Novel linked esters of polylactic acid and polyglycolic acid and compositions thereof

Abstract

Acid-linked esters of polylactic acid (including polyethylene glycol esters of polylactic acid) are disclosed. Exemplary linked esters of polylactic acid can be used as textile finishes. Methods for producing linked esters of polylactic acid directly and / or via transesterification are also disclosed.

Description

[Technical Field]

[0001] This international application claims the benefit of pending U.S. patent application Ser. No. 62 / 740,944 (filed October 3, 2018) directed to novel linked esters of polylactic acid and polyglycolic acid and compositions thereof, and pending U.S. patent application Ser. No. 62 / 828,961 (filed April 3, 2019) directed to novel linked esters of polylactic acid and polyglycolic acid and compositions thereof, each of which is incorporated herein in its entirety.

[0002] The present invention relates to novel linked esters of polylactic acid and polyglycolic acid containing couplers, and to a method for making the novel linked esters. The present invention also relates to compositions containing the novel linked esters. [Background technology]

[0003] High molecular weight polymers such as polyesters and polyolefins are commonly used to manufacture fibers and fiber articles such as yarns, fabrics, and nonwovens. The surfaces of articles made from polyesters and polyolefins are hydrophobic by their chemical nature. In many applications, it is desirable for the surfaces of the articles to be hydrophilic. Topical coatings or finishes are often used on polyester and polyolefin articles to counteract their hydrophobicity and impart hydrophilic properties. Polyolefin andPolyesters such as polylactic acid ("PLA") are used in many products, including absorbent products such as diapers. Because polylactic acid can be derived from renewable sources such as corn instead of petroleum, polylactic acid is compostable and biodegradable. Polylactic acid has properties similar to polypropylene ("PP"). Polylactic acid can be used in place of polypropylene and other non-biodegradable plastics, which are produced from non-renewable petroleum. Due to concerns about the toxicity of low molecular weight compounds used in consumer products, low molecular weight esters of polylactic acid (polymers) that may have advantageous properties may not be approved or permitted for use. Therefore, it would be beneficial to overcome the toxicity issues so that low molecular weight esters could be used. Summary of the Invention

[0004] Applicants have discovered that esters of polylactic acid ("PLA") can form high molecular weight esters of PLA ("linked esters of PLA" or "linked esters"), yet can provide advantageous properties to fibers and fabrics made from the fibers comparable to those of unlinked, low molecular weight esters of PLA ("unlinked esters of PLA"). Linked esters of PLA, such as PEG-linked esters of PLA, can be compostable and / or biodegradable and thus can be useful with PLA polymers to produce compostable and / or biodegradable products. Esters of polyglycolic acid ("PGA") can also be linked together to form high molecular weight esters ("linked esters of PGA"), yet can provide advantageous properties to fibers and fabrics made from the fibers comparable to those of unlinked, low molecular weight esters of PGA ("unlinked esters of PGA").

[0005] In one aspect, the present invention relates to linked esters of polylactic acid. In one embodiment, the linked ester of polylactic acid can comprise a diol, such as polyethylene glycol ("PEG") or 1,3 propanediol. In other embodiments, the linked ester of PLA can comprise a polyol, such as polyglycerol, a sugar, and a sugar alcohol. In other embodiments, the linked ester can comprise a combination of one or more diols. In other embodiments, the linked ester can comprise a combination of one or more polyols. In yet other embodiments, the linked ester can comprise a combination of one or more diols and one or more polyols.

[0006] In another aspect, the present invention relates to linked esters of PGA. In one embodiment, the linked esters of PGA can comprise a diol, such as polyethylene glycol ("PEG") or 1,3 propanediol. In other embodiments, the linked esters of PGA can comprise a polyol, such as polyglycerol, sugar, and sugar alcohol. In yet other embodiments, the linked esters can comprise a combination of one or more diols. In other embodiments, the linked PGA esters can comprise a combination of one or more polyols. In still other embodiments, the linked PGA esters can comprise a combination of one or more diols and one or more polyols.

[0007] In another aspect, the present invention relates to a method for producing linked esters of PLA (i.e., producing chemical compounds containing reaction products). Such esters of PLA can be produced by reacting (i) diols and / or polyols, (ii) polylactic acid, lactide, or lactic acid, and (iii) a carboxylic acid (or "coupler"). A mixture or blend of diols and / or polyols can also be reacted with polylactic acid, lactide, or lactic acid to produce linked esters of PLA. Optionally, an alcohol (e.g., an aliphatic C1-C14 alcohol) can be added to the reactants.

[0008] In another aspect, the present invention relates to a method for preparing esters of PGA (i.e., producing chemical compounds containing reaction products). Such esters of polyglycolic acid can be prepared by reacting (i) a diol and / or polyol, (ii) a PGA or glycolic acid, and (3) a coupler. Mixtures or combinations of diols and / or polyols can also be reacted with PGA or glycolic acid to form linked esters of PGA. Optionally, an alcohol (e.g., an aliphatic C1-C14 alcohol) can be added to the reactants.

[0009] In another aspect, the invention relates to textiles treated with compositions containing linked esters of PLA and / or PGA. Linked esters of polylactic acid and polyglycolic acid can be compostable and / or biodegradable and are therefore useful with polylactic acid polymers to make compostable and / or biodegradable products. DETAILED DESCRIPTION OF THE INVENTION

[0010] In one aspect, the present invention relates to esters of PLA coupled together with an acid (e.g., an acid coupler). Suitable acids that can be coupled together (coupled) esters of PLA include dicarboxylic acids (e.g., succinic acid, malonic acid, glutaric acid, and / or adipic acid), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, and / or 2,6-naphthalenedicarboxylic acid), and tricarboxylic acids (e.g., citric acid, aconitic acid, and / or trimesic acid). The coupled esters of PLA can include at least PLA-PEG-coupler-PEG-PLA ester, PLA-PEG-coupler-PEG-PLA ester, PEG-PLA-coupler-PLA-PEG, and PEG-PLA-coupler-PEG-PLA-coupler-PEG-PLA.

[0011] In another embodiment, the present invention provides a PGA coupled with an acid (e.g., an acidic coupler). Regarding esters, suitable acids that can be used to link esters of PGA include dicarboxylic acids (e.g., succinic acid, malonic acid, glutaric acid, and / or adipic acid), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, and / or 2,6-naphthalenedicarboxylic acid), and tricarboxylic acids (e.g., citric acid, aconitic acid, and / or trimesic acid). The linked esters of PGA can include at least PGA-PEG-coupler-PEG-PGA ester, PGA-PEG-coupler-PEG-PGA ester, PEG-PGA-coupler-PGA-PEG, and PEG-PGA-coupler-PEG-PGA-coupler-PEG-PGA.

[0012] In another aspect, the present invention relates to compositions comprising linked esters of PLA. These compositions comprise: Polyolefin and The PLA linking esters can be used as finishes for textiles made from polyesters such as PLA. The PLA linking esters can also be beneficially used as finishes for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and man-made fibers (e.g., acetate, lyocell, and rayon). The PLA linking esters can also be beneficially used on natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). The PLA linking esters and compositions containing the PLA linking esters can coat the surface of hydrophobic materials, such as textiles made from PLA and / or polypropylene, and can change the surface of the material from hydrophobic to hydrophilic, or, if the material is already hydrophilic, increase the hydrophilicity of the material. Accordingly, another aspect of the present invention is a material to which one or more PLA linking esters are applied.

[0013] In another aspect, the present invention relates to compositions comprising linked esters of PGA. These compositions comprise: Polyolefin andThe PGA-linked esters can be used as finishes for textiles made from polyesters such as PGA. The PGA-linked esters can also be beneficially used as finishes for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and man-made fibers (e.g., acetate, lyocell, and rayon). The PGA-linked esters can also be beneficially used on natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). The PGA-linked esters and compositions containing the PGA-linked esters can coat the surface of hydrophobic materials, such as textiles made from PGA and / or polypropylene, and can change the surface of the material from hydrophobic to hydrophilic, or, if the material is already hydrophilic, increase the hydrophilicity of the material. Accordingly, another aspect of the present invention is a material to which one or more PGA-linked esters are applied.

[0014] In another aspect, the present invention relates to compositions comprising linked esters of PLA. These compositions comprise: Polyolefin and The PLA linking esters can be beneficially used as finishes for textiles made from polyesters such as PLA. The PLA linking esters can also be beneficially used as finishes for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and man-made fibers (e.g., acetate, lyocell, and rayon). The PLA linking esters can also be beneficially used on natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). The PLA linking esters and compositions containing the PLA linking esters can coat the surface of hydrophobic materials, such as textiles made from PLA and / or polypropylene, and can change the surface of the material from hydrophobic to hydrophilic, or, if the material is already hydrophilic, increase the hydrophilicity of the material. Accordingly, another aspect of the present invention is a material to which one or more PLA linking esters are applied.

[0015] In another aspect, the present invention relates to compositions comprising linked esters of PLA and / or PGA. These compositions comprise: Polyolefin and PLA etc. The PLA linking esters can be advantageously used as finishes for textiles made from polyesters such as polyesters. The PLA linking esters can also be advantageously used as finishes for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and man-made fibers (e.g., acetate, lyocell, and rayon). The PLA linking esters can also be advantageously used on natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). The PLA linking esters and compositions containing the PLA linking esters can coat the surface of hydrophobic materials, such as textiles made from PLA and / or polypropylene, and can change the surface of the material from hydrophobic to hydrophilic, or, if the material is already hydrophilic, can increase the hydrophilicity of the material. Accordingly, another aspect of the present invention is a material to which one or more PLA linking esters are applied.

[0016] In one embodiment, nonwoven materials can be used, such as spunbond, meltblown, carded, airlaid, wetlaid, or combinations thereof. Examples of nonwoven materials include polyester topsheets for diapers. In other embodiments, textiles can be woven or knitted (e.g., clothing, including sportswear). Textiles include fibers, filaments, yarns, woven fabrics, nonwovens, and knitted fabrics.

[0017] In one embodiment, the ester of PLA comprises one or more polyols and an ester of PLA. As used herein, the term "polyol" can include, without limitation, compounds having more than one hydroxyl group, for example, two hydroxyl groups (also referred to herein as diols) and / or three or more hydroxyl (-OH) groups.

[0018] Diols include, without limitation, C2-C20, e.g., C2-C3, C2-C4, C2-C5, C2-C6, C2-C7, C2-C8, C2-C9, etc., linear, branched, and / or cyclic diols, and / or polymers thereof (e.g., polyethers). Examples of diols include, without limitation, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, PEG, polypropylene glycol (PPG), etc., and / or combinations and / or mixtures thereof. In one embodiment, the PEG can include a single capped PEG.

[0019] Polyols having three or more hydroxyl groups include, without limitation, C3-C20, e.g., C3-C4, C3-C5, C3-C6, C3-C7, C3-C8, C3-C9, etc., linear, branched, and / or cyclic polyols, and / or polymers thereof (e.g., polyethers). Examples of polyols having three or more hydroxyl groups include, without limitation, glycerol and / or its polymers (e.g., triglycerol, pentaglycerol, and / or decaglycerol), sugar alcohols, sugars, etc., and / or combinations and / or mixtures thereof. Examples of sugar alcohols include, without limitation, erythritol, threitol, arabitol, ribitol, xylitol, mannitol, sorbitol, galactitol, iditol, volemitol, fucitol, maltitol, lactitol, isomalt, etc., and / or mixtures and / or combinations thereof. Examples of sugars include, without limitation, monosaccharides and / or disaccharides, such as glucose, fructose, galatose, sucrose, lactose, maltose, and the like, and / or combinations and / or mixtures thereof.

[0020] Thus, in one embodiment, the linked ester of PLA comprises a linked PEG ester of PLA. In another embodiment, the linked ester of PLA comprises a linked 1,3 propanediol ester of PLA. In yet another embodiment, the linked ester of PLA comprises a linked polyol (e.g., polyglycerol, sugar, and / or sugar alcohol) ester of PLA. In further embodiments, the linked ester of PLA can comprise two or more of the following linked esters of PLA: a linked PEG ester of PLA, a linked 1,3 propanediol ester of PLA, a linked polyol ester of PLA, and / or combinations thereof. The linked ester of PLA can comprise a linked ester made by reacting (i) a diol (e.g., PEG or 1,3 propanediol) and / or a polyol (e.g., glycerol, e.g., tri-, penta-, or deca-glycerol), or a sugar, or a sugar alcohol, with (ii) PLA, lactide, or lactic acid. The lactide can be D-, L-, or DL-lactide. Thus, the linked ester of PLA can include a PEG-linked ester of PLA, a glycerol-linked ester of PLA, a 1,3 propanediol-linked ester of PLA, a sugar-linked ester of PLA, and a sugar alcohol-linked ester of PLA. In another embodiment, the linked ester of PLA includes a PEG-linked ester of PLA. In another embodiment, the composition includes a glycerol-linked ester of PLA. In another embodiment, the composition includes a 1,3 propanediol-linked ester of PLA. In another embodiment, the composition includes a sugar-linked ester of PLA. In another embodiment, the composition includes a sugar alcohol-linked ester of PLA. In another embodiment, the linked ester of PLA can include a combination of two or more of a PEG-linked ester of PLA, a glycerol-linked ester of PLA, a 1,3 propanediol-linked ester of PLA, a sugar-linked ester of PLA, and a sugar alcohol-linked ester of PLA. The composition can include water and / or another solvent along with one or more of the linked esters of PLA to provide a textile finish.

[0021] In another aspect, the present invention relates to a method for producing a linked ester of PLA. In one embodiment, the linked ester of PLA can be made by reacting (i) a diol (as described above, which can include, without limitation, PEG or 1,3 propanediol) and / or a polyol (as described above, which can include, without limitation, polyglycols, polyglycerols, including tri-, penta-, or deca-glycerol), or a sugar or sugar alcohol, (ii) a coupler, and (iii) PLA, lactic acid, and / or lactide. The reaction can be carried out by heating the reactants in the presence of a catalyst. The catalyst can be a basic catalyst (e.g., sodium carbonate and / or calcium carbonate). The catalyst can also be a Lewis acid catalyst, such as stannous octoate. The reaction can be carried out without a catalyst. The reaction is carried out at a temperature sufficient to melt the PLA and initiate the reaction to form the linked ester of PLA. The temperature to initiate the reaction between PEG and PLA can be between 140°C and 200°C, but the temperature required to melt the PLA is at least about 160°C. Therefore, the reaction between PEG and PLA can be carried out at temperatures between 160°C and 200°C or 170°C and 190°C. A solvent can be used to dissolve the diol and / or polyol, or a combination of diol and polyol, to facilitate the reaction with PLA. Optionally, an alcohol (e.g., an aliphatic C1-C14 alcohol, such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, or a C8C10 alcohol) can be added to the reactants. Typically, the alcohol is added to the reactants before the reaction begins. Alternatively, the alcohol can be added after the reaction begins. Adding an alcohol can advantageously produce a PLA ester with a higher pH to partially offset the effect of the acid on the pH of the PLA ester. The aliphatic alcohol can be added in an amount 1 to 2 times the amount of the diacid coupler.

[0022] The weight percentage of the initial PLA to the diols and / or polyols of the reactants can be 25-75 percent PLA and 75-25 percent diols and / or polyols, 30-70 percent PLA and 70-30 percent diols and / or polyols, 35-65 percent PLA and 65-35 percent diols and / or polyols, 40-60 percent PLA and 60-40 percent diols and / or polyols, or 45-55 percent PLA and 55-45 percent diols and / or polyols. In one embodiment, the initial weight percentage of PLA is greater than 50 percent of the reactants, and therefore the initial weight percentage of the diols and / or polyols is less than 50 percent of the reactants. The initial weight percent PEG to PLA ratio (PEG:PLA) can be 75:25 to 25:75, 70:30 to 30:70, 65:35 to 35:65, or 60:40 to 40:60. The initial molar ratio of acid coupler to polyethylene glycol can be 0.2 to 1.0, such as 0.4 to 1.0 (e.g., 0.4 to 0.8). The reaction temperature is typically 160°C to 200°C or 170°C to 190°C.

[0023] The reaction time required to provide a sufficient yield of linked esters of PLA can vary based on the molecular weight of the PLA, diol, and / or polyol, the reaction temperature and pressure, the use of a catalyst, and, in the case of direct esterification, the rate of water removal during the reaction. The reaction time must be sufficient to achieve adequate conversion of PLA to PLA esters to provide a clear, stable emulsion with water. The color of the emulsion can be less than 4, e.g., less than 3 (e.g., less than 2) on the Gardner color scale. The reaction time can be 1 to 10 hours, 2 to 6 hours, or 3 to 5 hours after the temperature reaches the melting point of PLA. Typically, the reaction is continued until a clear to cloudy mass is formed, indicating substantial completion of polylactic acid ester formation (i.e., until the conversion of PLA to PLA ester exceeds 75, 80, 85, 90, or 95 percent).

[0024] When PEG and PLA are reacted with a coupler, esters formed by the reaction (for example, representative reaction products) include esters having the following formula: [ka] JPEG0007795197000002.jpg202170

[0025] For representative esters having the above formula, n can be an integer greater than 1 and less than 90, 80, 70, 60, 50, 40, 30, 20, 10, or 5, and a, b, o, r, s, x, y, and z can be integers greater than 1 and less than 10 or greater than 1 and less than 5. The integers a, b, n, o, r, s, x, y, and z can be equal or unequal.

[0026] PLA is made from renewable materials such as corn, sugarcane, sugar beet, and cassava. The PLA that can be used is not limited by molecular weight, but by weight average molecular weight. Molecular mass (M w) can be (e.g., 10,000 to 150,000 daltons (g / mol)). PEG is typically produced from petroleum, but can also be produced from all-natural renewable materials such as corn, sugarcane, sugar beet, and cassava. Thus, the linked esters of PLA can be made from all-natural renewable materials and are compostable and / or biodegradable. The weight-average molecular weight of the PEG units in the linked esters of PLA can be 100 to 5000 daltons, 100 to 4000 daltons, 100 to 2000 daltons, 100 to 1000 daltons, 100 to 800 daltons, and 100 to 600 daltons. In one embodiment, the weight-average molecular weight is about 400 daltons. The weight average molecular weight of the attached PEG ester of the PLA can be less than 5000 daltons, less than 4000 daltons, less than 3000 daltons, less than 2000 daltons, less than 1000 daltons, less than 975 daltons, less than 950 daltons, less than 900 daltons, less than 800 daltons, less than 700 daltons, less than 600 daltons, less than 500 daltons, or less than 400 daltons. The weight average molecular weight of the linked ester of PLA made by reacting a diol or polyol with PLA can be less than 5000 daltons, less than 4000 daltons, less than 3500 daltons, less than 3000 daltons, less than 2500 daltons, less than 2000 daltons, less than 1500 daltons, less than 1000 daltons, less than 975 daltons, less than 950 daltons, less than 900 daltons, less than 800 daltons, less than 700 daltons, less than 600 daltons, less than 500 daltons, or less than 400 daltons.

[0027] In one embodiment, the linked ester of PGA comprises a linked PEG ester of PGA. In another embodiment, the linked ester of PGA comprises a linked 1,3 propanediol ester of PGA. In yet another embodiment, the linked ester of PGA comprises a linked polyol (e.g., polyglycerol, sugar, and / or sugar alcohol) ester of PGA. In further embodiments, the linked ester of PGA can comprise two or more of the following linked esters of PGA: a linked PEG ester of PGA, a linked 1,3 propanediol ester of PGA, a linked polyol ester of PGA, and / or combinations thereof. The linked ester of PGA can include a linked ester made by reacting (i) a diol (e.g., PEG or 1,3 propanediol) and / or a polyol (e.g., glycerol, such as tri-, penta-, or deca-glycerol), or a sugar, or a sugar alcohol, with (ii) polyglycolic acid or glycolic acid. Optionally, an alcohol (e.g., an aliphatic C1-C14 alcohol, such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, or a C8C10 alcohol) can be added to the reactants. Typically, the alcohol is added to the reactants before the reaction begins. Alternatively, the alcohol can be added after the reaction begins. The addition of the alcohol can advantageously partially offset the effect of the acid on the pH of the PGA ester, thereby producing a PGA ester with a higher pH. The aliphatic alcohol can be added in an amount 1 to 2 times the amount of the diacid coupler.

[0028] Thus, the linked ester of PGA can include a PEG-linked ester of PGA, a glycerol-linked ester of PGA, a 1,3-propanediol-linked ester of PGA, a sugar-linked ester of PGA, and a sugar alcohol-linked ester of PGA. In another embodiment, the linked ester of PGA includes a PEG-linked ester of PGA. In another embodiment, the composition includes a glycerol-linked ester of PGA. In another embodiment, the composition includes a 1,3-propanediol-linked ester of PGA. In another embodiment, the composition includes a sugar-linked ester of PGA. In another embodiment, the composition includes a sugar alcohol-linked ester of PGA. In another embodiment, the linked ester of PGA can include a combination of two or more of a PEG-linked ester of PGA, a glycerol-linked ester of PGA, a 1,3-propanediol-linked ester of PGA, a sugar-linked ester of PGA, and a sugar alcohol-linked ester of PGA. The composition can include water and / or another solvent along with one or more linked esters of PGA to provide a textile finish.

[0029] The initial PGA to diol and / or polyol weight percentages of the reactants can be 25 to 75 percent PGA and 75 to 25 percent diol and / or polyol, 30 to 70 percent PGA and 70 to 30 percent diol and / or polyol, 35 to 65 percent PGA and 65 to 35 percent diol and / or polyol, 40 to 60 percent PGA and 60 to 40 percent diol and / or polyol, and 45 to 55 percent PGA and 55 to 45 percent diol and / or polyol. In one embodiment, the initial weight percentage of PGA is greater than 50 percent of the reactants, and therefore the initial weight percentage of diol and / or polyol is less than 50 percent of the reactants. The initial weight percent PEG to PGA ratio (PEG:PGA) can be 75:25 to 25:75, 70:30 to 30:70, 65:35 to 35:65, or 60:40 to 40:60. The reaction temperature is typically 160°C, and 200°C or 170°C to 190°C.

[0030] As described herein, the weight-average molecular weights of the linked esters of PLA and PGA can be determined by gel permeation chromatography (GPC) using a standard high-performance liquid chromatography (HPLC) system with a GPC column and evaporative light scattering detection (ELSD). The retention times of the standards are fitted to a calibration equation, and this equation is used to determine the weight-average molecular weight of the unknown polymer. The column used is a Jordi Gel DVB 500A (300 x 7.8 mm, catalog number 15071). The method is isocratic using tetrahydrofuran (THF) at 1 ml / min. The standard run time is 30 minutes, with most components eluting within 15 minutes. Detection is achieved using an evaporative light scattering detector (ELSD). The ELSD unit used is an Alltech 500 ELSD with an ELSD LTA accessory. The LTA unit is set to operate at 41°C. The ELSD unit drift tube was set at 70°C and the nitrogen gas flow rate was set at 1.84 SLPM. In accordance with the above, accompanying Figure 1 shows a representative calibration equation used to determine the weight average molecular weight of a polymer.

[0031] [Figure 1] TIFF0007795197000003.tif136170

[0032] In another aspect, the present invention relates to a method for producing a linked ester of PGA. In one embodiment, the linked ester of the present invention can be prepared by reacting (i) a diol (e.g., PEG or 1,3 propanediol) and / or a polyol (e.g., polyglycol, polyglycerol including tri-, penta-, or deca-glycerol), or a sugar, or a sugar alcohol, (ii) a coupler, and (iii) PGA, glycolic acid, and / or poly(lactic-co-glycolic) acid. The reaction can be carried out by heating the reactants in the presence of a catalyst. The catalyst can be a basic catalyst (e.g., sodium carbonate and / or calcium carbonate). The catalyst can also be a Lewis acid catalyst such as stannous octoate. The reaction can be carried out without a catalyst. The reaction is carried out at a temperature sufficient to melt the PGA and initiate the reaction to form the linked ester of PGA. The temperature to initiate the reaction between PEG and PLA can be from 140°C to 200°C, but the temperature required to melt the PGA is at least about 160°C. Thus, the reaction between PEG and PGA can occur between 160° C. and 200° C., or between 170° C. and 190° C. To facilitate the reaction with PGA, a solvent can be used to dissolve the diol and / or polyol, or a combination of diol and polyol.

[0033] In another embodiment, the linking esters of the present invention can be prepared by direct esterification by reacting (i) a diol (e.g., PEG or 1,3 propanediol) and / or a polyol (e.g., glycerol, such as tri-, penta-, or deca-glycerol), or a sugar, or a sugar alcohol, with (ii) lactide, a lactide intermediate, or lactic acid, and a coupler. The lactide can be D-lactide, L-lactide, and / or DL-lactide. To facilitate the reaction with lactide, a lactide intermediate, or lactic acid, a solvent can be used to dissolve the diol or polyol, or a combination of diols and / or polyols. The reaction can occur in the presence of an inorganic acid (e.g., sulfuric acid or dry hydrogen chloride), which acts as a catalyst to accelerate the reaction and remove water. Water removal can also be achieved, for example, by contacting the reaction mixture with an inert or dry gas (e.g., nitrogen) that does not interfere with the reaction, for example, by stirring, and / or by distilling the reaction product.

[0034] Table 1 (below) identifies representative PEG esters of polylactic acid and linked PEG esters of polylactic acid made along with the components (i.e., reactants) used to make the esters and linked esters (i.e., typical reaction products), along with the component input ratios, properties of the esters and linked esters, and GPC results for the esters and linked esters.

[0035] [Table 1] TIFF0007795197000005.tif217170

[0036] In another aspect of the invention, the linked ester of PLA can be combined with other compounds or compositions that do not contain the linked ester of PLA to form a finish (i.e., a finish composition). The weight percent of the linked ester of PLA in the finish can be 0.1 to 99.9 percent or 5 to 95 percent of the weight of the linked ester of PLA. Examples of other compounds and / or compositions include water, lubricants, emulsifiers, antistatic agents, flocculants, These include antioxidants, corrosion inhibitors, viscosity modifiers, wetting agents, biocides, pH adjusters, soil release agents, and antifouling agents. Representative lubricants include PEG fatty acid esters, ethoxylated fatty acids, ethoxylated triglycerides, glycerol esters, sorbitan esters, and alkyl esters, other than the linked ester of PLA, derived from mineral, vegetable, and / or animal oils, and / or combinations thereof. Representative emulsifiers include nonionic agents (e.g., alkyl alcohol ethoxylates, alkylphenol ethoxylates, fatty amine ethoxylates, and fatty acid ethoxylates, and / or combinations thereof); cationic agents (e.g., quaternary fatty amines, quaternary fatty amine ethoxylates, quaternary imidazolines, and / or combinations thereof); and anionic agents (e.g., ethoxylated alkyl alcohol sulfates and phosphates, fatty acid soaps, and / or alkyl sulfosuccinate esters, and / or combinations thereof). Representative antistatic agents include nonionic agents (e.g., alcohol ethoxylates, alkylphenol ethoxylates, fatty amine ethoxylates, polyoxyalkylene glycols, ethers, and / or esters, and / or combinations thereof), cationic agents (e.g., quaternary amines, quaternary imidazolines, and / or combinations thereof), and anionic agents (e.g., alkyl alcohol sulfates and / or phosphates, and / or alkyl alcohol ethoxylate sulfates and / or phosphates, and / or combinations thereof).

[0037] A typical soil release formulation includes a permanent press resin, a catalyst for the permanent press resin, a wetting agent, a high-density polyethylene resin, a fluorinated soil release agent, and acetic acid. Typical weight percentages of the above compounds are 4.0 to 10.0 parts permanent press resin, 5.0 to 10.0 parts catalyst for the permanent press resin, 0.25 to 1.0 parts wetting agent, 3.0 to 6.0 parts high-density polyethylene resin, 5.0 to 10.0 parts fluorinated soil release chemical, and 0.0 to 0.25 parts acetic acid. PEG esters of PLA can be added to soil release formulations containing a fluorinated soil release chemical relative to the soil release agent, so that the soil release agent can be absorbed into fabrics more quickly (e.g., less than 10 seconds, less than 5 seconds, less than 4 seconds, less than 3 seconds, or less than 2 seconds) as determined by applying a drop to fabric, thereby reducing the time required to treat fabrics with the soil release agent. Furthermore, when a PEG ester of PLA is added to a soil release formulation containing a fluorochemical soil release chemical, the amount of fluorochemical can be reduced by 25, 50, or 75 percent, and the soil release agent still provides soil release results that are equivalent to or better than soil release agents containing a typical amount of fluorochemical (e.g., 5.0 to 10.0 weight percent) without the PEG ester of PLA.

[0038] The linked esters of PLA act as surfactants and can be used in personal care products, such as soaps, shampoos, and conditioners. Compositions containing linked esters of PLA can include other surfactants, such as all-natural polyglucosides.

[0039] In yet another aspect, the present invention relates to textiles treated with linking esters of PLA. Textiles treated with linking esters of PLA have improved surface properties, such as hydrophilicity. In one embodiment, the textile is a nonwoven fabric, such as spunbond, meltblown, carded, airlaid, wetlaid, and / or a combination thereof. In other embodiments, the textile is woven or knitted. In one embodiment, the textile is made from or includes polyester, such as PLA and / or polyethylene terephthalate. In other embodiments, the textile is made from or includes polypropylene. In other embodiments, the textile is made from or includes polyethylene. In other embodiments, the textile is made from or includes a combination of polypropylene and polyethylene. In other embodiments, the textile is made from polyamide, acrylic, aramid, and / or a combination thereof. In still further embodiments, the textile is made from or includes man-made fibers (e.g., acetate, lyocell, and rayon). In other embodiments, the textile is made from or includes natural fibers (e.g., bamboo, cotton, flax, hemp, wool, and / or combinations thereof). In other embodiments, the textile can be made from poly(ρ-phenylene-2,6-benzobisoxazole), also known as "PBO." In other embodiments, the textile can be made from polyetheretherketone, also known as "PEEK." In other embodiments, the textile is made from polyetherketoneketone, also known as "PEKK." When applied to textiles, the linked esters of PLA provide improved wetting properties (e.g., relatively fast and multiple strikethrough times and / or relatively low rewet (or wetback)).

[0040] Compositions including the linked esters of PLA of the present invention can provide a single liquid strikethrough time of 5 seconds or less, 4 seconds or less, or 3 seconds or less for 15 grams per square meter (gsm) spunbond nonwoven fabrics made from polypropylene or PLA, as determined by EDANA (European Disposable and Nonwoven Association) and INDA (Nonwovens Industry Association) Standard Test: WSP 070.3.R3(12) for Nonwoven Liquid Strikethrough Time, which is incorporated herein by reference. Compositions including linking esters of PLA of the present invention can provide multiple or repeated liquid strikethrough times of 5 seconds or less, or 4 seconds or less for the first three strikethroughs on 15 gsm PLA or polypropylene spunbond nonwoven fabrics, as determined by Standard Test: WSP 070.7.R4(12) for Repeated Liquid Strikethrough Times, which is incorporated herein by reference.

[0041] Compositions containing the linking esters of PLA of the present invention can also provide a rewet of at least 0.25 grams or less for a 15 gsm PLA spunbond nonwoven, as determined by Standard Test: WSP 080.10.R3(12) for Nonwoven Coverstock Wetbacks, which is incorporated herein by reference. Compositions containing one or more linking esters of PLA typically include water such that the weight percent of the one or more linking esters of PLA in the composition can be 0.1 to 10.0 weight percent, 0.1 to 5.0 weight percent, and 0.1 to 1.0 weight percent of the one or more linking esters of PLA.

[0042] Compositions containing linked esters of PLA can provide finishes such as bleaching, scouring, hydrophilic, antistatic, soil release (or stain release), stain resistant, and anti-abrasion finishes, and / or combinations thereof. In one embodiment, the PEG-linked esters of PLA used in these finishes are commercially available PEG 200, PEG 300, PEG 400, PEG 500, PEG 600, PEG 700, PEG 800, PEG 900, PEG 1000, PEG 1100, PEG 1200, PEG 1300, PEG 1400, PEG 1500, PEG 1600, PEG 1700, PEG 1800, PEG 1900, PEG 2000, PEG 2100, PEG 2200, PEG 2300, PEG 2400, PEG 2500, PEG 2600, PEG 2700, PEG 2800, PEG 2900, PEG 3000, PEG 3100, PEG 3200, PEG 3300, PEG 3400, PEG 3500, PEG 3600, PEG 3700, PEG 3800, PEG 4000, PEG 4100, PEG 4200, PEG 4300, PEG 4400, PEG 4500, PEG 4600, PEG 4700, PEG 4800, PEG 4900, PEG 5000, PEG 5100, PEG 5200, PEG 5300, PEG 5400, PEG 5500, PEG 5600, PEG 5 The PEG-linked ester of PLA can be made from PEG 400, PEG 600, PEG 800, PEG 1000, PEG 1200, PEG 1400, PEG 1450, and / or mixtures thereof. The PEG-linked ester of PLA can also be made from PEGs having molecular weights of 100-1000, 200-800, and 300-700. The PEG-linked PEG ester of PLA can have a PEG:PLA ratio of 30:70 to 70:30, 40:60 to 60:40, and 45:55 to 55:45. In a preferred embodiment, the PEG-linked ester of PGA is made from PEG 400, and the PEG:PGA ratio is 50:50. PEG esters of PGA, i.e., PEG 400 ester of PGA with a PEG:PGA ratio of 44:56, PEG 200 ester of PGA with a PEG:PGA ratio of 50:50, PEG 400 ester of PGA with a PEG:PGA ratio of 50:50, PEG 600 ester of PGA with a PEG:PGA ratio of 50:50, and PEG 1450 ester of PLA with a PEG:PGA ratio of 50:50, have favorable smoke and flash point properties (e.g., smoke is 171 o F and ignition temperature is 244°C. oF) and favorable friction characteristics. For example, the stain release finish can include a PEG ester of PLA, such as those identified above, an oil / water repellent, a wetting / wicking agent, and a hydrophilic binder. In one embodiment, the stain release finish includes an ester of PLA, a permanent press resin, a catalyst for the permanent press resin, a wetting agent, a high-density polyethylene resin, a fluorinated stain release chemical, and / or an acid for pH adjustment (e.g., acetic acid, citric acid, or glycolic acid). The addition of an ester of PLA can reduce the amount of expensive fluorinated stain release chemical required by 10 percent, 20 percent, 30 percent, 40 percent, 50 percent, or 60 percent while providing comparable or improved stain release results. The addition of an ester of PLA improves droplet reflectance. One liter of stain release finish can include 1 to 40 grams, 1 to 30 grams, 1 to 20 grams, 1 to 15 grams, or 1 to 10 grams of a PEG ester of PGA. Two liters of finish can contain twice the amount of PEG ester of PGA in one liter, and three liters of finish can contain three times the amount of PEG ester of PLA in one liter.

[0043] The composition comprising a linked ester of PLA and / or a linked ester of PGA is applied by roll coating, padding, dripping, or spraying to the textile in an amount that provides the desired strike-through and / or rewet properties. Coating For example, compositions containing esters of PLA can be applied to provide FOY (a finish on yarn) levels of 0.1 to 10.0 weight percent, 0.2 to 3.0 weight percent, 0.3 to 1.0 weight percent, and 0.3 to 0.8 weight percent. Accordingly, another aspect of the present invention is a textile treated with one or more esters of PLA as described above, or a composition containing one or more esters of PLA as described above.

[0044] The results of tests comparing conventional soil release formulations without bound PEG esters of PLA and soil release formulations containing PEG esters of PLA are shown in Tables 2b-2c, 3b-3c, 4b-4c, 5b-5d, 6b-6d, and 7b-7d below. The soil release formulations containing PEG esters of PLA and linked esters of PLA were tested on 100% polyester, polyester / cotton blends (65:35 poly / cotton), and nylon fabrics. The results were compared with Nonax® MM, a conventional polyester copolymer used as a release agent sold by Pulcra Chemicals.

[0045] Polyester copolymers are used to impart water absorption or wicking properties to synthetic fibers, particularly for apparel and sportswear. They are also said to improve the soil release properties of fabrics. PEG esters of PLA were also tested to determine whether they improve the static electricity of textiles. Three esters of PLA were compared to a common polyester copolymer finish sold by Pulcra Chemicals LLC under the trade name Nonax® MM. Nonax® MM and the PEG ester of PLA were applied to fabrics by padding, then dried and allowed to cure. The formulations were applied to 100% polyester woven fabric, 65 / 35 polyester / cotton woven fabric, and 100% nylon woven fabric. To measure water wicking, one end of a strip of treated fabric was immersed in water and the water was allowed to wick into the fabric. The more water the fabric wicked, the better the wicking properties. The distance the water was wicked by the fabric was measured in millimeters ("mm"). The same test procedure was used for soil release described above in the wicking soil release experiment. When measuring the wicking properties of the esters of PLA in the soil release agent, the following soil release agent formulation was padded, then dried and cured on the fabric at 177°C.

[0046] The soil release formulations and test results are set out in several tables (below), where higher numbers correspond to better soil release performance.

[0047] [Table 2a]

[0048] [Table 2b]

[0049] [Table 2c]

[0050] [Table 2d]

[0051] [Table 3a]

[0052] [Table 3b]

[0053] [Table 3c]

[0054] [Table 4a]

[0055] [Table 4b]

[0056] [Table 4c]

[0057] [Table 4d]

[0058] The wicking and soil release tests were repeated as described above for 100% polyester, 65% / 35% polyester / cotton, and 100% nylon. The results for 100% polyester are shown below in Tables 5b-5d. The pH of the soil release agents was adjusted to a pH of 4-5. The soil release agent tests were then repeated for 100% polyester as described above. The test results for wicking performance, soil release performance, and whiteness for the initial fabrics before washing, after five wash cycles, and after ten wash cycles are shown below in Tables 5a-5e. The pH of each soil release agent was adjusted to between pH 4-5.

[0059] [Table 5a]

[0060] [Table 5b]

[0061] [Table 5c]

[0062] [Table 5d]

[0063] [Table 5e]

[0064] The wicking and soil release agent tests were then repeated as described above for 65 / 35 percent polyester / cotton. The test results for wicking and soil release performance for the initial fabric before washing, the fabric after five wash cycles, and the fabric after 10 wash cycles are shown in Tables 6a-6d below. The pH of each soil release agent was adjusted to between pH 4 and 5.

[0065] [Table 6a]

[0066] [Table 6b]

[0067] [Table 6c]

[0068] [Table 6d]

[0069] [Table 7a]

[0070] [Table 7b]

[0071] [Table 7c]

[0072] [Table 7d]

[0073] The foregoing detailed description illustrates exemplary embodiments. The present disclosure is not limited to such exemplary embodiments. The present disclosure may utilize any of various aspects, features, or steps, or combinations thereof.

[0074] In the specification and / or drawings, example embodiments are disclosed. Unless otherwise indicated, specific terms are used in a generic and descriptive sense only and not for purposes of limitation.

[0075] The use of the term "and / or" includes any and all combinations of one or more of the associated listed items. With respect to ranges of temperatures, percentages, Daltons, etc. described above (e.g., in the form "between x and y"), "between" means "inclusive" such that the numbers provided in the range are included in the range (e.g., between 1 and 10 includes 1 and 10).

[0076] While various aspects, features, and embodiments have been disclosed herein, other aspects, features, and embodiments will be apparent to those skilled in the art. The various disclosed aspects, features, and embodiments are for illustrative purposes only and are not intended to be limiting. The scope of the present invention is intended to include at least the following claims and their equivalents.

Claims

1. Polyethylene glycol; with a dicarboxylic acid as a coupler; Polylactic acid; A compound comprising the reaction product of A material in which one or more compounds are applied by roll coating, padding, dripping, or spraying, wherein the weight average molecular weight of the compound is less than 5000 Da; The material is a nonwoven, woven or knitted material.

2. 10. The material of claim 1, wherein the polyethylene glycol has a weight average molecular weight of 124 to 1450 daltons as measured by gel permeation chromatography ("GPC").

3. 3. The material of claim 1, wherein the coupler comprises an aromatic dicarboxylic acid.

4. The material according to any one of claims 1 to 3, wherein the weight percent ratio of the polyethylene glycol to the polylactic acid is 80:20 to 20:

80.

5. The material of any one of claims 1 to 4, wherein the coupler is present in an amount of 0.2 to 1.0 molar equivalent relative to the polyethylene glycol.

6. The material of any one of claims 1 to 5, wherein the reaction product is biodegradable and / or compostable.

7. The material according to any one of claims 1 to 6, wherein the compound has one of the following formulae: 【Chemistry 1】 (In the above formula, n is an integer greater than 1 and less than 90, a, b, o, r, s, x, y, and z are integers greater than 1 and less than 10, and the integers a, b, n, o, r, s, x, y, and z may or may not be equal.) 8. The compound of claim 7, introducing the polyethylene glycol, the coupler, and the polylactic acid into a reaction vessel; reacting the polyethylene glycol, the coupler, and the polylactic acid at a temperature of 165°C to 200°C for 1 hour to 6 hours; By a manufacturing method including A method for producing a material according to any one of claims 1 to 7, comprising producing

9. The method for producing the compound comprises:

10. A method for making the material of claim 8, wherein the final reaction product when mixed with water provides a clear, colorless emulsion.

10. Use of the composition as a finish for textiles made from any of polyester, polyolefin, polyamide, acrylic, nylon, polypropylene, aramid, acetate, lyocell, rayon, bamboo, cotton, flax, hemp, and wool to increase the hydrophilicity of the material; The composition comprises at least one compound, the compound comprising: Polyethylene glycol; with a dicarboxylic acid as a coupler; Polylactic acid; A compound comprising the reaction product of The weight average molecular weight of the compound is less than 5000 Da.

11. 11. The use according to claim 10, wherein the finishing agent is a wetting agent, a soil release agent, an antistatic agent, a lubricant, an antifoaming agent or a scouring agent.

12. 12. The use according to claim 10 or 11, wherein the finishing agent is a soil release agent further comprising a fluorine-based compound.

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