Agent, or Firm-Leonard Horn; Ralph M. Pritchett  ABSTRACT Polyacrylic acid having a high chelation value is produced by polymerizing acrylic acid at elevated temperature in the presence of an alkali metal or ammonium persulfate initiator and, in a concentration of about 0.5 to 4% by weight of the acrylic acid, a chain transfer agent selected from the group consisting of alkanethiols, hydroxy alkanethiols, and carboxy a1- kanethiols. Preferably the chain transfer agent is present in about 1% by weight concentration and is octanethiol, butanethiol, thioglycolic acid, or 2- thioethanol.
7 Claims, No Drawings POLYACRYLIC AID HAVING HIGH CHELATION VALUE AND ITS PRODUCTION BACKGROUND OF THE INVENTION This invention relates to the production of polyacrylic acid having a high chelation value, e.g., a chelation value which is in excess of 500 milligrams of calcium carbonate per gram of chelant obtained in water with a 200 ppm hardness, pH 9.5 and at the point at which 80% of the hardness has been sequestered. The significance of this 80% chelation level as an index for comparing various chelating agents will be explained later hereinbelow.
Most common detergents, e.g. common household detergents, comprise, in addition to other components, phosphates such as sodium tripolyphosphate. These are inexpensive and effective, but their use is now consid ered to present a water pollution problem in that the phosphate component has the undesired effect of promoting excessive growth of algae in lakes and streams (eutrophication).
Accordingly, there has been much research aimed at developing detergents which contain little or no phosphate but which will still be safe and effective. In particular, this research has been aimed at developing de tergent components which can sequester calcium, magnesium, and like ions found in hard water and which have an economically feasible price/performance ratio. Aside from effectiveness and economic feasibility, it is also important that these detergent components be free from health hazard and that they have no adverse effects on mechanical equipment used in laundering. For example, highly alkaline detergent components such as washing soda have effective detergent action but are hazardous household substances because of their high alkalinity (pl-I l l or higher). There is also a question as to whether they may cause mechanical problems in, for example, washing machines. Likewise nitrilotriacetic acid and ethylenediaminetetraacetic acid are very ef fective in sequestering a large amount of calcium but are relatively expensive and, in addition, have recently been questioned from the health standpoint inasmuch as a question has arisen as to whether they are potentially carcinogenic.
Finally, polyacrylic acid, as such or in the saltform, has also been proposed as a chelant or sequestering agent which does not cause eutrophication, but this material as known heretofore has been of only mediocre effectiveness.
It has now been discovered, however, that polyacrylic acid, when made by a certain procedure which will be described hereinbelow, can be made to have an unexpectedly high chelating value. It is, accordingly, an object of the present invention to provide a method for producing a polyacrylic acid chelating agent which is unexpectedly effective as compared with similar materials known to the prior art and which will be free from the drawbacks which are associated with those alternative detergent components known to the art.
SUMMARY OF THE INVENTION In accordance with the present invention it has been found that polyacrylic acid having an unexpectedly high chelating value (which will be defined hereinbelow) can be produced by polymerizing acrylic acid at elevated temperature in the presence of an alkali metal or ammonium persulfate initiator and also in the presence of about 0.5 to 4% (calculated on the basis of the weight of the acrylic acid) of a chain transfer agent selected from the group consisting of alkanethiols, hydroxy alkanethiols, and carboxy alkanethiols. Preferably the chain transfer agent is present in a concentration of about 1% by weight based on the acrylic acid and is a member of the group consisting of octanethiol, butanethiol, thioglycolic acid, and Z-thioethanol. Other thiols which can be employed include methanethiol, ethanethiol, propanethiol, pentanethiol, hexanethiol, heptanethiol, nonanethiol, decanethiol, dodecanethiol, and their branched isomers, e.g. sec.-butanethiol, isopropanethiol, tert.-butanethiol, and the like, as well as their hydroxy and carboxy substitution products, e.g., 3-mercaptopropanol, 3-mercaptopropionic acid, 6- mercaptohexanoic acid and the like.
The initiators may be present in amounts ranging from as little as about 0.5 up to 10% or more by weight of acrylic acid although preferably they are present in about 0.5 to 4%. A concentration of about 1% is especially useful. Preferred initiators include sodium, potassium, or ammonium persulfates or mixtures thereof.
The polymerization can be conducted in bulk but it is preferably conducted in aqueous solution at a concentration of about 5 to 40% and preferably about 10 to 30% acrylic acid by weight. The temperature may be room temperature or lower but, since polymerization rate increases with temperature, the temperature is desirably elevated but below the boiling point so that special equipment will not be required, e.g. about C. The time will typically run about 1 to 2 hours until there is substantially no residual free acrylic acid.
The molecular weight will directly determine the viscosity of the resulting solution, and the viscosity may range from about 25 centipoise or lower up to 200 or more although preferably it is about 50 to centipoise for a 2025% polyacrylic acid solution by weight.
The solutions may if desired be concentrated to any desired degree, including completely to dryness, optionally after neutralization to form sodium and/or potassium polyacrylate. Alternatively, the solution may be blended with one or more'other ingredients of a detergent composition in dry or liquid state and the mixture spray or drum dried.
In assessing the effectiveness of chelating agents it is convenient to employ a term referred to as the chelating value, the significance and determination of which are explained by J. A. Blay and J. H. Ryland in Analytical Letters, Vol. 4, No. 10, pp 653-663 (1971). Numerically, the chelation value (CV) is expressed as the milligrams of calcium carbonate chelated or sequestered per gram of chelating agent. The chelation reaction is, in effect, a reversible chemical reaction so that the CV depends, numerically, upon the concentration of hardness, e.g. calcium ions, in the solution to which the chelating agent is added, the pH, and also the amount of chelating agent which has been added to that solution. This is particularly noticeable for chelants with a formation constant (log K) smaller than 5 (K 10 For these reasons it is desirable, in making practical comparisons of one chelating agent with another, to test them at a constant level of hardness at constant pH and to add each of the several chelants being tested in an amount that the proportion of the hardness which is chelated is the same in each of the several samples being tested.
The polyacrylic acid produced by the present process has a chelation value (CV) which is normally equal to,
or in excess of, about 500 milligrams of calcium carbonate per gram of the polyacrylic acid at an 80% chelation level in an aqueous solution containing a hardness equivalent to 200 ppm of calcium carbonate. This is essentially as good as, if not better than, chelation values characteristic of other chclants known to the prior art which, however, have drawbacks of cost, water-pollution tendency, health hazard, or adverse mechanical effects in washing equipment.
The invention will be further illustrated in the following examples wherein all parts are by weight unless otherwise expressed. It will be understood that these examples are given by way of illustration, rather than limitation, of the invention. The polyacrylic acid (or its salts including especially alkali metal salts) to the production of which this invention is directed will be seen to have very broad applications in combination with surfactants, buffering agents, scouring agents, and other ancillary substances well known in the art, in all enduses in which a sequestrant or chelant is customarily employed and including specifically such applications as laundry detergents, automatic dishwashing detergents, scouring powders, boiler scale removal, metal degreasing and cleaning, leather and textile treating solutions, ore leaching and benefication, and ion-exchange operations to name a few.
EXAMPLE I 250 g of 92% acrylic acid, 3.0 g of potassium persulfate, and 2.3 g octanethiol were reacted in a 1000 g total aqueous solution for 2 hours at 96-98 C. The resulting aqueous polyacrylic acid solution had a viscosity of I25 cps and contained 20.4 weight percent solids. Only 0.4 g/l of this polyacrylic acid was required to sequester 94% of Ca ions present in a pH 9.5 buffer containing 200 ppm of Ca ions. Expressed differently, the polyacrylic acid had the capacity to chelate 560 mg CaCO per gram of polyacrylic acid with 80% of the total calcium present in the medium being sequestered. The chelation power of some known sequestering agents under comparable conditions were as follows: citric acid, 350 mg/g; tripolyphosphoric acid, 370 mg/g; ethylenediaminetetraacetic acid, 330 mg/g.
When evaluated under similar conditions, a typical commercial polyacrylic acid (Versicol E5, from Allied Colloids Co.) required 1.1 g of polyacrylic acid to sequester 95% of the Ca ions present in a pH 9.5 buffer containing 200 ppm Ca, corresponding to a chelation capacity of 390 mg CaCO /g chelant when 80% of Ca ions have been chelated.
EXAMPLE II 250 g of 92% acrylic acid, 3.0 g of potassium persulfate, and 2.3 g butanethiol were reacted in a 1000 g total aqueous solution for 2 hours at 96-98 C. The resulting aqueous polyacrylic acid solution had a viscosity of cps and contained 23.9 weight percent solids. Only 0.51 g/l of this polyacrylic acid was required to sequester 95% of the Ca ions present in a pH 9.5 buffer containing 200 ppm of Ca ions. Expressed differently, the polyacrylic acid had the capacity to chelate 520 mg CaCO per gram of polyacrylic acid with of the total calcium present in the medium being sequestered.
EXAMPLE III To evaluate the performance of sodium polyacrylate in detergent compositions, formulations A-F listed below were prepared. Formulation F consists of distilled water and serves as a control only. Formulation E in which no builder is utilized contains the surfactants and the auxiliary components used in a typical heavyduty laundry formulation. Formulations A-D have the builder added to the basic formulation in E and provide a direct comparison between sodium polyacrylate and other available builders.
Evaluation of the performance of the formulations was by the well established procedure of Spangler, Journal of the American Oil Chemists Society 42, 723-727 (1966). Cotton swatches were uniformly soiled in a blend of synthetic sebum and particulate soil and separated into groups with similar aggregate de gree of soiling. Measurements of soiling were performed with standard commercial reflectometer (Colormaster Model V, Manufacturers Engineering and Equipment Corporation).
The soiled swatches were washed in a standard laboratory Terg-O-Tometer (trade name of US. Testing Company, Hoboken, NJ.) operated at 100 rpm. Five swatches were used for each formulation. One and onehalf grams of each of the formulations A-F were used in a liter of water containing 160 ppm hardness composed of Ca and 15% Mg. After washing for ten minutes at 120F, the swatches were hand squeezed and put through a 5 minute rinse at F. The swatches were next dried in a print dryer, and their reflectance determined again. The operation was repeated three times (3 cycles). The performance of the formulations in terms of changes in reflectance (A Rd) along with the compositions of formulations A-F are shown in the table below:
COMPOSITION WEIGHT A B C D E F Linear alkylbenzene sulfonate 10 IO l0 l0 Nonionic surfactant (C -C alcohol ethoxylate 6()'/(") 2 2 l l 2 2 Tallow fatty acids soap 2 2 2 2 Sodium silicate (SiO- :Na O 2.411) 7 7 9 7 7 Sodium sulfate 40 40 40 40 Distilled water 4 4 l0 4 39 I00 Sodium polyacrylate 35 Sodium tripolyphosphate 35 Sodium carbonate 70 Sodium oxydiacetate 35 PERFORMANCE (3 cycles) Reflectance, Rd, of soiled swatches I 6L4 60.6 55.0 58.9 58.6 61.2 Reflectance, Rd, of washed swatched 76.9 76.2 69.6 68.l 64.8 65.8
-continued COMPOSlTlON WEIGHT A B I C D E F A RD 15.5 l5.6 14.6 92* 6.2 4.6
Performed in water of 200 ppm hardness. 60'7: Ca. 4071 Mg -continued Composition Wt7r r 1 As the detergency results above clea ly nd cate, so 10 Sodium mew Silicate l0 drum polyacrylate is an excellent performer in heavy- Trisodium phosphate 5 duty laundry composition. Its closest competition, 50- Sodwm polyacrylam 20 Alkylbenzene sulfonate 5 drum tripolyphosphate, is suspected of contributing to eutrophication of lakes and rivers, and its use in laundry detergents is thought by many to be undesirable.
EXAMPLE IV The formulation given below is suitable for cleaning metal parts prior to use. It cleanses metal-surfaces free of oil and grease and removes surface scale and rust.
Composition Wt% Sodium silicate (Na sio 24.0 Sodium silicate (sio zNa C) 3.1:1) 48.0 Nonionic surfactant (C -C alcohol 1.5 ethoxylate, 607r) Sodium polyacrylate 25.0 Sodium sulfite 1.5
EXAMPLE V Formulation below is a low foaming dishwashing powder with excellent grease removal and gentle scouring action.
Composition Wt7r Soda ash 5 O The embodiments of the invention in which an exclu sive property or privilege is claimed are defined as follows:
1. The process for producing a polyacrylic acid of high chelation value at chelation which comprises polymerizing acrylic acid in aqueous solution at elevated temperature in the presence of an alkali metal or ammonium persulfate as initiator and about 0.5 to 4% by weight of acrylic acid of a chain transfer agent selected from the group consisting of an alkanethiol, a hydroxy alkanethiol and a carboxy alkanethiol.
2. The process of claim 1, wherein the chain transfer agent is an alkylmercaptan and is present in a concentration of about 1% by weight of the acrylic acid, and wherein the polymerization is conducted at about C for about 1 to 2 hours.
3. The process of claim 2, wherein the chain transfer agent is octanethiol.
4. The process of claim 2, wherein the chain transfer agent is butanethiol. I
5. The process of claim 1 wherein the chain transfer agent is thioglycolic acid.
6. The process of claim 1 wherein the chain transfer agent is 2-thioethanol.
7. Polyacrylic acid produced by the process of claim 2 and having a chelation value at 80% chelation in excess of about 500 mg CaCO per gram in an aqueous solution containing calcium ions in a concentration equivalent to 200 ppm of CaCO Disclaimer 3,904,685.Imj Kfiwtib Shahz'di, Fiorham Park, N.J., and J orge Alberto Blay, Corpus Christi, Tex. POLYACRYLIC ACID HAVING HIGH CHELATION VALUE AND ITS PRODUCTION. Patent dated Sept. 9, 1975. Disclaimer filed Apr. 14:, 1976, by the assignee, Oe-Zamese Oarpomtz'on. Hereby enters this disclaimer to the remaining term of said patent.
[Ofiiaial Gazette June 1, 1.976.]
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2833745 *||Jun 15, 1954||May 6, 1958||Basf Ag||Production of the salts of polymerized alpha.beta-unsaturated aliphatic acids|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4008164 *||Mar 21, 1974||Feb 15, 1977||Nalco Chemical Company||Process for scale inhibition|
|US4031022 *||Mar 2, 1976||Jun 21, 1977||Hoechst Aktiengesellschaft||Builders for detergent and cleaning compositions|
|US4079016 *||Jun 19, 1975||Mar 14, 1978||Solvay & Cie.||Solid compositions for washing, cleaning and bleaching and processes for their manufacture and their use|
|US4095035 *||Jun 27, 1975||Jun 13, 1978||Lever Brothers Company||Aligomeric polyacrylates|
|US4203858 *||Oct 17, 1977||May 20, 1980||Gaf Corporation||Phosphate-free machine dishwashing composition|
|US4657693 *||Dec 23, 1985||Apr 14, 1987||The Procter & Gamble Company||Spray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate|
|US4743394 *||Feb 20, 1986||May 10, 1988||Kaufmann Edward J||Concentrated non-phosphate detergent paste compositions|
|US4797223 *||Jan 11, 1988||Jan 10, 1989||Rohm And Haas Company||Water soluble polymers for detergent compositions|
|US5081209 *||Oct 23, 1989||Jan 14, 1992||Phillips Petroleum Company||Compositions and methods for inhibiting corrosion|
|US5118536 *||Aug 9, 1991||Jun 2, 1992||Phillips Petroleum Company||Compositions and methods for inhibiting corrosion|
|US5135999 *||Aug 9, 1991||Aug 4, 1992||Phillips Petroleum Company||Compositions and methods for inhibiting corrosion|
|US5234505 *||Jun 10, 1992||Aug 10, 1993||Church & Dwight Co., Inc.||Stabilization of silicate solutions|
|US5234506 *||Jun 10, 1992||Aug 10, 1993||Church & Dwight Co., Inc.||Aqueous electronic circuit assembly cleaner and method|
|US5261967 *||Jun 10, 1992||Nov 16, 1993||Church & Dwight Co, Inc.||Powdered electric circuit assembly cleaner|
|US5264046 *||Jun 10, 1992||Nov 23, 1993||Church & Dwight Co., Inc.||Aqueous electronic circuit assembly cleaner and cleaning method|
|US5264047 *||Jun 10, 1992||Nov 23, 1993||Church & Dwight Co., Inc.||Low foaming effective hydrotrope|
|US5393448 *||Jun 9, 1993||Feb 28, 1995||Church & Dwight Co., Inc.||Aqueous electronic circuit assembly cleaner and method|
|US5397495 *||Jun 9, 1993||Mar 14, 1995||Church & Dwight Co. Inc.||Stabilization of silicate solutions|
|US5431847 *||Oct 13, 1993||Jul 11, 1995||Charles B. Barris||Aqueous cleaning concentrates|
|US5433885 *||Jun 10, 1993||Jul 18, 1995||Church & Dwight Co., Inc.||Stabilization of silicate solutions|
|US5549761 *||Apr 6, 1995||Aug 27, 1996||Church & Dwight Co., Inc.||Method for removing rosin soldering flux from a printed wiring board|
|US5597794 *||Oct 17, 1994||Jan 28, 1997||Henkel Kommanditgesellschaft Auf Aktien||Process for the production of detergent surfactant granules comprising a recycle step|
|US5714450 *||Mar 15, 1996||Feb 3, 1998||Amway Corporation||Detergent composition containing discrete whitening agent particles|
|US5714451 *||Mar 15, 1996||Feb 3, 1998||Amway Corporation||Powder detergent composition and method of making|
|US5990068 *||Mar 10, 1998||Nov 23, 1999||Amway Corporation||Powder detergent composition having improved solubility|
|US5998351 *||Mar 10, 1998||Dec 7, 1999||Amway Corporation||Discrete whitening agent particles method of making, and powder detergent containing same|
|US6008174 *||Oct 23, 1997||Dec 28, 1999||Amway Corporation||Powder detergent composition having improved solubility|
|US6080711 *||Mar 10, 1998||Jun 27, 2000||Amway Corporation||Powder detergent composition and method of making|
|US6177397||Mar 10, 1997||Jan 23, 2001||Amway Corporation||Free-flowing agglomerated nonionic surfactant detergent composition and process for making same|
|US6458752 *||Mar 23, 1999||Oct 1, 2002||National Starch And Chemical Investment Holding Corporation||Powder laundry detergent having enhanced soils suspending properties|
|US8246780 *||Aug 21, 2012||Nalco Company||Methods for enhancing brightness and resistance to thermal yellowing of bleached kraft pulp and paper|
|US8652816||Oct 28, 2011||Feb 18, 2014||Opx Biotechnologies, Inc.||Compositions and methods for 3-hydroxypropionate bio-production from biomass|
|US8809027||Sep 27, 2010||Aug 19, 2014||Opx Biotechnologies, Inc.||Genetically modified organisms for increased microbial production of 3-hydroxypropionic acid involving an oxaloacetate alpha-decarboxylase|
|US8883464||Sep 27, 2010||Nov 11, 2014||Opx Biotechnologies, Inc.||Methods for producing 3-hydroxypropionic acid and other products|
|US8927669 *||Jan 5, 2007||Jan 6, 2015||Basf Se||Copolymers, method for producing them and their use for treating surfaces|
|US9388419||Jun 12, 2013||Jul 12, 2016||Cargill, Incorporated||Methods for producing 3-hydroxypropionic acid and other products|
|US20070062653 *||Mar 23, 2006||Mar 22, 2007||Prasad Duggirala||Compositions and processes for paper production|
|US20100210017 *||Jan 11, 2008||Aug 19, 2010||Gill Ryan T||Compositions and methods for enhancing tolerance for the production of organic chemicals produced by microorganisms|
|US20100273015 *||Jan 5, 2007||Oct 28, 2010||Basf Se||Copolymers, method for producing them and their use for treating surfaces|
|US20110125118 *||May 26, 2011||Opx Biotechnologies, Inc.||Production of an Organic Acid and/or Related Chemicals|
|US20120187051 *||Oct 8, 2010||Jul 26, 2012||Total S.A.||Method for the oxidation of organic compounds|
|USRE35017 *||Jun 8, 1994||Aug 15, 1995||Church & Dwight Co., Inc.||Method for removing soldering flux with alkaline salts, an alkali metal silicate and anionic polymer|
|USRE35045 *||Jun 8, 1994||Oct 3, 1995||Church & Dwight Co., Inc.||Method for removing soldering flux with alkaline metal carbonate salts and an alkali metal silicate|
|USRE35115 *||Jun 8, 1994||Dec 12, 1995||Church & Dwight Co. Inc.||Low foaming effective hydrotrope|
|DE3240780A1 *||Nov 4, 1982||May 11, 1983||Nalco Chemical Co||Verfahren zur kesselspeisewasser-aufbereitung und hierfuehr geeignetes mittel|
|EP1038944A2 *||Dec 30, 1999||Sep 27, 2000||National Starch and Chemical Investment Holding Corporation||Powder laundry detergent having enhanced soil suspending properties|
|U.S. Classification||562/594, 526/211, 510/361, 510/476, 510/533, 510/230, 510/245, 526/224, 526/215|
|International Classification||C08F120/06, C08F120/00, C11D3/37|
|Cooperative Classification||C08F120/06, C11D3/3761|
|European Classification||C08F120/06, C11D3/37C6B|