Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent

Definitions

• the present invention relates generally to certain polyesters polyols suitable for blending with other polyols or other materials mutually compatible with the polyester polyols to achieve polyurethane and polyisocyanurate products.
• Aromatic polyester polyols are widely used in the manufacture of polyurethane and polyurethane-polyisocyanurate foams and resins.
• Aromatic polyester polyols are attractive because they tend to be low in cost, yet can be used to produce a wide variety of cellular foams having excellent properties and adaptable for many end use applications.
• One class of aromatic polyester polyols used commercially is polyol products produced by esterification of phthalic acid or phthalic acid anhydride with an aliphatic polyhydric alcohol, for example, diethylene glycol.
• This type of polyester polyol is capable of reacting with organic isocyanates to produce, for example, coatings, adhesives, sealants, and elastomers (“CASE materials”), that can have excellent characteristics, such as tensile strength, adhesion, and abrasion resistance.
• Such aromatic polyester polyols may also be used in formations for production of rigid polyurethane or polyisocyanurate foam.
• aromatic polyester polyols with a desirable high aromatic ring content, are generally characteristically high in dynamic viscosity, making handling very difficult.
• aromatic polyester polyols must be diluted or dissolved in relatively large amounts of a suitable solvent to enable producing low viscosity, easy-to-apply coating compositions upon being mixed with a curing or crosslinking agent.
• an aromatic polyester polyol has a dynamic viscosity that is sufficiently low to allow ease of pumping and mixing without the use of solvents or other viscosity modifying additives.
• An aromatic polyester polyol having too great a dynamic viscosity can cause difficulties in transfer of the material, as for example from storage to reactor or from the final product to the final application of the product. Excessive dynamic viscosity also can be a serious obstacle to efficient mixing with other CASE material ingredients, such as an isocyanate.
• 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 terephthalic acid and at least one polyethylene diol.
• the invention also relates to methods for making such aromatic polyester polyols and methods for using such aromatic polyester polyols to produce CASE materials.
• the invention further relates to cellular polyurethane and polyurethane/polyisocyanurate foams made using such aromatic polyester polyols.
• the polyester polyols of the present invention may be utilized with a wide variety of blowing agents, including water, hydrocarbon, chlorofluorocarbon, 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 formulation of resin pre-polymer blends.
• the aromatic polyester polyols of the invention are prepared by an inter-esterification process that is simple, reliable, and well adapted for conventional chemical processing equipment.
• the present invention provides a polyester polyol comprising the reaction product of:
• A, B, and C are present in the reaction on a percent weight bases of 20 to 60 weight percent A); 40 to 75 weight percent of B); and 0 to 40 weight percent of C).
• polyol blend suitable for use in preparing polymeric foams or elastomers comprising urethane units.
• the polyols blends are particularly useful in polyol formulations for rigid spray foam applications. These blends comprise from 10 to 90 weight percent of an aromatic polyester polyol as described above and the remainder is at least one second polyol wherein the second polyols is a monol, a polyether polyol or a combination thereof having a functionality of 2 to 8 and a molecular weight of 100 to 10,000.
• a sprayable blend for making a rigid foam comprising urethane units.
• the rigid foam made from a sprayable polyol blend is the reaction product of a polyisocyanate and a polyol blend where the polyol blend comprises 30 to 60 weight percent of an aromatic polyester polyol of the present invention and at least one second polyol having a functionality of 2 to 6 and a hydroxyl number of 200 to 1,200.
• the isocyanate index in preparing such rigid foams is from 90 to 400.
• the present invention further provides for use of the aromatic polyester polyols of the present invention as a viscosity cutter for polyol formulations, particularly for sprayable polyol formulations for producing rigid foam.
• the present invention provides a reaction system for production a rigid foam comprising a polyol composition comprising:
• A, B, and C are present in the reaction on a percent weight bases of 20 to 60 weight percent A); 40 to 75 weight percent of B); and 0 to 40 weight percent of C);
• additives or auxiliaries are selected from the groups consisting of dyes, pigments, internal mold release agents, physical blowing agents, chemical blowing agents, fire retardants, fillers, reinforcements, plasticizers, smoke suppressants, fragrances, antistatic agents, biocides, antioxidants, light stabilizers, adhesion promotors and combination of these.
• the aromatic polyester polyols of the present invention are prepared from a reaction mixture comprising A) terephthalic acid and B) a at least one polyethylene glycol.
• the reaction mixture may contain a further glycol, component C), which is a glycol other than the polyethylene glycol.
• Such polyols generally have nominal functionally of 2.
• the present invention has found a combination of polyethylene glycol with terephthalic acid gives an aromatic polyester having a low viscosity while maintaining an acceptable level of aromatic content in the polyester to maintain acceptable properties of the final produced material.
• terephthalic acid generally gives enhanced flame retardant properties to the final polyurethane product versus other phthalic acid isomers
• the use of terephthalic acid generally increases the viscosity of the polyester.
• the low viscosity polyester polyols allows the use of terephthalic based materials in various end-use application.
• the aromatic component (component A) of the present polyester polyols is derived from terephthalic acid.
• the terephthalic acid component will generally comprise 80 mole percent or more of the aromatic content. In further embodiments, terephthalic acid will comprise 85 mole percent or more of the aromatic component. In another embodiment, terephthalic acid will comprise 90 mole percent or more of the aromatic component for making the aromatic polyester polyol. In another embodiment the aromatic content comprises greater than 95 mole percent is derived from terephthalic acid. In another embodiment the aromatic content is essentially derived from terephthalic acid.
• polyester polyols can be prepared from substantially pure terephthalic acid, more complex ingredients can be used, such as the side-stream, waste or scrap residues from the manufacture of terephthalic acid. Recycled materials which can be broken down into terephthalic acid and diethylene glycol, such as the digestion products of polyethylene terephthalate may be used.
• Component A) will generally comprise from 20 to 60 wt % of the reaction mixture. In a further embodiment, component A) comprise 25 wt % or greater of the reaction mixture. In a further embodiment, component A) comprised 55 wt % or less of the reaction mixture.
• the polyethylene glycol, component B is a polymer of ethylene glycol and generally has a molecular weight of from 150 to 1,000. In one embodiment, the molecular weight is 160 or greater. In a further embodiment the molecular weight is less than 800, less than 600 or even less than 500. In a further embodiment the molecular weight is less than 400.
• the polyethylene glycol generally comprises from 30 to 80 weight percent of the reaction mixture. In further embodiment the polyethylene glycol will comprise 35 weight percent or more of the reaction mixture. In another embodiment the polyethylene glycol will comprise 40 weight percent or more of the reaction mixture. In another embodiment, the polyethylene glycol will comprise 75 weight percent or less of the reaction mixture. In a further embodiment the polyethylene glycol will comprise 70 weight percent or less of the reaction mixture.
• Polyethylene glycols are commercially available or may be produced by the addition of ethylene oxide to a 2 functional initiator by processes well known in the art.
• component B is described in terms of a polyethylene glycol, polyglycols based on glycols containing greater than 2 carbon atoms may be used provided such polyglycols are within the molecular weight as given for component B). Furthermore, it may be possible to use glycols which contain secondary hydroxyl groups. When using such glycols with secondary hydroxyl groups, it is generally preferred to cap such polyols to give a primary hydroxyl, i.e. capping with ethylene oxide, such that the polyglycol contains greater than 75% primary hydroxyls.
• the reaction mixture may include a glycol (component C) which is different from B).
• a glycol component C
• component C may have a glycol with a functionality of greater than 3, to avoid an increase in the viscosity of the material, it is generally preferred the functionally of such a blend of glycols comprising component C) will be 3 or less.
• the glycol of component C) may be ethylene glycol, diethylene glycol, or an oxyalkylene glycol of the formula:
• R is hydrogen or a lower alkyl of 1 to 4 carbon atoms and n is from 1 to 5 with the proviso that at least 10 percent of the R moieties are a lower alkyl group.
• n is 4 or less.
• n is 3 or less.
• all the R moieties will be a lower alkyl.
• R is a methyl group.
• alkylene glycols include propylene glycol and di-propylene glycol.
• the glycol component C) will have an overall average molecular weight of 180 or less.
• three functional glycols include glycerin and trimethylolpropane.
• component C) When present, component C) will generally comprise greater than 1 weight percent of the reaction mixtures. In a further embodiment component C) will comprise 5 weight percent or greater of component C) and my at least 10 weight percent of component C). Generally when present, component C) will be less than 40 weight percent of the reactions mixture. In further embodiments, less than 35 weight percent. In another embodiment, component C) will be less than 30 weight percent of the reaction mixture.
• component C) When component C) is present, commercial products which contain a crude blend of materials may be used to provide components B) and C). For examples, production process may provide for crude glycols which contain from 15-20 weight percent diethylene glycol and the remainder triethylene and higher glycols.
• the polyester will have a nominal functionality of two.
• component C) is present and comprises a glycol having 3 or more hydroxyl groups
• the aromatic polyester may have a nominal functionality of greater than 2. In such circumstances, the functionality will generally be less than 2.3.
• the amount of materials used in making the polyester will generally provide for a polyester having a hydroxyl number of from 200 to 400. In further embodiments the hydroxyl number of the polyester is less than 350 and in a further embodiment less than 300.
• the viscosity of the resulting polyester is generally less than 5,000 mPa*s at 25° C. as measured by UNI EN ISO 3219. In a further embodiment the viscosity of the polyester polyol is less than 4,000 mPa*s. In other embodiments the viscosity of the polyester polyol is 3,000 mPa*s or less. In yet another embodiment the viscosity may be 2,500 mPa*s or less. In further embodiments the viscosity is 2000 mPa*s or less. While it is desirable to have a polyol with as low a viscosity as possible, due to practical chemical limitations and end-use applications, the viscosity of the polyol will generally be greater than 350 mPa*s.
• An aromatic polyester polyol of the invention may include any minor amounts of unreacted glycol remaining after the preparation of the polyester polyol.
• the aromatic polyester polyol can include up to about 40 weight percent free diol.
• the free glycol content of the aromatic polyester polyols of the invention generally is from about 0 to about 30 weight percent, and usually from 1 to about 25 weight percent, based on the total weight of polyester polyol component.
• the polyester polyol may also include small amounts of residual, non-inter-esterified aromatic component. Typically the non-inter-esterified materials will be present in an amount less than 25 percent by weight based on the total weight of the components combined to form the aromatic polyester polyols of the invention.
• the polyester polyols are formed by the polycondensation/transesterification and polymerization of component A and B, and if present component C under conditions well known in the art. See for Example G. Oertel, Polyurethane Handbook , Carl Hanser Verlag, Kunststoff, Germany 1985, pp 54-62 and Mihail Ionescu, Chemistry and Technology of Polyols for Polyurethanes , Rapra Technology, 2005, pp 263-294.
• the reaction is done at temperature of 180 to 280° C.
• the reaction is done at a temperature of at least 200° C.
• the reaction is done at a temperature of 215° C. or greater.
• the transesterification is done at a temperature of 260° C. or less.
• reaction may take place under reduced or increased pressure, the reaction is generally carried out near atmospheric pressure conditions.
• reaction may take place in the absence of a catalyst, catalysts which promote the esterification/transesterification/polymerization reaction may be used.
• Such catalysts include tetrabutyltitanate, dibutyl tin oxide, potassium methoxide, or oxides of zinc, lead or antimony; titanium compounds such as titanium (IV) isopropoxide and titanium acetylacetonate. When used, such catalyst is used in an amount of 0.05 to 1 weight percent of the total mixture. In further embodiments the catalyst is present in an amount of from 0.1 to 0.75 weight percent of the total mixture.
• the volatile product(s) of the reaction for example water and/or methanol, is generally taken off overhead in the process and forces the ester interchange reaction to completion.
• the reaction usually takes from one to five hours.
• the actual length of time required varies, of course; with catalyst concentration, temperature etc.
• the polyesters of the present invention can be used as part of a polyol formulation for making various polyurethane or polyisocyanurate products.
• the polyol also referred to as the isocyanate-reactive component, along with an isocyanate component make us a system for producing a polyurethane or polyisocyanurate.
• the polyesters may be used as part of a formulation for making a polyurethane and are particularly applicable in formulations for producing rigid foam, spray foam application, appliance insulation, elastomer formation, and various coatings, adhesives and sealant formulation.
• the polyesters of the present invention may be used alone or can be blended with other known polyols to produce polyol blends. Depending on the application, the polyester will generally range from 10 to 90 wt % of the total polyol formulation.
• the amount polyester polyols which can be used for particular applications can be readily determined by those skilled in the art.
• the polyester can generally comprise from up to 80 weight percent of the polyol formulation. In other such embodiments, the polyester will comprise less than 70 weight percent of the polyol formulation.
• the polyester In spray formulations for rigid foam applications, the polyester will generally be 60 weight percent or less of the polyol blend.
• the amount of polyester used in such formulations may be from 10 to about 30 weight percent of the total formulation.
• polyols include polyether polyols, polyester polyols different from the polyester of the present invention, polyhydroxy-terminated acetal resins, and hydroxyl-terminated amines.
• Alternative polyols that may be used include polyalkylene carbonate-based polyols and polyphosphate-based polyols.
• Preferred are polyether or polyester polyols.
• Polyether polyols prepared by adding an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide or a combination thereof, to an initiator having from 2 to 8 active hydrogen atoms. The functionality of polyol(s) used in a formulation will depend on the end use application as known to those skilled in the art.
• typically polyols suitable for preparing rigid polyurethanes include those having an average molecular weight of 100 to 10,000 and preferably 200 to 7,000. Such polyols advantageously have a functionality of at least 2, preferably 3, and up to 8, preferably up to 6, active hydrogen atoms per molecule.
• the polyols used for rigid foams generally have a hydroxyl number of about 200 to about 1,200 and more preferably from about 300 to about 800.
• Monols may also be used as part of the polyol formulation.
• the functionality of the polyol or polyol blend is generally from 1.8 to 2.2.
• the average functionality of the polyol blend does not include any chain extenders or cross-linkers which may be included in a formulation.
• the average equivalent weight of the polyol or polyol blend for producing elastomer is generally from 500 to 3,000, preferably from 750 to 2,500 and more preferably from 1,000 to 2,200.
• Polyether polyols are made by processes will known in the art. Catalysis for this polymerization of the alkylene oxide can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
• catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
• DMC double cyanide complex
• Polyols that are derived from renewable resources such as vegetable oils or animal fats can also be used as additional polyols.
• examples of such polyols include castor oil, hydroxymethylated polyesters as described in WO 04/096882 and WO 04/096883, hydroxymethylated polyols as described in U.S. Pat. Nos. 4,423,162; 4,496,487 and 4,543,369 and “blown” vegetable oils as described in US Published Patent Applications 2002/0121328, 2002/0119321 and 2002/0090488.
• Suitable polyisocyanates for producing polyurethane products include aromatic, cycloaliphatic and aliphatic isocyanates. Such isocyanates are well known in the art.
• suitable aromatic isocyanates include the 4,4′-, 2,4′ and 2,2′-isomers of diphenylmethane diisocyante (MDI), blends thereof and polymeric and monomeric MDI blends, toluene-2,4- and 2,6-diisocyante (TDI) m- and p-phenylenediisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanate-3,3′-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4′-diisocyanate and diphenyletherdiisocyanate and 2,4,6-triisocyanatotoluene and 2,4,4′-triisocyanatodiphenylether.
• MDI diphenylmethane diisocyante
• TDI 2,6-diisocyante
• a crude polyisocyanate may also be used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine.
• TDI/MDI blends are used.
• aliphatic polyisocyanates examples include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3- and/or 1,4-bis(isocyanatomethyl)cyclohexane (including cis- or trans-isomers of either), isophorone diisocyanate (IPDI), tetramethylene-1,4-diisocyanate, methylene bis(cyclohexaneisocyanate) (H 12 MDI), cyclohexane 1,4-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, saturated analogues of the above mentioned aromatic isocyanates and mixtures thereof.
• IPDI isophorone diisocyanate
• H 12 MDI methylene bis(cyclohexaneisocyanate)
• cyclohexane 1,4-diisocyanate 4,4′-dicyclohexylmethane diisocyanate,
• Derivatives of any of the foregoing polyisocyanate groups that contain biuret, urea, carbodiimide, allophonate and/or isocyanurate groups can also be used. These derivatives often have increased isocyanate functionalities and are desirably used when a more highly crosslinked product is desired.
• the polyisocyanate is generally a diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, polymers or derivatives thereof or a mixture thereof.
• the isocyanate-terminated prepolymers are prepared with 4,4′-MDI, or other MDI blends containing a substantial portion or the 4,4′-isomer or MDI modified as described above.
• the MDI contains 45 to 95 percent by weight of the 4,4′-isomer.
• the isocyanate component may be in the form of isocyanate terminated prepolymers formed by the reaction of an excess of an isocyanate with a polyol or polyester, including polyester of the present invention.
• the polyesters of the present invention may be used for the production of hydroxyl terminated prepolymers formed by the reaction of an excess of the polyester with an isocyanate.
• the polyisocyanate is used in an amount sufficient to provide an isocyanate index of from 80 to 600.
• Isocyanate index is calculated as the number of reactive isocyanate groups provided by the polyisocyanate component divided by the number of isocyanate-reactive groups in the polyurethane-forming composition (including those contained by isocyanate-reactive blowing agents such as water) and multiplying by 100. Water is considered to have two isocyanate-reactive groups per molecule for purposes of calculating isocyanate index.
• a preferred isocyanate index is from 90 to 400.
• the isocyanate index is generally from is from 100 to 150.
• the isocyanate index will generally be greater than 150.
• chain extenders in the formulation for production of polyurethane products.
• the presence of a chain extending agent provides for desirable physical properties, of the resulting polymer.
• the chain extenders may be blended with the polyol component or may be present as a separate stream during the formation of the polyurethane polymer.
• a chain extender is a material having two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400, preferably less than 300 and especially from 31-125 daltons.
• Crosslinkers may also be included in formulations for the production of polyurethane polymers of the present invention.
• Crosslinkers are materials having three or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400. Crosslinkers preferably contain from 3-8, especially from 3-4 hydroxyl, primary amine or secondary amine groups per molecule and have an equivalent weight of from 30 to about 200, especially from 50-125.
• amounts of crosslinkers generally used are from about 0.1 to about 1 part by weight, especially from about 0.25 to about 0.5 parts by weight, per 100 parts by weight of polyols.
• a catalyst may be included within the polyol component.
• Suitable catalysts include the tertiary amine and organometallic compounds such as described in U.S. Pat. No. 4,495,081.
• an amine catalyst advantageously it is present in from 0.1 to 3, preferably from 0.1 to 1 and more preferably from 0.4 to 0.8 weight percent by total weight of polyol and optional chain extending agent.
• the catalyst is an organometallic catalyst, advantageously it is present in from 0.001 to 0.2, preferably from 0.002 to 0.1 and more preferably from 0.01 to 0.05 weight percent by total weight of polyol and optional chain extending agent.
• Particularly useful catalysts include in the case of amine catalysts; triethylenediamine, bis(N,N-dimethylaminoethyl)ether and di(N,N-dimethylaminoethyl)amine and in the case of the organometallic catalysts; stannous octoate, dibutyltin dilaurate, and dibutyltin diacetate. Combinations of amine and organometallic catalysts advantageously may be employed.
• the polyesters of the present invention are particularly suitable for use in applications where it is desired to have flame retardant properties provided by the aromatic content.
• the low viscosity of the polyols renders them suitable for use in rigid spray insulation foam.
• the low viscosity is also suitable for producing isocyanate terminated prepolymers where a low viscosity is desired.
• the polyols may also be used as a viscosity reducing additive in conventional polyol formulations.
• Blowing agents used in polyurethane-forming composition include physical blowing agents such as a hydrocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, dialkyl ether or fluorine-substituted dialkyl ethers, or a mixture of two or more thereof. It is generally preferred to further include water in the formulation, in addition to the physical blowing agent. In many polyol formulations, a physical blowing can act as a viscosity cutter. An advantage of the low viscosity polyester of the present invention is it may allow for greater variation in polyol formulations as there is a reduced need to rely on the physical blowing to modify system viscosity.
• Blowing agent(s) are generally used is used in an amount ranging from about 10 to about 40, preferably from about 12 to about 35, parts by weight per 100 parts by weight polyol(s).
• Water reacts with isocyanate groups to produce carbon dioxide, which acts as an expanding gas.
• Water is suitably used in an amount within the range of 0.5 to 7.5, preferably from 1.5 to 5.0 parts by weight per 100 parts by weight of polyol(s). In further embodiments the amount of water will be from 1.5 to 3.5 parts by weight per 100 parts by weight of polyol(s).
• the polyurethane-forming composition may include various auxiliary components, such as surfactants, fillers, colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, and the like known in the art.
• auxiliary components such as surfactants, fillers, colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, and the like known in the art.
• Suitable flame retardants include phosphorus compounds, halogen-containing compounds and melamine.
• fillers and pigments include calcium carbonate, titanium dioxide, iron oxide, chromium oxide, azo/diazo dyes, phthalocyanines, dioxazines, recycled rigid polyurethane foam and carbon black.
• UV stabilizers examples include hydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiarybutyl catechol, hydroxybenzophenones, hindered amines and phosphites. Except for fillers, the foregoing additives are generally used in small amounts, such as from 0.01 percent to 3 percent each by weight of the polyurethane formulation. Fillers may be used in quantities as high as 50% by weight of the polyurethane formulation.
• the polyurethane-forming composition is prepared by bringing the various components together under conditions such that the polyol(s) and isocyanate(s) react, the blowing agent generates a gas, and the composition expands and cures. All components (or any sub-combination thereof) except the polyisocyanate can be pre-blended into a formulated polyol composition, if desired, which is then mixed with the polyisocyanate when the foam is to be prepared.
• such a polymer is typically prepared by intimately mixing the reaction components at room temperature or a slightly elevated temperature for a short period and then pouring the resulting mixture into an open mold, or injecting the resulting mixture into closed mold, which in either case is heated.
• the mixture on reacting out takes the shape of the mold to produce a polyurethane polymer of a predefined structure, which can then when sufficiently cured be removed from the mold with a minimum risk of incurring deformation greater than that permitted for its intended end application.
• Polyester 1 Diethylene glycol (289.5 g), polyethylene glycol 200 (1800 g) and terephthalic acid (910.5 g) are charged to a 5000 ml glass flask equipped with a nitrogen inlet tube, pneumatic stirrer, thermometer and condenser. Heat is applied and the flask contents raised to 230-235° C. At a temperature of 220° C. a titanium acetylacetonate catalyst (Tyzor AA-105 from Du Pont) is charged (0.15 g) and a little flow of nitrogen is applied. The mixture is held at 230-235° C. for 5 hours. The polyester polyol at this point has an acid No. below 0.5 mgKOH/g. The content of the flask is cooled to room temperature under atmospheric conditions.
• Tyzor AA-105 titanium acetylacetonate catalyst
• Polyester Into the apparatus described for Polyester 1 is added diethylene glycol (1820 g), and terephthalic acid (1680 g). The process for production the control polyester is as given for the production of Polyester 1.
• Polyester 1 prepared as described above is used in formulations to prepare rigid polyisocyanurate insulation for discontinuous panels, using a high pressure machine (Cannon A40).
• a control formulation uses Terate 4026 polyester polyol (from Invista), an aromatic polyester polyol having a hydroxyl number of about 205 and a viscosity of approximately 2500 mPa*s @ 25° C.
• the formulated polyols are given in Table 1.
• M-600 is a polymethylene polyphenylisocyante, available from The Dow Chemical Company, having an isocyanate content of about 30.3% and an average functionality of 2.85.
• the data indicates the foam produced with the polyesters of the present invention are capable of meeting the B2 test.
• Polyester 1 is used in formulations for the production of elastomers as given in Table 5.
• elastomers it is generally preferred to have a high Tg of the final elastomer to avoid deformation/stress at high temperatures.
• the comparative utilizes the aromatic polyester Stepanpol PS 3152.
• polyester of the present invention although having a lower aromatic content than the polyester, due the low viscosity, can be used in higher levels in formulations giving a product with Tg properties similar to a control.

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