United States Patent US006664363B1 (2) (10) Patent No. US 6,664,363 BL Faunce (45) Date of Patent: Dec. 16, 2003 (4) wo woos ams AND M WO WOSKITTS 51996 (75) Inventor: James A. Faunce, North Aurora, IL OTHER PUBLICATIO! ws) International Search Report for Intemational Application No, PCT/US99/03823, international filing date of Feb. 23, (73) Assignee: Stepan Company, Northfield, IL (US) 1999, . , Polyethers, Part I: Polyalkylene Oxides and Other Poly- (-) Notice: Subject to any disclaimer, the term of this NG ie haeeione, 1063 pp, o3-97 patent is extended or adjusted under 35 col, et ab, “Hydrocarbon Blown Foams for US. Con- Kb) by 0 days siruction Applications", 35¢h Annual Polyurethane Teclni- (1) Appl. No: 09/806,066 callMarketing Conference, Oct. 9-12, 1994, pp. 412-417. vvan der Wouden, et aly "The Use of Polyester Polyols in ) PCT Filed: Feb. 23, 1999 CFC-free Rigid Forms’, Uiech "94, Papet 21, pp. 1-3 OnTe ener iasencas van dee Wouden, 1 Oleochemical Based Polyester Polyols in Polyurethanes”, Utech Asia °95, Paper $371 XD), 34 pp. 1-7. @), @) Date 9, 2002 Nicola, etal, “Improved Hydrocarbon Blowa Foams for noe North America", Pofwrethane, 1995, pp. 150-162 7) PCT Pub, No: WO99/425\ i Se area Matsumoto, et al., “Development of Cyclopentane Blown PCT Pub, Date: Aug. 26, 1999 Foam System for Appliances Use", Polyurethane, 1995, pp. 202-295 Related U.S. Application Data Burkhart, et al. “Optimized Silicone Surfactants for HCFC (60) Provisional application No. 601075657, filed on Feb. 3, and Pentane Blown Polyisoeyanurate and. Polyurethane 1998, Rigid Foams", Polyurethane, 1995, pp. 296-302, «1» CORG 63/48 Hanne, et al. "Patented, Pentane—Process Technology Ke (2) 528275; 528283, 1 US. CycloPentane-Blown Refrigerator Production” 528/300; 528/300; 528/308; 528/308,6 Polyurethane, 1995, pp. 481-483 (58) Fletd of Search 528995, 295.3, Chillin, “Increasing the Solubilily of Pentane in Ridig 528/300, 302, 308, 308.6, 283 Foam Systems", Urech °96, Paper 56, pp. 1-6. Ballhaus, etal, “Hydrocarbons Provide Zero ODP and Zero (56) References Cited GWP Insulation for Household Refiigeraion”, Proceedings S , . of the Polyurethanes World Congress, 1993, pp. 3-38. U.S. PATENT DOCUMENTS Encyclopedia of Chemical Technology, vol. 7,pp. 257-263 1,922,459 A 1933. Schmidt published by Interscicace Publishers, Inc, 1951 Sowvitse A + 31972. Walker 528/29 Chemical Abstracts, vol. 84, No, 10, Mar 8, 1976, abstract S199 A * 1Q/1983. Sailr oa “28/3084 No, 61333, p. 103, col. 2. AS20744 A TH1985. Wood 4598711 A 6/1986. Wood * cited by examiner 4008452 A 8/1985. Magnus ta. Aiotsoo7 A+ 2/1987 Magnus ea: saqans Primary Examiner—Samuel A. Acquah ‘esas A 2/1987 Magnus eta. (14) Attorney, Agent, or Firm—MeAndews, Held. & 4nia717 A+ 1211987 Londigan et a Malloy, Lid 4sizsas A + 3/1989 Simone et . 459729 A * 1/1980 Trowell eal. 67 ABSTRACT Susza07 A 1/1993 Huzen | Susiois A 9/1908 Birch The present invention relates to low viscosity aromatic SAeds02 A A/S Palen polyester polyols having an average functionality of two and SamS01 A 11/1095. Fishack eta methods for preparing such polyols. In particular, the iaven- Sagesi7 A "1/1996 Paterson tion relates to low viscosity aromatic polyester polyols Sas8071 A 1/1996 Paterson prepared by reacting a phthalic acid based material with 5804125 A 4/1996 Fishback etal diethylene glycol, a higher functional polyol having. an 5523392 A 6/1996 Fishback la: average functionality of greater than two and a long chain 5,632,898 A Saree cae alkyl acid, ester or oil. The resulting aromatic polyester 5,922,779 A 7/1999 Hickey aus I has fi ‘ ie ih Pr k Caren clear polyol has an average functionality of two and has a lower ‘dynamic viscosity as compared to the esterification product FOREIGN PATENT DOCUMENTS of a phihalic acid based) material with diethylene glycol EP 0209962 + 6/1988 ae i Oar3m AZ 402 @ 0.593959 + 41994 ms, No DrawingsUS 6,664,363 BL 1 LOW VISCOSITY POLYESTER POLYOLS AND METHODS FOR PREPARING SAME ‘This application claims the benefit of provisional appli- cation No. 60/075,657 filed Feb. 23, 1998. BACKGROUND OF THE INVENTION 1. Field of the Invention ‘The present invention relates to low viscosity aromatic polyester polyols having an average functionality of about two and methods for preparing sich polyols. In particular the invent polyols having an average functional by intersterication ofa phthalic acid based material with diethylene glycol, higher funetional polyol having an average functionality of greater than two, and a long chain atkyl acid, ester or oil. The resulling aromatic polyester polyol has am average functionality of about two and has a lower dynamic viscosity as compared to the esterification product of « phthalic acid based material with diethylene slyeolslone 2. Description ofthe Related Art Polyols are useful reactants in preparing a variety of polymeric or resin compositions. Aromatic plyestr polyols. dre widely used in the manufacture of polyurethane and polyurethane-polyisocyanurate foams and resins. ‘Typically, polyols are employed in reactions involving curing or ‘roslinking with polysocyanate materials having at least two isocyanate groups per mole, reactions involving imelamines or formaldehyde resins, ant esterification reac- tions with unsaturated monobasic fatty acks t form allyl ‘Aromatic polyester polyols are atractive because they tend to be low in cost, yet can he used to produce a wide variety of celular foams having excellent properties and apttble for many end use applications, One class of aromatic polyester polyols that has enjoyed wide commer- al success comprises the polyol products produced by ‘sterfcation of phthalic ai or phthalic acid anhydride with an aliphatic polyhydric alcohol. For example, a diethylene glycol phthalate is available commercially from Stepan Company, Northfield, Il. Such a polyol is a somewhat viscous liquid proc, with « desirably high aromatic ring content, and a desirably low acid: number. This type of polyester polyol is capable of reacting with organic Isocy- nates. produce, for example, voatings, adhesives, scalants, and clastomers (“CASE materials”), that can have fxcellem characteristics such as tensile strength, adhesion, and abrasion resistance One problem generally encountered when using aromatic polyester polyols is that they are characteristially high in ‘ynamic viscosity, making handling very cifieu.. Often, aromatic polyester polyols must be diluted or dissolved in relatively large amounts of a suitable solvent t0 enable producing low viscosity, e8sy-io-apply coating compos tions upon being mixed with a curing oF crosslinking agent Ideally, an aromatic polyester polyol fas. a dynamic viscosity that is suficiently low to allow ease of pumping and mixing without the use of solvents or other viscosity modifying additives, An aromatic polyester polyol ving too great a dynamic viscosity can cause dllielties in transfer of the material, as for example from slorage to reactor or from the final product to the final application of the product. Excessive dynamic viscosity also can be a serious obstacle to elicient mixing with other CASE mate- Til ingredients, such as an isocyanate. Several solutions to 10 1s » as 4s 50 os 2 this viscosity problem have been offered. See, for example, US. Pat. No. 4,644,027 (to Stepan Company) and U.S. Pat No. 4,812,533 (to CasChem, Inc.), and Romanian Pat. App. 83,203, See also, for example, Liu, Det a, Tuliao Gengye, 1988, 5, 1-3: High Solid alkylated Resin Baked Paint (Shenyang Inst. Chem. Co.). However, these prior art solu- tions are often complicated, expensive, difficult to readily implement, and may produce a polyol having a functionality of less than 2 ‘Thus, there isa need for low viscosity aromatic polyester polyols having an average functionality of about two that are economical 10 produce and can be coaverted into cellular foams and other CASE materials having excellent proper- ties. SUMMARY OF THE INVENTION ‘The present invention relates to a new and surprisingly useful class of low viscosity aromatic polyester polyols having an average functionality of about two, comprising the inter-esterification reaction product of at least one phthalic acid based material, at least one aliphatic diol, at least one higher functional polyol compound, and at least ‘one hydrophobic material. The invention also relates to methods for making such aromatic polyester polyols and methods for using such aromatic polyester polyols to pro- duce CASE materials. The invention further relates to cel- lular polyurethane and polyusethane/polyisocyanurate foams made using such aromatic polyester polyols. The polyester polyols of the present invention may be utilized h a wide variety of blowing agents, including water, hydrocarbon, chloroflurocarbon, and non- chlorofluorocarbon blowing, agents. ‘The aromatic polyester polyols of the present invention ‘can be readily blended with prior art polyols, if desired, and also with various additives conventionally used in the for- mulation of resin pre-polymer blends. The aromatic poly= ester polyols of the invention are prepared by an inter- esterification process that is simple, reliable, and well adapted for conventional chemical processing equipment, In a first aspect, the invention provides low viscosity aromatic polyester polyols having an average functionality of about two. Thus, there is now provided an aromati polyester polyol comprising the inter-esterification product of (@) from about 20 to about 80 mole percent of at least one phthalic acid based material selected from the group Consisting of phthalic anhydride, phthalic acid, isoph- thalic acid, terephthalic acid, methyl esters of phthalic, isophthalic, or terephthalic acid, dimethyi terephthalate, polyethylene terephthalate, trimelltic anbydride, pyromelltie dianhydride, maleic anhydride, for mixtures thereof; b) from about 20 to about 80 mole percent of at least one Jow molecular weight aliphatie diol of the formula HO—R,—o1 wherein R, is a divalent radical selected from the group consisting of {) alkylene radicals each containing from 2 through 12 carbon atoms; ii) radicals of ‘the formula —{CH.—R.—CH.]— wherein R, is a radical selected from the group consisting ofUS 6,664,363 BL iit) radicals of the formula A1RO.-R wherein R, is an alkylene radical containing from 2-4 carbon atoms and a is an integer from 1 through 10; ‘or mixtures thereof; 6) from about 0.1 to about 20 mole percent of a higher functional polyol of the formula Ho—R,—o1t wherein Ry is a divalent radical selected from the group consisting of ’) radicals of the formula —{CH,—R,—CH,]}— wherein Ry is a radical selected from the group consisting of on cas enon | 1 I qo ion aon Gout ii) radicals selected from the group consisting of slyecrine, alkoxylated glycerine, suerose, alkoxy= Tated sucrose, methyl glucoside, alkoxylated methyl slucoside, glucose, alkoxylated glucose, fructose, alkoxylated frutose, sorbitol, alkoxylated sorbitol, lactose, and alkoxylated lactose; ‘or mixtures thereof; and 4) from about 0.1 to about 20 mole percent of atleast one hydrophobic material characterized by i) having an equivalent weight of about 130-1000; ‘containing from about § 10 60 carbon atoms; and ‘containing at least one and not more than four radicals per molecule, which are selected from the group consisting of carboxyl, hydroxyl, and mixtures thereof. ‘The inter-esterification reaction may be performed with or without suitable esterification catalyst. Typically, and preferably, the inter-esterification reaction is performed with suitable esterification catalyst known to those of ordinary skill in the art Although the above components may be ‘combined in any order to produce the low viscosity aromatic polyester polyols of the invention, in a somewhat preferred ‘embocliment, components (a), (b), and (¢) initially are com- bined and the inter-esterification is allowed 10 proceed 10 ‘substantial completion, forming an intermediate polyester polyol which is then inter-estrified with component (d) to form the low viscosity aromatic polyester polyol of the present invention, Generally, the inter-esterfication reactions of the present invention are carried out under vacuum conditions, at tem= peratures sulficient 10 effect the desired esterification reaction, and water is removed from the reaction contents as the esterification proceeds. Typically, the esterification reac~ tion is performed at a temperature of about 100° C. to about 300° C. More preferably, the esterification is performed at a temperature of about 180° C. to about 220° C. 10 1s » as 4s 50 os 4 In another aspect, the invention provides a process for producing low viscosity aromatic polyester polyols having & functionality of about two. Accordingly, there is now pro- vised a process for producing low viscosity aromatic poly- ester polyols comprising inter-esterifying ia any order (a) from about 20 to about 80 mole percent of at least one phthalic acid based material selected from the group Consisting of phthalic anhydride, phthalic acid, isoph- thalic acid, terephthalic acid, methyl esters of phthalic, isophihalic, or terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, trimellitic anhydride, pyromellitie dianhydride, maleic anhydride, for mixtures thereof; by) from about 20 to about 80 mole percent of at least one low molecular weight aliphatic diol of the formula HO-R,—om ‘wherein R, is a divalent radical selected from the group consisting of ') alkylene radicals each containing fom 2 through 12 carbon atoms; ii) radicals of the formula —[CH.—R.—CH.]— wherein R is a radical selected from the group consisting of cus ' calls cas cy ) radicals of the formula AAR.O,—R- whervia R, is an alkylene radical cont carbon atoms and n is an integer from for mixtures thereof; «) from about 0.1 to about 20 mole percent of « higher functional polyol of the formula ing from 2-4 through 10; Ho—R,—o81 ‘wherein R, is a dvalent radical selected from the group consisting of 1) radicals of the formula —{CH,—R,—CHy wherein Ry is a radical selecied from’ the group consisting of chy cats cron 8 I 1 I 1 ao te I I L I cHoH —CHLOH cH.08 on i) radicals selected ftom the group consisting of alyeerine, alkoxylated glyeerine, suerose, alkoxy Iaied sucrose, methyl shicoside,alkoxylated methyl hucoside, glucose, alkoxylated glucose, fructose, alkoxylated frutose, sorbitol, alkoxylated sorbitol, Tactose, and alkoxylated lactose; or mixtures thereof; and 4) from about 0.1 to about 20 mole percent of at least one hydrophobic material characterized by i) having an equivalent weight of about 130-1000; i) containing from about & to 60 carbon atoms; and ii) containing at least one and not more than four radicals por molecule, which are selected from the group consisting of carboxyl, hydroxyl, and mixtures, thew.