TWI359160B - Polytrimethylene ether glycol with excellent quali - Google Patents

Description

1359160 IX. INSTRUCTIONS: PRIORITY This application is filed on May 6, 2003, US Priority Application No. 60/468,228 and August 5, 2003. US Priority Application No. 1〇/634,61 Priority 1 is hereby incorporated by reference in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of homotrim and copolymerization of polytrimethylene ether glycol having an excellent texture, particularly its color and functionality, which is preferably obtained by using propylene glycol. Renewable biological source. [Prior Art] 1,3·propanediol (hereinafter also referred to as "pD〇") is a single product which can be used for the production of various polymers including polyesters, polyurethanes, polyethers and cyclic compounds. The homogeneous and copolymeric mystery of polytrimethylene ether glycol (hereinafter also referred to as "p〇3G") is an example of such a polymer. The polymer can be used in a variety of applications, including: fibers, films. Et. The chemical route for the production of hydrazine, 3_propanediol is known. For example: 1,3-propanediol can be prepared from: 1. Ethylene oxide 9, in the catalyst and phosphine, water, carbon monoxide, hydrogen and an acid In the presence of ("hydroquinone pathway") 2) acrolein catalytic solution phase hydration and then reduction of acrolein pathway ") Both of these pathways for the formation of 1,3-propanediol involve interproducing products Synthesis of 3-hydroxypropanal (hereinafter referred to as "ΗΡΑ"). Reduction of hydrazine to PDO in the final catalytic hydrogenation step. Subsequent final purification involves several procedures, including 93144.doc 1359160 including vacuum evaporation. Biochemical pathway for the production of 1,3-propanediol It has been stated that it utilizes bio-raw raw materials and renewable resources, such as corn raw materials. These pDs are referred to hereinafter as "biochemical PDO". For example, bacterial strains which convert glycerol to 1,3-propanediol have been found, for example, in the genus Klebsiella, Citr〇 bacter, Clostridium. And Lactobacillus. This technique is disclosed in a number of patents, including U.S. Patent Nos. 5,633,362, 5,686,276, and 5,821, the entire disclosure of each of each of In particular, Nagarajan et al. disclose a biological method for producing 1,3-propanediol from glycerol using recombinant organisms. The method uses a heterogeneous pdu diol hydrogenase gene transformation, which has a specific Escherichia coli (E. coh) for hydrazine and 2-propanediol. The transformed Escherichia coli was grown in a medium containing glycerol as a carbon source and propylene glycol was separated from the growth medium. Since both bacteria and yeast can convert glucose (eg, corn sugar) or other carbohydrates to glycerol, the method of the invention provides a fast, inexpensive, and environmentally friendly polyester, polyether, and other polymerization. The source of the production of 3-propylene glycol monomer. The early precipitation method (e.g., propylene glycol and delayed or other materials) has been used to separate colored and odorous ingredients from desired products (e.g., enzymes) to obtain purified preparations. The precipitation of high molecular weight constituents from the fermentation broth and the bleaching of these components with a reducing agent (DE 39i7645) are known. In addition, micro (four) and then nanometer to remove residual compounds is also known to help (listen 7529), which molecular weight is higher than the separation size of 93l44.doc 1359160 ^ can be gone m, nano too _ will be very It is blocked quickly and its cost is high. Various processing methods have been disclosed in the prior art to remove color precursors present in pD〇t, however, such methods are laborious, expensive, and add to the cost of the polymer. For example, Kelsey, U.S. Patent No. 5,527,973 discloses a method for providing purified 1,3-propanediol which can be used as a starting material for light colored polyester. This method has several drawbacks, including: the use of a variety of preparations and the need to dilute with large amounts of water, which is difficult to remove from the product. A method for removing color-producing impurities from 1,3-propanediol by preheating, which is preferably a heterogeneous acid catalyzing agent, for example, perfluorination, is disclosed in U.S. Patent No. 6,235,948. The catalyst is removed by crystallization and further separated by propylene glycol, preferably ^ = empty distillation. The addition of polytrimethylene ether glycol prepared from the purified diol? 11 octagonal value is 30-40, however, the molecular weight of the polymer is not mentioned. The polyalkylene ether glycols are typically prepared by catalytically eliminating the catalytic ring opening of water or alkylene oxides from the corresponding alkylene glycol oxime. For example, the preparation of polytrimethylene glycol can be carried out by dehydration of propylene glycol or by ring opening polymerization of dioxane using a soluble acid catalyst. The use of sulphuric acid to produce P03G from glycerol is fully described in U.S. Patent Publication No. 2002/0007043 A1 and U.S. Patent Application Serial No. 2,374, the entire disclosure of each of which is incorporated herein by reference. The polyether diols prepared in this manner can be purified by methods known in the art. The purification method for polytrimethylene ether glycol typically includes: (1) a hydrolysis step for hydrolyzing an acid ester formed during polymerization (2) removal of an acid catalyst 'unreacted monomer, low molecular weight linear oligomer and ring The water extract of the ether of the 93l44.doc class is treated with the acid in the presence of the acid (3), which is typically treated with hydroxide to remove residual forest 2 and (4), and (4) the polymer is dried and passed. It is well known that it has 13 trimethacrylates. The polycondensation produced by the catalytic polymerization of the dicarboxylic acid is accepted. Polymerization t::!, in particular: its color cannot be industrial = σ豸 usually depends on the quality of the raw material · PDO. apart from

In addition to the original sputum, the conditions of the cypress and the stability of the polymer are also related to the discoloration. _ _ 'In the case of polydiethylene ether glycol, polyether

- Alcohol tends to have I® family + & A desire. _ _ s work color, this feature is not used for many end uses. The second propylene diol is used as the hexahydrin. It is easy to change color due to contact with oxygen or air, especially when it is under temperature, a ▲ will be poly & The action is carried out under nitrogen and the polydecyl alcohol is stored in pure gas. Another preventive method is to add a low concentration of appropriate antioxidant. Preferred is butyl (tetra)f benzene (BHT, 2,6-butyl- 4-methylphenol), the concentration of which is 1 〇〇 5 〇〇 microgram / gram poly ii | 〇, again, by tradition There are not many successful examples of ways to reduce the color of polytrimethylene ether glycol. For example, M 〇rris et al., U.S. Patent No. 2,520,733, teaches a unique tendency to discolor from the polymerization of pD oxime to form polymethylene ether glycol in the presence of an acid catalyst. Many of the methods they tried did not improve the color of polytrimethylene ether glycol, including the use of activated carbon, activated aluminum, silicone, separate filtration, and separate hydrogenation. As a result, they developed a method for purifying a polyol prepared from i,3-propanediol in the presence of an acid catalyst (2.5 to 6% by weight;) at a temperature of about 175 ° C to 200 ° C. The purification process, stepwise and passing the t compound through the bleaching earth earth, is then hydrogenated by 93144.doc 1359160. Such a large number of purification methods can give a pale yellow final product. In fact, the color of the polytrimethylene ether glycol (in which example ι) obtained by this weighting is only reduced to the No. 8 color (Gardner), and its color quality. Equivalent to ΑρΗΑ value>3〇〇 and generally not suitable for today's needs.

A procedure for preparing a molecular weight in the range of 1200-U00 and having an improved color is disclosed in U.S. Patent No. 3,326,985, the disclosure of which is incorporated herein by reference. However, its chromaticity is not quantitative and should not meet the above requirements. SUMMARY OF THE INVENTION The present invention provides a process comprising contacting 1,3-propanediol with a suitable polymerization catalyst to produce a polytrimethylene ether glycol, wherein the oxime, 3-propanediol comprises about 1 Torr prior to contacting. Micrograms per gram or less of peroxidic compound based on the weight of 1,3-propanediol. Preferably, the propylene glycol comprises a carbonyl compound of about 1 μg/g or less, based on the weight of pD〇. Also preferably, the u-propanediol comprises a monofunctional alcohol compound of about 1 μg/g or less, based on the weight of the PDO. Unless otherwise stated, the percentages, parts, ratios, etc. are weights. ratio. Trademarks are shown in uppercase. In addition, if the content, concentration or other value or parameter is expressed by a range, a preferred range, and preferably a higher value, and preferably a lower value, it is known that it is a preferred value and an arbitrary value. The lower limit or the preferred value is any range of the formation of the pairing, regardless of the range. The present invention is directed to the production of a polytrimethylene diol which is excellent in texture by the polymerization of a (acid) catalyzed diol. The present inventors have found that propylene glycol produced from the stone 93144.doc 1359160 process is not good enough to produce high quality p(10) polymers: this is due to the presence of impurities, such as: a few base compounds such as: propyl group, uncertain structure a peroxide-forming compound alcohol (for example, 2···································· The acidic compound can be measured by pH. The monofunctional alcohol is polymerized as X as a chain terminator, and its insertable polymer can be used as a terminating end point which can affect the polymer Lu Yue b. Monofunctional group Alcohols may be associated with color formation: nothing. However, in general, carbonyl compounds are often associated with color bodies. The more we can expect the number of carbonyl groups, the darker the color. The impurities in some of the above PDOs can be in acid. The color is produced in a catalytic polymerization process. According to a first aspect, the invention comprises contacting propylene glycol with a suitable polymerization catalyst to produce polytrimethylene ether glycol, wherein the propylene glycol comprises about 10 micrograms per gram prior to contacting. or A small amount of peroxidic compound based on the weight of 1,3-propanediol. In general, olefins, ethers and allyls are easy to form peroxides, and the peroxides formed are commercially available. Commercially available test strips or by iodine reduction titration known in the art. According to another aspect of the invention, the 1,3-propanediol further comprises about 1 microgram per gram or less of carbonyl compound The weight of the PDO is based on. Preferably, the PDO comprises about 75 micrograms per gram or less, more preferably about 5 micrograms per gram or less, and most preferably about 25 micrograms per gram or less of the base compound. 'Based on the weight of PDO. Illustrative examples of a few base compounds are acetal aldehydes and aldehydes in the form of acetals, for example, the reaction of 3 hydroxypropyl and 1,3-propanediol The determination of the number of bases can be detected by uv after conversion of the carbonyl compound to dinitrophenylhydrazine in a manner well known in the art of 93144.doc 11 1359160. According to another aspect of the invention, 1,3-propanediol further comprises about 1 μg/m Or less monofunctional alcohol compound based on the weight of PD. Preferably, the PDO comprises about 75 micrograms per gram or less, more preferably about 50 micrograms per gram or less, most preferably about 25 μg/g or less of the carbonyl compound 'based on the weight of the PDO. Illustrative examples of the monofunctional alcohol compound are HED and 3-tetrahydropyrene oxime. According to another aspect of the invention, 1, 3-propanediol comprises at least 99.95% of the diol, i.e., has a purity of at least 99.95%. According to another aspect of the invention, the pH of the mixture of 1,3-propanediol and an equal weight of water ("50/50 pH" The invention is in the range of 6.0 to 7.5, preferably 6 〇 and 7.0 〇. According to another aspect of the invention, the invention provides a method comprising the step of formulating a biochemically derived 1,3 -propanediol The polymerization catalyst is contacted to produce polytrimethylene ether glycol, wherein the propylene glycol has a pH of 6.0 to 7.5 and contains about 10,000 micrograms per gram or less of carbonyl compound, about 1 microgram/ a gram or less peroxy compound and a monofunctional alcohol of about 1 μg/g or less Thereof, with reference to the weight of the PDO. The present inventors have discovered that the subsequent treatment of PDO and P〇3G can be substantially reduced or eliminated substantially as a starting material with a low amount of such impurities, particularly those lower than those specified herein. demand. Preferably, the pD oxime is a biochemically derived PDO (biochemically derived p-optimal, the PD0 system used in the method according to the invention is derived from the above-mentioned biological and regenerative properties 93J44.doc -12- 1359160 Source, ie, prepared from a fermentation process and corn raw material. According to another aspect of the invention, a composition comprises a biochemically derived 1,3 propanol wherein the hydrazine propylene glycol comprises about (7) μg/g or Fewer Ik-based compounds, about 10 μg/g or less peroxy compound, and about 1 μg/g or less of a monofunctional alcohol compound based on the weight of u-propanediol. According to the present invention In another aspect, the polytrimethylene ether glycol is derived from the polymerization of a biol of the biochemical. Preferably, the 1,3-propanediol used in accordance with the present invention has a color value of less than about 10 APHA. Preferably, according to The color value of u-glycerin used in the present invention is less than about 5 APHA. The determination of the color of APHA is described in Test Method 1 below. A simple procedure provides a rapid method for confirming the quality of PDO for P03G production, It does not require time-consuming steps Production of p〇3G. This method relies on the discovery that the impurities in the PD〇 which can cause the color generation of P〇3G will rapidly manifest themselves under the mild conditions of the accelerated acid heat test (AAHT, Test Method 6). The AAHT method involves A period of transient heat-up with sulfuric acid (1% of PD〇 weight). The heating time is 1 〇 minutes, below 17 〇〇c. Therefore, the AAHT method can convert the color precursor into color, but does not occur significantly. Preferably, the color value of the PD 〇 after AAHT is less than about 15 APHA. Preferably, the color value after PDCmAAHT is less than about ι ApHA. P03G obtained from the PDO of the present invention. It may be a homo- or copolymer. For example, 'PDO may be polymerized with other diols (see below) to produce a copolymer. The PD-based copolymer useful in the present invention may contain up to 5% by weight (preferably 20) % by weight or less), comonomer other than 3_ propylene glycol II 93144.doc 13 1359160 Alcohol and / or its violent body. Suitable for the comonomer of this side armor _ aliphatic diol, For example: ethylene glycol-% includes fat 1, 〇-hexanol, 17 I* π octanediol... diol, U 〇 -decanediol, U2= know 3'3'4'4'5'54U, 5j:, '2,2,3:~ 1,6-hexanediol, ',W-gossip- 丨ί ,7 '7'8,8,9,9,10,1〇,- 十丄 stupid 1,12-dodecanediol, 璜灿 t '丁虱-

Intoxication of the genus Acacia diol H alcohol, cyclohexane dimethanol and isosorbide, more (four) 7 hexanes such as: glycerol, tri-methyl propyl acetate and erythritol. / 聚单物,优选优选的 groups are selected from the group consisting of: 2 ^ - each alcohol, 2,2-dimethyl-^-propanediol, 22_ two soil _1,3- Propyldiethyl-2-(hydroxymethyl H,3-propylene glycol, ; 1:] '3-propanediol, ι'ιο-decanediol, isosorbide' and mixtures thereof. Available. Thermal stabilizer , anti-oxidation k # 10 10 - alcohol in a special polymerization mixture or in the final polymer. 砚 need to be broken into, in some cases, a certain amount of oligos that can be used up to 10% or more, if可 刀 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± The 1,3-propanediol, preferably 99% by weight or more. The method for producing + + 〇 3G from PDO is generally known in the art. For example, U.S. Patent No. 2, 52, 733 No., which is incorporated herein by reference, discloses a polytrimethylene ether-轳% polymer and copolymer and a catalyst for dehydration catalysis such as: broken, inorganic acid (eg sulfuric acid) and organic hydrazine 'Methods for preparing such polymers from 1,3-propanediol. ^Preparation of the hydrazine linkage is preferably carried out by polymerization condensation of an acid-catalyzed 1,3 · 93144.doc • 14-1359160 propylene glycol, such as Speaking of the US public patents, swollen _~ and 2_(four), both of which are listed as reference. The preparation of polytrimethylene ether glycol can also be achieved by ring-opening polymerization of cyclic ethers and alkylene oxides. , ρ〇1_(10) shirt 28, 429_444 (1985), which is also incorporated herein by reference. The polymerization condensation of i ^ propylene glycol is preferably the use of epoxy. If required, the polyether prepared by the method of the invention The diol can be further purified by methods known in the art to remove the acid present. It should be understood that in certain applications, the product can be used without further purification. However, the purification procedure can significantly improve the polymer quality. It is composed of the following: (1) a hydrolysis step for hydrolyzing an acid ester during polymerization, (2) typically (4) removal of acid, unreacted monomer, low molecular weight linear oligo and ring Water extraction step of ester oligo, (b) - The solid base is treated to neutralize the residual acid present and (c) the polymer is dried and filtered to remove residual water and solids. The color value of P03G produced from the PDO of the present invention is preferably less than about 5 〇 APHA. More preferably, the p〇3G has a color value of less than about 3 APHA. Preferably, the p〇3G product produced using the PDO monomer/collector has a molecular weight of from about 250 to about 5,000. Preferably, it is from about 5 Torr to about 4 Torr, and most preferably from about 1000 to about 3000. The process of the present invention provides a polytrimethylene ether glycol material having improved functionality and polymer color. Test Method 1. Determination of APHA Value The color of 93144.doc -15 - 1359160 PD 〇 and polymer was determined using a Hunterlab ColoQuest spectrophotometer (Reston, VA). The color number is determined by APHA according to ASTM D-1209 (platinum-cobalt system). The molecular weight of the polymerization is calculated from the number of hydroxyl groups obtained by titration. Test Method 2. n> Determination of strontium content and HED (by gas chromatography) A sample of two diluted PD 注入 was injected into a wax (for example: Phenomenex Zorbax Wax, DB-Wax, UP Innowax or equivalent) In a gas chromatograph of a capillary column and a flame ionization detector (FID). The FID will generate a signal proportional to the concentration of the analyte over time and capture the signal to the integrator or store it in the computer with x, y data. Each component that is separated and detected appears as a "Crest" when the sfl number is plotted against time. It is assumed that the weight % response factor of all impurities on the FID is the same as pD〇. % purity is calculated in % area. The detection limit is: 5 μg / g. Test Method 3 Determination of carbonyl content (by spectrophotometric analysis) The carbonyl compound is converted to dinitrophenyl hydrazine prior to quantification by a spectrophotometer. The detection limit is: 2 μg / g. Test Method 4 Determination of peroxide content The peroxide in pd〇 was determined using a commercially available peroxide test piece, _ 5_25 μg/g EM Quant® or iodine reduction titration. The titration method involves adding a 5 gram sample to 5 mM of a 2-propanol/acetic acid solution and titrating the solution with a 0.01 N sodium thiosulfate solution. The detection limit is: 〇 5 μg / g. If a test piece is used, it can be quantified by diluting the sample to a concentration of 5-25 μg/g to a concentration greater than 25 μg/g or using a test piece designed for a higher concentration. Test Method 5 Determination of pH (pH shows the content of acidic impurities on a logarithmic scale) 93144.doc -16- 1359160 The pH of the solution was measured by a pH meter using a mixture of PDO and distilled water of 50:50. Test Method 6 AAHT Process PDO (150 g) and 1.5 g of concentrated sulfuric acid were poured into a 250 ml three-necked flask. The solution was mechanically stirred under nitrogen and heated to 1 70 ° C for 10 minutes. After 10 minutes, the solution was cooled to room temperature and its color was determined according to Test Method 1. [Examples] Example 1_3 1,3-propanediol was purchased from two petrochemical routes. DuPont manufactures 1,3-propanediol from acrolein; PDO can also be derived from ethylene oxide. DuPont also uses glucose derived from corn as a renewable raw material to make 1,3-propanediol. The PDO content, 2-hydroxyethyl-1,3-dioxane (HED) content, minority group content, peroxide content, and acidity of the PDO samples from various synthetic routes were analyzed as described in the above methods. The results are shown in Table 1. The APHA values of PDO before and after the AAHT procedure were determined and the results are shown in Table 2. Table 1: Chemical analysis of 1,3-propanediol Example PDO purity of raw material PDO % HED Microgram / gram carbonyl microgram / gram peroxide microgram / gram Ph 50 / 50 1 Corn 99.997 ND* ND* ND* 6.82 2 Propylene 99.968 80 93 56 4.87 3 Oxygenethane 99.917 310 198 ND* 5.88 ND* not measurable (see limits of test methods) 93144.doc 1359160 The results of Table 1 indicate: compared to PDO derived from the petrochemical pathway, derived from The biochemical pathway of PDO has the highest purity and contains the least amount of impurities. Table 2. Discoloration of 1,3-propanediol treated with acid at i7〇°c for 1 minute. Example PDO raw material PDO color before AAHT (APHA) PDO color after AAHT (APHA) 1 Corn 3 8 2 C Dilute acid 3 50 3 ethylene oxide 4 14

Table 2 shows that the pD in Example 1 has the least discoloration after the AAHT test, and there is no color precursor impurity in the dark. The acrolein-based oxime, 3-propanediol, is higher in purity than the ethylene oxide base diol and contains less carbonyl compound (as shown in Table 1). However, the acrolein-based diol has a stronger color in the aaht method, which represents the presence of a relatively high concentration of color precursor-type impurities. It was also confirmed by the presence of a peroxide that these pD〇 contained a peroxide-generating compound.

Example 4 Preparation of p〇3G from biochemically derived pD〇 As described below, the U3·propylene glycol obtained from the biochemical route was used to polymerize: a 22 liter bottle was placed in a nitrogen inlet and a steaming head, and poured into 8392 grams.丨, 3_ propylene glycol. The nitrogen is applied to the liquid at a speed of 1 liter liter per minute and mechanically transferred for about 15 minutes. 3 The magnetic stirrer driven by the flask is driven by a stirrer. The funnel is slowly raking 93144.doc -18- 1359160 for at least 5 minutes and adding 76.35 grams of «. After completion, 15 grams of pD was added to the separatory funnel and rotated to remove any residual sulfuric acid. Add it to the flask. The mixture was stirred and blown as above and heated to 16 Torr. The reaction was removed by a library and the reaction was continued for 38.5 hours during the polymerization, after which it was cooled (continuously stirred and blown) to 4 passages. The crude polymer obtained had an average molecular weight of 213 NMR and an eight-ship color of 59. This crude material was hydrolyzed as follows. The crude polymer and an equal volume of steamed water were added to a 22 liter 5-neck round bottom flask (with condenser and mechanical stirrer). The mixture was mechanically mixed, and nitrogen gas was blown at a rate of about i5 G ml/min and heated to 1 Torr (rc. It was refluxed for 4 hours, after which the heating was turned off and the mixture was cooled to a price. Mix and minimize the blowing. Phase separation occurs during cooling. The water of the aqueous phase is removed and discarded. The distilled water mixed with the original is added to the wet polymer remaining in the flask. Gas and add 敎..., to 100 c 1 day, then turn off the addition... and let the material cool as described above. Remove the water phase and discard it. Determine the residual ββ Μ β by titration , Shiliu sulphuric acid and an excess of calcium hydroxide: "The polymer is reduced, c dry for 3 hours and then passed through the CELPURE C-65 遽 遽 遽 遽 ^ 加以 加以 加以 加以 加以The resulting purified polymer had an average molecular weight of _ measured and an APHA color of 32.

Example S from 1,3-propanediol 锖p〇3G Prepared as described in Example 4 except that the 1,3-propanediol used was derived from propylene. 93144.doc -19- 1359160

Example 6 Preparation of P03G from 1,3-propanediol A polymer was prepared as described in Example 4 except that the 1,3-propanediol used was derived from the ethylene oxide route. Table 3: P03G polymer color example PDO raw material crude polymer purified polymer Μ color (ΑΡΗΑ) Μη color (ΑΡΗΑ) 4 corn 2130 59 2229 32 5 acrolein 2256 185 2341 157 6 ethylene oxide 2157 102 2170 109 Table 3 shows that purified P03G derived from PDO of Example 1 has the lowest chroma compared to polymers derived from other PDOs. 93144.doc 20-

Claims (1)

135^160 October 14th, 100th, the scope of application for patents: 1. A method for preparing polytrimethylene ether glycol, comprising the following steps: know: for a 1,3-propanol, wherein the 1,3 - propylene glycol comprises a peroxo compound of 1 〇 microgram/g or less based on the weight of 1,3-propanol (PDO) and a carbonyl compound of 100 μg/g or less; and the 1,3 - Propylene glycol is contacted with an acid polymerization catalyst to produce a polytrimethylene glycol; wherein the polytrimethylene ether glycol has a color of less than 5 〇 APHA. 2. The method of claim 1, wherein the 1,3-propanediol further comprises a monofunctional alcohol compound having a basis weight of pD〇 of 100 μg/g or less. 3. The method of claim 1, wherein the 1,3-propanediol has a purity of at least 99.95% 〇 4. The method of claim 1 wherein the 1,3-propanediol comprises biochemically derived 1,3·propanediol. 5. The method of claim 4, wherein the 1,3-propanediol is derived from a fermentation process utilizing a renewable biological source. 6. The method of claim 1 wherein the hydrazine propylene glycol is treated with 1% by weight of sulfuric acid at 17 ° C for 10 minutes and has a color value of less than 15 APHA. 7. The method of claim 1, wherein the polytrimethylene ether glycol has a molecular weight of from 250 to 5 〇〇〇 0 8 such as the method of claim 1 wherein the polytrimethylene ether glycol comprises homopolymerization And/or copolymer. 9. For example. The method of claim 1, wherein the polytrimethylene ether glycol comprises 1,3-propane di 10 10 π. 12. 13. 14. 15. A copolymer of an alcohol and at least one other C6 to Cl2 diol. • The method of claim i, wherein the 5 〇 / 5 〇 〇 of the U propylene glycol is 60 · 7.5. A method for producing a polytrimethylene ether glycol, comprising the steps of: contacting a biochemically-derived L 3 -propanediol with an acid polymerization catalyst to produce a polytrimethylene ether glycol, characterized in that the hydrazine, 3_ 5 〇 / 5 丙 of propylene glycol: 6. 〇 - 7.5 and contains 1 〇〇 microgram / gram or less of carbonyl compound, 1 〇 microgram / gram or less based on the weight of 1,3 propylene glycol a peroxy compound and a monofunctional alcohol compound of 100 μg/g or less; and the polytrimethylene ether glycol has a color of less than 50 APHA. The method of claim 1 or 11, wherein the 153-propane: alcohol has a color lower than 1 〇 APHA ^ a polytrimethylene ether diol by providing 1,3-propanediol and a polymerization catalyst and using the polymerization catalyst Prepared by polymerizing hydrazine, 3· propylene glycol to form polytrimethylene ether monool, wherein the hydrazine, 3-propylene glycol comprises a carbonyl compound of 100 μg/g or less based on the weight of 1,3-propanediol, 10 μg / Δg or less peroxy compound and 1 〇〇 microgram / gram or less of a monofunctional alcohol compound. The polytrimethylene ether glycol of claim 13, wherein the hydrazine, 3-propylene glycol is a biochemically derived 1,3-propanediol prepared from a carbohydrate of renewable origin. The polytrimethylene ether glycol of claim 13, wherein the polytrimethylene ether glycol has a molecular weight of from 250 to 5,000 and a color of less than 30 Å.