BE702520A - - Google Patents

Description

  

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 EMI1.1
 



  ; P.?: 'N? 1,' INVENTION
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 r '' = ,. r1C 'disposantes e-t u., .. Jw'C: b â iïl. '. "'. r".
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  '.¯ .. v. . n¯ 1.y F: 1.n .-- .: fi <: '.on ... , y .r.r 1 Yi ws¯. ^ .a ^ t o. m from: -: ...,.-.....



  'T', ¯. ' '-' ": 1"; 1.w - '..' .. ce. '. Âs'i c ..' .. :: 'ar :: 0stJ t :: j ..: 1.' n5: #: fl bÎ: -. . ': 1 ":":; (.. iJ¯ "': Dl, l4: C '(':.: '., C!' :: 1st 1" *. L;: w., ... ., against. '.'. '. .. ¯'¯v!'.: .. C ': 0', entartrace: .. d Lethals, 1, "Q = ;; 8. Chr; r ' 1E.:!l-+: '\ f' 1 .. i .ria: 1.; ifJtion of iron dissolved in the '0' :, r ::. On. 'Ji:': n ''> '' '..:. Q: è -'0 ::' ';.:;:. T1.èrea solids (1st 8ucpension drroe {,,: s, ysj ::. Ne = n; c, a,:. 7n par.rtioT.'LLier, the invention oonoerr-? the processing of f; 1Ei.UX to reduce 'corrosion of!: 1vice ::
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 ferrous and non-ferrous, to delay the formation of
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 tartar scabs on the surface of Ot metals to remove these scabs after they have formed.

   Another tomorrow:

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 EMI2.1
 to which the invention relates is the prevention of
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 precipitation of dissolved iron as Fe (11), restricting its oxidation to Fe (III). Another area of interest
 EMI2.3
 sant is the dispersion of pigment and other
 EMI2.4
 solids suspended in aqueous ayatas.



  2 "what concerns Ilanti-corrosiont we know ':' Ty; L ''.;: ,, :)" 'lg> l;' 9!: R: x: '"yc-li' te! ' the waters of the o: you are cooled by a -: -. ":. ';."',;: o?:;. ';?. e such as ra .... (' I, .. 0 2H0 '\. 1 The chromates, that is to say' .t -. '. # .4l *, <ge with a special name of soluble tino. Un: .-'; =: t. Ln <J # ,;> riqu.e de = T4tx ?. sJ.cal-.n! l1oléou.le d6e- 1 <c <.ri ': #; des:'. nhibLf; e'J.re corrosion t "" '.. = .. ".?;"; 2 ü..it effective in water systems "". ''. '' ;: ', "" .. J'; itiiiisa ": ion of oce ma-1-4ères is acple ! Bent "z., I .. =:: '> = c.; O c-es tcs United of Aadric 2'. Èqe-iù.; Z, the !: 5.i: Cbin # <Jur = Î = base of chro- "'-i': '.:;;, Rc';.? - t> z <. -; ¯ # .. l- e ;; in iJie 1s.

   Ec'-d.l-ure; J. 'i.zr; <vi. # Fl; .ld' 1 "T.,.;:. Is, o == - ier é.lns u - = ilie .; j = j. = ,,., =,. j,, o; -r ;; ,,.;. ,, jns., - ;;:., d '' 1 '. cT.iLr.'. 'oz, j =, rzj¯c, jij, at ==, = ¯-:, z = z ;.: ", #.;. >:.,; ± .- ', 1 ;:.' ;; ez and ', the color' - ".'.-"; --.- 'j'ot'. 'r: z i, = .i:. <. '.e'j .ours; r1-> r lc? r' is '"ed.'. t a-: t: 1, -cc; r.oeif3 to. ba ::> 3".: - .. : .... c;?;. en laa c = -; ;.;. ruc = 1, mnn and il --- = .:> .i = -1 Z .., - le-. i i; c ;; es r = .i =; Tliz => 1, the crops so <; 1 ..



  : - ..;. t <m .: '.; = r # .i:; /, ..' f. "isin9a> 1 # iJ.ii: .nt dos chroaatep 4ani 'a: -:' '; o- ". '' of -cooling water: cnt i re c 1 r ul t io n the .i: J ;; t ':; E <; '' 'h'oriatc rsooltos has been a proirl.éme because:' / 3b chromates can make food 07.CCssj. '. e!' ien ":: toxic and by eon-4qu nt '! .noomeat1ble.

   In areas where reducing agents are used in

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   the supply in addition to cooling water or come from washing the air (SO2, HS2, etc.) the reduction product, the chromium (III) ion has little or no 'inhibitory action,
Another serious problem created by the use of chromates is the risk of disease to workers handling these materials due to surface contact and inhalation of dust and mists containing chromate.

   The danger to man, animals and marine flora and fauna is aggravated by the entrainment of chromates from circulating water systems which eventually flow to rivers, laos, etc. and as a consequence, constitute a potential pollution matter of natural water supplies.



  Chromate pollution of our natural waters is the reason that prompted the demand for an adequate and relatively non-toxic replacement of anti-corrosion products with ohromate. Some substitutes which have been proposed fall into the category of materials represented by inorganic alkali metal polyphosphates, such as sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.

   These compounds, either alone or in addition to a soluble zinc compound, are currently used in fields where chromate-based inhibitors are no longer permitted. Unfortunately, inorganic polyphosphates are much inferior anti-corrosives compared to chromates. In addition to being less effective inhibitors of metal corrosion, inorganic polyphosphates pre-

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 feel their disadvantages due to their reversion to orthophosphates.

   The orthophosphates react with the caleium (II) ions in the cooling water, thus forming a strongly adherent scale on the surface of the heat exchange apparatus which reaches proportions which seriously limit the efficiency in heat exchange, In addition, orthophoaphates are known to be excellent nutrients for microbiological species which in turn contribute to the fouling of heat exchange surfaces in circulating cold water systems.



   In consideration of the above problems, the objects of the invention are as follows - To provide inhibitor products which protect against excessive corrosion on metal surfaces in aqueous systems in general and in the case of cooling waters in particular. without creating the staining and toxicity problems which are characteristic of ohromate inhibitor products.



   - Provide a series of anti-corrosive compounds such as those mentioned above, which at concentrations of 5 to 1000 parts per million, give ferrous and non-ferrous metals good protection against corrosion in aqueous systems with a pH of 4.0 to 10.0.



   - To provide a series of anti-corrosive polyfunctional organophosphate compounds which, at cooling water pHs and at usable temperatures, have a marked resistance to reversion to orthophosphates.



   - Provide a series of organic materials

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 polyfunctional phosphate which, with the addition of small amounts of a soluble Zn (II) salt, will markedly reduce the corrosion of the metal in normally corrosive water, - Provide a series of anti-corrosive polyfunctional organophosphate compounds which not only exhibit satisfactory anticorrosive performance, but in addition have the power to prevent the formation of particulate matter, both mineral and organic, which is usually found in circulating cooling water systems; including preventing the formation of scaling materials such as CaCO3. as well as adherent sludge-forming materials such as Ca3 (PO4) 2.



   - Prevent the precipitation of hydrated ferric oxide in water containing dissolved Fe (II).



   - Provide an effective means for the dispersion or deflocculation of suspended solids in aqueous media.



   The foregoing and other related objects are easily achieved by treating water with a novel inhibitory composition which consists essentially of polyfunctional acid phosphates of polyols, esters which have the formula
R-OPO3H2) x wherein R is any organic residue of a polyol used as a starting material and x is a number from 2 to 300.



   Practically any polyol is useful for forming the new compositions of the present invention. Among the most suitable alcohols, mention may be made of

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 glycerol, polyglyoerol (dimer, trimer, tetramer, etc.) pentaerythritol, dipentaerythritol, 2,5-hexanediol, 1,2,6-hexanetriol, polyvinyl alcohols including aqueous solutions of 4 % have a viscosity of the order of 2 to 25 centipoise, trimethylolethane, trimethylolpropane, 1.2-propanediol, ethylene glycol, diethylene glycol,

   "Sutro" polyols (which are commercially available mixtures of essentially straight chain polyols with a chain length of 3 to 6 carbon atoms), sucrose, and low molecular weight phenolic novolacs,
A preferred procedure for the preparation of the inhibitory organophosphate compounds of the present invention is to react polyphosphoric acid, the P 2 O 5 content of which is greater than 72% (and preferably between 82 and 84%). %) with a polyol.



   A residue of orthophosphoric acid and polyphosphoric acid remains when the reaction is complete. If the P2O5 content of the polyphosphoric acid is greater than about 85% the product will also contain some esters of the formula:
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 in which R is at least one fragment of the remaining residue of the polyalcohol used as starting material and x is a number ranging from 2 to 300. In a simple composition of the formula indicated, the values of each of the Rs can be identical or different.

   Preferably, the polyfonotional polyol phosphates, esters obtained are prepared.

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 by this method, with amounts of polyphosphorus acid containing from 0.5 to about 1 molar equivalent of P2O5 for each equivalent of the polyalcohol. The term “polyaloool equivalent” means the hydroxyl equivalents of the alcohol.

   For example, one mole of glyoerol corresponds to 3 equivalents of it, one mole of pentaerythritol corresponds to four equivalents, and, If desired, a larger amount of polyphosphoric acid can be used, i.e. i.e. an amount 1 containing more than one molar equivalent of P205 per equivalent of the polyalcohol. The conversion of the polyfonational acid phosphates to their alkali or ammonium salts can be carried out by reacting the acid esters with appropriate amounts of polyalcohol. alkali metal hydroxides or ammonium hydroxide,
A variant of the procedure for the preparation of polyfunctional phosphate polyols uses urea phosphate as the phosphating agent,

   that is, urea mixed with orthophosphoric acid. For the preparation of urea phosphate, the preferred molar ratios of urea to orthophosphoric acid are from 1 to about 2.

   The urea-phosphoric acid phoaphattion process is particularly desirable for the phosphating of low molecular weight polyvinyl alkols, that is, those whose 4% aqueous solutions have viscosities of the order of 2 to 25. dentipoises. To prepare the esters with urea phosphate, it is preferable to use 1 part of polyol with 4 to 5 parts of urea phosphate.



   Another process for the preparation of polyols

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 Polyfunctional phosphates consists in using phosphorus pentoxide itself, as the phosphating agent, also using from 0.5 to 1 mole of P2O5 per hydroxyl equivalent of the polyol. However, this process suffers from a drawback, namely that a mixture of primary and secondary phosphato is obtained.

   These mixtures are much more insoluble than are the polyphosphoric acid phosphated polyols which all contain predominantly primary phosphate groups. However, the mixtures do possess metal corrosion inhibiting properties which can be useful in many applications. ,
In the above-mentioned processes, when the phosphating agents are either polyphosphoric acid or phosphoric anhydride, the temperatures used are of the order of 60 to about 110 C. When urea phosphate is used, temperatures of at least about 160 ° C must be reached for the reaction to proceed successfully. The time to completion of the reaction in each case is normally a direct function of the temperature used.

   However, in general, reacting the polyol directly with the phosphating agent takes about 4 to 6 hours at a temperature of about 70 to 110 C when the phosphating agent is polyphosphoric acid or phosphoric anhydride. ,
Examples have been set forth below which fully explain the manner in which the present invention is used and the success achieved thereby.

   Since the measure of this success has been made by means of certain tests, a description of these tests is

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 in the rules, and they will be explained before the description of the comparative examples ,,
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 g @ g # µfiy) µé f @ u, the enluatioz¯dūrefficiency¯dn¯l'igentio # Test of, erte de j22.îdet n up.e..1o}! l '!
The inhibitory action tests which took only one day were carried out on test specimens, or test panels, which are made of mild steel and whose dimensions are 50.8 mm; 25.4mm and 3.3mm. The specimens are rotated at an average peripheral speed of about 0.304 m per second for one day in a constant volume of water. Similar sized non-ferrous grades are evaluated in the same manner.

   The water used in this test is of synthetic origin and it melts into
 EMI9.2
 Finally, 300 ppm Oa2 +, 100 ppm Mg2 ', both as CACO3 500 ppm and 01- and 500 ppm SO42- Water was prepared by dissolving suitable salts in water. deionized water. We vary the alkali-
 EMI9.3
 nitrated from 45 to 90 ppm to OaCO3 'by addition to the solution of appropriate amounts of NaHCO3. The final solutions, therefore, contain 625 to 800 ppm Na depending on whether the total alkalinity has been brought to 90 ppm or 45 ppm, as CaCO3, respectively. Systems are tested at 49 to an initial pH of 7.0. Sometimes the initial pH is varied in order to obtain data on the relationship between pH and corrosion rate.



   Before immersion, the test specimens are machine sanded with emery cloth H 120 to
 EMI9.4
 e., that they are free of hollow, then washed and rubbed with soapy water, and detergent powder "Bon Ami" free of chlorine, rinsed in deionized water

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 and then with aoetone, and finally weighed to the nearest 0.1 mg.

   At the end of a test, the type of attack, corrosion products and gnawing are observed, with an enlargement of 20 diameters. After these observations, the metal test specimens are cleaned in the same manner, except sanding, as they were prepared and then reweighed, and the corrosion rate is calculated in microns per year ( micron per year) MPA from weight loss.



   Long-term tests; Inhibitor yields are determined over a period of 2 weeks in an apparatus consisting of 6 cells immersed in a constant temperature bath of 49 C. Each cell is complete and independent of the others, In each test vessel, rotating glass stirrers, each of which has
6 hooks. The rotational speeds can be varied so that the average peripheral speed of the specimens fixed is between 0 and 1.2 m / second.



   Each test vessel contains 2500 ml of corrosion test water and the initial concentrations of the inhibitors under test are in the range of 100 to 200 ppm. Above each test vessel is a reservoir of 50 liters of corrosion test water, with a concentration of the inhibitor under test of 20 to 50 ppm, to help maintain the barrier. protective layer that formed at the initial high concentration. Make-up water containing inhibitor from the
50 liters, is automatically added to each of the test vessels at a rate of 40 ml every 18

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 minutes.

   To ensure this constant rate of flow from the reservoirs, which varies in water height pressure as a function of time, a constant difference flow regulator is available, arranged in line between each 50 liter reservoir and the test vessel supplied.



  Typically, cola takes about 3 days for the systems to reach a point where maintenance inhibitor concentrations become relatively stable. A spout disposed on each test vessel at the 2500 ml level opens to a bao which receives the overflow from periodic additions of make-up water. Once a day, the overflow is collected from each system and the water is analyzed for total solids, hardness, inhibitor degradation products, eto.



   Air is bubbled through each system at a rate which ensures saturation at the test temperature. A test piece is periodically withdrawn and subjected to the same scrutiny as discussed above. A plot of the corrosion rate MPA versus time is then drawn for all the systems tested.



   The pH is kept moderately constant throughout the duration of the test period by addition of sulfamic acid (2 M) from time to time. The reason for the use of this acid is that it avoids the introduction into the system of any anions which could form insoluble salts with the cation responsible for the hardness.



  We do not use HCl because we want to maintain a strict control of the content of this corroding anion and

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 aggressive. Sulfamic acid has oxy- stability. dation- reduction with the components of the tested systems. dispersal power
One-day studies were made on the sedimentation rates of a 200 ppm suspension of kaoin in deionized water at varying temperatures from 25 to 80 C and with varying pHs from 2 to 12. Kaolin well known under the designation of "Barden clay" has an average particle size of less than one micron and a specific surface area of 23 m2 / g (BET method, from Brunauer-Emmett-Teller,

   for measuring the specific surface area by gas absorption). This material is investigated by adding 60 ml of the 200 ppm suspensions to 200 x 25 mm test tubes which are placed in a constant temperature bath. After the addition of the anti-coagulant inhibitor to the test at a concentration of 25 ppm, the suspensions are vigorously stirred with shaking, in order to obtain a homogeneous dispersion of suspended kaolin. After leaving at rest for one day, an aliquot of the counterpart is carefully taken from the test tube and the anti-coagulation yield is determined by photometry, The ratio of the light absorption capacity of the suspension (which has been carefully taken from the center of the test tube) after leaving to oneself for one day,

   to the absorption capacity of an identical suspension which is thoroughly stirred and analyzed immediately thereafter, without allowing any settling time, is referred to as "anticoagulation efficiency". Previously, it was established that the concentration of the suspension is a direct linear function of the absorption capacity

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 for a wavelength of 340 millimicrons, on a "Bausch & Lomb Spectronic Example 1
Using the hard, corrosive test water of the composition described above, which is part of the one-day weight loss test, and whose alkalinity is 90 ppm, as CaCO3,

   the anti-corrosive yield is measured by treatments consisting in adding to the water 50 to 100 ppm of a polyglycerol phosphated with PPA (polyphosphoric acid) (average of 3.25 glyorol units), 50 to 100 ppm of Sutro-100 PPA-phosphated (5 equivalents per mole), 50-100 ppm PPA-phosphated glycerol, 50-100 ppm PPA-phosphated pentaerythritol, 50-100 ppm PPA-phosphated 1,2,6-hexanetriol and 50-100 ppm low molecular weight polyvinyl alcohol phosphated with urea phosphate. All of these compounds possess excellent inhibitory action as indicated by the data in Table 1 below.

   These compounds are significantly superior or at least at the level of chromate-based inhibitor systems and absolutely superior to inorganic polyphosphate-based inhibitor systems currently used in recirculating cooling water systems.

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 TABXEAU 1
 EMI14.1
 'dos n i-corrosive effects of different Q.o; ari.son ... J..9..s ... e:

  ff.ēt.ā.Mt..i-.corro, si.f.É'Adj.f..rn compositions (By carrying out weight-gate tests in one day on mild steel *)
 EMI14.2
 
<tb>
<tb> Concentration
<tb> Compositions <SEP> initial <SEP> in <SEP> Speed <SEP> of
<tb> corrosion inhibitor <SEP> <SEP> (MPA
<tb> Witness <SEP> (no inhibitor <SEP>) <SEP> 2000
<tb> Polyglycerol <SEP> phosphated <SEP> by <SEP> PPA
<tb> (3,25 <SEP> patterns <SEP> of <SEP> glycerol) <SEP> 50 <SEP> 63
<tb> Sutro-100 <SEP> phosphated <SEP> by <SEP> PPA <SEP> 50 <SEP> 53
<tb>
 
 EMI14.3
 30/70 NR2Cr207,2HOH / Zn8fl4.HOH 50 167 60/35/5 Na0ro.2HoX / Na hoxrunetaphosphato / ZnS04.HOH 50 91 Na tetra-pyrophosphate (Na4P207) 50 79 Tripolyphosphate do Il (Na5P30) 50 1005 Hexnmetaphosphate Na Na2o # 'p2o5 m 1:

   50 500 Na2 Crfl? e 2 HoH 50 290 Glycerol phosphated with PPA 50 94 rentaerythritol phosphated with PPA 50 71
 EMI14.4
 
<tb>
<tb> 1,2,6-hexanetriol <SEP> phosphated
<tb> by <SEP> PPA <SEP> 50 <SEP> 97
<tb> <SEP> polyvinyl alcohol <SEP> of <SEP> low <SEP> weight
<tb>
 
 EMI14.5
 Ololéoulaire (about 27,500) phos-
 EMI14.6
 
<tb>
<tb> phaté <SEP> with <SEP> of <SEP> phosphate <SEP> of urea <SEP> 50 <SEP> 203
<tb> Novolac <SEP> Phenolic <SEP> Phosphated
<tb> by <SEP> PPA <SEP> 100 <SEP> 188
<tb> Dipentaerythritol <SEP> phosphated <SEP> by
<tb> PPA <SEP> 100 <SEP> 33 <SEP>
<tb>
 

 <Desc / Clms Page number 15>

 TABLE I (Continued)
 EMI15.1
 
<tb>
<tb> Concentration
<tb> Compositions <SEP> initial <SEP> in <SEP> Speed <SEP> of
<tb> corrosion inhibitor <SEP> <SEP> (MPA)

  
<tb> Ethylene <SEP> glycol <SEP> phosphated <SEP> by
<tb> PPA <SEP> 100 <SEP> 66
<tb>
 
 EMI15.2
 'D1ethylene glycol pho rh; v ±
 EMI15.3
 
<tb>
<tb> by <SEP> PPA <SEP> 100 <SEP> 79
<tb> Hexanediol <SEP> phosphated <SEP> by <SEP> PPA <SEP> 100 <SEP> 53
<tb> 1,2,6-hexanetriol <SEP> phosphated
<tb> by <SEP> PPA <SEP> 100 <SEP> 45
<tb> Trimethylol <SEP> ethane <SEP> phosphated <SEP>,
<tb> by <SEP> PPA <SEP> 100 <SEP> 23
<tb> Trimethylol <SEP> propane <SEP> phosphated
<tb> by <SEP> PPA <SEP> 100 <SEP> 18
<tb> 1,2-propane <SEP> diol <SEP> phosphated <SEP> by
<tb> PPA <SEP> 100 <SEP> 20
<tb>.!, 3-propane <SEP> diol <SEP> phosphated <SEP> by
<tb> PPA <SEP> 100 <SEP> 25
<tb> Sucrose <SEP> phosphated <SEP> by <SEP> PPA <SEP> 100 <SEP> 20
<tb>
   * pH = 7 and temperature maintained at 12000 in each case,

   
 EMI15.4
 'Sxem!) On 2.



  Two owirant-p non-ferrous metals of ETP (hard electrolytic pitch) copper and Il Admiralt y "brass, as well as the same hard and corrosive water cast iron as described above and forming part of the test, were subjected to one-day weight gate test All show good protection using 50 ppm PPA phosphate polyols solutions Table II below shows the inhibitory action of the compounds in

 <Desc / Clms Page number 16>

 present invention when used to protect these non-ferrous metals. Again, for the sake of comparison, data from a few chromate-based systems, and also sodium hexametaphosphate, have been introduced.



  As shown in Table II, the polyfunctional orthophosphates of the present invention work better or at least as well as all prior art materials. By checking all the test pieces no gnawing was observed after the one day test in which 50 ppm of the different polyfonotional organophosphates were used. Blue colorations, which ordinarily occurred when copper or copper-based metals were chelated, were not observed at the end of each of the runs in which the composition of the invention was used.

 <Desc / Clms Page number 17>

 
 EMI17.1
 ïAB7FAU IT O. omliaraison, of,

  s antiprosive effects of different ROitions (By performing one day weight loss tests on copper base metal and cast iron *)
 EMI17.2
 
<tb>
<tb> Compositions <SEP> Metals <SEP> tested <SEP> Speed <SEP> of
<tb> oorrosion <SEP> (MPA)
<tb>
 
 EMI17.3
 r,, r 1 w-
 EMI17.4
 
<tb>
<tb> Indicator <SEP> (no inhibitor <SEP>) <SEP> Copper <SEP> ETP <SEP> 152
<tb> Brass <SEP> "Admiralty" <SEP> 225
<tb> Fonte238
<tb> Polyglycerol <SEP> Phosphated <SEP> Copper <SEP> ETP <SEP> 117
<tb>
 
 EMI17.5
 by PPA Laiton Il Adroiraltyll 106, 1
 EMI17.6
 
<tb>
<tb> (3,25 <SEP> patterns <SEP> of <SEP> glycerol)

   <SEP> Font <SEP> 99
<tb> Sutro-100 <SEP> phosphated <SEP> by <SEP> PPA <SEP> Copper <SEP> ETP <SEP> 127
<tb> Brass <SEP> "Admiralty" <SEP> 122
<tb> Font <SEP> 51
<tb> Pentaerythritol <SEP> Phosphated <SEP> Copper <SEP> ETP <SEP> 134
<tb>
 
 EMI17.7
 by PPA Brass "Ad ralty" 1i7
 EMI17.8
 
<tb>
<tb> Font <SEP> 127
<tb>
 
 EMI17.9
 30/70 Na.cro7,2H0H / Copper ETP Zn80.HOH Brass Il Ad \ Diral ty "94
 EMI17.10
 
<tb>
<tb> Font <SEP> 83
<tb>
 
 EMI17.11
 60/35/5 Na2Cr20,, 2H0H / Copper ETP 109
 EMI17.12
 
<tb>
<tb> hexametaphosphate <SEP> from <SEP> Brass <SEP> "Admiralty" <SEP> 117
<tb> Na / ZnSO4.HOH <SEP> Cast iron <SEP> 136
<tb>
 
 EMI17.13
 Na Copper Hexametaphosphate BTP 144
 EMI17.14
 
<tb>
<tb> Na2O: P2O5 <SEP> = <SEP> 1:

  1 <SEP> Brass <SEP> "Admiralty" <SEP> 129
<tb> Font <SEP> 89
<tb>
 * Concentration = 50 ppm, pH = 7, and temperature = 49 0 in each case

 <Desc / Clms Page number 18>

 
Example 3
To explain the importance of the polyfunctionality of phosphate polyols for the prevention of corrosion of mild steel, a series of one-day weight loss tests are carried out using 50 ppm mono-beta-glycerol phosphate, of monobeta-glycerol phosphate / NaHPO4 (62.5 / 37.5) and of glycerol phosphated with PPA, the product of which, by addition of NaOH to pH = 9.6, contains 37.5% of Na2HPO4 in weight.

   Glycerol alone was also tested at a concentration of 1000 ppm. The? results of these tests are shown in Table III below. It is quite obvious by observing the data of this table III that neither the monofonotional glycerol phosphate (2150 MPA), the monofunction 1 glycerol phosphate added - with NaHPO4 (735 MPA), nor the glycerol alone have provides an anti-corrosive activity comparable to that obtained with the polyfunctional phosphated glycerol, in accordance with the present invention.

 <Desc / Clms Page number 19>

 TABLE, III
 EMI19.1
 ±, OE1P; 'lr,:' ll.aon der l .rtO.tion r.: Ti.-Tç.pF.: r: <?. s.:t:

  .v, ap..1?, o1Y.9 JA ho ",, hrtés mor" "oîonat onne3s roxt ol Jth..9J1P.hi1fe .p. J.Yj'.oJlo.iq. {lM1I1 (By carrying out tests weight door in one day *)
 EMI19.2
 
<tb>
<tb> Compositions <SEP> Concentration <SEP> Speed <SEP> of
<tb> initial <SEP> (ppm) <SEP> corrosion <SEP> (MPA)
<tb> Glycerol <SEP> 1000 <SEP> 3100
<tb>
 
 EMI19.3
 Mono-beta-glycerol phosphate 50 2150
 EMI19.4
 
<tb>
<tb> Phosphate <SEP> from <SEP> mono-beta-phosphate /
<tb> Na2HPO4 <SEP> (62.5 / 37.5) <SEP> 50 <SEP> 735
<tb> Glycerol <SEP> phosphated <SEP> by <SEP> PPA <SEP> 50 <SEP> 99
<tb>
 * pH = 7.0 and temperature maintained at 49 C in each case,

  
Example 4
Because one of the major restrictions on the use of inorganic polyphosphatos as anti-corrosive agents is the ease with which they
 EMI19.5
 hydrolyze to orthophosphates, and Example is intended to compare the orthophosphate hydrolysis of these materials with the hydrolysis of the PPA phosphate polyols of the present invention. The test consists in bringing solutions to 0.2% of each of the compounds listed in Table IV below at the desired pH, at room temperature and in subjecting the solutions for one week to
 EMI19.6
 temperatures of 2000, 50 C and 60 i3.

   At the end of the test period, the orthophosphate of these solutions is determined by colorimetry with the procedure of Robertson (J. American Water Works Assoa. 52, 483-91, 1960). The percentage reversion is calculated from the amount of orthophosphate that could form, representing the

 <Desc / Clms Page number 20>

 total reversion, and that obtained analytically representing the proportion of the actual reversion which took place, At the start of the experiment, the polyglycerol phosphated by PPA conforms to 24.8% orthophosphate, in PO4, and the calculations
 EMI20.1
 on the importance of the reversion for this composition are based on the amount of orthophosphate formed in addition to the amount.

   It can be seen from Table IV that the hydrolytic stability of the phosphated polyglycerol pnr PPA is greater than that of the inorganic polyphosphates at all pH and temperatures tested, in the one week hydrolytic stability test.



   TABLE IV
 EMI20.2
 c.2.n.:t"-R a revers.! 9-n-2..n..ortho-phoBPhate, to different. i @ .méFat! - \ r¯ieJlX d -PH.
 EMI20.3
 Compositions 1! p.it).!,! 20 C 50. 0 60 110 Hex-, Na metaphosphate 5 4 15 30 (N20.P205 1, i) 6 4 14 36
 EMI20.4
 
<tb>
<tb> 7 <SEP> 3 <SEP> 12 <SEP> 29
<tb> 8 <SEP> 2 <SEP> 7 <SEP> 21
<tb> Tripolyphosphate <SEP> of <SEP> Na <SEP> 5 <SEP> 5 <SEP> 42 <SEP> 99
<tb> 6 <SEP> 5 <SEP> 19 <SEP> 85
<tb> 7 <SEP> 4 <SEP> 9 <SEP> 30
<tb> 8 <SEP> 2 <SEP> 4 <SEP> 14
<tb>
 
 EMI20.5
 Sodipa tetrs-pyrophosphate 5 4 44 99
 EMI20.6
 
<tb>
<tb> 6 <SEP> 5 <SEP> 29 <SEP> 86
<tb> 7 <SEP> 3 <SEP> 9 <SEP> 43
<tb> 8 <SEP> 2 <SEP> 2 <SEP> 14
<tb> Polyglyoerol <SEP> phosphated <SEP> by <SEP> PPA <SEP> 5 <SEP> neg, <SEP> 1 <SEP> 1
<tb> (average <SEP> of <SEP> 3.25 <SEP> patterns <SEP> of <SEP> 6 <SEP> 1 <SEP> 1 <SEP> 1
<tb> glycerol) <SEP> 7 <SEP> 1 <SEP> neg.

   <SEP> 1
<tb> 8 <SEP> neg, <SEP> neg, <SEP> 1
<tb>
 

 <Desc / Clms Page number 21>

 
Example 5
In this example, the antioagulant property of the polyfunctional organophosphates of the present invention is demonstrated. This also explains the stability at temperatures and pHs which are usually present in cooling towers. Because there is a wide temperature range in a recirculating water cooling system, the heat sensitivity of the clayey polyfunctional organophosphate dispersion is of extreme importance.

   Suspended matter often coagulates on heating, and therefore it is important to observe the stabilizing activity of polyfonotional clay-organophosphate dispersions at usable cooling tower pHs. This comparison is shown in Table V where other materials such as sodium hexametaphosphate, sodium tripolyphosphate, disodium phosphate, low molecular weight polymethacrylic acid sodium salt are also shown, and the sodium salt of a low molecular weight diisobutylene-maleic anhydride copolymer.



   Following the procedure described above concerning the dispersion test, the various materials are added to suspensions of Bardon clay in deionized water, the concentrations of which are of the order of 25 pp. at 200 ppm. The anticoagulation efficiency of these different materials is measured at temperatures of 25 ° C, 40 ° C. and 60 C and at pHs of 6.7 and 8.

   As shown in tab @@ u V, it was found that the anticoagulant activity of the three polyols phosphated by PPA is as good as superior to that of the anti-precipitation agents specific to @ els.

 <Desc / Clms Page number 22>

 ile its%. Compared over the entire temperature range, NaHPO4 (orthophosphate) is found to be very medicinal, especially at higher temperatures.

 <Desc / Clms Page number 23>

 



  TABLE V
 EMI23.1
 Onaraison des. ['Element ad' 1 t-? W, ati; .o "j¯e.jj. !! os, o, o, o .ti.oM (Using the test described above for dispersive power)
 EMI23.2
 Tempera: j; ure. 0 C rotOJ3j.t1 M rit Sl 2i 60
 EMI23.3
 
<tb>
<tb> Witness <SEP> (without <SEP> addition <SEP> of anti-coagulant) <SEP> 6 <SEP> 4 <SEP> -
<tb> 7 <SEP> 7 <SEP> 2,3 <SEP> 2,

  3
<tb> 8 <SEP> 6
<tb> Glycerol <SEP> phosphate <SEP> by <SEP> PPA <SEP> 6 <SEP> 86 <SEP> 84 <SEP> 67
<tb> 7 <SEP> 8
<tb> 8 <SEP> 91 <SEP> 85 <SEP> 66
<tb>
 
 EMI23.4
 Polyglycerol phosphated with PPA 6 go 79 78
 EMI23.5
 
<tb>
<tb> 7 <SEP> 91 <SEP> 81 <SEP> 70
<tb> 8 <SEP> 91 <SEP> 88 <SEP> 69
<tb>
 
 EMI23.6
 9enkdry% 1B4kol phosphated by PPA 6 S3 59 6i
 EMI23.7
 
<tb>
<tb> 7 <SEP> 77
<tb> 8 <SEP> 82 <SEP> 67 <SEP> 75
<tb>
 
 EMI23.8
 Na rexametaphoophate 6 83 86 55
 EMI23.9
 
<tb>
<tb> 7- <SEP> - <SEP> 67
<tb> 8 <SEP> 87 <SEP> 80 <SEP> 79
<tb>
 
 EMI23.10
 Na tripol hoophate 6 86 79 71
 EMI23.11
 
<tb>
<tb> 7 <SEP> - <SEP> 73 <SEP> 70
<tb> 8 <SEP> 89 <SEP> 77 <SEP> 71
<tb> Na2HPO4 <SEP> 6 <SEP> 53 <SEP> 34
<tb> 7 <SEP> 62 <SEP> 40 <SEP> 36
<tb> 8 <SEP> 68 <SEP> 50 <SEP> 39
<tb>
 
 EMI23.12
 Na salt of diaobutyJ.ene-copolymer 6 49 44

  
 EMI23.13
 
<tb>
<tb> maleic anhydride <SEP> <SEP> 7 <SEP> - <SEP> 42 <SEP> 35
<tb> 8 <SEP> 86 <SEP> 53 <SEP> 41
<tb>
 
 EMI23.14
 Pothao17l1qU8 acid Na salt 6 63 44 52
 EMI23.15
 
<tb>
<tb> 7 <SEP> 66 <SEP> 46 <SEP> 56
<tb> 3 <SEP> 67 <SEP> 53 <SEP> 69
<tb>
 

 <Desc / Clms Page number 24>

 
Example 6
In this example, a comparison is made of the sodium salts of the inhibitory compositions of the present invention supplemented with Zn (II) with the compositions of the prior art. A comparison is made relating to the hardness and alkalinity of the. water.

   The results shown in Table VI below clearly indicate that the sodium salt of PPA-phosphated polyglyoterol, glycerol, etc., which does not impart adequate corrosion protection to mild steel in low hardness waters. High alkalinity and high solids content, work satisfactorily in water of high hardness and low alkalinity and also in water of high hardness and high alkalinity.

   When the PPA-phosphated polyols are added with Zn (II), they have a satisfactory anti-corrosive action in both high alkalinity and low hardness waters and low alkalinity and low hardness adhesives, although the ratio of Any PPA-phosphated Zn (II) polyol which is necessary for optimum proteotion should be determined for a particular water, the general rule is to use ratios of PPA-phosphated polyols to Zn (II) from
10: 1 to 2: 1. Hardness, or other divalent ions than zino, are believed to be necessary to form, with orthophosphate or oarbonate in high alkalinity waters, insoluble protective barriers on the metal surface.

   After forming a thin insoluble barrier layer, the polyfonotional phosphates appear to stabilize the protective layer by adsorption, thus preventing significant scale formation on the metal surface.

 <Desc / Clms Page number 25>

      
 EMI25.1
 



  Cannaraison of the inhibitory action of nrn.xvel 2s co osiions, without acïàit.on of? N (II? Cone. Alkalinity Hardness Solid matter Speed of 0 imposition PPM pl = (in C <0) ppm (in CaCO3 ) total dissolved (ppm) - corrosive yc6oa, pot pr (. ae c +.) 50 5 4ùo 2000 103
 EMI25.2
 
<tb> 50 <SEP> 90 <SEP> 400 <SEP> 2000 <SEP> 84
<tb> 50 <SEP> 90 <SEP> 2 <SEP> 1200 <SEP> 3910
<tb> 100 <SEP> 5 <SEP> 2 <SEP> 10 <SEP> 405
<tb>
 
 EMI25.3
 Polyglycerol phosphated by PPA (Na + jrZntI salt)

   
 EMI25.4
 
<tb> 2/1 <SEP> 50 <SEP> 90 <SEP> 2 <SEP> 1200 <SEP> 58
<tb> 3/1 <SEP> 50 <SEP> 90 <SEP> 2 <SEP> 1200 <SEP> 53
<tb> 5/1 <SEP> 50 <SEP> 90 <SEP> 2 <SEP> 1200 <SEP> 48
<tb> 10/1 <SEP> 50 <SEP> 90 <SEP> 2 <SEP> 1200 <SEP> 242
<tb> 3/1 <SEP> 100 <SEP> 5 <SEP> 2 <SEP> 10 <SEP> 66
<tb> 5/1 <SEP> 100 <SEP> 5 <SEP> 2 <SEP> 10 <SEP> 79
<tb>
 
 EMI25.5
 Mltro-loo.-phosphated by M (Na + salt) 50 90 2 1200 3130 50 90 400 2000 89 sa.-to..pspat p, (a -3 / t> / i 50 90 2 1200 52 Glycerol phosphated by PPA (801 dena +) 50 90 2 1200 2780 {3rol phosphated by PPL (Na4- sa) 50 90 400 2000 94, Plwspté by PP.A (Salt of Ia +) IZntII) = 5 / t 50 90 1200 52 petaphospha.e of sadït (O:

  P205 = 1 a) 620 90 400 2000 56
 EMI25.6
 
<tb> 90 <SEP> 2 <SEP> 1200 <SEP> 400
<tb> 5 <SEP> 2 <SEP> 10 <SEP> 900
<tb> * the <SEP> pH <SEP> Initial <SEP> is <SEP> from <SEP> 7 <SEP> in <SEP> each <SEP> case.
<tb>
 

 <Desc / Clms Page number 26>

   example 7
Using the extended assay technique discussed above, the general anti-corrosion activity of three PPA phosphated polyols against mild steel is compared with the chromate treatments of the art. earlier which are widely used.

   For initial inhibitor concentrations of 150 ppm, which adjust to 50 ppm within three days, PPA-phosphated polyglyoerol, PPA-phosphated glyoerol, and PPA-phosphated Sutro-100- have an anti-oorrosive action. as good or better than two of the commercially available chromate inhibitor compositions and more
 EMI26.1
 known:

   7/3 by weight of ZnSO, HOH / Na2ur24..2HQH and 6 / 3.5 / 0.5 by weight of NaOrp0.y.2HOH / sodium hexametaphosphate (NeC: P205 = 1s1): ZnSOHOH, The last two com - positions are initiated at 125 ppm and after three days they adjust to their maintenance concentrations of 30 ppm, The pH of the PPA-phosphated polyol treatments is maintained at 6.8 0.3, while the inhibitory treatments at Chromate base are maintained at a preferred pH of 6.5 0.3 by periodically adding a saturated solution of sulfamic acid (NH2SO3H). Each system uses the same corrosive test water with a hardness of 400 ppm and an alkalinity of 45 ppm (both as CaCO3) as discussed above.

   When the comparative actions of each of the treatments, as well as a control which does not contain an inhibitor, are plotted, the curves of all the systems including an inhibitor treatment are practically of the same type, that is - say that after an initial corrosion rate of 250-500 MPA

 <Desc / Clms Page number 27>

 where a corrosion barrier is formed, a drop in corrosion rates below 1 MPA is obtained which is maintained by the lower maintenance concentrations.



   Example 8
In this example, the yield, as dispersing agents, of a primary and secondary triethylene glycol phosphate, prepared from P2O5, as well as the primary and secondary polyphosphatos, esters prepared from reactive polyglyomerol, is evaluated. with polyphosphoric acid or P2O5 and a phenolic novolak reacting with polyphosphoric acid, they are evaluated by comparing their dispersing powers with those of conventional commercial and well known dispersing agents (see Table VII below) such as as the sodium salt of diisobutylene-maleic anhydride copolymer, the sodium salt of polymethacrylic acid and sodium hexametaphosphate.



   The data in Table VII was obtained by a well known test (see US Pat. No. 2,930,775) concerning the ability of certain compounds to thin thin suspensions of pigment or pigment. load or aqueous suspensions of certain water insoluble solids. In accordance with this test method, a concentrated paste of each solid is titrated with additions of a 10% aqueous solution of a test compound until fluidity is obtained. The mixture is stirred after each addition with a high speed stirrer for about 1/2 minute and examined for fluidity.

   Table VII indicates in the

 <Desc / Clms Page number 28>

 first column different dispersing agents and in the following columns under each pigment (1) the percentage of dispersing agent (calculated on the weight of pigment) necessary to obtain the fluidity and (2) the percentage of pigment in the final dispersion. the data in Table VII indicate that triethylenoglycol phosphate and eoters prepared from polyglycerol and phenolic de novolacs, according to the present invention, are comparable to commercial dispersing agents based on polyopolymers. maleic anhydride and polymethaorylic acid.

   The present invention is found to have a main advantage over sodium hexametaphosphate in that the phosphate polyols in solution have a superior stability to hydrolysis over that of hexametaphosphate when submitted to. a test for this purpose, keeping saline solutions of 10% Na + of each of them at 95 C, for 24 hours and then comparing their respective dispersing powers of CaCO3.

   Before storage, to achieve the fluidity of the test suspensions, it is necessary (to use 0.06% of the phosphated polyglycerol dispersing agent (primary) and to use 0.04% of hexametaphos- sodium phate to obtain an equivalent result. After storage, the composition of the invention still requires 0.06%, but it is found that it is necessary to use 2% sodium hexametaphosphate to obtain the dismal degree of fluidity Sodium hexametaphosphate under the conditions of the storage test hydrolyzed and transformed back to a form which is relatively ineffective as a dispersing agent.

 <Desc / Clms Page number 29>

 



   Similar tests have demonstrated that as little as 0.04% and as high as 4% by weight of the dispersing agent of the present invention can fluidize in an aqueous suspension all types of water-insoluble solids. water including pigmenta, chargea, etc. However, the amounts used for this purpose are generally on the order of about 0.1 to 1%.



   Another advantage of phosphate polyols is that at low concentrations they do not usually decrease the surface tension of the water to the point of foaming. Accordingly, aqueous and concentrated dispersions of foam free of pigment can easily be prepared using the phosphate polyols,

 <Desc / Clms Page number 30>

   TABLE VII
 EMI30.1
 
<tb> Agent <SEP>% <SEP> of <SEP> dispersion <SEP> required <SEP> to <SEP> to get <SEP> the <SEP> fluidity, <SEP> calculates <SEP> on <SEP> the <SEP> weight <SEP> of <SEP> pigment
<tb> Pigment <SEP> A <SEP> B <SEP> D
<tb>
 
 EMI30.2
 5 L6mk do%% Agent%% Agent%% Zip agent Dispersing agent .disperse Pigoeno dispersion Pisnent * dispersion Pi ^ ent 'di.sperszw,

  t Pigment * dispersion Plgm = 't * 1 - Ra gel of the copolymer 0.06 71.2 O, OB 71.1 ineffective 0.17 70.7 0.14 70.8
 EMI30.3
 
<tb> of <SEP> diisobutylene-
<tb>
 
 EMI30.4
 snbydrj.de maleiqoa 2-Salt decade acid 0.04 71.3 0, to '11sot3 0.14 57.9 4su? fl, r'J 0.14 70.8 polymethaczyl 3 - Na-nozametaphosphate 0.04 '' 1.3 O, OB 71.1 0.17 57.8 C, C9 71.1 0, 91 70.9 4 - Primary phosphate and D, ü ° 71.3 COB 71 3trce 0.14 70.8 ineffective
 EMI30.5
 
<tb> secondary <SEP> of <SEP> triethylene <SEP> glycol
<tb>
 
 EMI30.6
 5 - Primary phosphate 0.06 71.2 0.06 71.2 0.19 57.7 0.12 71.0 0.12 70, @
 EMI30.7
 
<tb> polyglycerol
<tb> 6 <SEP> - <SEP> Phosphate <SEP> primary <SEP> and- <SEP> 0.10 <SEP> 71.0 <SEP> -
<tb>
 
 EMI30.8
 secoehbw paoevaJdrd
 EMI30.9
 
<tb> secondary <SEP> of <SEP> polvglycerol
<tb>
 
 EMI30.10
 7 - Primary phosphate of t?, T7B 71,

  1 - - - novolac ¯¯¯ ¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ #####. ¯¯¯¯¯
 EMI30.11
 Renarau: t I} siōn des p3s: A CaCO- - B = Ti02 (RA - rutile) - C Ti <(FF - anatase) - D TiCJ.2 (R-610 -: rnti1e) Bu i302 (Tipuro 900 - ntti? e3 * = Final pirrwnt dispersion.

 <Desc / Clms Page number 31>

 



   Example 9 We introduce solutions each containing
 EMI31.1
 10 ppm phosphated triclyrerol, 10 ppm phosphated Sutro-100 or 10 ppm sodium h8xamtaphasphtte consists of three sets of 14 x 150 mm test tubes, each set comprising
 EMI31.2
 four test tubes. In ohique tube with ssani an add sufficient üatr) 904.6Hfl to obtain a Fe (II) coincidence of 10 ppm. The solutions are then temporned to pH 6.8 and 10. A set of four control test tubes containing 10 ppm Fe (II) tnmpoanea is also prepared in a similar manner but 8-na add upstream. smpchM.t la prdeipïtrtiont All the aolutiories are exposed to air and stirred periodically to ensure uno saturation with O2.

   The solutions are checked time by time to see if precipitates of ferric oxide hydrate form.
 EMI31.3
 



  A reddish-brown precipitate takes its form within a few days for each pH tested <1 in the solutions initially containing 10 ppm of iron in the form of Fe (II) in the absence of an agent preventing the precipitation. In solutions which reinforce the various agents preventing precipitation, no precipitate is formed after two
 EMI31.4
 weeks. In f? 4t, with cLeo -., H da 8 and 10, a faint yellow color is observed, indicating hydrated Fe (III), while clear solutions like water remain at a pH of 4.



   Example 10
In this example, a method of phosphorylation of polyglyoerol is indicated. 50 g (1.06 m) of polyglyoerol (OH index = 1196; equivalent weight = 47), under

 <Desc / Clms Page number 32>

 nitrogen atmosphere is added slowly (with stirring and cooling to keep the temperature below
 EMI32.1
 h 8000) 180 g (1.06 m in P205) decides polyphopphoric, at 115 81 and 1 eq, ui v "'etlt ortho. of" VICTOR ùHhHl0Al t0'R'ldtX ". Then the mixture is heated to 110 0 for 1 hour,
 EMI32.2
 as the mixture thickens, becomes rubbery and then liquefies. It is kept for an additional hour at 100-110 C and then it is bottled.



   It goes without saying that the present invention has been described above for explanatory purposes only, but in no way limiting, and that any variants can be made to it without departing from its scope.



   -? He is-
 EMI32.3
 A) - Anti-corrosive product characterized by the following points taken separately or in combinations:
1) The product consists essentially of a polyfonotional polyol phosphate ester of the formula
R-OPO3H2) x wherein R is a residue of a polyalcohol used for the preparation of said polyol ester ot x is a number ranging from 2 to 300.



   2) The ester has been converted to the alkali metal salt or the corresponding ammonium salt.



   3) The ester was converted to the corresponding alkali metal salt and then combined with Zn (II) ions in phosphate polyol ratios (by the acid
 EMI32.4
 polyphosphoriquo): Zn (II) from 10: 1 to 2: 1.

** ATTENTION ** end of DESC field can contain start of CLMS **.

 

Claims (1)

4) Formula product R-OPO3H2) x where R is: <Desc / Clms Page number 33> (a) a number of ethylenic groups fixed by ether bonds where the number of said ether bonds is equal to the number of said ethylenic groups minus one and in this c @ sx is equal to 2 or (b) a number of groups propylenic groups attached by ether bonds wherein the number of said ether bonds is equal to the number of said propylene groups monk one and in this x this a number which is equal to said number of propylene groups plus 2, or (o) 2 to 12 phenyl-methylenic groups, and in this case x is a number which is equal to the number of said phenyl-methylenic groups or (d) a. a mixture of polyalcohols with an essentially straight chain, the chain length of which is 3 h 6 carbon atoms ot in this case x is equal to 4 or 5, or (e) a neopentyl group and in this case x is equal to 4 or (f) two neopentyl groups attached by an ether bond, and in this case x is equal to 6, or (g) a residue of an n-hexyl group, and in this case x is equal to 2 or 3, or (h) a propylenic residue and in this case x is equal to 2, to CH2 Ci) a structural group -9 - CH2 in which CH2 # is methyl or ethyl and x is 3, or <Desc / Clms Page number 34> EMI34.1 (j) a polyethylenic residue originating from a polyyl alcohol in which the 4% aqueous solution has a viscosity of the order of 2 to 25 oentipoise, and in this case x is equal to 1/2 to 1/4 of the number of groups EMI34.2 polyethylenes which are found in polyvinyl alcohol originally. EMI34.3 5j Product oon9lat-tnt an alkali metal salt or an ammonium salt of the reaction product of a polyol with polyphosphoric aoido, said acid having a EMI34.4 P20S content greater than 72% and said polyol being such as 61yo6role, diglycerol., tr: glycerol, tetrnglyo6rol, pantaerythritol, dipentadrythritolp 2,5-hexanodiol, 1, 2, 6-hexraxzetrlal, a polvinyl alcohol in which the 4% aqueous solution has a viscosity of the order of 2 to 2 ocntipoisost or trimethylolethane , tr .methylo3.praaua g 10! , -prop.trYedio, 1, 3-propanediol, 1 ethy. = nelyco., diethylene glyool, a mixture of essentially straight chain polyalcohols comprising from 3 to 6 HtOf110S d ,. chk-tin-length carbon, sucrose $ and a low molecular weight phenolic novolak. 6) R; nti-corrosive product consisting of; entialla.m: nt a blend of polyfunctional polyol esters of formulas EMI34.5 in which R is at least a fragment of a residue of the polyalcohol used as a starting material in the <Desc / Clms Page number 35> preparation of said polyol ester and x is a number from 2 to 300. 7) The esters have been converted to the corresponding alkali metal or ammonium salts. 8) The esters were converted to the corresponding alkali metal salts and then combined with Zn (II) ions at phosphate polyols: Zn (II) ratios of 10: 1 to 2: 1. 9) Product consisting of an aloalin metal salt or an ammonium salt of the reaction product of a polyol with P2O5, said polyol being such as the polyols mentioned in point 5. B) - Process for the preparation of a polyfunctional phosphate polyol ester characterized by the following points taken separately or in combinations: 10) The process consists in reacting a polyol with polyphosphoric acid, the amount of said acid used corresponding to at least 0.5 molar equivalent of P2O5 for each hydroxyl equivalent of the polyalcohol, and said polyalcohol being one of the polyalcohols mentioned in point 5, II) The process consists in reacting a polyol with at least 0.5 mole of P2O5 per equivalent of polyol hydroxyl, said polylaoool being one of the polyalcohols mentioned in point 5. 0) - A method of maintaining a non-corrosive and scale-free environment in aqueous systems and of preventing sedimentation, on the surface of metals in such systems, of the type of particulate matter which is usually found in water, this method being temperamental <Desc / Clms Page number 36> EMI36.1 by the following points isolation or combinations; 12) The proceeds from the stages of treatment of said systems p ''. R 5 to 1000 parts per million of water from a C01 (1 "Ú - :; 1tio.r. Oonsist-mt assentiellemont in an ost-: r poll -. Ollc "':;:" Y1nel and ,. phosphated polyol, the pH of said system being'.: B ': ,,:'. 1 $: "'-' 1 (; i.ln'1 ^ v ' 'l, al6 of 4 10. '1) L, "" r0ÙÙit'.; Out 1'.u 'at 5 h 1000 per l. - 'Mi? .Ât3 :: co:.' Io4,; o essentially in a salt of mtr.l ", J .. u ':! 2.r.1 .: yes"' .. 1.11 d '1 = 1c polyfunctional ext er of polyol -'-, ''. '). The holy rH p S? naked dpjis .t! .e.14 G Z '# r ï, .i..a.0 of' -C ', 0. f ... '"- ??: =?' 3dl" for i, 1f11C181 the precipitation of Fe (II) ¯ '.';.: "? Zir: '<1.! 18 water, and do c '3 fact, fight the'. '^: - ,.:' ij ':;: 3 hydrated ferriarc oxide which can pro- - a df- c.cr¯ i.nn} Jar 44 if, lrcnce <: '?, éro.tîçln, des .t "3. .. r rrl # ferrous, ('{i ¯'J'océd "cOtlai:;. 1,:,' nt '' '-'. <l, '1 li 1 0 1)" r "'; '' '', ', 1.i produced aelcn 1)} DO'1 =' - ', ¯ ï',. 1 dissolved '11 .11 F) O '; IJr5G (J1lt dn.nc J.'O'1.11. ".\CC.' G e4ïp ;: L:, r: que al;. Solid eras; c., .. '1.q'v (Ctl: J-3 f; t 1, cfinai, s'; J hi out, 4 l' 1 ?. 'ru /'.r>, <1>: ea'; rit2, i of the product according to 1).