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 U.S. Patent Application No. 62 / 740,944, filed Oct. 3, 2018, and U.S. Patent Application No. 62 / 828,961, filed Apr. 3, 2019, both of which are related to novel linking esters of polylactic acid and linking esters of polyglycolic acid and compositions thereof, and each of which is incorporated herein by reference in its entirety.

[0002] The present invention relates to novel linking esters of polylactic acid and linking esters of polyglycolic acid, including a coupler, and to methods of making the novel linking esters. The present invention also relates to compositions comprising the novel linking esters.

Background Art

[0003] High molecular weight polymers such as polyester and polyolefins are commonly used to manufacture fibers and textile articles such as yarns, cloths, and nonwovens. The surfaces of articles made from polyester and polyolefins are hydrophobic due to their chemical properties. In many applications, it is desirable for the surface of the article to be hydrophilic. Topical coatings or finishes are often used on polyester and polyolefin articles to counteract their hydrophobicity and impart hydrophilicity. Polyesters such as polylactic acid ("PLA") and polyolefins 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, it is compostable and biodegradable. Polylactic acid has similar properties to polypropylene ("PP"). Polylactic acid can be used as a substitute for polypropylene and other non-biodegradable plastics 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), which may have advantageous properties, may not be approved or permitted for use. Therefore, overcoming the toxicity issues would be beneficial in order to enable the use of low molecular weight esters. [Overview of the project]

[0004] The applicant has discovered that esters of polylactic acid ("PLA") can form high molecular weight esters of PLA ("linked PLA esters" or "linked esters"), which can provide advantageous properties for fibers and textiles made from these fibers, comparable to those of unlinked low molecular weight esters of PLA ("unlinked PLA esters"). Linked PLA esters, such as PEG-linked PLA esters, can be compostable and / or biodegradable, and can therefore be beneficial in conjunction with PLA polymers for producing compostable and / or biodegradable products. Esters of polyglycolic acid ("PGA") can also be linked together to form high molecular weight esters ("linked PGA esters"), which can provide advantageous properties for fibers and textiles made from these fibers, comparable to those of unlinked low molecular weight esters of PGA ("unlinked PGA esters").

[0005] In one embodiment, the present invention relates to linked esters of polylactic acid. In one embodiment, the linked ester of polylactic acid may include a diol, such as polyethylene glycol ("PEG") or 1,3-propanediol. In another embodiment, the linked ester of PLA may include a polyol, such as polyglycerol, sugars, and sugar alcohols. In yet another embodiment, the linked ester may include a combination of one or more diols. In yet another embodiment, the linked ester may include a combination of one or more polyols. In yet another embodiment, the linked ester may include a combination of one or more diols and one or more polyols.

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

[0007] In other embodiments, the present invention relates to a method for producing PLA-coupled esters (i.e., a chemical compound containing a reaction product). Such PLA-coupled esters can be produced by reacting (i) a diol and / or polyol, (ii) polylactic acid, lactide, or lactic acid, and (iii) a carboxylic acid (or "coupler"). A mixture or formulation of diols and / or polyols can also be reacted with polylactic acid, lactide, or lactic acid to produce PLA-coupled esters. Optionally, alcohols (e.g., aliphatic C1-C14 alcohols) can be added to the reactants.

[0008] In other embodiments, the present invention relates to a method for producing esters of PGA (i.e., producing chemical compounds containing reaction products). Such polyglycolic acid esters can be produced by reacting (i) a diol and / or polyol, (ii) PGA or glycolic acid, and (iii) a coupler. A mixture or combination of diols and / or polyols can also be reacted with PGA or glycolic acid to form a coupled ester of PGA. Optionally, an alcohol (e.g., an aliphatic C1-C14 alcohol) can be added to the reactants.

[0009] In other embodiments, the present invention relates to textiles treated with a composition containing linked esters of PLA and / or PGA. Linked esters of polylactic acid and polyglycolic acid can be made compostable and / or biodegradable and are therefore useful together with polylactic acid polymers to produce compostable and / or biodegradable products. [Modes for carrying out the invention]

[0010] In one embodiment, the present invention relates to esters of PLA that are coupled with an acid (e.g., an acid coupler). Suitable acids that can couple PLA esters together 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 coupling esters of PLA may 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 relates to a PGA that is coupled with an acid (e.g., an acid coupler) Regarding esters: Suitable acids that can be used to link PGA esters together 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). Linked PGA esters may include at least PGA-PEG-coupler-PEG-PGA esters, PGA-PEG-coupler-PEG-PGA esters, PEG-PGA-coupler-PGA-PEG, and PEG-PGA-coupler-PEG-PGA-coupler-PEG-PGA.

[0012] In other embodiments, the present invention relates to compositions comprising PLA linkage esters. These compositions can be used as finishing agents for textiles made from PLA and polyesters such as polyolefins. PLA linkage esters can also be usefully used as finishing agents for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and artificial fibers (e.g., acetate, liocell, and rayon). PLA linkage esters can also be usefully used for natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). PLA linkage esters and compositions comprising PLA linkage 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 embodiment of the present invention is a material to which one or more PLA linkage esters are applied.

[0013] In other embodiments, the present invention relates to compositions comprising PGA linkage esters. These compositions can be used as finishing agents for textiles made from PGA and polyesters such as polyolefins. PGA linkage esters can also be usefully used as finishing agents for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and artificial fibers (e.g., acetate, liocell, and rayon). PGA linkage esters can also be usefully used for natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). PGA linkage esters and compositions comprising PGA linkage 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, can increase the hydrophilicity of the material. Accordingly, another embodiment of the present invention is a material to which one or more PGA linkage esters are applied.

[0014] In other embodiments, the present invention relates to compositions comprising PLA linkage esters. These compositions can be usefully used as finishing agents for textiles made from PLA and polyesters such as polyolefins. PLA linkage esters can also be usefully used as finishing agents for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and artificial fibers (e.g., acetate, liocell, and rayon). PLA linkage esters can also be usefully used for natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). PLA linkage esters and compositions comprising PLA linkage 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 embodiment of the present invention is a material to which one or more PLA linkage esters are applied.

[0015] In other embodiments, the present invention relates to compositions comprising linked esters of PLA and / or PGA. These compositions can be usefully used as finishing agents for textiles made from PLA and polyesters such as polyolefins. Linked esters of PLA can also be usefully used as finishing agents for other synthetic polymers (e.g., polyamide, acrylic, nylon, polypropylene, and aramid) and artificial fibers (e.g., acetate, liocell, and rayon). Linked esters of PLA can also be usefully used for natural fibers (e.g., bamboo, cotton, flax, hemp, and wool). Linked esters of PLA and compositions comprising linked esters of PLA 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 embodiment of the present invention is a material to which one or more linked esters of PLA are applied.

[0016] In one embodiment, the material may be a nonwoven fabric such as spunbond, meltblown, carded, airlaid, wetlaid, or a combination thereof. An example of a nonwoven fabric is a polyester top sheet for diapers. In other embodiments, the fabric may be a woven or knitted fabric (e.g., clothing including sportswear). Fabrics include fibers, filaments, yarns, textiles, nonwovens, and knitted fabrics.

[0017] In one embodiment, the PLA ester comprises one or more polyols and the PLA ester. As used herein, the term “polyol” may 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 diols, such as C2-C3, C2-C4, C2-C5, C2-C6, C2-C7, C2-C8, C2-C9, linear, branched and / or cyclic diols, and / or polymers thereof (such as 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), and / or combinations and / or mixtures thereof. In one embodiment, PEG may 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 polymers thereof (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, treitol, arabitol, ribitol, xylitol, mannitol, sorbitol, galactitol, iditol, boremitol, fusitol, maltitol, lactitol, isomalt, etc., and / or mixtures and / or combinations thereof. Examples of sugars include monosaccharides and / or disaccharides, such as glucose, fructose, galatose, sucrose, lactose, maltose, etc., and / or combinations and / or mixtures thereof without limitation.

[0020] Accordingly, in one embodiment, the PLA linkage ester includes the PLA linkage PEG ester. In another embodiment, the PLA linkage ester includes the PLA linkage 1,3-propanediol ester. In yet another embodiment, the PLA linkage ester includes the PLA linkage polyol (e.g., polyglycerol, sugar, and / or sugar alcohol) ester. In further embodiments, the PLA linkage ester may include two or more of the following PLA linkage esters: the PLA linkage PEG ester, the PLA linkage 1,3-propanediol ester, the PLA linkage polyol ester, and / or a combination thereof. The PLA linkage ester may include a linkage ester produced by reacting (i) a diol (e.g., PEG or 1,3-propanediol), and / or a polyol (e.g., glycerol, e.g., tri-, pent-, or deca-glycerol), or a sugar, or a sugar alcohol with (ii) PLA, lactide, or lactic acid. The lactide may be D-, L-, or DL-lactide. Therefore, the PLA linkage ester may include PLA PEG linkage ester, PLA glycerol linkage ester, PLA 1,3-propanediol linkage ester, PLA sugar linkage ester, and PLA sugar alcohol linkage ester. In other embodiments, the PLA linkage ester may include PLA PEG linkage ester. In other embodiments, the composition may include PLA glycerol linkage ester. In other embodiments, the composition may include PLA 1,3-propanediol linkage ester. In other embodiments, the composition may include PLA sugar linkage ester. In other embodiments, the composition may include PLA sugar alcohol linkage ester. In other embodiments, the PLA linkage ester may include a combination of two or more of PLA PEG linkage ester, PLA glycerol linkage ester, PLA 1,3-propanediol linkage ester, PLA sugar linkage ester, and PLA sugar alcohol linkage ester. The composition may contain water and / or another solvent together with one or more PLA linkage esters to provide a finishing agent for textiles.

[0021] In other embodiments, the present invention relates to a method for producing PLA-linked esters. In one embodiment, the PLA-linked ester can be produced by reacting (i) a diol (which may contain an unlimited amount of PEG or 1,3-propanediol as described above) and / or a polyol (which may contain an unlimited amount of polyglycerol including polyglycol, tri-, penta-, or deca-glycerol as described above), 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 with a catalyst. The catalyst may be a basic catalyst (e.g., sodium carbonate and / or calcium carbonate). The catalyst may also be a Lewis acid catalyst such as stannous octanoate. 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 PLA-linked ester. The temperature to initiate the reaction between PEG and PLA may be 140°C to 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 between 170°C and 190°C. A solvent can be used to dissolve diols and / or polyols, or combinations of diols and polyols, to facilitate the reaction with PLA. In some cases, alcohols (e.g., methanol, ethanol, propanol, butanol, 2-ethylhexanol, C8C10 alcohols, and other aliphatic C1-C14 alcohols) can be added to the reactants. Typically, the alcohol can be added to the reactants before the start of the reaction, or it can be added after the start of the reaction. The addition of alcohol can be advantageous in producing a PLA ester with a higher pH, as it partially counteracts the effect of the acid on the pH of the PLA ester. Aliphatic alcohols can be added in amounts 1 to 2 times the amount of the diacid coupler.

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

[0023] The reaction time required to provide a sufficient yield of PLA-linked esters may vary depending on the molecular weight of PLA, diols and / or polyols, 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 in order to provide a clear and stable emulsion with water. The color of the emulsion, based on the Gardner color scale, may be less than 4, e.g., 3 or less (e.g., less than 2). The reaction time may be 1 to 10 hours, 2 to 6 hours, and 3 to 5 hours after the temperature reaches the melting point of PLA. Typically, the reaction is continued until a clear or cloudy mass is formed, indicating that the formation of the polylactic acid ester is substantially complete (i.e., until the conversion of PLA to PLA-ester exceeds 75, 80, 85, 90, or 95 percent).

[0024] When reacting PEG and PLA with a coupler, the esters formed by the reaction (e.g., typical reaction products) include esters having the following formula: [Chemical formula] JPEG2022509726000035.jpg202170

[0025] Regarding the typical esters having the foregoing 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 may or may not be equal.

[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 the molecular weight, and the weight average Molecular weight (M w) can be (e.g., 10,000 to 150,000 daltons (g / mol)). PEG is typically manufactured from petroleum, but can also be manufactured from all natural renewable materials such as corn, sugarcane, sugar beet and cassava. Thus, the linking 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 linking 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 linked PEG esters of PLA is 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 linking esters of PLA produced by reacting a diol or polyol with PLA is 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 PGA linkage ester includes the PGA linkage PEG ester. In another embodiment, the PGA linkage ester includes the PGA linkage 1,3-propanediol ester. In yet another embodiment, the PGA linkage ester includes the PGA linkage polyol (e.g., polyglycerol, sugar, and / or sugar alcohol) ester. In further embodiments, the PGA linkage ester may include two or more of the following PGA linkage esters: PGA linkage PEG ester, PGA linkage 1,3-propanediol ester, PGA linkage polyol ester, and / or combinations thereof. The PGA linkage ester may include a linkage ester produced 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. Depending on the circumstances, alcohols (e.g., methanol, ethanol, propanol, butanol, 2-ethylhexanol, C8C10 alcohols, and other aliphatic C1-C14 alcohols) may be added to the reactants. Typically, alcohols can be added to the reactants before the start of the reaction, or they can be added after the start of the reaction. The addition of alcohols can be advantageous in that it partially counteracts the effect of the acid on the pH of the PGA ester, resulting in the production of a PGA ester with a higher pH. Aliphatic alcohols can be added in amounts 1 to 2 times the amount of the diacid coupler.

[0028] Therefore, the PGA linkage ester may include PGA PEG linkage ester, PGA glycerol linkage ester, PGA 1,3-propanediol linkage ester, PGA sugar linkage ester, and PGA sugar alcohol linkage ester. In other embodiments, the PGA linkage ester may include PGA PEG linkage ester. In other embodiments, the composition may include PGA glycerol linkage ester. In other embodiments, the composition may include PGA 1,3-propanediol linkage ester. In other embodiments, the composition may include PGA sugar linkage ester. In other embodiments, the composition may include PGA sugar alcohol linkage ester. In other embodiments, the PGA linkage ester may include a combination of two or more of PGA PEG linkage ester, PGA glycerol linkage ester, PGA 1,3-propanediol linkage ester, PGA sugar linkage ester, and PGA sugar alcohol linkage ester. The composition may contain water and / or another solvent together with one or more PGA linkage esters to provide a finishing agent for textiles.

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

[0030] As described herein, the weight-average molecular weights of linked esters of PLA and linked esters of PGA can be determined by a standard high-performance liquid chromatography (HPLC) system using a GPC column and by gel permeation chromatography ("GPC") using evaporative light scattering detection ("ELSD"). Standard retention times are fitted into a calibration equation, which is used to determine the weight-average molecular weight of unknown polymers. The column used is a Jordi Gel DVB 500A (300 × 0.78 mm, catalog number 15071). This method is isocratic, using tetrahydrofuran ("THF") at 1 ml / min. The standard run time is 30 minutes, but most components elute 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 is set to 70°C, and the nitrogen gas flow rate is set to 1.84 SLPM. Accordingly, Figure 1 shows a typical calibration equation used to determine the weight-average molecular weight of the polymer.

[0031] [Figure 1] TIFF2022509726000036.tif136170

[0032] In other embodiments, the present invention relates to a method for producing linked esters of PGA. In one embodiment, the linked esters of the present invention can be produced by reacting (i) a diol (e.g., PEG or 1,3-propanediol) and / or polyol (e.g., polyglycerol including polyglycol, tri-, penta-, or deca-glycerol), or sugar, or sugar alcohol, (ii) a coupler, and (iii) PGA, glycolic acid, and / or poly(lactic acid-coglycolic acid). The reaction can be carried out by heating the reactants with a catalyst. The catalyst may be a basic catalyst (e.g., sodium carbonate and / or calcium carbonate). The catalyst may also be a Lewis acid catalyst such as stannous octanoate. 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 for forming linked esters of PGA. The temperature for initiating the reaction between PEG and PLA may be 140°C to 200°C, but the temperature required to melt the PGA is at least about 160°C. Therefore, 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 other embodiments, the linked esters of the present invention can be produced 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-, pent-, or deca-glycerol), or a sugar, or a sugar alcohol, or (ii) a lactide, a lactide intermediate, or lactic acid, and a coupler. The lactide may be D-lactide, L-lactide, and / or DL-lactide. To facilitate the reaction with lactide, a lactide intermediate, or lactic acid, a solvent may be used to dissolve the diol or polyol, or a combination of diol and / or polyol. The reaction may 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. Removal of water can also be achieved, for example, by contacting the reaction mixture with an inert or dry gas that does not interfere with the reaction (e.g., nitrogen), for example by stirring, and / or by distillation of the reaction product.

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

[0035] [Table 1] TIFF2022509726000038.tif217170

[0036] In other aspects of the present invention, the PLA linkage ester can be combined with other compounds or compositions that do not contain the PLA linkage ester to form a finishing agent (i.e., a finishing agent composition). The weight percentage of the PLA linkage ester in the finishing agent may be 0.1 to 99.9 percent or 5 to 95 percent of the weight of the PLA linkage ester. 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, defouling agents, and antifouling agents. Typical lubricants include PEG fatty acid esters, ethoxylated fatty acids, ethoxylated triglycerides, glycerol esters, sorbitan esters, and alkyl esters, and / or combinations thereof, derived from mineral oil, vegetable oil, and / or animal oil, other than PLA linkage esters. Typical 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., sulfates and phosphates of ethoxylated alkyl alcohols, fatty acid soaps, and / or alkyl sulfosuccinates, and / or combinations thereof). Typical 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 defouling formulation includes a permanent press resin, a catalyst for the permanent press resin, a wetting agent, a high-density polyethylene resin, a fluorinated defouling agent, and acetic acid. Typical weight percentages of the above compounds are 4.0-10.0% permanent press resin, 5.0-10.0% catalyst for the permanent press resin, 0.25-1.0% wetting agent, 3.0-6.0% high-density polyethylene resin, 5.0-10.0% fluorinated defouling chemical, and 0.0-0.25% acetic acid. PEG esters of PLA can be added to defouling formulations containing a fluorinated defouling chemical relative to the defouling agent, resulting in the defouling agent being absorbed more rapidly into the cloth (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 one drop to the cloth, thus reducing the time required to treat the cloth with the defouling agent. Furthermore, when PLA PEG ester is added to a defouling formulation containing a fluorinated defouling chemical, the amount of the fluorinated chemical can be reduced to 25, 50, or 75 percent, and the defouling agent still provides defouling results equivalent to or better than those of a defouling agent containing a typical amount of the fluorinated chemical (e.g., 5.0-10.0 weight percent) without PLA PEG ester.

[0038] PLA linkage esters act as surfactants and can be used in personal care products, such as soaps, shampoos, and conditioners. Compositions containing PLA linkage esters may also contain other surfactants, such as all-natural polyglucosides.

[0039] In further embodiments, the present invention relates to fabrics treated with linked PLA esters. Fabrics treated with linked PLA esters have improved surface properties, such as hydrophilicity. In one embodiment, the fabric is a nonwoven fabric, such as spunbond, meltblown, carded, airlaid, wetlaid, and / or a combination thereof. In other embodiments, the fabric is woven or knitted. In one embodiment, the fabric is made from or contains polyester, such as PLA and / or polyethylene terephthalate. In other embodiments, the fabric is made from or contains polypropylene. In other embodiments, the fabric is made from or contains polyethylene. In other embodiments, the fabric is made from or contains a combination of polypropylene and polyethylene. In other embodiments, the fabric is made from polyamide, acrylic, aramid, and / or a combination thereof. In further embodiments, the fabric is made from or contains artificial fibers (such as acetate, lyocell, and rayon). In other embodiments, the fabric is made from or contains natural fibers (e.g., bamboo, cotton, flax, hemp, wool, and / or combinations thereof). In other embodiments, the fabric can be made from poly(ρ-phenylene-2,6-benzobisoxazole), also known as "PBO". In other embodiments, the fabric can be made from polyether ether ketone, also known as "PEEK". In other embodiments, the fabric is made from polyether ketone ketone, also known as "PEKK". When applied to a fabric, the linked ester of PLA provides improved wetting properties (e.g., relatively fast strike-through time and multiple strike-through times and / or relatively low re-wetting (or wet-back)).

[0040] The composition comprising the PLA linkage ester of the present invention can provide a single liquid strike-through time of 5 seconds or less, 4 seconds or less, or 3 seconds or less for 15 gs / m² (gsm) spunbond nonwoven fabric made from polypropylene or PLA, as determined by the EDANA (European Association of Disposable and Nonwoven Fabrics) and INDA (Nonwoven Fabrics Industry Association) standard test: WSP 070.3.R3(12) for nonwoven liquid strike-through time. The EDANA (European Association of Disposable and Nonwoven Fabrics) and INDA (Nonwoven Fabrics Industry Association) standard test: WSP 070.3.R3(12) for nonwoven liquid strike-through time is incorporated herein by reference. The composition comprising the PLA linking ester of the present invention can provide multiple or repeated liquid strike-through times of 5 seconds or less or 4 seconds or less for the first three strike-throughs against a 15gsm PLA or polypropylene spunbond nonwoven fabric, as determined by the standard test for repeated liquid strike-through times: WSP 070.7.R4(12). The standard test: WSP 070.7.R4(12) for repeated liquid strike-through times is incorporated herein by reference.

[0041] The compositions comprising the PLA linkage esters of the present invention can also provide at least 0.25 grams or less of re-wetting to a 15 gsm PLA spunbond nonwoven fabric, as determined by the standard test: WSP 080.10.R3(12) for nonwoven coverstock wet bags. The standard test: WSP 080.10.R3(12) for nonwoven coverstock wet bags is incorporated herein for reference. The compositions comprising one or more PLA linkage esters typically contain water such that the weight percentage of the one or more PLA linkage esters in the composition may 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 PLA linkage esters.

[0042] Compositions containing PLA-linked esters can provide finishing agents, such as bleaching, scouring, hydrophilic, antistatic, stain-resistant (or stain-resistant), anti-friction finishing agents, and / or combinations thereof. In one embodiment, the PLA-linked esters used in these finishing agents are commercially available PEG 200, PEG 300, PEG These can be prepared from PEG 400, PEG 600, PEG 800, PEG 1000, PEG 1200, PEG 1400, PEG 1450, and / or mixtures thereof. PLA-linked PEG esters can also be prepared from PEGs having molecular weights of 100-1000, 200-800, and 300-700. PLA-linked PEG esters can have PEG:PLA ratios of 30:70-70:30, 40:60-60:40, and 45:55-55:45. In a preferred embodiment, the PGA-linked PEG ester is prepared from PEG 400, and the PEG:PGA ratio is 50:50. PGA's PEG esters, namely PGA's PEG 400 ester with a PEG:PGA ratio of 44:56, PGA's linked PEG 200 ester with a PEG:PGA ratio of 50:50, PGA's linked PEG 400 ester with a PEG:PGA ratio of 50:50, PGA's linked PEG 600 ester with a PEG:PGA ratio of 50:50, and PLA's PEG 1450 ester with a PEG:PGA ratio of 50:50, have preferred smoke and flash point characteristics (e.g., smoke is 171%). o It is less than F and flammable at 244 oIt has a pH of less than F and desirable friction properties. For example, the defouling finish may include PEG ester of PLA, e.g., those confirmed above, an oil-repellent / water-repellent agent, a wetting agent / absorbent agent, and a hydrophilic binder. In one embodiment, the defouling finish includes ester of PLA, permanent press resin, a catalyst for the permanent press resin, a wetting agent, high-density polyethylene resin, a fluorinated defouling chemical, and / or an acid for pH adjustment (e.g., acetic acid, citric acid, or glycolic acid). The addition of ester of PLA can reduce the required amount of expensive fluorinated defouling chemical by 10 percent, 20 percent, 30 percent, 40 percent, 50 percent, or 60 percent while simultaneously providing comparable or improved defouling results. The addition of ester of PLA improves droplet reflectance. One liter of defouling finish may contain 1 to 40 grams, 1 to 30 grams, 1 to 20 grams, 1 to 15 grams, or 1 to 10 grams of PEG ester of PLA. Two liters of finishing agent can contain twice the amount of PEG ester in one liter of PGA, and three liters of finishing agent can contain three times the amount of PEG ester in one liter of PLA.

[0043] Compositions comprising PLA linkage esters and / or PGA linkage esters can be applied to fabrics by roll coating, padding, dripping, or spraying in amounts that provide desired strike-through and / or re-wetting properties. For example, compositions comprising PLA esters can be applied to give FOY levels of 0.1–10.0 wt percent, 0.2–3.0 wt percent, 0.3–1.0 wt percent, and 0.3–0.8 wt percent (a finish on yarn). Accordingly, other embodiments of the present invention are fabrics treated with one or more of the above-mentioned PLA esters, or compositions containing one or more of the above-mentioned PLA esters.

[0044] The results of tests comparing conventional stain-removing formulations without PLA-bound PEG esters with stain-removing formulations containing PLA-bound PEG esters are shown in Tables 2b-2c, 3b-3c, 4b-4c, 5b-5d, 6b-6d, and 7b-7d below. Stain-removing formulations containing PLA-bound PEG esters and PLA-bound esters 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 stain remover sold by Pulcra Chemicals.

[0045] Polyester copolymers are used to impart water absorption or water-absorbing properties to synthetic fibers, particularly for apparel and sportswear fabrics. Polyester copolymers are also said to improve the stain-removing properties of fabrics. PLA PEG esters were also tested to determine whether PLA PEG esters improve the static electricity of fabrics. Three PLA esters were compared to a common polyester copolymer finish sold by Pulcra Chemicals LLC under the trade name Nonax® MM. Nonax® MM and PLA PEG esters were applied to fabrics using the pad method, then dried and cured. This formulation was applied to 100% polyester fabrics, 65 / 35 polyester / cotton fabrics, and 100% nylon fabrics. To measure water absorption, one end of a narrow strip of the treated fabric was immersed in water, allowing the fabric to absorb the water. The more water the fabric absorbed, the better the water absorption properties. The distance the cloth absorbed water was measured in millimeters ("mm"). The same test procedure was used for the stain removal experiment described above. To measure the absorption characteristics of the PLA ester in the stain remover, the following stain remover formulations were padded, dried, and then cured on the cloth at 177°C.

[0046] The formulations and test results for dirt removal are listed in several tables (below), where higher values ​​correspond to higher dirt removal 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] As described above, the suction and stain removal tests were repeated for 100% polyester, 65% / 35% polyester / cotton, and 100% nylon. The results for 100% polyester are shown in Tables 5b to 5d below. The pH of the stain remover was adjusted to 4 to 5. Subsequently, the stain remover test was repeated for the 100% polyester described above. The test results for suction performance, stain removal performance, and whiteness for the first cloth before washing, the cloth after 5 washing cycles, and the cloth after 10 washing cycles are shown in Tables 5a to 5e below. The pH of each stain remover was adjusted to between pH 4 and 5.

[0059] [Table 5a]

[0060] [Table 5b]

[0061] [Table 5c]

[0062] [Table 5d]

[0063] [Table 5e]

[0064] Next, the absorbent and stain remover tests were repeated on 65 / 35 percent polyester / cotton as described above. The test results for absorbent and stain remover performance for the first cloth before washing, the cloth after 5 washing cycles, and the cloth after 10 washing cycles are shown in Tables 6a to 6d below. The pH of each stain remover 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 detailed description above illustrates typical embodiments. This disclosure is not limited to such exemplary embodiments. Any various aspects, features, or processes, or combinations thereof, may be utilized within this disclosure.

[0074] Examples of embodiments are disclosed in this specification and / or drawings. Unless otherwise specified, specific terms are used in a general and descriptive sense and are not intended to be limiting.

[0075] The use of the term "and / or" includes any and all combinations of one or more related enumerated items. For ranges such as temperature, percentage, Dalton, etc., as described above (for example, in the form "between x and y"), "between" means "including between" so that the numbers provided for the range are included in the range (for example, 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 limit the scope. The scope of the present invention is intended to include at least the following claims and their equivalents.

Claims

1. polyethylene glycol; dicarboxylic acid as a coupler; polylactic acid; a compound comprising a reaction product thereof, wherein one or more compounds having a weight average molecular weight of less than 5000 Da are materials to be applied by roll coating, padding, dripping, or spraying, and the material is a non-woven fabric, a woven fabric or a knitted fabric.

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

3. The material according to claim 1 or 2, wherein the coupler comprises an aromatic dicarboxylic acid.

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

80.

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

6. The material according to 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 is a compound having any one of the following formulas selected therefrom. 【Chemical Formula 1】 (In the above formula, n is an integer greater than 1 and less than 90, and 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. 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; A method for producing a compound to be applied by roll coating, padding, dropping, or spraying onto the material according to any one of claims 1 to 7, comprising:

9. The production method according to claim 8, wherein when mixed with water, the final reaction product provides a clear and colorless emulsion.

10. Use of a composition as a finishing agent for fibers made of any one of polyester, polyolefin, polyamide, acrylic, nylon, polypropylene, aramid, acetate, lyocell, rayon, bamboo, cotton, linen, hemp, and wool to increase the hydrophilicity of the material, The composition contains at least one compound, and the compound is polyethylene glycol; a dicarboxylic acid as a coupler; polylactic acid; a compound containing a reaction product of The weight average molecular weight of the compound is less than 5000 Da.

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 refining agent.

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

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