US3433658A - Warm water-dilutable paste rosin size and process for the manufacture thereof - Google Patents

Description

March 18, 1969 M. J. D'ERRICO ETAL 3,433,353

WARM WATER-DILUTABLE PASTE ROSIN SIZE AND PROCESS FOR THE MANUFACTURE THEREOF File'd Jan. 17. 1968 II n 70m/0W anvar/1175* INYENTORS. MICHAEL J. D ERR/C0 RUSSELL J. KUL/CK ATTORNEY United States Patent O 3,433,658 WARM WATER-DILUTABLE PASTE ROSIN SIZE AND PROCESS FOR THE MANUFACTURE THEREOF Michael Joseph DErrico, Stamford, Conn., and Russell Joseph Kulick, Lee, Mass., assignors t American Cyanamid Company, Stamford, Conn., a corporation of Maine Continuation-impart of applications Ser. No. 413,603, Nov. 24, 1964, and Ser. No. 584,194, Oct. 4, 1966. This application Jan. 17, 1968, Ser. No. 698,655 U.S. Cl. 106-123 8 Claims Int. Cl. D21c 3/00; C11d 15/04; C09f 1/04 ABSTRACT OF THE DISCLOSURE A fluid rosin size consisting of an aqueous dispersion of a rosin saponied at least 85% with an alkali metal of which at least about 75 =mol percent of the metal cations are potassium, and 9-20% of an anti-gel agent selected from the group consisting of ethanol and iso-propanol, the rosin size solids content of said size being between about 65% and 80% by weight.

This is a continuation-in-part of our copending applications Ser. Nos. 413,603 and 584,194, respectively tiled on Nov. 24, 1964 and Oct. 4, 1966 and now abandoned.

The present invention relates to paste rosin size of improved uidity and of improved dilutability with water to a solids content of less than 10% by weight. More particularly, the present invention relates to paste rosin size which is of pumpable viscosity at normal storage temperature and which in preferred instances is of pumpable viscosity at room temperature', and which can be readily diluted with warm and in preferred instances with cold water to a solids content of less than 10% by weight,

and to processes for manufacturing and 4diluting such size.

Rosin size is customarily manufactured by partially neutralizing a papermakers rosin (gum rosin, tall oil rosin, fumarated rosin, formaldehyde-reacted rosin, etc.) with aqueous sodium hydroxide solution. The amount of sodium hydroxide is predetermined so that the rosin is neutralized or saponitied to the extent of about 75 85% and the amount of water is predetermined so that the resulting size is barely of pumpable viscosity at normal storage temperature (170 F. or 71 C.) to avoid the necessity of shipping more water than is absolutely necessary. The resulting rosin is termed paste rosin size, and contains about 65%-80% rosin size solids by weight. Check U.S. Patent No. 3,321,325. It is a sticky almost solid mass at room temperature, but becomes a viscous pumpable fluid when hot. It is consequently prepared for shipment at as high a temperature as is practical (in the range of 150 F.210 F.) and is shipped suiiiciently rapidly so that it is of pumpable viscosity when received by the user.

Paste rosin size is generally transported by tank cars and is discharged from the cars by pumping. The cars are thermally insulated but receive no heat. They consequently cool in transit more or less, depending on the length of the trip and the season of the year. If the size arrives at a non-pumpable viscosity when received by the user, it must be re-heated, and this is a slow and inconvenient task, which, if not performed carefully, may burn the size.

Moreover, the size must be diluted to low (2%-5%) solids content before it can be used in papermaking. Dilution of paste rosin size with cold water presents a serious diiculty, which arises as follows.

3,433,658 Patented Mar. 18, 1969 When a quantity of hot paste rosin size is mixed with a quantity of cold water, the size transforms itself into a stiff gel, after which further dilution of the size -becomes ydilicult and slow. This phenomenon is generally regarded as independent of the extent to which the rosin has been saponied and occurs even in the case of a rosin size wherein the rosin is completely saponiiied, so that the rosin size contains no free rosin acids at all. 'Ihe phenomenon is described more in detail in Howell U.S. Patent No. 2,573,024 (1951), which discloses a number of expedients for overcoming this difficulty.

The discovery has now been made that rosin size which consists essentially of an aqueous dispersion of a rosin which is at least 85% saponiiied with an alkali metal alkali at least about mol percent of the metal cations of which are potassium, and which contains between about 2% and 20% (based on the weight of rosin size solids in the size) of a water-soluble saturated monool, is fluid (i.e., is of pumpable viscosity) at standard storage temperatures when of rosin size solids content between 65% and 85% by weight, yet is readily dilutable with warm (40 C.) water and inA preferred instances with cold and even with ice water through the range of solids at which formation of a stiff slow-dissolving gel would otherwise occur. In other words, We have ydiscovered that paste rosin size of the composition described does not pass through a viscous gel stage when it is extensively diluted with Water in any amount.

The size of the present invention possesses the following advantageous properties:

(1) It can be diluted to as low as 1%5% solids by introducing the size, at a temperature at which it is uid, into an appropriate amount of warm water or in preferred instances cold water with gentle agitation (c g., sufficient agitation to break up the size into small globules). The globules 4dissolve within a few minutes; the result is a clear soap solution. As a result, an excellent size solution is easily and quickly obtained at high dilution direct from paste rosin size without need for special equipment.

(2) The invention permits a major economy in the handling of rosin size. Heretofore, tank cars of rosin size have typically required 36 hours to be discharged at 160 F. The size of the present invention, because of its greater fluidity, can be discharged under similar conditions in 6 hours. Moreover, in preferred instances, sizes of the present invention at solids content of 70% or more are of pumpable viscosity at temperatures down to 60 F. Hence tank cars containing such size can usually be discharged at the .temperatures at which they are received by the customer, and need not be reheated.

(3) The size of the present invention is used in the manufacture of paper in the same manner as ordinary rosin size, and the paper manufacturer need not learn any new techniques. Paper having a content of the size of the present invention is of normal appearance and properties.

The invention is further illustrated by the drawing, which is a three-dimensional graph showing the principal parameters of rosin size in general (parameters A, B, and C), of the size of the present invention viewed generically (parameters D, E, and F), and of one preferred embodiment of rosin size of the present invention (parameter-s G, H, and I).

In the drawing, parameter A represents the mol percent of potassium ions which may be present in rosin size (based on the total number of mols of metal ions present); parameter B represents the weight of saturated monool which may be present based on the weight of rosin size solids in the size, and parameter B represents the extent (mol percent) to which the rosin in the size has been saponiiied.

Parameters D, E, F define the rosin size of the present invention generically. As shown by parameter D, at least about 75 mol percent of the metal ions in the size are potassium ions. As shown by parameter E, the size contains between about 2% and 20% of a saturated monool based on the weight of the size solids in the size. As shown by parameter F, the rosins in the size are at least about 85% saponied. The sizes thus defined are of pumpable viscosity at normal storage temperatures and rapidly and completely dissolve to 1% solids when gently stirred in water at 40 C.

In one preferred size illustrated, at least S5 mol percent of the metal ions are potassium ions as is shown by parameter G, the amount of the monool is 9% to 12% of the weight of rosin size solids in the size as is shown by parameter H, and the amount of the rosin which is saponied is at least 85%. This size at rosin size solids content of 60%-75% is fluid at room temperature and dissolves to 1% solids readily even in water at room temperature. It may but need not contain a larger proportion of monool.

In another instance, the size is of about 80% rosin solids size content, the rosin therein is 85%-90% saponied. The weight of the monool is 2%-4% of the weight of rosin size solids in the size, and more than 95 mol percent of the metal ions in the size are potassium ions. Such size, although containing a very small amount of monool, dissolves readily to 1% solids in warm (50 C.) water.

When the rosin is more than 95% neutralized, when more than 95 mol percent of the metal ions are potassium, and when the amount 0f monool is 9%-20% of the weight of size solids, the size is of pumpable viscosity at room temperature and is readily soluble in ice water.

When the proportion of potassium cations to all the metal cations present in any given size of the present inven tion is decreased below about 75%, the size becomes unduly ditlicult to disperse even in warm water, and hence the resulting size is outside the present invention.

When the amount of saturated monool and the extent of saponication of the rosin are below the indicated minimum in any instance, the size tends to form a stili gel on admixture with water, and such size too is outside the present invention. Excess monool (i.e., more than based on the weight of size solids) is disadvantageous because the excess monool increases the unit cost of the size without contributing any significant off-setting advantage. On the other hand the rosin may advantageously be substantially completely saponilied, and substantially cornplete saponification is preferred where lowest fluidity and maximum ease of dispersibility in water are desired.

The term cation as used in the present application designates not merely metal ions in dissociated state, but also metal in combined rosinate form as, for example, in potassium rosinate. Preferably, substantially all the cations of the size of the present invention are potassium as in such instance the size possesses better dispersibility than would otherwise be the case.

The saturated monools which are present in the 4size of the present invention include the water-soluble C1-C4 alkanols, for instance methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and isobutanol, and saturated lower monohydric alcohols such as 3-chloro-lpropanol, 2-methyloxyethanol, ethanolamine, and 2-nitroethanol. Mixtures of these or other similar lower monools may be used. So far, isopropyl alcohol has proved the most effective monool on a cost basis and posesses nearly the effectiveness of ethanol without possessing its great volatility and is therefore preferred. Humectant diols (for example, ethylene glycol and glycerol) predispose the rosin sizes of the present invention to gel when diluted with water, and therefore should not be used.

The monool content of the size is at least that amount which prevents formation of a viscous gel when the size is diluted with water. For this purpose, 2% of the monool is about the least amount which is effective. Size containing this amount of monool is of pumpable viscosity and the gel which it forms when it is mixed with water dissolves rapidly. On the other hand it is generally unnecessary for the amount of monool to be more than about 12% of the weight of the rosin size solids, and the latter amount is therefore regarded as satisfactory to most commercial users.

We have found that sizes containing 9%-12% of the monool and substantially no free rosin acid are especially beneficial when the only metal cation present is potassium. In such event, the size possesses the most important and surprising properties of being a mobile liquid at room temperature and at solids, and of dispersing rapidly in ice water with no more than moderate agitation. The amount of monool may advantageously be larger, up to about 20%, and such larger amount is specially advantageous when the size is to be pumped long distances in cold weather.

The paste rosin size of the present invention can be manufactured by saponifying any of the numerous papermakers rosins (such as have been named above) with an alkali at least of the cations of which are potassium, and adding a saturated monool, the amounts of water, monool and alkali, and the proportion of potassium cations to the other metal ions therein, being predetermined so that the size falls within the parameters D, E, and F of the drawing and is of pumpable viscosity at F. while having a rosin size solids content of at least 60% by weight.

Suitable proportions are readily established in any instance by preparing a series of sizes in the laboratory, and determining the viscosity of the size and the amount and solubility of the gel which it forms during dilution with water. Formation of insoluble or slow-dissolving gel or too high a viscosity indicates that the composition should be modified in the direction of parameters G, H and I.

In rosin size manufacture, the term pumpable viscosity is generally taken to mean a viscosity of about 3,500 centipoises (Hoeppler), but in special instances a size of higher viscosity is regarded as pumpable, depending on the power of the pump which is available, the length of pipe through which the size must be pumped, the number of bends in the pipe, etc.

The saturated monools generally do not react with the alkali or with the rosin or rosin size. Consequently they can be introduced during or after saponication. However, they are volatile at the temperatures at which rosin is saponied, and hence in instances where the saponication step is performed in an open vessel, they are most conveniently metered into the size as it is pumped into closed storage tanks or into tank cars for shipment.

When the size is made in a continuous saponier such as is shown in Anderson et al. U.S. Patent No. 2,842,453 the alkanol may be introduced as a component of the caustic solution or into the discharge from the saponier as preferred.

Dilution of the r-osin size of the present invention is readily affected in one step from 60%-80% rosin size solids by weights to 2%-5% rosin size solids by agitating the size with an appropriate quantity of water. The temperature of the water should be that at which the size undergoes rapid and complete dispersion. Homogenization or even intensive agitation is not required. lf preferred, a continuous stream of dilute size can be provided by introducing the size as a iine stream into water in turbulent ow. The minimum suitable temperature of the water in any instance can be determined by introducing the size through a hypodermic needle into a beaker of water agitated by a propeller-type stirrer operating at moderate speed. Formation of globules of size which dissolve rapidly and completely show that the water is of suitable temperature. Slow or partial dissolution of the size shows that the temperature of the Water should be raised.

The monool does not appear in the paper when the size is employed in papermaking, but remains in the white water. The monool thus has no significant effect upon the amount of water resistance, lactic acid resistance, etc., which is imparted by the size.

The paste rosin size of the present invention may contain minor amounts of other materials such as are customarily present in paste rosin size, for example, sodium side Wall lof the beaker to act as bae. Sizes are regarded as dispersible when a clear solution or dispersion forms within three minutes. The presence of iloc or other insoluble matter in the water at the end of three minutes is evidence of only partial dissolution of the size and indicates that the size is unsatisfactory.

The tests show that the sizes can be satifactorily dispersed in water without homogenization.

Description of Sizes l Autodilutaability i in H2O Appearance Percent Percent Percent Saturated Monool at of Solutions Run No. Rosin Solids Rosin 3 Saponied 2 Percent 4 Name 20 C. 50 C.

Tall oil 5 75 90 None N G. N. G. (9). G 75 90 100 N. G. N. G. (D) 75 90 100 1 N.G. N.G. (9). 75 90 100 2 N. G. O.K. Clear. 75 90 100 3 N. G. O.K. Do. 75 90 100 3 N.G. O.K. D0. 75 90 100 2 N.G. O.K. Do. 75 90 75 2 N.G. O K. Do. 75 95 100 4 O.K. O.K. Do. 75 85 100 2 N. G. O.K. D0. 75 90 100 2 N.G. O.K. Do. 75 85 100 4 O.K. O.K. Do. 75 100 100 5 O.K. O.K. Do. 75 90 100 3 N.G. O.K. Do. 75 95 100 4 O.K. O.K. Do.

1 Based on the weight of the size.

2 Molpercent of rosin acids saponified.

3 Metal cation content (mol percent) of size.

1 Based on Weight of solids in lsize.

5 For description of test, see text above.

5 Tall Ioil rosin somerized ait 275 C. for 30 minutes.

or potassium acetate, chloride or nitrate, as fluidifying assistants; pentachlorophenol as mold growth inhibitor, a cationic resin or limonene as auxiliary fortier; and emulsified wax or a hydrophobic synthetic thermoplastic resin as a supplementary size.

The invention will be further illustrated by the examples that follow. These examples are illustrations of the invention and are not to be construed as limitations thereon.

Example 1 The following illustrates a number of rosin sizes according to the present invention which are fluid at 170 F and which dissolve completely 1% solids without homogenization rapidly in warm or cold water in one step, without formation of slow-dissolving gel.

The sizes are prepared by saponifying a rosin with aqueous potassium hydroxide (or with an aqueous mixture of potassium hydroxide and sodium hydroxide); the amounts of alkali and water are pre-determined so that the free acid content and size solids content in the resulting size is as shown in the table below, which also shows the particular rosin which is saponified in each instance and the m-ol percent of potassium ions in the size. There is then stirred into the sizes at 70 C. a C2 0r C3 saturated monool, as is shown in the table below.

Control sizes are prepared without use of potassium alkali or any saturated monool, and a control size is prepared by luse of a potassium alkali but with an insufficient amount of monool.

The control sizes do not dissolve in water at 50 C.

The remaining sizes which exemplify sizes of the present invention dissolve readily when parts (or less than l0 parts) by weight of the sizes are stirred into 90 parts of water at 50 C. In several instances (where the rosin is more than 90% saponied and the amount of alkanol present is 8-12% of the weight Iof size solids), the sizes dissolve readily when the temperature of the water is C. or less.

The dispersibility test is performed by dropping 1.0 g. of size at 65 C. from a hypodermic syringe into 99 g. of water having the temperature shown in the table contained in a Z50-cc. laboratory beaker rotating from the effect of a magnetic capsule turning at 1500 r.p.m. and then placing a 1/2" wide spatula vertically along the in- Taillall oil rosin reacted with 1/5 m01 of fumarie acid at 8 Tall oil rosin reacted `with 1/5 mol of paraforrnaldehyde at 150 C. and heated for 30 minutes at 275 C.

9 Size Adoes not dissolve. When stirring fstops, size droplets settle to bottom of beaker and form a layer.

The rst three (control) runs show that when the amount of monool is too low, the resulting size is not dispersible in warm water even when all of the metal ions present are potassium.

Example 2 The following illustrates a fluid rosin size according to the present invention which is cold water dilutable to 2% solids in one step without homogenization to form a clear solution.

A mixture of (a) 178.0 g. of tall oil rosin fortified by a reacted content of fumaric acid and (b) 460.2 g. of tall oil rosin having a reacted content of 9.0 g. of paraformaldehyde and which had subsequently been heated at 275 C. for 15 minutes to decrease its latent foaming capability is melted in a vessel provided with stirrer and reflux column. To the mixture is slowly added a mixture of g. of water at C. having a dissolved content 9.0 g. of sodium chloride, and 221 g. of a 45% by weight aqueous solution of potassium hydroxide. The mixture is heated to reux. After about 15 minutes, when saponication is complete, the mixture is cooled to 70 C., 17.9 g. (3% based on the weight of sizing solids) of isopropyl alcohol is added, and the mixture is allowed to cool. The product contains about 80% solids by weight and 13% free rosin acid (equivalent to about 87% saponication), and has a viscosity of 1500 cp. at 170 F. The size dissolves rapidly and completely when 2 g. is introduced as droplets from a hypodermic syringe into 98 g. of water at 50 C. which is gently stirred in a laboratory beaker. A clear solution forms.

Example 3 The following illustrates a fumarie acid-fortified formaldehyde-containing rosin size according to the present invention and further shows a preferred method of diluting the size in one step with water.

To 302 g. (l mol) of tall oil rosin is added with stirring at C., 6.0 g. (Ms mol) of paraformaldehyde. After ve minutes the mixture is heated to 275 C. and is maintained there for 30 minutes. The mixture is cooled to 200 C. and 23.2 g. (1/5 mol) of fumaric acid is added with stirring. After two hours at that temperature the resulting resin is cooled to 140 C. and saponified in an 7 8 open vessel by adding thereto a solution of 70 g. of potas- Six aliquots each weighing 89.8 g. (and containing 67.6 sium hydroxide in 130 g. of water. A fluid rosin size of g. of size solids) are removed. To each is added with 75% solids and 8% free rosin acid content is obtained. stirring 6.8 g. of one of the monools shown below. The

There is then added with stirring 15.0 g. (4% on the samples each contain 10% of monool based ori the dry weight of sizing solids) of isopropyl alcohol. The Viscosity weight of the solids therein; the products are paste rosin of the product is such that it is a fluid viscosity at C. 5 size containing 70% solids by weight. The samples are The size dissolves rapidly when aspirated through a placed in 100 cc. vials kwhich are capped and cooled to pipe 1A6" in diameter into water at 20 C. flowing at a 25 C.

brisk pace from a laboratory faucet through a pipe about The presence or absence of gel in the samples of size 1A in inside diameter. The discharge from the pipe is a 10 is determined in each instance by observing the flow made clear solution and contains about 7% by weight of rosin of the size when a cylindrical vial is quarter-filled with size solids. a sample of the size at 18 C. and the vial is u1u-ended, so that the size flows over the inside of the vial as a Example 4 thin film. A size which ows freely, as a clear amber The following illustrates the preparation of a preferred 15 uld Wlihout trlatlons (bke map1e Sym?) ,1S free frm size of the present invention and the outstanding solugel' A slze which ow ffeeiy 'but mib s matlons miams bility properties which it possessesgel, but of the type `which dissolves within a commercially To 100 g of tau oil rosin at 200 C is added 16 g of acceptable time. A size which flows rapidly in a stringy fumarie acid with stirring, and the mixture is maintained Pattern contams .a cfmmerclauy unafceptafbly large at 200 C. for 2 hours' To the product is added 300 g- 20 amount of -gel which is of the type which dissolves in of tall oil rosin which had previously been reacted with too lorlg a time* Slow ow 1S eYldence of the presence of 2% by weight of paraformaldehyde at 160 C. and then Slow .dlsolvmg gel arid Such Size may appear to be free heated at 275 C for 30 minutes. of Strlatlons and strmginess The resulting mixture is cooled to 125 C. and is sub- .The Compara/uve vlscoslty of. the. size 1S then deter' stantially 100% saponied by addition of 78.4 g. of potas- 25 use of a Brookeld vlscoslmeter at 100 r'p'm sium hydroxide in water. an

To the resulting size is added 115 g of potassium The comparative ease with which the sizes can be chloride 48 g of isopropyl alcohol (10% on the Weight diluted with cold `water is determined by gently stirring of size solids) and suicient water to adjust the solids With a Spatula 2-5 g- Of the SiZ iI 1 each instance iIlO content 0f the size to 70% 30 97.5 g. of water at 18 C. and recording the time required The resulting size has a viscosity of less than 200 foraclear and sparkling solution to form. centipoises at 71 C. and is of pumpable Viscosity (ap- Results are as follows.

Monool Visc. of size l Percent Flow mode ofsize2 Amount Cp. at Percent Dilute- Naine added of gel C. decr. bility of size Run No..

1 Methanol 10 46.8 6 2 Ethanol 10 77. 8 5 3..- n-Propanol 10 71. 4 5 4- Iso-propanol. 10 72.5 3 5 n-Butanol 10 60.5 11

1 Based on solids in the size.

2 Observed by reversing vials of size at 18 C. Fast=like maple syrup.

3 See text above. Much indicates gel is of putty-like consistency; slight indicates that size is easily fluid and that only faint striations are observable during flow.

Minutes to form clear 2.5% by weight solution, when pipetted with gentle stirring into water at 18 C.

proximately 3500 centipoises) at 15.5 C.,'and dissolves We claim: rapidly when stirred into ice water. 1. Fluid rosin size of between about 65% and 85% The size prepared above imparts substantially the Same solids content which is of pumpable viscosity at standard water-resistance to paper as the size described in Exstora-ge temperatures and which uniformly dissolves to a amples 1-3. clear solution when one part by weight is stirred with 99 The size of Example 4 illustrates our discovery that parts by weight of water at 40 C., consisting essentially size of extraordinary fluidity and dispersibility in cold of an aqueous dispersion of a rosin at least about 85 water is achieved when the size contains substantially no saponified with an alkali metal alkali at least about 75 free rosin acid, when substantially all of the metal cations mol percent of the metal cations which are potassium, in the size are potassium, and when the amount of and as an anti-gel agent, between about 9% and 20% riionool in the size is between about 8% and 12% of the (based on the weight of rosin size solids in said size) of weight of size solids in the size. At 71 C. these sizes are a C1-C4 saturated monool, the rosin size solids content fluid liquids even lwhen their size solids content is as of said size being between about 65% and 80% by Weight much as by weight. and the weight of water in said size being greater than the weight of said monool.

2. Rosin size according to claim 1 which when of 60%- rosin size solids content disperses readily in water at 20 C. wherein the rosin is more than 85% neutralized, the weight of the nionool is 9%-12% of the weight of ing 600 g. (2.3 mols or equivalents) of commercial fortirosin size Solids i? th? Sife more thai? m01 percent ed rosin (tau oil rosin fored by a content of 2/10 m01 of the metal ions .in said size are potassium ions, and the of fumarie acid), adding 246.5 g. of a 45.6% by weight 70 temperature of Sald S12/e 1S below 100 F- ZExample 5 The following illustrates the comparative effectiveness of a number of Cl-Ci monools in paste rosin sizes of 65 the present invention.

A master batch of paste rosin size is prepared by heatsolution of potassium hydroxide in water 2.0 mols) and 3' Rosin Size according i0 Claim 2 wherein the TOSiIl g of Water stirring, and maintaining the reaciS more than neutralized and 'wherein more than tion mixture at 90 C. with stirring. The water lost by m01 Percent 0f the metal iOTiS are Potassium, Said Sile evaporation is then replaced; the product is paste size being of pumpable viscosity at room temperature and weighing 898.4 g. of which 676.4 g. (75.3% is solids. 75 being readily soluble to 1% solids in ice water.

4. Size according to claim 1 wherein the rosin is a References Cited fumarafed rOSirl- UNITED STATES PATENTS 5. Size according to claim 1 wherein the rosin is more 2 262 454 11/1941 F1 enner 106 237 than 95% Saponied- 2,373,203 2/1959 Hopkins et a1 E 10s- 233 6. Size according to claim 1 `wherein substantially all 5 3,321,325 5 /1967 Wisenbaker et aL 106..;39 of the metal cations therein are potassium.

7. Size according to claim 1 wherein the monool is iso JULIUS FROME Pnmmy Examiner Propyl alcohoL T. MORRIS, Assz'slant Examiner.

8. Size according to claim 1 wherein the monool is 10 U.S CL X R ethanol.

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