New! View global litigation for patent families

US3360547A - Polyesters of tetraalkylcyclobutanediol - Google Patents

Polyesters of tetraalkylcyclobutanediol Download PDF

Info

Publication number
US3360547A
US3360547A US43468465A US3360547A US 3360547 A US3360547 A US 3360547A US 43468465 A US43468465 A US 43468465A US 3360547 A US3360547 A US 3360547A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
acid
complex
ester
esters
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
Earl W Wilson
Charles W Hequembourg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/286Esters of polymerised unsaturated acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/30Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/30Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/304Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/34Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives

Description

United States Patent 3,360,547 POLYESTERS 0F TETRAALKYL- CYCLUBUTANEDIOL Earl W. Wilson and Charles W. Hequembourg, Kingsport, Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Feb. 23, 1965, Ser. No. 434,684 Claims. (Cl. 260-485) This application is a continuation-in-part application of copending US. Ser. No. 106,550 filed May 1, 1961, of which US. Ser. No. 361,926 of Apr. 6, 1964, now abandoned is a division.

This invention relates to lubricant compositions and more particularly to novel complex esters useful as thickeners for synthetic lubricants.

Synthetic ester lubricants are widely used today for a number of purposes for which they have advantages over mineral oil lubricants. A principal use is as lubricants for jet aircraft engines, which require a lubricant that can be used over wide ranges of temperature. The lubricant must remain fluid at very low temperatures yet must retain sufficient viscosity at the high operating temperatures of jet engines to lubricate properly. In addition to other stringent requirements, it must be thermally stable at such high temperatures and must not be excessively corrosive to metals with which it comes in contact.

Because no single type of ester appears to possess all of the desirable properties, it has been the practice to mix modifier ingredients with a synthetic ester that serves as the base oil of the synthetic lubricant. For instance, most base oils for synthetic lubricants require thickening to meet high temperature viscosity requirements. However, the thickeners known in the art are often not sufficently stable thermally or they are too corrosive to metals to meet specification requirements. In accordance with the present invention, we have developed novel complex esters that are useful as thickeners for ester base oils and are characterized by excellent thermal stability and low corrosivity.

In general the novel esters of our invention are complex esters or polyesters formed by reacting a dicarboxylic acid with a tetraalkylcyclobutanediol and with a chainterminating monohydric alcohol or monocarboxylic acid. The products have the general structure:

when a monohydric alcohol is used for terminating the polyester chain, or the general structure:

when a monocarboxylic acid is used for terminating the polyester chain.

In Formula I, R is the alkyl residue of the monohydric alcohol, R is the alkylene radical of the dicarboxylic acid, R is a lower alkyl radical and x is an integer from 1 to 10.

In Formula II, R is the alkyl residue of the monocarboxylic acid and the other symbols are as indicated for Formula I.

An essential feature of the complex esters of the invention is that they are derived from a tetraalkylcyclobutanediol of the formula:

wherein the substituents, R, are the same or different straight or branched chain lower alkyl groups, i.e. alkyl groups of from about 1 to 4 carbon atoms. Such diols are advantageously prepared by the method described in the patent to R. H. Hasek and E. U. Elam, U.S. 2,936,324.

The acids used in preparing the complex esters are aliphatic, dicarboxylic acids of the formula,

wherein R is an alkylene radical of about 4 to 10 carbon atoms. Examples of particularly suitable acids include adipic acid, azelaic acid, sebacic acid and decane- 1,10-dicarboxylic acid.

The rnonohydroxy alcohols used in the preparation of the novel esters of Formula I are of the formula, R OH, wherein R is a straight or branched chain alkyl group of from 1 to 20 carbon atoms. The alcohol preferably is a primary alcohol of 4 to 12 carbons atoms. Certain secondary and tertiary aliphatic alcohols can be used but are less desirable because they are less reactive and their products have lower thermal stability. The especially preferred alcohols are 2,2-disubstituted, aliphatic, primary alcohols of from 6 to 12 carbon atoms, of which 2,2-dimethyl butanol, 2,2,4-trimethylpentanol and 2,2-dimethyl decanol are examples. Such alcohols having a beta quaternary alkyl radical, are especially preferred because of the superior stability of the resulting complex ester product. Other suitable alcohols include methanol, ethanol, n-butanol, isobutanol, 2-ethylhexanol, Z-methylpentanol, Z-ethylbutanol, 3,5,5-trimethylhexanol, l-methyl petanol, lauryl alcohol, mixtures of C saturated, branched chain rnonohydroxy alcohols derived from the well-known 0x0 synthesis, cetyl alcohol, no-octadecanol, n-eicosanol, and the like.

The novel esters of the invention also include those of Formula II that are terminated with a monocarboxylic acid. The alcohol-terminated esters of Formula I have the advantage of being less corrosive than the acid-terminated esters of Formula 11. However, in uses for which acid corrosion is not a problem, the products of Formula II are valuable and exhibit in general the same useful properties as lubricant components that characterize the alcohol-terminated products. The monocarboxylic acids used in the preparation of the novel esters of Formula II are of the formula R COOH, wherein R is a straight or branched chain alkyl radical of from 1 to 19 carbon atoms, thus including acids of from 2 to 20 carbon atoms. Examples of suitable acids include acetic, propionic, nbutyric, isobutyric, 2-ethylhexanoic, pivalic, pelargonic, lauric, stearic and eicosanoic acids and the like. Preferably R is a straight or branched chain alkyl radical of from 3 to 11 carbon atoms, as in the alkanoic acids in the range from butyric to lauric.

The complex esters of our invention can be prepared by heating a mixture of the tetraalkylcyclobutanediol, the dicarboxylic acid and the rnonohydroxy alcohol or monocarboxylic acid in the presence of an esterification catalyst. Catalysts providing the most satisfactory results include: titanium esterification catalysts such as disclosed in Caldwell and Wellman, U.S. Patent No. 2,727,881, particularly titanium alkoxides such as tetraisopropyl titanate: tin esterification catalysts such as disclosed in Caldwell, U.S. Patent No. 2,720,507, and especialy tin akoxides' such as dibutyl tin oxide and alkyl tin compounds such as tetrabutyl tin: as well as various zinc salts, calcium salts, magnesium salts, and the like, known "in the. art as esterification catalysts. The esterification catalysts are usually employed in concentrations varying from 0.001 to 2 weight percent of the reaction mixture, although somewhat higher or lower concentrations can be used.

The reaction is carried out in an inert atmosphere at a temperature in the range of about 80-250 C., preferably at atmospheric pressure. When a titanium catalyst is employed, the temperature should be at least about 180 C. To avoid product decomposition, the temperature should not exceed about 220 C.

Approximately equal molar proportions of the dicarboxylic acid and the diol are employed in the reaction.

, The molar proportions of the chain terminator, i.e., the

monohydroxy alcohol or monocarboxylic acid, with respect to the other reactants can be varied, depending upon the desired chain length of the complex ester product. For a low molecular weight product, a molar proportion of the chain terminator approaching that of the diacid or the diol will be used. For products of longer chain length and higher molecular weight, the amount of the chain terminator will be substantially less than 1 mole per mole of diacid or diol. The preferred products of our invention have an average molecular weight of about 900 to 1800. (Number-average molecular weight as defined by Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, pp. 273 et seq.) For obtaining such products, the proportion of the chain terminating alcohol or acid in the reaction mixture should be in the range of about 20 to 80 mole percent of the amount of diacid or diol employed.

Preferably an inert organic solvent such as benzene, toluene or xylene that forms an azeotrope with water is employed to aid in. distilling water from the reaction mixture. The reaction is continued until a product of the desired molecular weight is obtained, i.e., until the average chain length of the complex ester comprises from 1 to repeating units of the structure illustrated above (number-average molecular weight about 600-6000), and preferably until the number-average molecular weight of the product is in the range of 900 to 1800. Conveniently, the degree of completion of the reaction can be followed by measuring the acid number of the reaction mixture, stopping the reaction when the acid number drops to a level corresponding to that determined by previous tests as corresponding to the desired product. Upon comple tion of the reaction the product is normally treated with alkali to neutralize any free acid, washed with water until neutral, and further purified by distillation, preferably at subatmospheric pressure.

The complex esters of the invention are employed as minorcomponents of lubricating compositions having as amajor component a synthetic ester base oil. The complex esters of the invention are useful for improving the temperature-viscosity relationship of synthetic ester lubricants in general, including, for example, monohydroxy alcohol diesters of dibasic acids, as exemplified by the diesters of acids such as adipic, azelaic and sebacic with alcohols such as 2-ethylhexanol, 2,2,4-trimethylpentanol, 2-methylbutanol and the like; monobasic acid diesters of dihydroxy alcohols, as exemplified by the diesters of glycols such as diethylene glycol, triethylene glycol and 3-methyl-1,5-pentanediol with acids such as propionic, isobutyric, hexanoic, 2-ethylhexanoic and the like; as well as triesters such as the 'heptanoic and hexanoic acid vtriesters of trimethylolpropane.

The amount of complex ester added to the base oil should be sufficient to improve the viscosity-temperature relationship of the oil, that is, to form a mixture having a high-temperatureviscosity, e.g. at 210 F., higher than that of the base oil while having a low-temperature viscosity, e.g. at 40 F., not excessively higher than that of the base oil. Generally, an amount of complex ester in the range of about 5 to 40 weight percent of the base oil will provide the desired thickening result.

In addition to the ester base oil and the complex ester thickener, the lubricant compositions of the invention can include minor amounts of various additives such as rust inhibitors, oxidation inhibitors, V. I. improvers, pour point depressants, anti-foam additives and the like.

The following example illustrates the preparation of an especially preferred complex ester of the invention. This ester is prepared from azelaic acid, 2,2,4,4-tetramethylcyclobutanediol and 2,2,4-trimethylpentanol-1, and is characterized by exceptionally good heat stability and low corrosivity toward lead. The latter property is especially desirable for jet engine lubricants that come in contact with lead or Babbitt metal bearings.

Example In a three-liter flask fitted with a stirrer, thermometer, nitrogen inlet tube,.steam condenser connected to a Dean Stark moisture trap which in turn is connected to two water cooled condensers, are charged the following:

Grams Azelaic acid 1017 2,2,4,4-tetramethyl-1,3-cyclobutanediol 730 2,2,4-trimethylpentanol 257 Xylol All of the above ingredients were heated simultaneously under a nitrogen atmosphere to 90 C. and tetraisopropyl titanate (1.9 grams) was added as the catalyst. Water of esterification removed from the reaction at C.200 C. totaled 193 grams or 98.5% of theoretical. The reaction time, including 2.5 hours of vacuum stripping at 200 C. and 1-5 mm. of mercury, was 20.5 hours. The final crude product was diluted with heptane, washed with 5% NaOH solution and washed with water until neutral. The crude mixture was filtered through a diatomaceous earth and stripped of low boilers to 90 C. at 150-200 mm. The final product was vacuum stripped to 200 C. at 50-200 microns. The final acid number was 0.2 and the number-average molecular weight was 1100.

Table I below records physical properties of a complex ester of the invention, A, prepared as described in the above example. It also records comparative data for two complex esters B and C prepared from diols other than the tetraalkylcyclobutanediol used in preparing our complex esters. Specifically, the two comparative complex esters were prepared by the reaction of azelaic acid and 2,2,4-trimethylpentanol with 2-,methyl-1,3-pentanediol or with 2,2-dimethyl-1,3-propanediol.

Table II below records properties of synthetic ester lubricant compositions employing the complex esters of Table I as thickeners. In each of the three compositions the base oil is bis(2,2,4-trimethylpentyl)azelate. The table shows that the complex ester of our invention (A) prepared from 2,2,4,4-tetranrethyl-1,3-cyclobutanediol imparted good high-temperature viscosity to the lubricant composition without having the mentioned drawbacks of known thickening agents. The table further shows reresults of other important lubricant tests. The foaming properties of jet engine lubricants is significant because foaming in the lubricant reservoir system of the jet engine would lead to bearing starvation and ultimate failure. Our composition demonstrates satisfactorily low foaming characteristics. The lead corrosion test indicates whether or not the lubricant will be corrosive to the lead-indium alloy in the jet engine bearing. The panel coking test is an indication of the amount of coking that the lubricant will undergo in tubing, bearing, bearing housing and other areas within the hot spots of the engine. Table II shows that the lubricant composition of our invention containing polyester A was markedly superior to the compositions containing polyesters B" and C in the lead corrosion, panel coking and thermal stability tests.

and

CH CHs TABLE II.-PROPERTIES OF LUBRICANT COMPOSITIONS [Lube base, bis(2,2,4-trimethylpentyl) azelate] Viscosity (centlstokes) Foaming, Initial (r301, ml; collapse, Lead Test 2 mm. Weight Percent Panel 3 536 F.,

Polyester Coking Thermal 4 Sequence 1, Sequence Sequence 3, Stored 2 Stability 100 F. 210 F. 40 F. 75 F. 2, 200 F. 75 after Initial Weeks 21% A" 38. 5 7. 70 9,190 Non-Foam. /0. 2 N on-Foam 0. 3 2. 6 1. 0 16.5%8- 36. 54 7. 74 8,561 .do l0/0.2 d0 0.0 0.2 4.7 52. 27% O 37.24 7. 48 10,003 .-..-d0 25/03 .....d0 12.7 -82 23.7 6.2

1 Fed. Test Meth., Standard No. 791, Meth. 3211.1; AS'IM D892-46l. 2 Lead Corrosion Test, Fed. Test Method Standard N o. 791, Meth. 5321.

wherein R is an alkyl radical of from 1 to 20 carbon atoms, R is an alkylene radical of from 4 to 10 carbon atoms, the substituents, R, are lower alkyl radicals, R is an alkyl radical of 1 to 19 carbon atoms and x is an integer from 1 to 10.

2. A complex ester of the structure selected from the group consisting of C CH3 X 3 Fed. Test Meth., Standard N o. 791, Meth. 3462. 4 D. E. R. B. 2487, Issue 3, par. 6.7, Thermal Stability.

wherein R is an alkyl radical of from 1 to 20 carbon atoms, R is the alkylene radical of an acid selected from the group consisting of adipic, azelaic, sebacic and decane-l,l0-dicarboxylic acids, R is an alkyl radical of 1 to 19 carbon atoms and x is an integer from 1 to 10 corresponding to a complex ester of average molecular weight in the range 600 to 3000.

4. A complex ester of the structure selected from the group consisting of:

wherein R is a beta quaternary alkyl radical containing from 6 to 12 carbon atoms, R is the alkylene radical of an acid selected from the group consisting of adipic, azelaic, sebacic, and decane-l,l0-dicarboxylic acids, R is an alkyl radical of 3 to 11 carbon atoms, and x is an 7 integer from 1 to 10 corresponding to a complex ester of average molecular weight in the range 600 to 3000.

5. A complex ester according to claim 4 in which R is the 2,2,4-trimethylpentyl radical and R is the alkylene radical of azelaic acid.

References Cited UNITED STATES PATENTS 2,319,575 5/1943 Agens 260-77 Muskat 260-77 Szayna 260--77 Cashman et a1. 252-56 Matuszak 252-56 Examiners.

I. VAUGHN, Assistant Examiner.

Claims (1)

1. A COMPLEX ESTER OF THE STRUCTURE SELECTED FROM THE GROUP CONSISTING OF
US3360547A 1961-05-01 1965-02-23 Polyesters of tetraalkylcyclobutanediol Expired - Lifetime US3360547A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10655061 true 1961-05-01 1961-05-01
US3360547A US3360547A (en) 1961-05-01 1965-02-23 Polyesters of tetraalkylcyclobutanediol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US3360547A US3360547A (en) 1961-05-01 1965-02-23 Polyesters of tetraalkylcyclobutanediol

Publications (1)

Publication Number Publication Date
US3360547A true US3360547A (en) 1967-12-26

Family

ID=26803791

Family Applications (1)

Application Number Title Priority Date Filing Date
US3360547A Expired - Lifetime US3360547A (en) 1961-05-01 1965-02-23 Polyesters of tetraalkylcyclobutanediol

Country Status (1)

Country Link
US (1) US3360547A (en)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705575A (en) * 1995-05-31 1998-01-06 Shell Oil Company Copolyester composition
US5998340A (en) * 1997-03-07 1999-12-07 Hitachi Maxell, Ltd. Lubricant and magnetic recording medium using the same
US20060019840A1 (en) * 2002-08-22 2006-01-26 New Japan Chemical Co., Ltd. Lubricating oil for bearing
US20060197246A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Process for the preparation of transparent shaped articles
US20060199871A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Multilayered, transparent articles and a process for their preparation
US20060199921A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Preparation of transparent multilayered articles from polyesters and homogeneous polyamide blends
US20060199904A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Transparent, oxygen-scavenging compositions and articles prepared therefrom
US20060199919A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Transparent polymer blends and articles prepared therefrom
US20060228507A1 (en) * 2005-03-02 2006-10-12 Hale Wesley R Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US20060226565A1 (en) * 2005-03-02 2006-10-12 Hale Wesley R Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US20060235167A1 (en) * 2005-03-02 2006-10-19 Hale Wesley R Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US20060247388A1 (en) * 2005-03-02 2006-11-02 Hale Wesley R Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US20070276065A1 (en) * 2005-10-28 2007-11-29 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7510768B2 (en) 2005-06-17 2009-03-31 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7704605B2 (en) 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7737246B2 (en) 2005-12-15 2010-06-15 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US8193302B2 (en) 2005-10-28 2012-06-05 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
US8198371B2 (en) 2008-06-27 2012-06-12 Eastman Chemical Company Blends of polyesters and ABS copolymers
JP2012517498A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Coating composition comprising a blend of acrylic and aliphatic polyester
JP2012517500A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Thermosetting polyester coating composition comprising tetramethyl cyclobutanediol
JP2012517499A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Coating compositions containing tetramethyl cyclobutanediol
US8287970B2 (en) 2007-11-21 2012-10-16 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8299204B2 (en) 2005-10-28 2012-10-30 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US8394997B2 (en) 2010-12-09 2013-03-12 Eastman Chemical Company Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420868B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420869B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8501287B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8895654B2 (en) 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
US9169388B2 (en) 2006-03-28 2015-10-27 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2319575A (en) * 1940-03-27 1943-05-18 Gen Electric Resinous composition
US2415366A (en) * 1943-01-16 1947-02-04 Marco Chemicals Inc Polymerizable diester compounds and method of making same
US2824840A (en) * 1953-04-01 1958-02-25 Exxon Research Engineering Co Lubricating oil composition
US2889312A (en) * 1955-11-07 1959-06-02 Us Rubber Co Alkyd resins modified with mono-allyl maleate end groups
US3016353A (en) * 1954-12-15 1962-01-09 Exxon Research Engineering Co Ester type synthetic lubricants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2319575A (en) * 1940-03-27 1943-05-18 Gen Electric Resinous composition
US2415366A (en) * 1943-01-16 1947-02-04 Marco Chemicals Inc Polymerizable diester compounds and method of making same
US2824840A (en) * 1953-04-01 1958-02-25 Exxon Research Engineering Co Lubricating oil composition
US3016353A (en) * 1954-12-15 1962-01-09 Exxon Research Engineering Co Ester type synthetic lubricants
US2889312A (en) * 1955-11-07 1959-06-02 Us Rubber Co Alkyd resins modified with mono-allyl maleate end groups

Cited By (88)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705575A (en) * 1995-05-31 1998-01-06 Shell Oil Company Copolyester composition
US5998340A (en) * 1997-03-07 1999-12-07 Hitachi Maxell, Ltd. Lubricant and magnetic recording medium using the same
US7517838B2 (en) * 2002-08-22 2009-04-14 New Japan Chemical Co., Ltd. Lubricating oil for bearing
US20060019840A1 (en) * 2002-08-22 2006-01-26 New Japan Chemical Co., Ltd. Lubricating oil for bearing
US20060228507A1 (en) * 2005-03-02 2006-10-12 Hale Wesley R Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US20060199921A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Preparation of transparent multilayered articles from polyesters and homogeneous polyamide blends
US20060199904A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Transparent, oxygen-scavenging compositions and articles prepared therefrom
US20060199919A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Transparent polymer blends and articles prepared therefrom
US20060199871A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Multilayered, transparent articles and a process for their preparation
US20060226565A1 (en) * 2005-03-02 2006-10-12 Hale Wesley R Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US20060234073A1 (en) * 2005-03-02 2006-10-19 Hale Wesley R Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparation
US20060197246A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Process for the preparation of transparent shaped articles
US20060247388A1 (en) * 2005-03-02 2006-11-02 Hale Wesley R Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US8133417B2 (en) 2005-03-02 2012-03-13 Eastman Chemical Company Process for the preparation of transparent shaped articles
US7462684B2 (en) 2005-03-02 2008-12-09 Eastman Chemical Company Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US20110201703A1 (en) * 2005-03-02 2011-08-18 Eastman Chemical Company Process for the preparation of transparent shaped articles
US8304499B2 (en) 2005-03-02 2012-11-06 Eastman Chemical Company Transparent polymer blends and articles prepared therefrom
US20110200774A1 (en) * 2005-03-02 2011-08-18 Eastman Chemical Company Transparent polymer blends and articles prepared therefrom
US7968164B2 (en) 2005-03-02 2011-06-28 Eastman Chemical Company Transparent polymer blends and articles prepared therefrom
US7964258B2 (en) 2005-03-02 2011-06-21 Eastman Chemical Company Transparent, oxygen-scavenging compositions and articles prepared therefrom
US7959998B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7959836B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US7786252B2 (en) 2005-03-02 2010-08-31 Eastman Chemical Company Preparation of transparent multilayered articles
US20060235167A1 (en) * 2005-03-02 2006-10-19 Hale Wesley R Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US7955533B2 (en) 2005-03-02 2011-06-07 Eastman Chemical Company Process for the preparation of transparent shaped articles
US7955674B2 (en) 2005-03-02 2011-06-07 Eastman Chemical Company Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7803441B2 (en) 2005-06-17 2010-09-28 Eastman Chemical Company Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7807775B2 (en) 2005-06-17 2010-10-05 Eastman Chemical Company Point of purchase displays comprising polyester compositions formed from 2,2,4,4-tetramethyl-1, 3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US7812111B2 (en) 2005-06-17 2010-10-12 Eastman Chemical Company LCD films comprising polyester compositions formed from 2,2,4,4-tetramethy1-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7812112B2 (en) 2005-06-17 2010-10-12 Eastman Chemical Company Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7834129B2 (en) 2005-06-17 2010-11-16 Eastman Chemical Company Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7838620B2 (en) 2005-06-17 2010-11-23 Eastman Chemical Company Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
US7842776B2 (en) 2005-06-17 2010-11-30 Eastman Chemical Company Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7807774B2 (en) 2005-06-17 2010-10-05 Eastman Chemical Company Vending machines comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US7868128B2 (en) 2005-06-17 2011-01-11 Eastman Chemical Company Skylights and windows comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7893188B2 (en) 2005-06-17 2011-02-22 Eastman Chemical Company Baby bottles comprising polyester compositions which comprise cyclobutanediol
US7893187B2 (en) 2005-06-17 2011-02-22 Eastman Chemical Company Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7902320B2 (en) 2005-06-17 2011-03-08 Eastman Chemical Company Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7906211B2 (en) 2005-06-17 2011-03-15 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7906212B2 (en) 2005-06-17 2011-03-15 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7906610B2 (en) 2005-06-17 2011-03-15 Eastman Chemical Company Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7915376B2 (en) 2005-06-17 2011-03-29 Eastman Chemical Company Containers comprising polyester compositions which comprise cyclobutanediol
US7951900B2 (en) 2005-06-17 2011-05-31 Eastman Chemical Company Dialysis filter housings comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7803439B2 (en) 2005-06-17 2010-09-28 Eastman Chemical Company Blood therapy containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7803440B2 (en) 2005-06-17 2010-09-28 Eastman Chemical Company Bottles comprising polyester compositions which comprise cyclobutanediol
US7781562B2 (en) 2005-06-17 2010-08-24 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7740941B2 (en) 2005-06-17 2010-06-22 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US9181388B2 (en) 2005-06-17 2015-11-10 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US9181387B2 (en) 2005-06-17 2015-11-10 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US7985827B2 (en) 2005-06-17 2011-07-26 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US7576171B2 (en) 2005-06-17 2009-08-18 Eastman Chemical Company Pacifiers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7510768B2 (en) 2005-06-17 2009-03-31 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US8063172B2 (en) 2005-06-17 2011-11-22 Eastman Chemical Company Film(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol
US8063173B2 (en) 2005-06-17 2011-11-22 Eastman Chemical Company Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom
US8067525B2 (en) 2005-06-17 2011-11-29 Eastman Chemical Company Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature
US8101705B2 (en) 2005-06-17 2012-01-24 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US8119762B2 (en) 2005-06-17 2012-02-21 Eastman Chemical Company Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US8119761B2 (en) 2005-06-17 2012-02-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8133967B2 (en) 2005-06-17 2012-03-13 Eastman Chemical Company Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US9534079B2 (en) 2005-06-17 2017-01-03 Eastman Chemical Company Containers comprising polyester compositions which comprise cyclobutanediol
US9175134B2 (en) 2005-06-17 2015-11-03 Eastman Chemical Company Containers comprising polyester compositions which comprise cyclobutanediol
US9169348B2 (en) 2005-06-17 2015-10-27 Eastman Chemical Company Baby bottles comprising polyester compositions which comprise cyclobutanediol
US9765181B2 (en) 2005-06-17 2017-09-19 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8507638B2 (en) 2005-06-17 2013-08-13 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US8415450B2 (en) 2005-06-17 2013-04-09 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8354491B2 (en) 2005-06-17 2013-01-15 Eastman Chemical Company Containers comprising polyester compositions which comprise cyclobutanediol
US7855267B2 (en) 2005-06-17 2010-12-21 Eastman Chemical Company Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US8299204B2 (en) 2005-10-28 2012-10-30 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US20070276065A1 (en) * 2005-10-28 2007-11-29 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US8193302B2 (en) 2005-10-28 2012-06-05 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
US8586701B2 (en) 2005-10-28 2013-11-19 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7737246B2 (en) 2005-12-15 2010-06-15 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US9765203B2 (en) 2006-03-28 2017-09-19 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US7704605B2 (en) 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US9169388B2 (en) 2006-03-28 2015-10-27 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US8501287B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8501292B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8287970B2 (en) 2007-11-21 2012-10-16 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8198371B2 (en) 2008-06-27 2012-06-12 Eastman Chemical Company Blends of polyesters and ABS copolymers
US8895654B2 (en) 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
JP2012517499A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Coating compositions containing tetramethyl cyclobutanediol
JP2016047915A (en) * 2009-02-06 2016-04-07 イーストマン ケミカル カンパニー Coating compositions containing tetramethyl cyclobutanediol
JP2012517498A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Coating composition comprising a blend of acrylic and aliphatic polyester
JP2012517500A (en) * 2009-02-06 2012-08-02 イーストマン ケミカル カンパニー Thermosetting polyester coating composition comprising tetramethyl cyclobutanediol
US8394997B2 (en) 2010-12-09 2013-03-12 Eastman Chemical Company Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420869B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420868B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols

Similar Documents

Publication Publication Date Title
US3250715A (en) Terpolymer product and lubricating composition containing it
US3247111A (en) High temperature jet lubricant
US3281359A (en) Neopentyl polyol derivatives and lubricating compositions
US3062852A (en) Esters of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols
US6160144A (en) Synthetic esters of alcohols and fatty acid mixtures of vegetable oils high in oleic acid and low in stearic acid
US3361672A (en) Stabilized organic compositions
US4292187A (en) Lubricating oils for the working of metals
US5047159A (en) Lubricant compositions having improved anti-deposition properties comprising a polyalkylene oxide-modified silicone oil
US2757139A (en) Synthetic lubricating composition
US4234497A (en) Iso-palmitate polyol ester lubricants
US3974081A (en) Biodegradable seal swell additive with low toxicity properties for automatic transmission fluids, power transmission fluids and rotary engine oil applications
US2407954A (en) Lubricating composition
US6475405B1 (en) Lubricating oil for refrigerator with compressor
US3790478A (en) Synthetic lubricant for aero gas turbines
US5458795A (en) Oils thickened with estolides of hydroxy-containing triglycerides
US4376711A (en) Lubricant composition
US6458288B1 (en) Lubricating oil for refrigerator with compressor
US5403503A (en) Refrigerator oil composition for hydrogen-containing hydrofluorocarbon refrigerant
US5798319A (en) High stability and low metals esters based on 3,5,5-trimethyl-1-hexanol
US6316649B1 (en) Biodegradable oleic estolide ester having saturated fatty acid end group useful as lubricant base stock
US4178261A (en) Carboxylic acid esters and their use as a base lubricating oil
US3090753A (en) Ester oil compositions containing acid anhydride
US4885104A (en) Metalworking lubricants derived from natural fats and oils
US3773668A (en) Lubricating compositions
US2909559A (en) Polymeric phosphate esters and their production