CA2767675A1 - Methods for synthesizing polyether diols and polyester diols - Google Patents
Methods for synthesizing polyether diols and polyester diols Download PDFInfo
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- CA2767675A1 CA2767675A1 CA2767675A CA2767675A CA2767675A1 CA 2767675 A1 CA2767675 A1 CA 2767675A1 CA 2767675 A CA2767675 A CA 2767675A CA 2767675 A CA2767675 A CA 2767675A CA 2767675 A1 CA2767675 A1 CA 2767675A1
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
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- Chemical Kinetics & Catalysis (AREA)
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- Polyesters Or Polycarbonates (AREA)
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Abstract
Processes for synthesizing polyether diols and polyester diols are provided. The processes include reacting diols and/or diacids in the presence of carbon black. The processes can be used to produce polymers of a variety of molecular weights.
Description
TITLE
METHODS FOR SYNTHESIZING POLYETHER DIOLS AND
POLYESTER DIOLS
CROSS- REF ERENQ E TO RELATED APPLICATIONS
This application claims the benefit of provisional U .S. Application Serial No. 61/227518, FIELD OF THE INVENTION
The invention relates to methods for synthesizing polyether dials and polyester dials. The methods provide reduced color as compared to such polymers made using conventional methods.
Polytrimethylene ether glycol (hereinafter also referred to as "P ") produced from the acid rata yzed polycondensation ofI 3-propanediol (hereinafter also referred to as ''PDO) can have quality problems, in particular the color of the polymer may not be acceptable to the industry. The raw material PDO and the polymerization process contihions and stability of the polymer are responsible for discoloration to some extent.
Various pre-polymerization treatment methods are disclosed in the prior art to remove color precursors present in the P. Attempts have also been made to reduce the color of clyt; methylene ether glycols past.
polymerization. For example: Sunkara et al. describes a process for reducing color in P03G by contacting P036 with an adsorbent and then separating the P036 from the adsorbent (U S. Patent 7,294,746).
Pre- or post-polymerization methods may undesireably add additional steps, time, and expense to production processes. Attempts have also been made to alter reaction conditions to control product color during polymerization. For exampe, U.S, Patent Application Publication No. 2005/272911 discloses methods of controlling color formation by _11_ carrying out the dehydration-condensation reaction in the presence of a catalyst composed of an acid and a base:
There exists a need for improvred and convenient methods to reduce color of P03G.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 illustrates the molecular wai ;lit development of 1,3-propanedioi polymerization with and without carbon black addition.
Figure 2 illustrates P030 product color development as a function of molecular weight with and without carbon black during polymerization.
SUMMARY OF THE INVENTION
One aspect of the present invention is a process comprising:
is contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactannts comprise at least one selected from the group consisting of: a diol of formula 0H( H2) OH where n is an integer of 2 or greater; or a polyol thereof; and a diacid of formula HOOC(CH2) C OH where z is an integer of 4 or greater, or a polymer thereof, Another aspect of the present invention is a process comprising contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactants comprise a dial of formula OH(CH_2),,OH
where n is an integer greater than or equal to 2 or a polyol thereof; and a diacid of formula H 0C(CH2)wCO0H where z is an integer greater than or equal to 4 or a polymer thereof; and wherein the reac'.on product is a polyester dial.
A further aspect of the present invention is a process comprising process comprising contacting reactants with a catalyst and carton black to form a reaction product:. wherein the reactants comprise a diol of formula 0H(CH2) OH where n is an integer greater than or equal to 3 or a polyol thereof; or a viol of formula H t C CH ),COOH where z is greater than or equal to or a polyol thereof; and wherein the reaction product is a polyaather dial.
METHODS FOR SYNTHESIZING POLYETHER DIOLS AND
POLYESTER DIOLS
CROSS- REF ERENQ E TO RELATED APPLICATIONS
This application claims the benefit of provisional U .S. Application Serial No. 61/227518, FIELD OF THE INVENTION
The invention relates to methods for synthesizing polyether dials and polyester dials. The methods provide reduced color as compared to such polymers made using conventional methods.
Polytrimethylene ether glycol (hereinafter also referred to as "P ") produced from the acid rata yzed polycondensation ofI 3-propanediol (hereinafter also referred to as ''PDO) can have quality problems, in particular the color of the polymer may not be acceptable to the industry. The raw material PDO and the polymerization process contihions and stability of the polymer are responsible for discoloration to some extent.
Various pre-polymerization treatment methods are disclosed in the prior art to remove color precursors present in the P. Attempts have also been made to reduce the color of clyt; methylene ether glycols past.
polymerization. For example: Sunkara et al. describes a process for reducing color in P03G by contacting P036 with an adsorbent and then separating the P036 from the adsorbent (U S. Patent 7,294,746).
Pre- or post-polymerization methods may undesireably add additional steps, time, and expense to production processes. Attempts have also been made to alter reaction conditions to control product color during polymerization. For exampe, U.S, Patent Application Publication No. 2005/272911 discloses methods of controlling color formation by _11_ carrying out the dehydration-condensation reaction in the presence of a catalyst composed of an acid and a base:
There exists a need for improvred and convenient methods to reduce color of P03G.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 illustrates the molecular wai ;lit development of 1,3-propanedioi polymerization with and without carbon black addition.
Figure 2 illustrates P030 product color development as a function of molecular weight with and without carbon black during polymerization.
SUMMARY OF THE INVENTION
One aspect of the present invention is a process comprising:
is contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactannts comprise at least one selected from the group consisting of: a diol of formula 0H( H2) OH where n is an integer of 2 or greater; or a polyol thereof; and a diacid of formula HOOC(CH2) C OH where z is an integer of 4 or greater, or a polymer thereof, Another aspect of the present invention is a process comprising contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactants comprise a dial of formula OH(CH_2),,OH
where n is an integer greater than or equal to 2 or a polyol thereof; and a diacid of formula H 0C(CH2)wCO0H where z is an integer greater than or equal to 4 or a polymer thereof; and wherein the reac'.on product is a polyester dial.
A further aspect of the present invention is a process comprising process comprising contacting reactants with a catalyst and carton black to form a reaction product:. wherein the reactants comprise a diol of formula 0H(CH2) OH where n is an integer greater than or equal to 3 or a polyol thereof; or a viol of formula H t C CH ),COOH where z is greater than or equal to or a polyol thereof; and wherein the reaction product is a polyaather dial.
DETAILED DES. RIPTION
Unless otherwise stated, all percentages, parts, ratios, etc_ are by height. Further, when an amount: concentration or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range l:Ã .i or preferred value., regardless of whether ranges are separately disclosed_ Processes disclosed herein employ carbon black. Carbon black is an adsorbent, and athough it is present during reactions in the processes described herein, it is not a "reactant" as the term is used herein. The term "adsorbent" refers to materials that commonly are used to remove relatively small amounts of undesired components, Whether such removal is by the process of adsorption or absorption, As used herein, :`carbon black' refers to carbon black, activated carbon, or charcoal. Activated carbon is available commercially in different forms such as powder, granular, and shaped products. The preferred form is powdered activated carbon, Various brands of carbon may be used, including, but not limited to, Merit America G60, NORIT RO 0.8, Calgon PWA, BL, and WPH, and Ceca ACTICARBONE ENO. Also suitable are Darco KB-G or Darco S-51 (Norit), or ADP Carbon' (CalgoÃa Carbon), Suitable forms of carbon black also include those having a particle size range of about 2.7 micron to about 130 micron. Other forms will be known to those skilled in the art, Other adsorbents suitable for the processes disclosed herein are commercially available from various sources and in many forms and include alumina, silica, diatomaceous earth, montmorillonite clays. Fuller's earth, kaolin minerals and derivatives thereof.
"Color" and " color bodies" refer to visible color that can be quantified by the use of a spectroeolori titer in the range of visible light, using wavelengths of approximately 400 to 800 nm, and by comparison with pure water. Color precursors in P00 are not visible in this range, but contribute color during and after polymerization.
Unless otherwise stated, all percentages, parts, ratios, etc_ are by height. Further, when an amount: concentration or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range l:Ã .i or preferred value., regardless of whether ranges are separately disclosed_ Processes disclosed herein employ carbon black. Carbon black is an adsorbent, and athough it is present during reactions in the processes described herein, it is not a "reactant" as the term is used herein. The term "adsorbent" refers to materials that commonly are used to remove relatively small amounts of undesired components, Whether such removal is by the process of adsorption or absorption, As used herein, :`carbon black' refers to carbon black, activated carbon, or charcoal. Activated carbon is available commercially in different forms such as powder, granular, and shaped products. The preferred form is powdered activated carbon, Various brands of carbon may be used, including, but not limited to, Merit America G60, NORIT RO 0.8, Calgon PWA, BL, and WPH, and Ceca ACTICARBONE ENO. Also suitable are Darco KB-G or Darco S-51 (Norit), or ADP Carbon' (CalgoÃa Carbon), Suitable forms of carbon black also include those having a particle size range of about 2.7 micron to about 130 micron. Other forms will be known to those skilled in the art, Other adsorbents suitable for the processes disclosed herein are commercially available from various sources and in many forms and include alumina, silica, diatomaceous earth, montmorillonite clays. Fuller's earth, kaolin minerals and derivatives thereof.
"Color" and " color bodies" refer to visible color that can be quantified by the use of a spectroeolori titer in the range of visible light, using wavelengths of approximately 400 to 800 nm, and by comparison with pure water. Color precursors in P00 are not visible in this range, but contribute color during and after polymerization.
Provided herein is a process of producing polymeric reaction product in the presence of carbon black. The processs comprnses polycondensing reactants comprising 1, -propanediiol, poly-1. -propanÃdiol or a mixture thereof in the presence of acid polycondensation catalyst and carbon black to form a reaction product. In some embodiments, the process further comprises separating the reaction product from the carbon black. In some embodiments, the reactants further comprise a co monomer dial.
In some embodiments, the reaction product has a molecular weight greater than about 500 or a molecular weight of about 500 to about 5000.
In some embodiments, the reaction product has an APHA color of less than about 250 or less than about 50.
In some embodiments, the reaction product comprises polytrimethylene ether glycol. In some embodiments, the polytrin thylene ether glycol is contacted with a monocarboxylic acid to form a dicarboxylic acid ester of polytrimethyiene ether glycol.
In accordance with the present invention, it has been found that carbon black reduces polymer color when present during polymerization (Figure 2, Examples). In preferred embodiments, the carbon black has a desirable effect on polymer color without substantially affecting polymer molecular weight development (Figure 1, Examples). At the same reaction temperature and acid concentration, for a given polymer molecular weight, polymer color decreases with an increase in amount of carbon black addition. Also, in situ removal of color species may allow a polymerization process to be operated at a higher temperature and higher catalyst concentrations facihtating produd:on of a certain molecular weight.
product in a shorter polymerization time pe6od, In one embodiment, a process comprises contacting reactants with a catalyst and carbon black to form a reaction product, wherein said reactants comprise at least one of;
(a) a dial of formula H(CH2) H where n is an integer greater than or equal to 2, or a polyol thereof; or (b)a diacid of formula HOOC(CH2) COOH where z is an integer greater than or equal to 4, or a polymer thereof.
In some embodiments, the reaction product has a molecular weight greater than about 500 or a molecular weight of about 500 to about 5000.
In some embodiments, the reaction product has an APHA color of less than about 250 or less than about 50.
In some embodiments, the reaction product comprises polytrimethylene ether glycol. In some embodiments, the polytrin thylene ether glycol is contacted with a monocarboxylic acid to form a dicarboxylic acid ester of polytrimethyiene ether glycol.
In accordance with the present invention, it has been found that carbon black reduces polymer color when present during polymerization (Figure 2, Examples). In preferred embodiments, the carbon black has a desirable effect on polymer color without substantially affecting polymer molecular weight development (Figure 1, Examples). At the same reaction temperature and acid concentration, for a given polymer molecular weight, polymer color decreases with an increase in amount of carbon black addition. Also, in situ removal of color species may allow a polymerization process to be operated at a higher temperature and higher catalyst concentrations facihtating produd:on of a certain molecular weight.
product in a shorter polymerization time pe6od, In one embodiment, a process comprises contacting reactants with a catalyst and carbon black to form a reaction product, wherein said reactants comprise at least one of;
(a) a dial of formula H(CH2) H where n is an integer greater than or equal to 2, or a polyol thereof; or (b)a diacid of formula HOOC(CH2) COOH where z is an integer greater than or equal to 4, or a polymer thereof.
Also provided is a process comprising contacting reactants with a catalyst and carbon black to form a polyester diol reaction product wherein the reactants comprise both (a) a dial of formula OH(CH2)ROH where n is an integer greater than or equal to 2 or a polyol thereof; and (b) ,a diacid of formula HOO (CH2) COON where z is an integer greater than or equal to 4 or a polymer thereof.
Further provided is a process comprising contacting reactant with a catalyst and carbon black to form a polyether dial reaction product wherein the reactants comprise a diol of formula OH(I2)SOH where n is an integer greater than or equal to 3 or polyols thereof; or a dial of formula HOOC( H2)COOH where z is an integer greater t; hare or equal to 6 or polyols thereof.
Also disclosed is a process comprising contacting reactants with a catalyst and carbon black to form a reaction product wherein the reactants comprise a dial of formula OH(CH ),OH where n is an integer greater t' an or equal to 2, or polyols thereof; and wherein said diol is 1,3-propane dial.
In another aspect, the reactants further comprise a comonomer Biol. In one embodiment, the reaction product comprises polytrimethyylene ether glycol.
In some embodiments, the carbon black is about 0.05 to about 5 weight percent based on the total weight of the reactants. In some embodiments, the process includes separating the reaction product from the carbon black by, for example, filtration.
In some embodiments, the catalyst for the processes comprises a titanium catalyst or an acid catalyst. In some embodiments, the reaction products of the processes have an APHA color of less than about 2g;
less than about 100, less than about 50, less than about 40, or less than about 30 Also provided is a process comprising polycondensing reactants comprising 1,3-propanediol, poly 1,3-propanediol or a mixture thereof, in the presence of acid and carbon black. In one embodiment, the reaction product comprises polytrimethylene ether glycol. In some embodiments, the I,3-pr'opanediol, the poly-1,3-propanediol or mixtures thereof comprise bio-derived I3-propanediol._ In some aspects the acid comprises sulfuric acid. In further embodiments the reactants comprise comonomer diol and the comonomer diol can, in some embodiments, be ethylene glycol.
In some embodiments, the process further comprises contacting the polytrimethyl ne ether glycol with a monocars)oxylic acid to form a dicarboxylic acid ester of polytrimethylene ether glycol. In some aspects, the monoc rboxylic acid is 2-ethylhexanoic acid.
In some embodiments, the molecular weight of the reaction product is greater than about 500. In some preferred embodiments, the molecular weight is from about 500 to about 5000. In some embodiments, the product has an APHA color of less than about 250, less than about 100, less than about 50, less than about 40 or less than about 30, The processes disclosed herein can, in some embodiments., be used to make polytrimethylene ether glycol, In the processes disclosed herein, carbon black may be added at any time dur3og the polycondensatÃon reaction, Depending on the reaction conditions and the time of addition, the reactants present during the polycondensation in fi~w presence of carbon black can include monomer dials or polyols thereof, or diacids or polymers thereof. In one example, the reactants comprise P00 monomer, poly-1, 3-propanediol. or mixtures thereof. Poly-I;3-propanedlol includes oligomers of P00 including PDO diner and PDO trimer.
The processes disclosed herein can be used to produce reaction products from reactants comprising at least one of a diol of formula QH(CHw)00H where n is an integer greater than or equal to 2, or a polyol thereof; or a diacid of formula HO0C%CH;_1,C OH where z is an integer greater than or equal to 4, or a polymer thereof, The reactants can include both a diol (or a polyol thereof) and a diacid (or a polymer therof) such as, for example, when the reaction product is a polyester dial.
Reaction products may be homopolymers or copolymers.
Polyester diol reaction products can be prepared using known methods from aliphatic, cycloaliphatic or aromatic dicarboxylic or polycarboxylic acids or anhydrides thereof (for example, succinic, glutaric, adipic, pimelic, subenc, azelaic, sebacic, nonanedicarboxylic, decanedicrboxylic, terephthalic, isophthalic, o-phthalic, tetra hydrophthalic, h x hydrop thafÃc or trimelH tic acid) as well as acid anhydrides (such as o-phthalic, trimellÃtic or succinic acid anhydride or a mixture thereof) and dihydric alcohols such as, for example,ethanediol., diethylene, triethylene, tetraethyl ne glycol, `I ,2wpropaned 1, dipropylene, tripropylene, tetrapropylene glycol, 1,3-propan diol, 1;4-hutanediol, 1, -butanediol', 2,3-butanediol, 1, -pentanediol, 1.S.hexanedlol, 2.2YdÃr ethyl-I ,3-propanedÃol, 1,4-dÃfydroxycyclohexane, I ,4_dimethylolcyclohexane, 1, -octanediol, 1,10-decanediol, 1.12-doc ecanediol or mixtures thereof.
Dols suitable for the processes disclosed herein include aliphatic diols, for example, ethylenediol, Il ,6-hexanediol; 1, 7-heptanediol _ 1,8-octanediol, 1,9-nonanediol. 1,10-decanedÃol, 1;12-dodecanedÃol, 3,3,4,4,5,5-hexafluro-1, -pentan diol, 2,2,3,3,4:4,5,5-octafluoro-1, -hexanedlol, 3.3,4,4,5, ,6, ,7,7,8,8; ,9,10 l0-hexadecafluoro-1,12-dbdecanediol, cycloaliphatic dials, for example, 1,4-c clohexanediol, 1, -cyclohexanedirethanol and isosorhide, polyhydroxy compounds, for example, glycerol, trimethylolpropane, and pentaerythritol. Other suitable dials include 2-methyl-1,3-propanedÃol, 2,2-dimethyl-1,3-propanediol, 2,2-di ethyl- 1, 3-propaneiol, 2-ethyl-2-(hydroxyme hyl)-1,3-propanediol, 1,6-hexa ed ol, 1,8-octanediol, 1;10-decanediol, isosorbide,and mixtures thereof. In some embodiments, preferred dials are 1.3-propanediol and ethylene glycol.
Catalysts suitable for the production of polyester dials include organic and inorganic compounds of titanium, lanthanum, tin, antimony, zirconium, manganese. zinc, phosphorus and mixtures thereof. Titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate are preferred and can be added in an amount of at least about 25 ppm and up to about 1000 ppm titanium by weight, based on the weight of the polymer.
The processes disclosed herein can be used to produce polyether dial reaction products. For example the processes can be used to produce reaction products from reactants comprising at least one of a dial of formula OH(CH2)õ H where n is an integer greater than or equal to 3, or a polyol' thereof, or a dial of formula H(CH~>) OH where nis an integer greater than or equal to 6, or a polyol thereof. Diols of formula OH(CH ),,OH where n is 2, 4, or 5 may not be preferred, as they may cyclize.
In one embodiments the reaction product comprises P03 G.
Methods of making PO from 1,-propanediol are described in the art, for example, in U.S. Application Publication Nos. 20020007043 and 20020010374. As shown in the Examples herein, polyether diols such as PO can be produced by polycondensing P00 using an acid catalyst.
Suitable catalysts, for processes to produce poiyether dials include those acids with a plea less than about 4, preferably with a pKa less than about 2, and include inorganic acids, organic sulfonic acids, heteropolyacids, perfluoro-alkyl sulfonic acids and mixtures thereof Also suitable are metal salts of acids with a plea less than about 4, including metal sulfonates, metal trifluoroacetates, metal triftates, and mixtures thereof including mixtures of the salts with their conjugate acids, Specific examples of catalysts include sulfuric acid, fluorosulfonic acid, phosphorous acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphorolybdic acid, trifluoromethanesulfonic acid, 1,1,2,2 tetrafluoroethanesulfonic acid, I .1 1,2, ,;3-hexafluoropropanesulfonic acid, bismuth triflate, yttrium tr;flate, ytterbium triflate, neodymium triflate, lanthanum triflate, scandium triflate, zirconium triflate. A preferred catalyst for P03 is sulfuric acid. Other suitable catalysts include superacids and N.A': iON solid catalysts (E.I. DuPont de Nernours & Co).
A particularly preferred source of PDO is via a fermentation process using a renewable biological source, As an illustrative example of a starting material from a renewable source, biochemical routes to PDO
have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock. For example, bacterial strains able to convert glycerol into 1,3-ropanediol are found in the species / !ebsle /ca, Citrobacter, Clostridium, and Lactobacillus, The tec;hIn:que is disclosed in several publications: including US 633362, U85686276 and U 58210 2. U 821 92 discloses, inter atria, a process for the biological production of PDO from glycerol using recombinant organisms. The process incorporates E. co/i bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for I ,2--s-propaaned()l. The transformed E. fcoti is grown in the presence of glycerol as a carbon source and PDO is isolated from the growth media. Since both bactena and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of P00 monomer.
The biologically-derived P00, such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the P00, In this way, the biologically-derived P00 preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon, The polymers based thereon utilizing the biological ly-den ved P0, therefore, have less impact on the environment as the P00 used does not deplete diminishing fossil fuels and, upon degradation, releases carbon back to the atmosphere for use by plants once again, Thus, the compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based dials.
Preferably the P00 used as a reactant or as a component of the reactants in the processes disclosed herein has a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis, Particularly preferred is purified P00 as discloser in US7088 8, US7084311 and US 00500999 Al In one embodiment the product of the process is P3. Product P03G can be P03G homo- or co-polymer. For example, the P0Ã can be polymerized with other diols ("comonomer diols') to make copolymer. The PDO copolymers useful in the process can contain up to 50 percent by weight (preferably 20 percent by weight or less) of comonomer diols in addition to the 1,8-propanediol and/or its oligomers. A preferred comonomer dial is ethylene glycol. Other coronorer dials that are suitable for use in the process include aliphatic diols, for example, ethylenediol, 1,6-hexane iol, 1,7-heptanediol, 1,8-octane iol, 1,9-nonanediol, 1,10-decanedÃol, 1,1 2-dod ne iol,, 3,,3 4,4, , -hexa uro-3,5- entanedÃol., 2:2:3 3,4,4,5,5 o>-Ctay~iSuoFo-1,$-hexane iotl, 3,3 4 4,5 ,6,6,7,7, ,5,g,9;10,10-hrexadecafluoro-1,12-dodecanediol, cycloalÃphatic di.c ls, for example, 1,4-cyclohexanediol, 1,4-cyc ohexanedimethanol and isosorbide, polyhydroxy compounds, for example, glycerol, trimethyÃo pÃo ane, and entaer'ythrntol. Other suitable comonomer diols are selected from the group consisting of 2-methyl-1 3-propanediol, 2,24methyl-1,3-propanedÃol, 2,2-dietÃhyÃ-1,3-proparne rol, 2-ethyl-2-(hydroxymethyÃ)-1,3-propanediol, 1,6-hexanediol, 1,8-octanÃedÃol, 1,1Ã3-decanediol, isosorbide, and mixtures thereof. Thermal stabilizers, antioxidants and coloring materials may be added to the polymerization mixture or to the polymer if desired.
In one embodiment, a process comprises causing reactants to polymerize in the presence of carbon black. For a given reaction temperature and catalyst concentration, product APIA color values for a polymer of a given molecular weight or molecular weight range are reduced as compared to the color values for the product polymerized without the presence of carbon black. It will be appreciated that preferred color values or preferred reductions may vary depending on the desired molecular weight or the desired end use of the product. However, armed with this disclosure, one of skill in the art will be able to adjust the process conditions to achieve the desired effect on the color of the product.
It is desired that reaction i the presence carbon black results in polymer with an APHA color of less than about 100, and, more preferably, less than 50. Preferably, the APIA color is less than about 40, more preferably, less than 30, So, in certain embodiments, the APHA color is about 30 to about 100 APHA. APHA color values are a measure of color as defined in A. TM-D-1209 (see Test Method 1, below).
The molecular weight of the product polymer is typically within the range of about 250 to about 5000. Preferably, the molecular weight is about 500 to about 4000. In some embodiments, the product polymer has a molecular weight of about 250 to about 2250. In some embodiments the product polymer has a molecular weight of about 1i 000 to 2250.
The amount of carbon black used depends on factors including the process conditions such as reaction volume, contact time and temperature. Carbon black can be added at any time during the reaction, but is preferably added at. the beginning of the reaction. It. can be premixed with reactant or catalyst before addition into the reactor. The amount added may be based on the weight of the monomer or polymer phase at the time of addition. For example, if the reactants comprise PDO
and comonomer, the amount will be based on the total weight of PDO and comonomer initially added. For continuous operations, it should be based on the total weight of reactants in the reactor, About 0.05 to about 5 weight percent carbon black may be employed, and about 0.1 to about 1 weight percent carbon black is preferred. It is preferred that the amount added is sufficient to reduce color, and preferably the amount added is sufficient to reduce color to less than 100 ARIA or more preferably to less than 50 APHA, The contacting of the reactants with carbon black is carved out under conditions suitable for polymerization. The contacting occurs in the presence of acid and preferably at a temperature of about 120 to . 0 C, preferably 150 to 180'C. The reaction is conducted for a period of about 3 to 50 hours, and preferably about 3 to about 15 hours.
Suitable processes for removal of the carbon black such as filtration are well known to those skilled in the art. Other filter media can be used and will be well known to those skilled in the art, the requirements being a fineness of filter sufficient to retain the carbon black and inert to the glycol.
A batch process can be used, wherein carbon black is added into the reactor at any stage of reaction, and, after a period of time, separated out by suitable means, for example, by filtration, cent,.ifugation, etc, The process of the invention may also be conducted in a continuous or semi-continuous fashion. For example, the reactants may be mixed with carbon black and be pumped from a storage tank into a reactor. Carbon black can be added into the reactor at any stage of reaction, The feed rate is adjusted for the kind, amount, and prior use of carbon black in the bed and the color level of the feedstock so that the carbon black is present in the reactor sufficiently long to give a product with the desired color reduction.
Other variations will be recognized by those skilled in the art. Although it is contemplated that the process described herein can be used in conjunction with methods known in the art wherein the raw materials are pretreated to remove color (such as, for example, in U.S. Patent 6,238,948) or methods wherein the polymer products are post-treated to remove color (such as, for example, in U.S. Patent 75294,746) it is also believed that use of the process described herein eliminate or diminish the necessity of such pretreatment steps and still produce polymer of desired low APIA color.in some embodiments, the product has desired ;PHA.
color at the end of the polymerization, and in other embodiments, the product achieves desired APHA color after further purification.The processes disclosed herein can be used for the decolorization of P03G
prepared by polymerization of PDO prepared from petrochemical sources, such as the process using acrolein, and for P03G prepared by polymerization of PDO prepared by biochemical routes.
In accordance with a further embodiment of the present invention, a product comprises (i) carbon black, and (ii) P03G wherein the P 03G has an APHA color of less than about 250, In certain embodiments, the.APH.A
color is less than about 100, less than about 50, less than about 40, or less than about 30. Also, the product may contain about 0.05 to about 5 weight percent of carbon black or preferably about 0.1 to about 1 weight percent of carbon black.
In one embodiment, the process forms P03G and further comprises esterification of the product P0 3G by reaction with a monocarboxylic acid and/or equivalent, as described in copending U.S;
Application Publication No. 20080108845. By "monocarbo ylic acid equivalent" is meant compounds that perform substantially like monocarboxylic acids in reaction with polymeric glycols and dials; as would be generally recognized by a person of ordinary skill in the relevant art. Monocarboxyxlic acid equivalents for the purpose of the present invention include, for example, esters of monocarboxylic acids, and ester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides. Preferably, a monocarboxylic acid is used having the formula R--COOH, wherein R is a substituted or unsubstituted aromatic, aliphatic or cycloaliphatic organic moiety containing from 6 to 40 carbon atoms.
Mixtures of different monocarboxylic acids and/or equivalents are also suitable.
The monocarboxylic acid (or equivalent) can contain any substituent groups or combinations thereof (such as functional groups like amide, amine, carbonyl, halsde, hydroxyl, etc.) so long as the substituent groups do not interfere with the esteriflcation reaction or adversely affect the roperties of the resulting ester product.
Suitable monocarboxylic acids and their derivatives include lauric, myristic, palmitic, stearic, arachidic, benzoic, caprylic, palmitic, erucic, palmitoleic, pentadecanoic, heptadecanoic, nonadecanoic, linoleic, arachidoniiic, oleic, valeric,roic, capric and 2-ethylhexanoic acids, and mixtures thereof. In a preferred embodiment, the monocarboxylic acid is 2-ethyihexancic acid. In some embodiments, the dic-arboxylic acid esters produced by the processes provided herein, in particular the bis-2-ethylhexanoate esters will have uses as functional fluids, for example, as lubricants.
For preparation of the carboxylic acid esters, the P 03G can be contacted, preferably in the presence of an inert gas, with the monocarboxyllc acid(s) at temperatures ranging from about 100 C to about 275 G, from about 1 0 C to 250'C, and most preferably at about 120"G, The process can be carried out at atmospheric pressure or under vacuum. During the contacting water is formed and can be removed in the inert gas stream or under vacuum to drive the reaction to completion, To facilitate the reaction of PO with carboxylic acid an ester/canon catalyst is generally used, preferably an acid catalyst.
Examples of suitable acid catalysts n,',ude but are not limited to sulfuric acid, hydrochloric acid, phosphoric acid, hydriodic acid. Other suitable catalysts include heterogeneous catalysts such as zeolites, heteropolyacid, amberlyst,. and ion exchange resin. A particularly preferred acid catalyst is sulfuric acid. The amount of catalyst used in the contacting of P03G with monocarbaxylic acid can be from about 0.01 wt % to about 10 wt % of the reaction mixture, preferably from 0.1 wt % to about 5 wE %, and more preferably from about . wt. % to about 2 *1 %, of the reaction mixture.
Any ratio of monocarbcxylic acid, or derivatives thereof, to glycol hydroxyl groups can be used, The preferred ratio of acid to hydroxyl groups is from about 31 to about 12, where the ratio can be adjusted to shift the ratio of monoester to diester in the product. Generally to favor production of diesters sightly more than a 11 ratio is used. To favor production of monoesters, a 0-5-1 ratio or less of monocarboxylic acid to hydroxyl is used.
A preferred process comprises pol'lycondensing 1,3-propanediol in the presence of carbon black to polytrinethylene ether glycol using an acid catalyst (as described herein), then subsequently adding monocarboxylic acid and carrying out the esterifcation to form a dicarboxylic acid ester of P0 3G, It is preferred that the contacting of P03G with a monocaà boxylic acid is carried out without first isolating and purifying the P03 G.
The polycondensation reaction is continued until desired molecular weight is reached, and then the monocarboxylic acid is subsequently added to the reaction mixture. The reaction is continued while the water byproduct is removed.. At this stage both esterification and etherification reactions occur simultaneously. Thus, in a preferred process, the acid catalyst used for polycondensation of diolis also used for esterification without adding addW.Wonal catalyst. However, it is contemplated that additional': catalyst can be added at the esterification stage.
In an alternative procedure, the esterification reaction can be carried out on purified P03G by addition of an ster fication catalyst and monocarboxylic acid followed by heating and removal of water, Regardless of which esterification procedure is followed, after the esterification step any by products are removed, and then the catalyst residues remaining from polycondensation and/or esterification are removed in order to obtain an ester product that is stable, ;particularly at high temperatures. This may be accomplished by hydrolysis of the crude ester product by treatment with water at from about 80T to about OO'C
for a time sufficient to hydrolyze any residual acid esters derived from the catalyst without impacting significantly the carboxylic acid esters. The time required can vary from about I to about 8 hours. If the hydrolysis is carried out under pressure, high r temperatures and correspondingly shorter times are possible. At this point the product may contain theaters, monoesters, or a combination of theaters and monoesters, and small amounts of acid catalyst, unreacted carboxylic acid and dial depending on the reaction conditions, However, dicarboxylic acid esters are preferred;
and processes which produce dicarboxylrc acid esters are preferred.
The hydrolyzed polymer is further purified to remove water, acid catalyst and unreacted carboxylic acid by the known conventional techniques such as water washings, base neutralization, filtration and/or distillation. Unreacted dial and acid catalyst can, for example., be removed by washing with deionized water. Unreacted carboxylic acid also can removed, for example, by washing with deionied water or aqueous base solutions, or by vacuum stripping) If desired, the product can be fractionated further toÃsolate lbw molecular weight esters by a fractional distillation under reduced po essure.
EXAMPLES
Materials, Equipment, and Test Methods The bio-derived PDO used in the Examples herein is commercially available from E.I. DuPont de Nemours & Co. as DuPont Tate & Lyle Bic-PD rr" For Examples 2, 3, and 4, carbon black (Nor it Carbon) was obtained from Univar (product name Dar o .) G-60). For examples 6, and 7, carbon black was type ADP carbon (Calgon Carbon).
Test Method 1. Color Measurement and APHA Values.
A Hunterlab Color Quest XE Spe trocolorimet r (Reston, Va.) was used to measure the polymer color resulting from the absence or presence of carbon black treatment. Color numbers of the polymer are measured as APHA values (Platinum-Cobalt System) according to ATM D-1209.
The polymer molecular weights were calculated from their hydroxyl numbers obtained from NMR or were determined using a previously generated standard curve based on polymer viscosity.
C :arative Example A: Control Pc:=Ãymer:zatio 12 kg of bio-based PDO monomer was added to a 20L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate 5L/min. The reactant was heated up to 170 C with agitation speed of 250 rpm. When the reactant temperature reached 170 C, 187.5 g of sulfuric acid was added into the reactor. The time of sulfuric acid addition was set as reaction starting point. Polymerization proceeded at 170 C.
The reaction volatiles were condensed in the condenser and the polymer product was accumulated in the reactor. Polymer samples were taken periodically for color and molecular weight analysis. The number average molecular weight of polymer was determined by N MR and the product color was determined using a Hunter Lab Color quest XE machine and expressed as APHA index. Molecular weight development is shown in Figure 1 and product color is shown in Figure 2.
Example 0,05 weight -percent of Carbon Black The equipment and polymerization procedures were the same as in Comparative Example A except for carbon black addition. 0.05 weight percent of carbon black (D f o G-60, Univar) on the basis of bÃo-based PLO was added together with the monomer at the beginning of the polymerization. Carbon black was mixed with monomer under agitation when the reactor temperature was increased to 170'C. 187.5 g of sulfuric acid was added at 170 C and the polymerization occurred in the present of carbon black, Product molecular weight and color were measured after carbon black removal by filtration at ambient temperature using a syringe filter. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA index. The molecular weight and color developments are shown in Figures1 and 2 respectively.
Examle 2: g.1 wei ht percent of Carbon Black The equipment and polymerization procedures were the same as in Example 1 except for amount. of carbon black addition. 0,1 weight percent of carbon black on the basis of bio-based PDO was added together with the monomer at the beginning of the polymerization, The molecular weight and color developments are shown in Figures 1 and 2 respectively Exam le 3: 0.5 wei. ht percent of Carbon Black The equipment and polymerization procedures were the same as in Example 1 excent for amount. of carbon black addition, 0.5 weight percent of carbon black on the basis of biowbased PDO was added together with the monomer at the beginning of the polymerization, The molecular weight and color developments are shown in Figures 1 and 2 respectively.
Comparative Ex m .le B: Control poi m rization 900 g of bio-based PDO monomer:. 11.5g of 0.98 percent purity sulfuric acid, and 6.1g of 10 weight percent sodium carbonate solution in dernineralized water (for color control) were added to a 1 L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of 35L/min. The reactant was heated up to 170'C with agitation speed of 120 rpm. The time the heat was turned on was set as the reaction starting point. Polymerization proceeded at 1 70C. The reaction volathles were condensed in the condenser and polymer product was accumulated in the reactor. The polymer samples were taken periodically for molecular weight analysis, using a viscometr. The total reaction time is 18 hours.
The number average molecular weight of polymer was determined from its viscosity, which is calibrated based on NMR measurements. The product color was determined using Hunter Lab Color quest ?E machine and expressed as APHA index. The molecular weight and color of final crude polymer are shown in Table 1.
Example 0. +ei tit percent of Carbon Black, added at reaction times of 2 and 5 hours 900 g of biro-based P00 monomer and 11.5g of 0.98 percent purity sulfuric acid were added to a 1 L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of 35L/min, The reactant was heated up to 170' wA,th agitation speed of 120 rpm. The time the heat was turned on was sat as the reaction starting point, Polymerization proceeded at 170 C. A mixture of 2 g of carbon black in about 10 g bio-P00 is added into the reaction at reaction times of 2 and 5 hours. The reaction volatiles were condensed in the condenser and polymer product was accumulated in the reactor, The polymer samples were taken periodically for molecular weight analysis, using a viscometer, Total reaction time is 25 hours. The number average molecular weight of polymer was determined from its viscosity. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA index. The molecular weight and color of final crude polymer are shown in Table 1.
Example 5., 0,5 !eight percent of Carbon Black, added at reaction time of 4 hours 900 g of bio-based P00 monomer and 11.5g of 0.98 percent purity sulfuric acid were added to a IL glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of ;'i>> 'rlmin. The reactant was heated up to 170`with agitation speed of 120 rpm. The time the heat was turned on was set as the reaction starting point. Polymerization proceeded at 170 C. A mixture of 4 g of carbon black in about 10 g bio-PDO is added into the reaction at reaction time of 4 hours. The reaction volatiles were condensed in the condenser and polymer product was accumulated in the reactor. The polymer samples were taken periodically for molecular weight analysis, using a viscometer. Total reaction time is 25 hours. The number average molecular weight of polymer was determined from its viscosity. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA
index. The molecular weight and color of final crude polymer are shown in Table 1 Table 1. Result summary ----------------------- ------------------------------------------ ---------------------------------------------------------------------------------------------- --------------------------------rumple Heat/Reacton Viscosity (Cp) M based on oior time (hr) viscosity(g/moi) (APHA) Conip 8 18 7,246 3,244 --500 ,444 4,836 200 --------------- ------------------------------------------------------------------------------------------------------------------------- ------------------------------Exam (PROPHETIQ .EsterÃfi tion fP0 G
PDO is polymerized to form P030 homopolymer in the presence of carbon black as described in other Examples. When the reaction product reaches a MW of about 300 (or a viscosity of 150 cP), -ethylhexanoic acid is added to the reaction mixture to esterify the P030 hor, mopolyr er, The amount of 2-ethylhexanoic acid addled is about 60 % of the original PLO charged into the reactor. No addl=tE anal acid catalyst is added. The temperature is reduced to 120'C,. and the reaction is carried out for about 6 to 7 additional hours with no changes in the pressure. The resulting ester product is tested for color as described and is analyzed using proton NMR and IR for MW and % esterification respectively. It is preferred that the color will be below about 200 APHA and that the % estenfcation will be at least 80%. The reaction product is then purified by rreutrali ing the acid and removing the impurities from the product using methods known in the art, for example as in Pat, Publication 20080108845.
Further provided is a process comprising contacting reactant with a catalyst and carbon black to form a polyether dial reaction product wherein the reactants comprise a diol of formula OH(I2)SOH where n is an integer greater than or equal to 3 or polyols thereof; or a dial of formula HOOC( H2)COOH where z is an integer greater t; hare or equal to 6 or polyols thereof.
Also disclosed is a process comprising contacting reactants with a catalyst and carbon black to form a reaction product wherein the reactants comprise a dial of formula OH(CH ),OH where n is an integer greater t' an or equal to 2, or polyols thereof; and wherein said diol is 1,3-propane dial.
In another aspect, the reactants further comprise a comonomer Biol. In one embodiment, the reaction product comprises polytrimethyylene ether glycol.
In some embodiments, the carbon black is about 0.05 to about 5 weight percent based on the total weight of the reactants. In some embodiments, the process includes separating the reaction product from the carbon black by, for example, filtration.
In some embodiments, the catalyst for the processes comprises a titanium catalyst or an acid catalyst. In some embodiments, the reaction products of the processes have an APHA color of less than about 2g;
less than about 100, less than about 50, less than about 40, or less than about 30 Also provided is a process comprising polycondensing reactants comprising 1,3-propanediol, poly 1,3-propanediol or a mixture thereof, in the presence of acid and carbon black. In one embodiment, the reaction product comprises polytrimethylene ether glycol. In some embodiments, the I,3-pr'opanediol, the poly-1,3-propanediol or mixtures thereof comprise bio-derived I3-propanediol._ In some aspects the acid comprises sulfuric acid. In further embodiments the reactants comprise comonomer diol and the comonomer diol can, in some embodiments, be ethylene glycol.
In some embodiments, the process further comprises contacting the polytrimethyl ne ether glycol with a monocars)oxylic acid to form a dicarboxylic acid ester of polytrimethylene ether glycol. In some aspects, the monoc rboxylic acid is 2-ethylhexanoic acid.
In some embodiments, the molecular weight of the reaction product is greater than about 500. In some preferred embodiments, the molecular weight is from about 500 to about 5000. In some embodiments, the product has an APHA color of less than about 250, less than about 100, less than about 50, less than about 40 or less than about 30, The processes disclosed herein can, in some embodiments., be used to make polytrimethylene ether glycol, In the processes disclosed herein, carbon black may be added at any time dur3og the polycondensatÃon reaction, Depending on the reaction conditions and the time of addition, the reactants present during the polycondensation in fi~w presence of carbon black can include monomer dials or polyols thereof, or diacids or polymers thereof. In one example, the reactants comprise P00 monomer, poly-1, 3-propanediol. or mixtures thereof. Poly-I;3-propanedlol includes oligomers of P00 including PDO diner and PDO trimer.
The processes disclosed herein can be used to produce reaction products from reactants comprising at least one of a diol of formula QH(CHw)00H where n is an integer greater than or equal to 2, or a polyol thereof; or a diacid of formula HO0C%CH;_1,C OH where z is an integer greater than or equal to 4, or a polymer thereof, The reactants can include both a diol (or a polyol thereof) and a diacid (or a polymer therof) such as, for example, when the reaction product is a polyester dial.
Reaction products may be homopolymers or copolymers.
Polyester diol reaction products can be prepared using known methods from aliphatic, cycloaliphatic or aromatic dicarboxylic or polycarboxylic acids or anhydrides thereof (for example, succinic, glutaric, adipic, pimelic, subenc, azelaic, sebacic, nonanedicarboxylic, decanedicrboxylic, terephthalic, isophthalic, o-phthalic, tetra hydrophthalic, h x hydrop thafÃc or trimelH tic acid) as well as acid anhydrides (such as o-phthalic, trimellÃtic or succinic acid anhydride or a mixture thereof) and dihydric alcohols such as, for example,ethanediol., diethylene, triethylene, tetraethyl ne glycol, `I ,2wpropaned 1, dipropylene, tripropylene, tetrapropylene glycol, 1,3-propan diol, 1;4-hutanediol, 1, -butanediol', 2,3-butanediol, 1, -pentanediol, 1.S.hexanedlol, 2.2YdÃr ethyl-I ,3-propanedÃol, 1,4-dÃfydroxycyclohexane, I ,4_dimethylolcyclohexane, 1, -octanediol, 1,10-decanediol, 1.12-doc ecanediol or mixtures thereof.
Dols suitable for the processes disclosed herein include aliphatic diols, for example, ethylenediol, Il ,6-hexanediol; 1, 7-heptanediol _ 1,8-octanediol, 1,9-nonanediol. 1,10-decanedÃol, 1;12-dodecanedÃol, 3,3,4,4,5,5-hexafluro-1, -pentan diol, 2,2,3,3,4:4,5,5-octafluoro-1, -hexanedlol, 3.3,4,4,5, ,6, ,7,7,8,8; ,9,10 l0-hexadecafluoro-1,12-dbdecanediol, cycloaliphatic dials, for example, 1,4-c clohexanediol, 1, -cyclohexanedirethanol and isosorhide, polyhydroxy compounds, for example, glycerol, trimethylolpropane, and pentaerythritol. Other suitable dials include 2-methyl-1,3-propanedÃol, 2,2-dimethyl-1,3-propanediol, 2,2-di ethyl- 1, 3-propaneiol, 2-ethyl-2-(hydroxyme hyl)-1,3-propanediol, 1,6-hexa ed ol, 1,8-octanediol, 1;10-decanediol, isosorbide,and mixtures thereof. In some embodiments, preferred dials are 1.3-propanediol and ethylene glycol.
Catalysts suitable for the production of polyester dials include organic and inorganic compounds of titanium, lanthanum, tin, antimony, zirconium, manganese. zinc, phosphorus and mixtures thereof. Titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate are preferred and can be added in an amount of at least about 25 ppm and up to about 1000 ppm titanium by weight, based on the weight of the polymer.
The processes disclosed herein can be used to produce polyether dial reaction products. For example the processes can be used to produce reaction products from reactants comprising at least one of a dial of formula OH(CH2)õ H where n is an integer greater than or equal to 3, or a polyol' thereof, or a dial of formula H(CH~>) OH where nis an integer greater than or equal to 6, or a polyol thereof. Diols of formula OH(CH ),,OH where n is 2, 4, or 5 may not be preferred, as they may cyclize.
In one embodiments the reaction product comprises P03 G.
Methods of making PO from 1,-propanediol are described in the art, for example, in U.S. Application Publication Nos. 20020007043 and 20020010374. As shown in the Examples herein, polyether diols such as PO can be produced by polycondensing P00 using an acid catalyst.
Suitable catalysts, for processes to produce poiyether dials include those acids with a plea less than about 4, preferably with a pKa less than about 2, and include inorganic acids, organic sulfonic acids, heteropolyacids, perfluoro-alkyl sulfonic acids and mixtures thereof Also suitable are metal salts of acids with a plea less than about 4, including metal sulfonates, metal trifluoroacetates, metal triftates, and mixtures thereof including mixtures of the salts with their conjugate acids, Specific examples of catalysts include sulfuric acid, fluorosulfonic acid, phosphorous acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphorolybdic acid, trifluoromethanesulfonic acid, 1,1,2,2 tetrafluoroethanesulfonic acid, I .1 1,2, ,;3-hexafluoropropanesulfonic acid, bismuth triflate, yttrium tr;flate, ytterbium triflate, neodymium triflate, lanthanum triflate, scandium triflate, zirconium triflate. A preferred catalyst for P03 is sulfuric acid. Other suitable catalysts include superacids and N.A': iON solid catalysts (E.I. DuPont de Nernours & Co).
A particularly preferred source of PDO is via a fermentation process using a renewable biological source, As an illustrative example of a starting material from a renewable source, biochemical routes to PDO
have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock. For example, bacterial strains able to convert glycerol into 1,3-ropanediol are found in the species / !ebsle /ca, Citrobacter, Clostridium, and Lactobacillus, The tec;hIn:que is disclosed in several publications: including US 633362, U85686276 and U 58210 2. U 821 92 discloses, inter atria, a process for the biological production of PDO from glycerol using recombinant organisms. The process incorporates E. co/i bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for I ,2--s-propaaned()l. The transformed E. fcoti is grown in the presence of glycerol as a carbon source and PDO is isolated from the growth media. Since both bactena and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of P00 monomer.
The biologically-derived P00, such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the P00, In this way, the biologically-derived P00 preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon, The polymers based thereon utilizing the biological ly-den ved P0, therefore, have less impact on the environment as the P00 used does not deplete diminishing fossil fuels and, upon degradation, releases carbon back to the atmosphere for use by plants once again, Thus, the compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based dials.
Preferably the P00 used as a reactant or as a component of the reactants in the processes disclosed herein has a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis, Particularly preferred is purified P00 as discloser in US7088 8, US7084311 and US 00500999 Al In one embodiment the product of the process is P3. Product P03G can be P03G homo- or co-polymer. For example, the P0Ã can be polymerized with other diols ("comonomer diols') to make copolymer. The PDO copolymers useful in the process can contain up to 50 percent by weight (preferably 20 percent by weight or less) of comonomer diols in addition to the 1,8-propanediol and/or its oligomers. A preferred comonomer dial is ethylene glycol. Other coronorer dials that are suitable for use in the process include aliphatic diols, for example, ethylenediol, 1,6-hexane iol, 1,7-heptanediol, 1,8-octane iol, 1,9-nonanediol, 1,10-decanedÃol, 1,1 2-dod ne iol,, 3,,3 4,4, , -hexa uro-3,5- entanedÃol., 2:2:3 3,4,4,5,5 o>-Ctay~iSuoFo-1,$-hexane iotl, 3,3 4 4,5 ,6,6,7,7, ,5,g,9;10,10-hrexadecafluoro-1,12-dodecanediol, cycloalÃphatic di.c ls, for example, 1,4-cyclohexanediol, 1,4-cyc ohexanedimethanol and isosorbide, polyhydroxy compounds, for example, glycerol, trimethyÃo pÃo ane, and entaer'ythrntol. Other suitable comonomer diols are selected from the group consisting of 2-methyl-1 3-propanediol, 2,24methyl-1,3-propanedÃol, 2,2-dietÃhyÃ-1,3-proparne rol, 2-ethyl-2-(hydroxymethyÃ)-1,3-propanediol, 1,6-hexanediol, 1,8-octanÃedÃol, 1,1Ã3-decanediol, isosorbide, and mixtures thereof. Thermal stabilizers, antioxidants and coloring materials may be added to the polymerization mixture or to the polymer if desired.
In one embodiment, a process comprises causing reactants to polymerize in the presence of carbon black. For a given reaction temperature and catalyst concentration, product APIA color values for a polymer of a given molecular weight or molecular weight range are reduced as compared to the color values for the product polymerized without the presence of carbon black. It will be appreciated that preferred color values or preferred reductions may vary depending on the desired molecular weight or the desired end use of the product. However, armed with this disclosure, one of skill in the art will be able to adjust the process conditions to achieve the desired effect on the color of the product.
It is desired that reaction i the presence carbon black results in polymer with an APHA color of less than about 100, and, more preferably, less than 50. Preferably, the APIA color is less than about 40, more preferably, less than 30, So, in certain embodiments, the APHA color is about 30 to about 100 APHA. APHA color values are a measure of color as defined in A. TM-D-1209 (see Test Method 1, below).
The molecular weight of the product polymer is typically within the range of about 250 to about 5000. Preferably, the molecular weight is about 500 to about 4000. In some embodiments, the product polymer has a molecular weight of about 250 to about 2250. In some embodiments the product polymer has a molecular weight of about 1i 000 to 2250.
The amount of carbon black used depends on factors including the process conditions such as reaction volume, contact time and temperature. Carbon black can be added at any time during the reaction, but is preferably added at. the beginning of the reaction. It. can be premixed with reactant or catalyst before addition into the reactor. The amount added may be based on the weight of the monomer or polymer phase at the time of addition. For example, if the reactants comprise PDO
and comonomer, the amount will be based on the total weight of PDO and comonomer initially added. For continuous operations, it should be based on the total weight of reactants in the reactor, About 0.05 to about 5 weight percent carbon black may be employed, and about 0.1 to about 1 weight percent carbon black is preferred. It is preferred that the amount added is sufficient to reduce color, and preferably the amount added is sufficient to reduce color to less than 100 ARIA or more preferably to less than 50 APHA, The contacting of the reactants with carbon black is carved out under conditions suitable for polymerization. The contacting occurs in the presence of acid and preferably at a temperature of about 120 to . 0 C, preferably 150 to 180'C. The reaction is conducted for a period of about 3 to 50 hours, and preferably about 3 to about 15 hours.
Suitable processes for removal of the carbon black such as filtration are well known to those skilled in the art. Other filter media can be used and will be well known to those skilled in the art, the requirements being a fineness of filter sufficient to retain the carbon black and inert to the glycol.
A batch process can be used, wherein carbon black is added into the reactor at any stage of reaction, and, after a period of time, separated out by suitable means, for example, by filtration, cent,.ifugation, etc, The process of the invention may also be conducted in a continuous or semi-continuous fashion. For example, the reactants may be mixed with carbon black and be pumped from a storage tank into a reactor. Carbon black can be added into the reactor at any stage of reaction, The feed rate is adjusted for the kind, amount, and prior use of carbon black in the bed and the color level of the feedstock so that the carbon black is present in the reactor sufficiently long to give a product with the desired color reduction.
Other variations will be recognized by those skilled in the art. Although it is contemplated that the process described herein can be used in conjunction with methods known in the art wherein the raw materials are pretreated to remove color (such as, for example, in U.S. Patent 6,238,948) or methods wherein the polymer products are post-treated to remove color (such as, for example, in U.S. Patent 75294,746) it is also believed that use of the process described herein eliminate or diminish the necessity of such pretreatment steps and still produce polymer of desired low APIA color.in some embodiments, the product has desired ;PHA.
color at the end of the polymerization, and in other embodiments, the product achieves desired APHA color after further purification.The processes disclosed herein can be used for the decolorization of P03G
prepared by polymerization of PDO prepared from petrochemical sources, such as the process using acrolein, and for P03G prepared by polymerization of PDO prepared by biochemical routes.
In accordance with a further embodiment of the present invention, a product comprises (i) carbon black, and (ii) P03G wherein the P 03G has an APHA color of less than about 250, In certain embodiments, the.APH.A
color is less than about 100, less than about 50, less than about 40, or less than about 30. Also, the product may contain about 0.05 to about 5 weight percent of carbon black or preferably about 0.1 to about 1 weight percent of carbon black.
In one embodiment, the process forms P03G and further comprises esterification of the product P0 3G by reaction with a monocarboxylic acid and/or equivalent, as described in copending U.S;
Application Publication No. 20080108845. By "monocarbo ylic acid equivalent" is meant compounds that perform substantially like monocarboxylic acids in reaction with polymeric glycols and dials; as would be generally recognized by a person of ordinary skill in the relevant art. Monocarboxyxlic acid equivalents for the purpose of the present invention include, for example, esters of monocarboxylic acids, and ester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides. Preferably, a monocarboxylic acid is used having the formula R--COOH, wherein R is a substituted or unsubstituted aromatic, aliphatic or cycloaliphatic organic moiety containing from 6 to 40 carbon atoms.
Mixtures of different monocarboxylic acids and/or equivalents are also suitable.
The monocarboxylic acid (or equivalent) can contain any substituent groups or combinations thereof (such as functional groups like amide, amine, carbonyl, halsde, hydroxyl, etc.) so long as the substituent groups do not interfere with the esteriflcation reaction or adversely affect the roperties of the resulting ester product.
Suitable monocarboxylic acids and their derivatives include lauric, myristic, palmitic, stearic, arachidic, benzoic, caprylic, palmitic, erucic, palmitoleic, pentadecanoic, heptadecanoic, nonadecanoic, linoleic, arachidoniiic, oleic, valeric,roic, capric and 2-ethylhexanoic acids, and mixtures thereof. In a preferred embodiment, the monocarboxylic acid is 2-ethyihexancic acid. In some embodiments, the dic-arboxylic acid esters produced by the processes provided herein, in particular the bis-2-ethylhexanoate esters will have uses as functional fluids, for example, as lubricants.
For preparation of the carboxylic acid esters, the P 03G can be contacted, preferably in the presence of an inert gas, with the monocarboxyllc acid(s) at temperatures ranging from about 100 C to about 275 G, from about 1 0 C to 250'C, and most preferably at about 120"G, The process can be carried out at atmospheric pressure or under vacuum. During the contacting water is formed and can be removed in the inert gas stream or under vacuum to drive the reaction to completion, To facilitate the reaction of PO with carboxylic acid an ester/canon catalyst is generally used, preferably an acid catalyst.
Examples of suitable acid catalysts n,',ude but are not limited to sulfuric acid, hydrochloric acid, phosphoric acid, hydriodic acid. Other suitable catalysts include heterogeneous catalysts such as zeolites, heteropolyacid, amberlyst,. and ion exchange resin. A particularly preferred acid catalyst is sulfuric acid. The amount of catalyst used in the contacting of P03G with monocarbaxylic acid can be from about 0.01 wt % to about 10 wt % of the reaction mixture, preferably from 0.1 wt % to about 5 wE %, and more preferably from about . wt. % to about 2 *1 %, of the reaction mixture.
Any ratio of monocarbcxylic acid, or derivatives thereof, to glycol hydroxyl groups can be used, The preferred ratio of acid to hydroxyl groups is from about 31 to about 12, where the ratio can be adjusted to shift the ratio of monoester to diester in the product. Generally to favor production of diesters sightly more than a 11 ratio is used. To favor production of monoesters, a 0-5-1 ratio or less of monocarboxylic acid to hydroxyl is used.
A preferred process comprises pol'lycondensing 1,3-propanediol in the presence of carbon black to polytrinethylene ether glycol using an acid catalyst (as described herein), then subsequently adding monocarboxylic acid and carrying out the esterifcation to form a dicarboxylic acid ester of P0 3G, It is preferred that the contacting of P03G with a monocaà boxylic acid is carried out without first isolating and purifying the P03 G.
The polycondensation reaction is continued until desired molecular weight is reached, and then the monocarboxylic acid is subsequently added to the reaction mixture. The reaction is continued while the water byproduct is removed.. At this stage both esterification and etherification reactions occur simultaneously. Thus, in a preferred process, the acid catalyst used for polycondensation of diolis also used for esterification without adding addW.Wonal catalyst. However, it is contemplated that additional': catalyst can be added at the esterification stage.
In an alternative procedure, the esterification reaction can be carried out on purified P03G by addition of an ster fication catalyst and monocarboxylic acid followed by heating and removal of water, Regardless of which esterification procedure is followed, after the esterification step any by products are removed, and then the catalyst residues remaining from polycondensation and/or esterification are removed in order to obtain an ester product that is stable, ;particularly at high temperatures. This may be accomplished by hydrolysis of the crude ester product by treatment with water at from about 80T to about OO'C
for a time sufficient to hydrolyze any residual acid esters derived from the catalyst without impacting significantly the carboxylic acid esters. The time required can vary from about I to about 8 hours. If the hydrolysis is carried out under pressure, high r temperatures and correspondingly shorter times are possible. At this point the product may contain theaters, monoesters, or a combination of theaters and monoesters, and small amounts of acid catalyst, unreacted carboxylic acid and dial depending on the reaction conditions, However, dicarboxylic acid esters are preferred;
and processes which produce dicarboxylrc acid esters are preferred.
The hydrolyzed polymer is further purified to remove water, acid catalyst and unreacted carboxylic acid by the known conventional techniques such as water washings, base neutralization, filtration and/or distillation. Unreacted dial and acid catalyst can, for example., be removed by washing with deionized water. Unreacted carboxylic acid also can removed, for example, by washing with deionied water or aqueous base solutions, or by vacuum stripping) If desired, the product can be fractionated further toÃsolate lbw molecular weight esters by a fractional distillation under reduced po essure.
EXAMPLES
Materials, Equipment, and Test Methods The bio-derived PDO used in the Examples herein is commercially available from E.I. DuPont de Nemours & Co. as DuPont Tate & Lyle Bic-PD rr" For Examples 2, 3, and 4, carbon black (Nor it Carbon) was obtained from Univar (product name Dar o .) G-60). For examples 6, and 7, carbon black was type ADP carbon (Calgon Carbon).
Test Method 1. Color Measurement and APHA Values.
A Hunterlab Color Quest XE Spe trocolorimet r (Reston, Va.) was used to measure the polymer color resulting from the absence or presence of carbon black treatment. Color numbers of the polymer are measured as APHA values (Platinum-Cobalt System) according to ATM D-1209.
The polymer molecular weights were calculated from their hydroxyl numbers obtained from NMR or were determined using a previously generated standard curve based on polymer viscosity.
C :arative Example A: Control Pc:=Ãymer:zatio 12 kg of bio-based PDO monomer was added to a 20L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate 5L/min. The reactant was heated up to 170 C with agitation speed of 250 rpm. When the reactant temperature reached 170 C, 187.5 g of sulfuric acid was added into the reactor. The time of sulfuric acid addition was set as reaction starting point. Polymerization proceeded at 170 C.
The reaction volatiles were condensed in the condenser and the polymer product was accumulated in the reactor. Polymer samples were taken periodically for color and molecular weight analysis. The number average molecular weight of polymer was determined by N MR and the product color was determined using a Hunter Lab Color quest XE machine and expressed as APHA index. Molecular weight development is shown in Figure 1 and product color is shown in Figure 2.
Example 0,05 weight -percent of Carbon Black The equipment and polymerization procedures were the same as in Comparative Example A except for carbon black addition. 0.05 weight percent of carbon black (D f o G-60, Univar) on the basis of bÃo-based PLO was added together with the monomer at the beginning of the polymerization. Carbon black was mixed with monomer under agitation when the reactor temperature was increased to 170'C. 187.5 g of sulfuric acid was added at 170 C and the polymerization occurred in the present of carbon black, Product molecular weight and color were measured after carbon black removal by filtration at ambient temperature using a syringe filter. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA index. The molecular weight and color developments are shown in Figures1 and 2 respectively.
Examle 2: g.1 wei ht percent of Carbon Black The equipment and polymerization procedures were the same as in Example 1 except for amount. of carbon black addition. 0,1 weight percent of carbon black on the basis of bio-based PDO was added together with the monomer at the beginning of the polymerization, The molecular weight and color developments are shown in Figures 1 and 2 respectively Exam le 3: 0.5 wei. ht percent of Carbon Black The equipment and polymerization procedures were the same as in Example 1 excent for amount. of carbon black addition, 0.5 weight percent of carbon black on the basis of biowbased PDO was added together with the monomer at the beginning of the polymerization, The molecular weight and color developments are shown in Figures 1 and 2 respectively.
Comparative Ex m .le B: Control poi m rization 900 g of bio-based PDO monomer:. 11.5g of 0.98 percent purity sulfuric acid, and 6.1g of 10 weight percent sodium carbonate solution in dernineralized water (for color control) were added to a 1 L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of 35L/min. The reactant was heated up to 170'C with agitation speed of 120 rpm. The time the heat was turned on was set as the reaction starting point. Polymerization proceeded at 1 70C. The reaction volathles were condensed in the condenser and polymer product was accumulated in the reactor. The polymer samples were taken periodically for molecular weight analysis, using a viscometr. The total reaction time is 18 hours.
The number average molecular weight of polymer was determined from its viscosity, which is calibrated based on NMR measurements. The product color was determined using Hunter Lab Color quest ?E machine and expressed as APHA index. The molecular weight and color of final crude polymer are shown in Table 1.
Example 0. +ei tit percent of Carbon Black, added at reaction times of 2 and 5 hours 900 g of biro-based P00 monomer and 11.5g of 0.98 percent purity sulfuric acid were added to a 1 L glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of 35L/min, The reactant was heated up to 170' wA,th agitation speed of 120 rpm. The time the heat was turned on was sat as the reaction starting point, Polymerization proceeded at 170 C. A mixture of 2 g of carbon black in about 10 g bio-P00 is added into the reaction at reaction times of 2 and 5 hours. The reaction volatiles were condensed in the condenser and polymer product was accumulated in the reactor, The polymer samples were taken periodically for molecular weight analysis, using a viscometer, Total reaction time is 25 hours. The number average molecular weight of polymer was determined from its viscosity. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA index. The molecular weight and color of final crude polymer are shown in Table 1.
Example 5., 0,5 !eight percent of Carbon Black, added at reaction time of 4 hours 900 g of bio-based P00 monomer and 11.5g of 0.98 percent purity sulfuric acid were added to a IL glass reactor equipped with a condenser and an agitator, purged with N2 at the rate of ;'i>> 'rlmin. The reactant was heated up to 170`with agitation speed of 120 rpm. The time the heat was turned on was set as the reaction starting point. Polymerization proceeded at 170 C. A mixture of 4 g of carbon black in about 10 g bio-PDO is added into the reaction at reaction time of 4 hours. The reaction volatiles were condensed in the condenser and polymer product was accumulated in the reactor. The polymer samples were taken periodically for molecular weight analysis, using a viscometer. Total reaction time is 25 hours. The number average molecular weight of polymer was determined from its viscosity. The product color was measured by visual comparison of the samples with a series of standard samples determined using a Hunter Lab Color quest XE machine and expressed as APHA
index. The molecular weight and color of final crude polymer are shown in Table 1 Table 1. Result summary ----------------------- ------------------------------------------ ---------------------------------------------------------------------------------------------- --------------------------------rumple Heat/Reacton Viscosity (Cp) M based on oior time (hr) viscosity(g/moi) (APHA) Conip 8 18 7,246 3,244 --500 ,444 4,836 200 --------------- ------------------------------------------------------------------------------------------------------------------------- ------------------------------Exam (PROPHETIQ .EsterÃfi tion fP0 G
PDO is polymerized to form P030 homopolymer in the presence of carbon black as described in other Examples. When the reaction product reaches a MW of about 300 (or a viscosity of 150 cP), -ethylhexanoic acid is added to the reaction mixture to esterify the P030 hor, mopolyr er, The amount of 2-ethylhexanoic acid addled is about 60 % of the original PLO charged into the reactor. No addl=tE anal acid catalyst is added. The temperature is reduced to 120'C,. and the reaction is carried out for about 6 to 7 additional hours with no changes in the pressure. The resulting ester product is tested for color as described and is analyzed using proton NMR and IR for MW and % esterification respectively. It is preferred that the color will be below about 200 APHA and that the % estenfcation will be at least 80%. The reaction product is then purified by rreutrali ing the acid and removing the impurities from the product using methods known in the art, for example as in Pat, Publication 20080108845.
Claims (12)
1. A process comprising:
contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactants comprise at least one, selected from the group consisting of a. a diol of formula OH(CH2)n OH where n is an integer of 2 or greater, or a polyol thereof; and b. a diacid of formula HOOC(CH2)z COOH where z is an integer of 4 or greater, or a polymer thereof.
contacting reactants with a catalyst and carbon black to form a reaction product, wherein the reactants comprise at least one, selected from the group consisting of a. a diol of formula OH(CH2)n OH where n is an integer of 2 or greater, or a polyol thereof; and b. a diacid of formula HOOC(CH2)z COOH where z is an integer of 4 or greater, or a polymer thereof.
2. The process of claim 1 wherein the reactants comprise a. a diol of formula OH(CH2)n OH where n is an integer greater than or equal to 2 or a polyol thereof; and b. a diacid of formula HOOC(CH2)z COOH where z is an integer greater than or equal to 4 or a polymer thereof; and wherein the reaction product is a polyester diol.
3. The process of claim 1 wherein the reactants comprise a. a diol of formula OH(CH2)n OH where n is an integer greater than or equal to 3 or a polyol thereof; or b. a diol of formula HOOC(CH2)z COOH where z is greater than or equal to 6 or a polyol thereof; and wherein the reaction product is a polyether diol.
4. The process of claim 1 further comprising separating the reaction product from the carbon black.
5. The process of claim 4 wherein the carbon black is separated by filtration.
6. The process of claim 1 wherein the carbon black is present in an amount from about 0.05 to about 5 weight percent based on the total weight of the reactants.
7. The process of claim 2 wherein the catalyst comprises a titanium catalyst.
8. The process of claim 3 wherein the catalyst comprises an acid catalyst.
9. The process of claim 1 wherein the reaction product has an APHA
color of less than about 250.
color of less than about 250.
10. The process of claim 1 wherein the reaction product has an APHA
color of less than about 50.
color of less than about 50.
11. The process of claim 1 wherein the reaction product has an APHA
color of less than about 40.
color of less than about 40.
12. The process of claim 1 wherein the reaction product has an APHA
color of less than about 30.
color of less than about 30.
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|---|---|---|---|
| US22752209P | 2009-07-22 | 2009-07-22 | |
| US61/227,522 | 2009-07-22 | ||
| PCT/US2010/042255 WO2011011276A2 (en) | 2009-07-22 | 2010-07-16 | Methods for synthesizing polyether diols and polyester diols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2767675A1 true CA2767675A1 (en) | 2011-01-27 |
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| CA2767675A Abandoned CA2767675A1 (en) | 2009-07-22 | 2010-07-16 | Methods for synthesizing polyether diols and polyester diols |
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| EP (1) | EP2456808A4 (en) |
| JP (1) | JP2012533676A (en) |
| KR (1) | KR20120047266A (en) |
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| AU (1) | AU2010274149A1 (en) |
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| CA (1) | CA2767675A1 (en) |
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| MX (1) | MX2012000853A (en) |
| TW (1) | TW201107370A (en) |
| WO (1) | WO2011011276A2 (en) |
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| CN103492460B (en) * | 2011-04-26 | 2016-05-11 | 纳幕尔杜邦公司 | Prepare the method for polytrimethylene ether glycol |
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| DE19753378A1 (en) * | 1997-12-02 | 1999-06-10 | Lurgi Zimmer Ag | Process for the production of polyesters with mixed catalysts |
| WO2001044150A2 (en) * | 1999-12-17 | 2001-06-21 | E.I. Du Pont De Nemours And Company | Continuous process for the preparation of polytrimethylene ether glycol |
| US6977291B2 (en) * | 1999-12-17 | 2005-12-20 | E.I. Du Pont De Nemours And Company | Production of polytrimethylene ether glycol and copolymers thereof |
| US6608168B1 (en) * | 2002-08-09 | 2003-08-19 | E. I. Du Pont De Nemours And Company | Polytrimethylene ether esters |
| US6875514B2 (en) * | 2003-03-21 | 2005-04-05 | E. I. Du Pont De Nemours And Company | Coating composition containing polytrimethylene ether diol useful as a primer composition |
| US7009082B2 (en) * | 2003-05-06 | 2006-03-07 | E.I. Du Pont De Nemours And Company | Removal of color bodies from polytrimethylene ether glycol polymers |
| US20100204439A1 (en) * | 2009-02-09 | 2010-08-12 | E.I. Du Pont De Nemours And Company | Processes for making poly(trimethylene ether) glycol using organophosphorous compound |
-
2010
- 2010-07-16 AU AU2010274149A patent/AU2010274149A1/en not_active Abandoned
- 2010-07-16 EP EP10802688A patent/EP2456808A4/en not_active Withdrawn
- 2010-07-16 CA CA2767675A patent/CA2767675A1/en not_active Abandoned
- 2010-07-16 IN IN349DEN2012 patent/IN2012DN00349A/en unknown
- 2010-07-16 CN CN2010800329131A patent/CN102471480A/en active Pending
- 2010-07-16 KR KR1020127004472A patent/KR20120047266A/en not_active Application Discontinuation
- 2010-07-16 WO PCT/US2010/042255 patent/WO2011011276A2/en active Application Filing
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| EP2456808A4 (en) | 2013-01-23 |
| CN102471480A (en) | 2012-05-23 |
| TW201107370A (en) | 2011-03-01 |
| BR112012001407A2 (en) | 2019-09-24 |
| WO2011011276A3 (en) | 2011-04-28 |
| KR20120047266A (en) | 2012-05-11 |
| JP2012533676A (en) | 2012-12-27 |
| MX2012000853A (en) | 2012-03-16 |
| EP2456808A2 (en) | 2012-05-30 |
| IN2012DN00349A (en) | 2015-08-21 |
| WO2011011276A2 (en) | 2011-01-27 |
| AU2010274149A1 (en) | 2012-02-02 |
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