Source: http://www.google.com/patents/US4180532?ie=ISO-8859-1
Timestamp: 2014-03-16 02:16:49
Document Index: 597238380

Matched Legal Cases: ['arts  10', 'arts 5', 'arts  33', 'arts 20', 'arts  56', 'arts 75']

Patent US4180532 - Phosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diols - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsPhosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diols are water soluble compounds which may be used in formulating light to heavy duty water-based metal working fluid compositions....http://www.google.com/patents/US4180532?utm_source=gb-gplus-sharePatent US4180532 - Phosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diolsAdvanced Patent SearchPublication numberUS4180532 APublication typeGrantApplication numberUS 05/912,439Publication dateDec 25, 1979Filing dateJun 5, 1978Priority dateJun 5, 1978Publication number05912439, 912439, US 4180532 A, US 4180532A, US-A-4180532, US4180532 A, US4180532AInventorsParitosh M. Chakrabarti, Mohammed M. HashemOriginal AssigneeGaf CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (2), Referenced by (3), Classifications (33), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetPhosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diolsUS 4180532 AAbstract Phosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diols are water soluble compounds which may be used in formulating light to heavy duty water-based metal working fluid compositions.
What is claimed is: 1. Compounds and mixtures of phosphoric acid esters poly(2-10) ethyleneoxy n butane 1,4 diol.
2. Compounds and mixtures of phosphoric acid esters of poly (2-10) ethyleneoxy n butane 1,4 diol as set forth in claim 1 wherein the compounds may be the mono-, di- or triester and the mixtures.
3. Compounds and mixtures of phosphoric acid esters of poly(2-10) ethyleneoxy n butane diol as set forth in claim 1 wherein the monoester is present in a major amount.
4. Compounds and mixtures of phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4 diol as set forth in claim 1 wherein the diester is present in a major amount.
5. Compounds and mixtures produced by reacting about 1 mole of n 1,4 butane diol with about 2-10 moles of ethylene oxide, then phosphating the ethoxylated n 1,4 butane diols produced with polyphosphoric acid.
6. Compounds and mixtures produced by reacting about 1 mole of n 1,4 butane diol with about 2-10 moles of ethylene oxide, then posphating the ethoxylated n 1,4 butane diols produced with P.sub.2 O.sub.5.
7. The compounds and mixtures produced as set forth in claim 5 wherein about 6 moles of ethylene oxide are reacted.
8. The compounds and mixtures produced as set forth in claim 6 wherein about 6 moles of ethylene oxide are reacted.
BACKGROUND OF THE INVENTION The use of synthetic cutting fluid compositions has grown rapidly. The oil-free compositions are designed to impart lubricity at high temperatures, inhibit rust, reduce surface tension, produce low foam and be compatible with concentrated electrolyte solutions for hard water.
Examples of synthetic metal working fluid compositions which may be both oil and water soluble are those formed from conventional non-ionic surfactants which consist of a hydrophobe which has been polyoxyethylated. Such non-ionic surfactants have been provided with a phosphate radical which improves several of the sought for characteristics including increasing the hydrophilic characteristic of such surfactants. Examples of such metal working fluids are the ANTARA are sold by the GAF Corporation. These metal working fluid compositions are based on aliphatic and aromatic hydrophobic moieties which are further alkoxylated and phosphated.
The present invention provides compounds particularly suitable for use in formulating synthetic aqueous based metal working fluids. The compounds are phosphated, polyethoxylated (2-10 EO) n butane 1,4 diols. They are completely hydrophilic in nature. They do not contain any hydrophobic moiety. The particularly novel aspect of the present invention resides in phosphoric acid esters of the condensation products of one mole of butane-1,4-diol with from 2 to 10 moles of ethylene oxide. These esters are useful in a variety of applications such as synthetic aqueous based metal working fluids. Other uses are as lubricating additives, corrosion inhibitors, hydraulic fluids, flame retardant additives, plasticizers and the like. The phosphate esters of the present invention may be represented as follows: ##STR1## wherein X is a member selected from the group consisting of H and polyoxyethylbutanol having the general formula: ##STR2## such that the compound can be either a mono-, di- or tri-ester of phosphoric or polyphosphoric acid, or mixtures of the three, m and n are positive integers of 1 or higher. In the case where m and n are greater than 1, their values are similar to the degree of polymerization occuring in polyphosphoric acid; q and p are positive integers the total of which is from 2 to 10 and wherein z is also an integer having a value of 1 or higher.
An examination of the general formula set forth above discloses a straight chain molecule which contains no branched chains. The component moieties of the compound are individually hydrophilic and in combination remain hydrophilic. This is believed to particularly distinguish the compounds of the present invention from those found generally available which are based on combinations of hydrophobic and hydrophilic moieties. The straight chain nature of the present compounds indicates a further characteristic that is particularly desirable that of being biodegradable. The compounds of the present invention may be further modified by forming ammonium, substituted ammonium, alkali metal or alkaline earth metal salts thereof.
The preparative methods for synthesizing the rather complex compounds and mixtures thereof of the invention follow well known synthetic procedures. The ethyoxylation is carried out by adding a pre-determined number of moles of ethylene oxide to the terminal hydroxyl groups of the butanediol. It is understood that this addition results in a well known random distribution of oxyethylene groups on either side of the butanediol moiety. The phosphation is also carried out by well known methods. The phosphating agent preferred in the present invention is polyphosphoric acid although P.sub.2 O.sub.5 may also be used. The choice between the two phosphating agents depends upon whether a proponderance of diester or monoester is preferred. Polyphosphoric acid produces more monoester while P.sub.2 O.sub.5 produces more diester.
n Butanediol is charged into a pressure vessel such as an autoclave. 0.05% NaOH catalyst based on the diol is added. A predetermined amount of ethylene oxide is charged into a cylinder which is coupled to the pressure vessel by means of a valved pipe. The valve is opened to permit the reaction to proceed at a pressure of 30 to 33 psig with the temperature controlled to 130 the pressure drop indicates no unreacted ethylene oxide remains.
Phosphation of ethoxylated n butanediols may be carried out using P.sub.2 O.sub.5 or polyphosphoric acid (PPA) of 115% strength. The phosphation was carried out in a four-necked flask which is equipped with a mechanical stirrer, a thermometer, an N.sub.2 inlet (or CaCl.sub.2 tube) and a vent tube (or a condenser). Prior to phosphation a color stabilizer may be added to the diol ethoxylate in amounts of 0.5 to 1 g. The stabilizer is hypophosphorous acid when P.sub.2 O.sub.5 is used and sodium hypophosphite when PPA is used.
P.sub.2 O.sub.5 is added in portions while holding the temperature to about 50 heated for about five hours at 90
PPA in a predetermined amount is placed in a dropping funnel which was provided to one neck of the flask. The PPA was added dropwise maintaining the temperature at 40 addition the reactants are heated for about two hours at 95 100
The products of either phosphation may be bleached using 1 to 3 ml of 30% H.sub.2 O.sub.2.
__________________________________________________________________________PREPARATIONS             Temp. During   Diol Phosphating Agent             Addition                     Reaction Temp.No.   g., Moles   g., Moles (Time of Add.)                     (Time of Reaction)                               Yield g.                                    % Monoester                                           % Diester__________________________________________________________________________1  B1D.4EO   P.sub.2 O.sub.5             50                     90   133, 0.5   55, 0.37  (30 min.)                     (5 hrs.)  188  44.5   65.42  B1D.6EO   P.sub.2 O.sub.5             60                     90   177, 0.5   55, 0.37  (30 min.)                     (5 hrs.)  232  41.0   50.03  B1D.6EO   PPA       50                     95   354, 1.   340, 2.   (25 min.)                     (2 hrs.)  694  71.9   13.44  B1D.6E0   PPA       40                     95   354, 1.   170, 1.   (30 min.)                     (2 hrs.)  524  47.8   11.15  B1D.6EO   PPA       40                     95   354, 1.   127, 0.75 (20 min.)                     (2 hrs.)  481  49.0    0.06  B1D.6EO   PPA       40                     95   354, 1.   85, 0.5   (20 min.)                     (2 hrs.)  439  35.6    3.17  B1D.6EO   P.sub.2 O.sub.5             60                     90   177, 0.5   26, 0.185 (20 min.)                     (5 hrs.)  232  45.4   45.7__________________________________________________________________________
The compounds of the present invention are all based on butanediol which for convenience sake will be indicated as B1D. The moles of ethylene oxide with which one mole B1D is ethyoxylated will be indicated as a number of EO and the phosphating agent will be indicated as P.sub.2 O.sub.5 or PPA for polyphosphoric acid. The ratio shown following the butanediol, ethylene oxide and phosphating agent indicates the ratio between 1 mole of the ethoxylated butanediol and the moles of phosphating agent with which it has been reacted.
The compounds of the present invention are all based on B1D. The degree of ethoxylation varies between 2 EO to 10 EO, and the phosphation may be of varying degrees with either PPA or P.sub.2 O.sub.5. The compounds falling within those described by such ratios are all suitable for use in synthetic metal working fluid compositions sometimes called coolants. When the compounds are diluted with water, they form true solutions. The compounds further produce little or no foam and such foam as may be produced is of a quick breaking character. The compounds of the invention further provide corrosion protection to most metals. They further stand up well under extreme pressure and elevated heat.
The desirable qualities of the ethoxylated phosphated butanediols of the present invention are demonstrated by comparison with two commercially available compounds used in preparing metal working fluid compositions. ANTARA one mole of P.sub.2 O.sub.5 for each 2.7 moles of the ethoxylated phenol. ANTARA and phosphated using 1 mole of P.sub.2 O.sub.5 for each 2.7 moles of the ethoxylated alcohol.
______________________________________ConcentrateCompound______________________________________Phosphate ester    10 Parts by WeightTriethanol amine   20 Parts by WeightWater              70 Parts by Weight______________________________________
TABLE I______________________________________BLENDER FOAM TEST(15 g Concentrate Diluted to 250 ml WithDistilled Water: 0.6% phosphate ester)PHOSPHATE ESTER         FOAM HEIGHT IN MM(Neutralized as in         0      1      2   3    4     5Concentrate)  Min    Min    Min Min  Min   Min______________________________________Antara LP-700(Nonbiodegradable)         70     58     50  48   46    45Antara LK-500(Biodegradable)         112    105    90  85   68    58B1D.2EO:P.sub.2 O.sub.5 (1:0.74)         73     38     25  15   10    7B1D.4EO:P.sub.2 O.sub.5 (1:0.74)         70     40     26  18   15    8B1D.6EO:P.sub.2 O.sub.5 (1:0.74)         78     32     16  8    3     0B1D.6EO:P.sub.2 O.sub.5 (1:0.37)         83     53     35  21   13    8B1D.4EO:PPA* (A:1)         52     24     9   7    6     5B1D.6EO:PPA* (1:0.5)         72     23     7   0    0     0B1D.6EO:PPA* (1:0.75)         71     25     1   0    0     0B1D.6EO:PPA* (1:1)         70     24     9   0    0     0B1D.6EO:PPA* (1:1.5)         63     26     7   0    0     0B1D.6EO:PPA* (1:2)         52     12     1   0    0     0______________________________________ *115% PPA
It is to be noted that all of the above metal working fluid compositions are biodegradable with the exception of ANTARA Biodegradability is a most desirable feature in metal working fluid compositions particularly with the raised awareness with respect to safeguarding the enviornment from unnecessarily contaminated effluents.
It is to be noted that all of the metal working fluid compositions based on ethoxylated, phosphated butanediols produce less foam than biodegradable alkoxylated phosphated alcohols, a foam which breaks more rapidly than either commercial product. The decrease in foam production and the relatively quick breaking of that produced, increases with the degree of ethoxylation. The compositions are further improved when the phosphating agent is PPA which produces a preponderance of monoester. The outstanding compound with respect to low foam is B1D.6EO:PPA (1:1). It was incorporated in compositions having various ratios with respect to triethanolamine and water and the pH noted. The compositions are set forth in Table II. The parts shown there are by weight.
TABLE II______________________________________     Composition             Composition                        Composition     A       B          C______________________________________B1D.6EO:PPA (1:1)       10     Parts  10   Parts 5     PartsTriethanolamine       20     Parts  33.5 Parts 20    PartsWater       70     Parts  56.5 Parts 75    PartspH          8.25          8.6        8.5______________________________________
TABLE III______________________________________BLENDER FOAM TEST(Compositions of Table II, Diluted to 0.6% Phosphate EsterConc. with Distilled Water)     FOAM HEIGHT IN MM       0      1      2    3     4     5COMPOSITIONS       Min    Min    Min  Min   Min   Min______________________________________A           70     25      8   0     0     0B           70     35     14   0     0     0C           70     27      3   0     0     0______________________________________
TABLE IV______________________________________BLENDER FOAM TEST(Compositions Diluted with Distilled Waterto 250 ml and 0.6%)     FOAM HEIGHT IN mm       0      1      2    3     4     5COMPOSITIONS       Min    Min    Min  Min   Min   Min______________________________________C           70     27     3    0     0     0C with Surfynal       25      1     0    0     0     0104E______________________________________
The lubricating properties of compounds of the present invention were measured in aqueous solution for wear protection be means of a standard Four Ball test and by the extreme pressure lubricating properties as measured by the Falex text.
The Four Ball test is carried out with a test load of 100 kg at 1500 rpm at an initial temperature of 100 diameter chrome alloy steel balls were used. Three balls are held stationary abutting one another below the fourth ball which is urged against the others at the load indicated, turning at the indicated speed while immersed in the various aqueous based metal working fluid compositions to be tested. The test was run for five minutes after which the balls were retrieved and examined for wear. The smaller the scar, the more effective compound tested.
The metal working composition for the purposes of carrying out the Four Ball wear test was prepared by diluting 121/2 grams of the stock compositions into sufficient water to 250 ml of solution. The resultant composition has a phosphate ester compound concentration of 0.5%. An adjustment was made in the total amount of triethanolamine present in the test solution in that the pH of each sample was adjusted to a consistent 8.3.+-1. The results of the test is shown in Table V. It will be seen that the compounds of the present invention give results comparable to the leading commercial product.
TABLE V______________________________________SHELL FOUR BALL WEAR TEST(0.5% Phosphate Ester-pH to 8.3 .+-. 0.1 with TEA)PHOSPHATE ESTER   WEAR SCAR DIAMETER______________________________________Water only to pH 8.3 with TEA             Failure.sup. (1)Antara LP-700     0.77B1D.2EO:P.sub.2 O.sub.5 (1:0.74)             0.74B3D.2EO:P.sub.2 O.sub.5 (1:0.74)             0.79B1D.4EO:P.sub.2 O.sub.5 (1:0.74)             0.85B2D.4EO:P.sub.2 O.sub.5 (1:0.74)             0.76B3D.4EO:P.sub.2 O.sub.5 (1:0.74)             0.79B1D.6EO:P.sub.2 O.sub.5 (1:0.74)             0.78B2D.6EO:P.sub.2 O.sub.5 (1:0.74)             0.76B3D.6EO:P.sub.2 O.sub.5 (1:0.74)             0.74B1D.6EO:PPA.sup.(2) (1:0.5)             0.77B1D.6EO:PPA.sup.(2) (1:2)             0.76______________________________________ .sup.(1) Failure means, the rpm could not be maintained and the test had to be abandoned before the required 5 minutes were over. A typical scar diameter at failure (Less than 5 min.) is well over 3 mm. .sup.(2) 115% PPA.
A Four Ball wear test was carried out comparing the preferred compound of the present invention B1D.6EO:PPA (1:1) was compared with a 0.5% solution of triethanolamine and the leading commercially available product ANTARA was the diluting of succeeding compositions by a half from the preceeding one in order to determine at what point the composition was no longer sufficiently effective to prevent undue wear. The results of this test are set forth in Table VI which follows.
TABLE V__________________________________________________________________________FOUR BALL WEAR TEST(pH of Test Solutions 8.3 .+-. 0.1)COMPOSITION/      SCAR DIAMETER (mm)CONCENTRATION      1.0%          0.5%              0.25%                   0.125% 0.062%                               0.031%__________________________________________________________________________Water alone (pH 8.3 with TEA)      FAILURE.sup.(1)0.5% Solution of TEA (pH-10.1)              FAILURE.sup.(1)Antara LP-700      0.75          0.77              0.80 1.42   Failure.sup.(1)                               Failure.sup.(1)B1D.6EO:PPA.sup.(2)(1:)      0.77          0.77              0.76 0.86   0.92 2.46__________________________________________________________________________ .sup.(1) For definition see footnote of Table V. .sup.(2) 115% PPA.
TABLE VII______________________________________FALEX LOAD-BEARING CAPACITY TEST(Compositions Diluted to Give 0.15%Phosphate Ester Compound)            JAW LOAD            MAX =            FAILURECOMPOUND TESTED  PRESSURE    TORQUE(0.15% Concentration)            (lbs.)      LBS/INCH______________________________________Water alone      --          --Antara LP-700    2200        66B1D.2EO:P.sub.2 O.sub.5 (1:0.74)            1900        70B1D.4EO:P.sub.2 O.sub.5 (1:0.74)            2000        70B2D.4EO:P.sub.2 O.sub.5 (1:0.74)            2000        70B3D.4EO:P.sub.2 O.sub.5 (1:0.74)            1800        70B1D.6EO:P.sub.2 O.sub.5 (1:0.74)            2000        72B2D.6EO:P.sub.2 O.sub.5 (1:0.74)            1800        72B3D.6EO:P.sub.2 O.sub.5 (1:0.74)            1800        72B1D.6EO:PPA* (1:0.5)            1900        74B1D.6EO:PPA (1:1)            2500        74______________________________________ *115% PPA
A second series of load bearing capacity tests were carried out comparing the preferred compound of the present invention, B1D.6EO:PPA (1:1) with a leading commercial compound ANTARA at three different concentrations of the metal working fluid composition. The results are shown in Table VIII.
TABLE VIII______________________________________FALEX LOAD CARRYING CAPACITY TEST(pH of Test Solutions 8.3 + 1)          JAW LOAD, MAXCONCENTRATION/ = FAILURE      TORQUECOMPOUND       PRESSURE (lbs.)                         LBS/INCH______________________________________0.15% Antara LP-700 2400           63 B1D.6EO:PPA* (1:1)          2500           730.075% Antara LP-700 1500           60 B1D.6EO:PPA* (1:1)          1800           650.037% Antara LP-700  800           -- B1D.6EO:PPA (1:1)          1800           65______________________________________ *115% PPA
The same two compounds, the preferred phosphate ester of the present invention and ANTARA materials used were cast iron blocks, 21/2 freshly polished with aluminum oxide paper of 240 grit to remove any oxides from the surface. The blocks were further cleaned with mineral spirits or hexane and wiped with a clean cloth till no black oxide appeared on the cloth.
Test solutions were applied as relatively uniform drops usually in a row of five across the face of the block. The test blocks were left undisturbed for 24 hours at ambient temperature. During this time all the water in the metal working fluid evaporates. Then the block may be examined for rust. The outlines of the dried solution are visible and an estimate of rust inhibition is made by averaging the areas of each spot which show rust.
ANTARA of the present invention. The test solutions were adjusted to a pH of 8.3.+-1 with triethanolamine. The results were rated on a scale of A through E. A equals no rust. B less than 10% of the area on which the compositions were allowed to dry are covered by rust. C between 10 to 50% are covered by rust. D between 50 and 99% are covered by rust. E 100% covered by rust.
TABLE IX______________________________________RUST INHIBITION TEST(Test Solution Adjusted to pH 8.3 + 0.1 with TEA)     CONCENTRATION IN                    AVERAGE     TEST SOL'N     RUSTCOMPOUND    % COMPOUND % NANO.sub.2                            RATING*______________________________________Water Alone --         None      EAntara LP-700       0.1        None      BB1D.6EO:PPA (1:1)       0.1        None      BAntara LP-700       0.3        None      AB1D.6EO:PPA (1:1)       0.3        None      AAntara LP-700       0.1        0.02      AB1D.6EO:PPA (1:1)       0.1        0.02      AAntara LP-700       0.1        0.06      AB1D.6EO:PPA (1:1)       0.1        0.06      A______________________________________
The compounds of the present invention have been shown to have rust inhibiting properties. They are compatible with electrolyte corrosion inhibitors commonly added to metal working fluid compositions such as sodium nitrite. Load bearing tests were run comparing the preferred compound of the present invention and a leading commercial product ANTARA shown in Table X.
TABLE X______________________________________FALEX LOAD BEARING CAPACITY TEST(In the Presence of NaNO.sub.2) pH of Test Solution: 8.3 + 0.1                            JAW LOAD,                            MAX. =        CONCEN-             FAILURE        TRATION             PRESSURECOMPOUND     %         NaNO.sub.2                            (lbs)______________________________________Antara LP-700        0.15      0.03      1300B1D.6EO:PPA* (1:1)        0.15      0.03      1900Antara LP-700        0.075     0.015     1200B1D.6EO:PPA* (1:1)        0.075     0.015     1600Antara LP-700        0.037     0.0075     850B1D.6EO:PPA* (1:1)        0.037     0.0075    1000______________________________________ *115% PPA
The various compounds and mixtures described above will be understood to be by way of exemplification and not by way of limitation.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3228998 *Oct 17, 1960Jan 11, 1966Union Oil CoLiquid polyphosphate estersUS3275667 *Jan 21, 1963Sep 27, 1966Hoechst AgProcess for the manufacture of phosphate ester derivatives of polyalkylene glycols* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4697029 *Jan 17, 1986Sep 29, 1987Solvay & Cie. (Societe Anonyme)Phosphobrominated polyetherpolyols and processes for production thereofUS8389756Jul 29, 2008Mar 5, 2013Clariant Finance (Bvi) LimitedMethod for producing alkoxylated phosphoric acid triestersWO2009015858A2 *Jul 29, 2008Feb 5, 2009Clariant Int LtdPhosphoric acid esters containing phosphorus atoms bridged by polyol units* Cited by examinerClassifications U.S. Classification558/165, 987/226, 987/224International ClassificationC08G65/327, C10M137/06, C10M173/02, C10M137/08, C07F9/09Cooperative ClassificationC07F9/098, C10M137/06, C10M137/08, C10M2223/04, C10M2225/02, C10M2201/083, C07F9/091, C10M173/02, C10M2223/042, C10N2240/40, C10N2240/08, C10M2225/00, C08G65/327, C10N2250/02, C10N2240/401, C10N2270/02, C10M2215/042, C10N2230/12, C10M2201/02European ClassificationC07F9/09A1, C10M173/02, C10M137/08, C10M137/06, C08G65/327, C07F9/09BLegal EventsDateCodeEventDescriptionJun 24, 1991ASAssignmentOwner name: RHONE-POULENC SURFACTANTS AND SPECIALTIES INC., NEFree format text: CHANGE OF NAME;ASSIGNOR:RHONE-POULENC SPECIALTY CHEMICALS INC.;REEL/FRAME:005748/0167Effective date: 19910123Owner name: RHONE-POULENC SURFACTANTS AND SPECIALTIES, L.P.Free format text: CHANGE OF NAME;ASSIGNOR:RHONE-POULENC SPECIALTY CHEMICALS, L.P.;REEL/FRAME:005753/0422Effective date: 19900430May 30, 1991ASAssignmentOwner name: RHONE - POULENC SPECIALITY CHEMICALSFree format text: A CORRECTIVE ASSIGNMENT TO CORRECT THE SINGLE SERIAL NUMBER 07194,259 IDENTIFIED IN PREVIOUSLY RECORDED ASSIGMENT ON REEL 5315/FRAME 589.;ASSIGNOR:GAF CHEMICALS CORPORATION;REEL/FRAME:005722/0439Effective date: 19910513Jan 22, 1991ASAssignmentOwner name: DORSET INC.,Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE,;REEL/FRAME:005597/0269Effective date: 19890329Oct 30, 1990ASAssignmentOwner name: DORSET INC., A DE CORP.Free format text: CHANGE OF NAME;ASSIGNOR:GAF CORPORATION, A DE CORP.;REEL/FRAME:005250/0940Effective date: 19890410Apr 6, 1990ASAssignmentOwner name: RHONE-POULENC SPECIALTY CHEMICALS, L.P., NEW JERSEFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CHEMICALS CORPORATION;REEL/FRAME:005315/0588Effective date: 19900404Oct 30, 1989ASAssignmentOwner name: GAF CHEMICALS CORPORATIONFree format text: CHANGE OF NAME;ASSIGNOR:DORSET INC.;REEL/FRAME:005251/0071Effective date: 19890411Jun 14, 1989ASAssignmentOwner name: CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATIONFree format text: SECURITY INTEREST;ASSIGNOR:DORSET INC. A CORP OF DELAWARE;REEL/FRAME:005122/0370Effective date: 19890329RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google