United States Patent 1 TRON A "050054120268 ty) Patent Number: 5,412,026 Holy et al. (451 Date of Patent: May 2, 1995 [58] HIGH TEMPERATURE AQUEOUS 4,963,629 10/1980 Dremel et a, eonnnnin 526/200 POLYMERIZATION PROCESS 5055540 10/1991 Hughes etl ‘26/3182 53156744 10/1992, Rideout et aly nn 210/698, [75] Inventors: Norman L. Holy, Penns Park; 5227446 7/1993 Densinger eta sai Newman M. Borinick, Oreland; S318 719 6/1994. Hughes etal. 352/174.23 Graham Swift, Blue Bell; Kathleen A. ; Hogiee Bloe'Ball alot Pe FOREIGN PATENT DOCUMENTS 4412389 2/1991 European Pat. Off. . 173] Assignee: Rohm and Haas Company, si ea 403172 8/1991 Germany Teaparie tasters sos OTHER PUBLICATIONS nm vied Spychaj, et al, High Temperature Continuous Bul Ce ee eee Copolymerization of Styrene and Acylic Acid: Ther- ; ‘al Behavior of the Reactants, pp. 2111-2119 (see espe- eel eeron Desa] cially p. 2113), 1991, J. Applied Polymer Science, vol. 162] Division of Se. No. 823,753, Jan. 22, 1992, Pat No. 42. 5268451 Primary Examiner—Mark Nagumo [51] Im. cs COBF 283/06 Attorney, Agent. or Firm—David T. Banchik [52] US.C. '525734.31; 525/59; 525/404; 525/411; 526/200; 526/209; 526/210; [57] eoeaeeeal $26/317.1; 526/271; 527/313; 527/314; This invention relates to high temperature aqueous 528/392 processes for the polymerization of monoethylenically [58] Field of Search «527/313, 314; 528/392; unsaturated carboxylic monomers to produce low mo- 526/200, 209, 210; $25/54.31, 59, 404, 411 Iecular weight, water-soluble polymer products useful 155) References Cited as detergent additives, scale inhibitors, dispersants and crystal growth modifiers. Suitable monomers include U5: PATENT DOCUMENES acrylic acid, methacrylic acid, maleic acid, maleic anhy- 3,379,102 4/1968. Spivey voowvnnrnnmnnnn 526/240 dride, erotonic acid, and itaconic acid. The reactions $301,266 11/1981 Muenster 5267212 4314044 2/1982 Hughes eal S24/08 $413;370 11/1983 526/88 4485223 11/1984 526/80 4,529,787 7/1985 ‘3267317 4,546,160 10/1985 526/320 4914,167 4/1990 526/65 are run at temperatures ranging from about 130° C. to 240" C., preferably from about 140° C. to about 230° C. ‘The process can be continuous, semi-continuous, or batch. 9 Claims, No Drawings5,412,026 1 HIGH TEMPERATURE AQUEOUS: POLYMERIZATION PROCESS This is a divisional of application Ser. No. $23,733, filed Jan. 22, 1992, now U.S. Pat. No. 5,268,437. FIELD OF THE INVENTION ‘This invention relates to processes for the production of low molecalar weight carboxylic acid polymers. In particular, this invention relates to high temperature aqueous polymerization processes which yield poly- ‘mers having number average molecular weights (M,) ‘below about 10,000 and having a polydispersity (ratio of the weight average molecular weight (M,) to the mum- ber average molecular weight) of below 2.5. Low molecular weight carboxylic acid polymers are known to be useful detergent additives, anti-redeposi- tion agents, hard surface cleaners, scale inhibitors, pig- ment dispersanis, water treatment additives and the like. However, production of very low molecular weight polymers of carboxylic monomers, especially acrylic acid, has proven to be a difficult task. In certain applications, such as detergent additives, it is becoming increasingly important that the carboxylic acid polymers are biodegradable. It is known that bio- degradability increases as molecular weight decreases. ‘Therefore, processes which produce very low molecu- lar weight polymers may provide routes to biodegrad- able polymer products. In other applications, such as water treatment, itis, particularly important that the polymer product have a narrow molecular weight distribution, ic. low polydis- persity. Polydispersity rises rapidly as the high molecu- lar weight fraction of the polymer mixture increases. In many processes designed to produce low molecular weight polymers, high molecular weight fractions are observed because there is insufficient control over chain-chain coupling and branching. These high molec ular weight fractions tend to dominate the viscosity characteristics of the polymer product and can detract from polymer performance. Other processes designed to produce low molecular weight polymers result in the formation of excessive amounts of dimers and trimers Which can also detract from the polymer performance. ‘These by-products do not have as much of an effect on the viscosity characteristics of the polymer mixture. However, they do affect the number average molecular ‘weight such that itis no longer indicative of the proper- ties of the polymer product. Tn addition to chain-chain coupling and branching, ‘processes for producing low molecular weight polymer Products tend to have high polydispersties resulting from the methods used to reduce the residual monomer content of the polymer product. Methods of reducing the residual monomer content of the polymer mixture include post-polymerization with additional initiator, extended holds at elevated temperatures and use of comonomeric scavengers. All of these methods will ‘broaden the molecular weight distribution. Therefore, unless the polymer mixture has a sufficiently low poly- dispersity to begin with, the methods used to reduce residual monomer content will raise polydispersity of the product to an unacceptable level. ‘The art has long sought an inexpensive, efficient and. environmentally sound way to produce low molecular weight polymers having a narrow molecular weight Gistribution. 2 2 0 45 « 6 2 One method of achieving low molecular weight poly- mers is through the use of efficient chain transfer agents, but this approach has several drawbacks. This approach incorporates the structure of the chain transfer agent into the polymer chain. This can be undesirable since that structure will have an increasing effect on the prop- erties of the polymer as molecular weight decreases. Furthermore, the chain transfer agents commonly em ployed are mercaptans. These materials are expensive and have objectionable odors associated with thei pres- fence. Other common chain transfer agents are hypo- phosphite, bisulfites and alcohols. These also ad to the Cost ofthe process, impart functionality tothe polymer, an introduce salts into the product, and may neces tate a product separation step ‘Another way of lowering the molecular weight ofthe polymers produced isby increasing the amount of initiae for. This approach adds considerably to the cost of production and may result in polymer chain degrada- tion, crosslinking, and high levels of unreacted intitor remaining in the product. In addition, high levels of initiator may also result in high levels of salt by-pro- ducts in the polymer mixture which is known to be moto “a0 ‘As can be seen from the data in Table 1, there is an increase in the Mu, Mz and polydispersity (D) of the polymer mixture produced at high solids levels, particu larly at 70 percent solids Example 2A ‘The procedure of Example 1A. was followed except the initistor solution also contained 20 percent by ‘weight poly(ethylene glycol) having My 600. At equi librium, the amount of acrylic acid in the reaction mix ture, either as monomer or polymer, was 10 percent and the amount of poly(ethylene glycol) in the reaction mixture was 10 percent. This is reported as 20% solids in Table 2 below. Example 2B The procedure of Example 1B was followed except the initiator solution also contained 40 percent by ‘weight poly(ethylene glycol) having My 600. At equi- librium, the amount of acrylic acid in the reaction mix- ture, either as monomer or polymer, was 20 percent and the amount of poly(ethylene glycol) in the reaction 0 20 2s 4s 6 10 mixture was 20 percent. This is reported as 40% solids in Table 2 below. Example 2C ‘The procedure of Example 1A was followed except the monomer solution was 60 percent by weight acrylic acid in deionized water, and the initiator solution was 6 percent by weight hydrogen peroxide (30 percent) in deionized water and also contained 60 percent by weight poly(ethylene glycol) having My, 600. At equi- 1ibrium, the amount of acrylic acid in the reaction mix- ture, either as monomer or polymer, was 30 percent and the amount of poly(ethylene glycol) in the reaction ‘mixture was 30 percent. This is reported as 60% solids in Table 2 below. TABLE 2 Eumgle Sols My My 2A 20 10170 Le 2D ” 10 Ls 20 o 201601 ‘The data in Table 2 show that even with the presence ofa reactive substrate, poly(ethylene glycol), the My of the resulting polymer mixture was kept fairly constant. ‘Again, My and D increased as the level of solids in- creased. Example 3A, A 155 ml CSTR equipped with a temperature probe, stirrer, heating jacket, outlet port and inlet ports for ‘monomer(s) and initiator solutions was filled to capacity ‘with deionized water. The stirrer was turned on and the water was heated to 215* C, Deionized water was pumped through the monomer inlet port at a rate of 15 ‘ml/min and through the initiator port at a rate of 3 ‘ml/min, The outlet port was opened to discharge con- tents of the CSTR at a rate of 20 ml/min thereby main- taining the level in the CSTR at capacity. The water being pumped into the CSTR was then replaced by a ‘monomer solution of 30 percent by weight acrylic acid, and 13 percent by weight sorbitol in deionized water, and an initiator solution of 6.2 percent by weight ter- tiary butyl hydroperoxide (BHP) and 0.9 percent by weight mercaptoacetic acid in deionized water, which were pumped simultaneously to the CSTR at rates of 15, ‘ml/min and 5 ml/min respectively. The results appear in Table 3 below. Example 3B ‘The same procedure as Example 3A was followed except that the monomer feed was 54 percent by weight acrylic acid in deionized water fed at $ ml/min, the initiator feed was 3.8 percent by weight tBHP and 9.7 percent by weight starch in deionized water fed at 5 ml/min, and the reaction temperature was 205° C. The results appear in Table 3 below. Example 3C ‘The same procedure as Example 3A. was followed except that the sorbitol was replaced with sucrose, no ‘mercaptoacetic acid was used, and the reaction temper- ature was 200° C. The results appear in Table 3 below.5,412,026 nn 12 TABLE 3 TABLE 4-continued Enape Suse Me MD Temp. __ Tne 3A Sorbet 3350 aa Example CC) Tye Level My Ms__D 2 Such io 25612) g SCSI BC Storowe 400031502 Ss orem sa ‘The data appearing in Table 3 show the process of the present invention using various reactive substrates. AS noted above, My, My, and D of the resulting polymer mixture remain fairly constant even in the presence of the reactive substrates. Example 4A, A 155 ml CSTR equipped with a temperature probe, stirrer, heating jacket, outlet port and inlet ports for ‘monomer(s) and initiator solutions was filled to capacity ‘with deionized water. The stirrer was turned on and the water was heated to 160° C. Deionized water was pumped through the monomer inlet port at a rate of 3.1 ‘ml/min and through the initiator port at a rate of 2.9 ‘ml/min. The outlet port was opened to discharge con+ tents of the CSTR at a rate of 60 ml/min thereby main- taining the level in the CSTR at capacity. The water ‘being pumped into the CSTR was then replaced by a monomer solution of 72 percent by weight acrylic acid in deionized water, and an initiator solution of 2 percent by weight hydrogen peroxide (30 percent) in deionized water, which were pumped simultaneously to-the CSTR at rates of 3.1 ml/min and 2.9 ml/min respec~ tively. Examples 4B through 41 were conducted in a similar manner as Example 4A with changes in reaction tem- perature and initiator level at noted below. Examples 4D and 4E used an initiator solution of 4 percent by weight hydrogen peroxide (30 percent) in deionized water. Example 4F was conducted in a similar manner as Example 4A except that the monomer solution was 33 percent by weight maleic anhydride in deionized water fed at 10 grams/min. and the initiator solution ‘was 33 percent by weight t-BHP fed at 5 ml/min. Ex- ample 4G was conducted in a similar manner 2s Exam- ple 4A except that the monomer solution was 33 per- cent by weight methacrylic acid in deionized water fed at 8 grams/min. and the initiator solution was 4.8 per- cent by weight -BHP fed at 4 ml/min. Examples 4H and 4T were conducted in a similar manner as Example 44 except that the monomer solutions were 33 percent bby weight maleic anhydride in deionized water fed at 8 .grams/min, and the initiator solution was 26 percent by weight initiator fed at 4 ml/min. Example 4 was con- ducted in a similar manner as Example 4A except that the monomer solution was 43 percent by weight acrylic acid in deionized water fed at 7 grams/min. and the initiator sofution was 4.3 percent by weight H202 and 23.5 percent by weight maleic anhydride fed at 7 ml/min. TABLE 4 Example CC) Type__teel My Ma 4A «1 Hho aD 3 1 MO; ae asa 30 {cm HO, |e 50270 4 1 ho ao soo ne a a 4G HR 5am aen0 2) BHP ome 58s 4S 5 4s ‘The data appearing in Table 4 show the increase in the My and M, of the polymer product as the tempera- ture decreases. The data also show the process of the present invention for other acid monomers, and for the production of copolymers. Tn an alternative embodiment of the present inven- tion, the polymerization can be conducted in a batch reactor. Example $A. A iter Fluitron brand pressure reactor equipped ‘with inlet ports for monomer and initiator, a thermome- ter, a pressure gauge, a rupture disc, a stirrer, heating coils, and a heating jacket was initially charged with 700 grams of PEG (My 3400) and 500 grams of deion- ized water. The contents of the reactor were stirred and ‘the reactor was inerted with nitrogen. A vacuum was applied to the reactor until the pressure was. 20-25 inches Hg. The reactor contents were then heated to 150° C. Two feeds were prepared: a monomer feed of 300 grams glacial acrylic acid and 200 grams deionized ‘water; and an initiator feed of 81 grams of 70 percent by weight -BHP and 289 grams of deionized water. These feeds were fed linearly and separately into the stirring, heated reactor over two hours. After the feeds were completed, 10 grams of deionized water were fed through each of the feed lines as a wash. The reactor contents were held for an additional 30 minutes at 150° . and then cooled to 60° C. The data appear in Table S below. Example 5B ‘The procedure of Example 5A. was followed except that 32.25 grams of 70 percent by weight BHP solu- tion was used. The data appear in Table 5 below. Example SC ‘The procedure of Example SA. was followed except that 48.64 grams of 70 percent by weight {BHP solu- tion was used. The data appear in Table 5 below. Example SD ‘The procedure of Example 5C was followed except ‘that the polymerization was conducted at 160° C. The data appear in Table 5 below. Example SE ‘The procedure of Example SA was followed except that the initial charge was 500 grams of PEG (M, 3400) ‘and 700 grams of deionized water; the monomer feed ‘was 500 grams of glacial acrylic acid; and the initiator feed was 135 grams of 70 percent by weight - BHP. The data appear in Table 5 below. Example SF ‘The procedure of Example 5A. was followed except that the initial charge was 300 grams of PEG (My 3400) ‘and 900 grams of deionized water: the monomer feed ‘was 700 grams of glacial acrylic acid; and the initiator feed was 189 grams of 70 percent by weight -BHP. The data appear in Table 5 below.5,412,026 13 Example 5G ‘The procedure of Example SA was followed except that the initial charge was 1,200 grams of deionized ‘water and no PEG. The data appear in Table 5 below. * Example SH. The procedure of Example 5A. was followed except that the monomer feed was eliminated. The data appear 19 in Table $ below. Example 51 ‘The procedure of Example 5A was followed except ‘that the initiator feed was 71.4 grams of 30 percent by 15 ‘weight Hz0z. The data appear in Table 5 below. TABLE 5 "We Ratio Example AA/PEG_ My My 20. 3A 3073501580 = 307% 0 sc 307% 401002 2D 307501035 = sys m0 Has sF mao SOS as 56 to 6801s oH oi Sa st 307% 1900 90a 30 ‘The data appearing in Table 5 shows the usefulness of the process of the present invention when conducted as a batch process. Furthermore, the high temperature aqueous batch process is also useful for reacting the carboxylic acid monomer with a reactive substrate. Example 64 ‘The same procedure of Example 5G was followed. except the initiator feed was 71.4 grams of 30 percent by 40 ‘weight Hz02. The data appear in Table 6 below. Example 6B ‘The same procedure of Example 5G was followed. except the initial charge was 926 grams of deionized 45 water; the monomer feed was 600 grams of glacial acrylic acid; and the initiator feed was 142.8 grams of 30 percent by weight H02. The data appear in Table 6 below. 35 0 Example 6C ‘The same procedure of Example 5G was followed except the initial charge was 810 grams of deionized water; the monomer feed was 1,200 grams of glacial 55 acrylic acid; and-the initiator feed was 285.6 grams of 30 percent by weight HaO2. The data appear in Table 6 below. TABLE 6 © Example Sole) My Ma. a 6 30210 LIS “ = yr 539037 6 ‘The data appearing in Table 6 also show the effect of solids on the polydispersity of the resulting polymer 4 ‘mixture made by a batch process. As the amount of ‘water in the process is reduced, the polydispersity tends to increase. Example 7A A 155 ml CSTR equipped with a temperature probe, stirrer, heating jacket, outlet port and inlet ports for ‘monomer(s) and initiator solutions was filled to capacity with deionized water. The stirrer was turned on and the water was heated to 215° C. Deionized water was Pumped through the monomer inlet port ata rate of 2.7, g/min and through the initiator port at a rate of 3.3 ‘ml/min. The outlet port was opened to discharge con- tenis of the CSTR at a rate of 60 ml/min thereby main- taining the level in the CSTR at capacity. The water being pumped into the CSTR was then replaced by a monomer solution of 75 percent by weight acrylic acid in deionized water, and an initiator solution of 7 percent by weight hydrogen peroxide (30 percent) and 42.5, percent by weight PEG having My of 3400 in deionized water, which were pumped simultaneously to the CSTR at rates of 3.1 ml/min and 2.9 ml/min respec tively. The contents of the CSTR were continuously discharged into a 40 mil static mixer maintained at 215° C. The contents ofthe static mixer were discharged into an unheated static mixer where a solution of 2 percent by weight sodium persulfate was added at arate of 1.6 ‘g/min and the mixture cooled to about 40" C. This mixture was then discharged into a 40 ml static mixer ‘maintained at 120° C. The data appears in Table 7 below. Example 7B ‘The procedure of Example 7A was followed except: the monomer feed was fed at 3.2 ml/min; the initiator feed was 2.7 percent by weight hydrogen peroxide in deionized water (ao PEG was used) fed at 2.8 ml/min; the temperature of the reactor and the first static mixer ‘was 220° C. The data appears in Table 7 below. Example 7¢ A 155 ml CSTR equipped with a temperature probe, stirrer, heating jacket, outlet port and inlet ports for ‘monomer(s) and initiator solutions was filled to capacity with deionized water. The stirrer was turned on and the water was heated to 20S" C. Deionized water was pumped through the monomer inlet port and the initia- tor port at a rate of 5 ml/min. The outlet port was opened to discharge contents of the CSTR at a rate of 10 ml/min thereby maintaining the level in the CSTR at capacity. The water being pumped into the CSTR was then replaced by a monomer solution of 45.4 percent by weight acrylic acid and 13.6 percent by weight sorbitol in deionized water, and an initiator solution of 2.2 per- cent by weight (BHP and 31.8 percent by sorbitol in deionized water, which were each pumped simulta- neously to the CSTR at a rate of 5 ml/min. The con- tents of the CSTR were continuously discharged into a second CSTR maintained at 95° C. to which a 12 per- cent by weight solution of sodium persulfate was con- tinually added at arate of 1 g/min. The data appears in Table 7 below.5,412,026 15 TABLE 7 Reser — Final Reidel Reda Monomet Monomer Ex Goa) Me Me (on) My Me 7A_12739 23801890 ios 25601960 eam ao 20 aors 202300 je "ees 330 3370, 45403120 “The data appearing in Table 7 show the results ofthe process of the present invention before and after a post- polymerization addition of initiator. The narrow molec- Ular weight distribution ofthe polymer product is main- tained after the polymer mixture i subjected to a post- polymerization addition of initiator. ‘We claim: 1. An aqueous process for polymerizing carboxylic acid monomers consisting essentially of (@) forming a reaction miature by feeding into # reac- tor containing water at a temperature in the range of from about 130° to about 240° C. under elevated pressure {@ one monomer or aqueous solution thereof se- lected from the group consisting of C3-Cemono- ethylenically unsaturated monocarboxylic acids, and the alkali metal and ammonium salts thereof C4-Cs monoethylenically unsaturated dicarbox- yl acids, and the alkali metal and ammonium Salts thereof, and anhydrides of Ca-Cs monocth- Ylenially unsaturated civdicarboxylic acids, and @ initiator, or an aqueous solution thereof, in an effective amount for initiating free-radical poly~ merization of said monomers, ii) one or more monoethylenically unsaturated carboxyl-free monomers, or aqueous solutions thereof, ata level of from 0 to 20 percent by ‘weight based on the monomer (i), such that water always makes up a last 35 percent by ‘weight of the reaction mixture and wherein the reaction “© ‘miature contains from about 10 to about 80 percent by Weight of a reactive substrate based on the reaction mixture wherein the reactive substrate fs selected from the group consisting of polyhydrie alcohols, poly(ethy- lee ly, po (propsiene even and polyapraac- tone; an (©) maintaining the reaction mixture in said tempere- ture range to form a polymer product having Ma ‘below 10,000. 2. The process of claim 1 wherein the reaction mix- ture comprises from about 10 to about 30 percent by weight of the reactive substrate. 3. The process of claim 1 wherein the reactive sub- strate is selected from the group consisting of poly- (ethylene glycol), poly(propylene glycol), polysaccha- Fides and sugars. 2s 35 45 50 55 16 1st 4. The process of claim 1 wherein the reactive sub- strate is poly(ethylene glyco). '5. The process of claim 1 wherein the reactive sub- strate is a sugar. 6. A continuous aqueous process for polymerizing carboxylic acid monomers consisting essentially of: (@) forming a reaction mixture by continuously feed- ing into a reactor containing water at a temperature in the range of from about 130° to about 240° C. under elevated pressure @ one monomer or aqueous solution thereof se- Tected from the group consisting of Cs-Cemono- ethylenically unsaturated monocarboxylic acids, and the alkali metal and ammonium salts thereof, ‘C4-Cs monoethylenically unsaturated dicarbox- yilic acids, and the alkali metal and ammonium salts thereof, and anhydrides of Cy-Cs monoeth- yylenically Unsaturated cis-dicarboxylic acids, and (i) initiator, or an aqueous solution thereof, in an effective amount for initiating free-radical poly- merization of ssid monomers, (ii) one or more monoethylenically unsaturated ccarboxyl-free monomers, or aqueous solutions thereof, at a level of from 0 to 20 percent by ‘weight based on the monomer (i), (iv) a reactive substrate or an aqueous solution of a reactive substrate, wherein the reactive substrate is selected from the group consisting of polyhyd- ric alcohols, poly(ethylene glycol), poly(propy- lene glycol) and polycaprolactone, such that water always makes up at least 35 percent by weight of the reaction mixture and such that the reac tion mixture comprises from about 10 to about 50 per~ cent by weight of the reactive substrate; and (©) maintaining the reaction mixture in said tempera- ‘ure range to form a polymer product having Mn below 10,000. 7. The process of claim 6 wherein the reactive sub- strate is selected from the group consisting of poly- (ethylene glycol), poly(propylene glycol), polysaccha- rides and sugars. 8, The process of claim 6 wherein the reactive sub- strate is poly(ethylene glyco). 9. The process of claim 6 wherein the reactive sub- strate is a sugar.