TW200829646A - Lactic acid polymers - Google Patents

Abstract

The incorporation of units derived from isosorbide and from a polycarboxylic acid or anhydride thereof in a lactic acid polymer can result in a polymer having a higher glass transition temperature than would otherwise be achieved.

Description

200829646 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to an improved polylactic acid polymer.

C is a dental unit]I 5 In recent years, the importance of environmental issues has increased, and the demand for biodegradable polymers that are stable under normal use conditions (especially for food and beverage packaging) has increased. It is. Lactic acid-based polymers are biodegradable and food-grade, so it may be advantageous for this purpose. Lactic acid can be used as a mono-, di-, tri-, tetra- or polyfunctional initiator by polymerization. (for example, compounds having a hydroxyl group and/or acid group) form polymers. However, such polymers are prone to low glass transition temperatures, thus limiting their value in the preparation of rigid or semi-rigid containers such as bottles. . The high molecular weight polymer formed by the C-ring ring-opening polymerization has a high molecular weight, but even so, the glass transition temperature is still lower than the 15 plastics generally used for rigid packaging, such as polyethylene terephthalate and poly Styrene. Further, lactide is produced by polycondensation of a history of lactic acid to decompose low molecular weight polylactic acid. These steps increase the complexity and cost of the manufacturing process and, therefore, require a suitable polymer that can be produced directly by lactic acid polymerization. Isosorbide has been incorporated into various types of polymers and has gained a variety of benefits. For example, WO 2004044032 A1 discloses that an isosorbide can be used to increase the glass transition temperature of a polyester. Other patents which disclose the use of isosorbide for various purposes include DE 2938464, US 6,656,577, US 7,049,390, US Pat. No. 6,818,730, US Pat. No. 6,063,495, US Pat. 5 200829646 We now disclose a method of combining the lactic acid derived from the unit of isosorbide liver from the unit of poly- _, which produces a polymer having a glass transition temperature of the rut. Although it is known that the isosorbide is 4 inches, and he "the glass transition temperature of the object, but I still feel shocked to see 5, it is not enough to see only the isosorbide liver in the saliva." It is desirable to have the presence of poly(4) to achieve the desired result. It is expected that similar benefits can be obtained by incorporating these monoterpenes into the water extract. Even by appropriately selecting a considerable amount of the polymer component, It can ensure that the polymer has a relatively high degradation temperature, which is an important consideration for the public to use the material. [10号号] In the present invention, the present invention relates to a polymer which is derived from 4 sorbitan anhydride and a monoterpene "Hyperic acid unit having a polycarboxylic acid having at least a tricarboxylic acid group includes at least 50% by weight of the polymer. The present invention relates to the preparation of lactic acid polymerization. Method of packaging 15 $ ♦ $乳5, isosorbide and a group having at least a tricarboxylic acid group or its phthalic anhydride. The lactic acid contains at least (10)% by weight of the polymer group The invention is more related to the preparation of lactic acid polymer a method comprising: a package of a mouthpiece, a parent, an isosorbide, and a polyacid having at least three antacid groups or an anhydride thereof, the lactide being present in an amount sufficient to provide at least 50% by weight The lactic acid unit in the lactic acid polymer. The polymerization reaction can be carried out under any of the conditions known in the art for the polymerization of such an early body, but is carried out in the presence of a catalyst (4), and is carried out by heating. Preferably, any catalyst known for such polymerization reactions is equally suitable for use herein, and examples of suitable catalysts include such 6200829646 esterification catalysts such as acids such as p-p-toluenesulfonic acid or sulfuric acid; Organometallic compounds containing elements of group I-VIIIA and / group IB - VIIB of the primary group, including compounds of the following formulas: lithium, calcium, magnesium, manganese, zinc, ergon, chin, ergon, osmium, cobalt or tin In particular, titanium, ruthenium, osmium, cobalt or tin compounds, such as titanium (4) tetrabutyl phthalate or titanium triacetate pyruvate. The polymerization reaction can take place at ambient temperature, depending on the catalyst and monomer used. But it is better to carry out heating, for example to heat 1 〇〇 to 25 (TC temperature, 14 (TC to 2HTC is better, and from 15 (^ to 190 ° C is the best. 10 lin in the water formed by the removable reaction towel) It is preferably carried out under conditions, that is, at least the temperature of the HKTC and preferably lower than the atmosphere, preferably in a vacuum. The reaction is carried out in the absence of any solvent other than the reagent. Preferably, but if necessary, there may be an organic solvent. If used, examples of such organic solvents include: diethyl ether, such as di-ethyl ether, and di-D-burn; and hydrocarbons such as p-toluene. Xylene and deuterium. It is preferred that the reaction be carried out under substantially anhydrous conditions. Lactic acid is a major component of the reaction mixture and is present in an amount sufficient to constitute at least 50% by weight of the polymer, at least 6〇% is preferred, and from _〇% to more U is preferably from 65 to 75%. The lactic acid can be [, d or see. The isosorbide is present in the final polymer in a small proportion, for example not more than 2% by weight 'and preferably used to provide from 2 to 20% by weight of the final polymer in the final polymer from 2 to 15% is better and 5 to 11% is best. 200829646 The polycarboxylic acid or anhydride thereof is a group of carboxylic acid groups having at least three (preferably from three to six) compounds or anhydrides of such compounds. It should be possible to react with isosorbide, and suitable examples of such acids include: 1,2,3,4,5,6,-cyclohexanehexacarboxylic acid, 1,2,3,4-butane Tetracarboxylic acid, trimellitic acid, 5 pyromellitic acid. An acid anhydride of these acids can also be used. Preferred polycarboxylic acids are 1,2,3,4,5,6,-cyclohexanehexacarboxylic acid and 1,2,3,4-butanetetracarboxylic acid. It is also preferred that the proportion of the carboxylic acid compound present in the final polymer is small, for example, not more than 20% by weight, and it is preferred to use a unit sufficient to provide from 3 to 20% by weight of the final polymer. 4 to 18% is more preferred and 5 to 11% is most preferred, and other monomers may be included in addition to lactic acid or lactide, isosorbide, and polycarboxylic acid or anhydride. The polymerization reaction is in the final polymer. Examples of such monomers include: other hydroxyl acids such as glycolic acid, hydroxyl butyrate or hydroxyhexanoate. If used, it is preferred to have less of such other monomers. 15 In practical use, it is preferred to formulate the copolymer of the present invention together with an additive generally used in the plastics industry, such as a plasticizer, a filler, a colorant, etc., if necessary, the copolymerization The composition may be formulated to be mixed with at least one polyester (other than the copolymer of the present invention, such as polylactic acid). The resulting polymer or composition can be formed into a film 20 or a shaped article, such as a container, such as a bottle or box, by known methods, and is particularly suitable for packaging human or veterinary materials, such as food, electronic equipment or Medical. The invention is further illustrated by the following non-limiting examples. I: Embodiment 3 Example 1-9 200829646 (aM lactic acid drying is carried out by a rotary evaporator attached to a water-cooled radiator to dry lactic acid. A known amount of lactic acid is placed in a flask at atmospheric pressure Heated in an oil bath. Place the bottle in an oil bath at ambient temperature and lift the temperature to 18 Torr in about 3 〇 5 minutes and keep it at this temperature for 4 hours (from the bottle After entering the oil bath), the bottle was capped and cooled to the surrounding degree. It was used for all polymerization of lactic acid and from the four batches used to determine the number of acids by titration. The sample is taken in. (b) Polymerization step 10 This I interaction is carried out in a vacuum using a rotary evaporator attached to a water-cooled heat sink. The polymerization temperature is 150 ° C and starts from about 22 ° C. It was reached within about 30 minutes after heating. The pressure setting of the vacuum pump was slowly reduced from about 800 mbar to 1 mbar over 15 hours after reaching rc temperature. After the pressure setting was reduced to 1 mbar, the polymerization was at 150. (:: lasts for a minimum of 54 15 hours. Allows the vacuum pump to stop and is specific After removing the flask interval to obtain a sample taken, immediately after the pressure was reduced in vacuo.

_(j〇 differential scanning calorimeter method (DSO is used to measure thermal conversion of differential scanning calorimetry (DSC) instrument is Perkin

Elmer (Bucks, United Kingdom) DSC 7. Use the indium and empty disk to calibrate the DSC 20 device for reference. The sample was placed in an aluminum pan and weighed completely. The sample was first heated from -30 °C to 200 °C. (:, then cooled to -3 (TC, after which a second heating was performed as in the first heating. The rate of heating and cooling was 10 ° C / min. The GPC results were presented for use with conventional calibration techniques, This conventional calibration technique uses a refractive index detector and this result is independent of the absolute concentration of the sample. 200829646 The results are shown in Table 1 below. Table 1 Example number LLA (%) BTCA (%) ISB (%) Time (h Tg(°C) Μη Mw Mz 1 85.5 8.8 5.5 5.5 13.47 807 1006 1284 24 44.31 1958 4306 7528 30 50.84 2204 5491 9814 48 55.49 2931 9924 53800 54 56.31 3636 14980 64600 2 88.3 8.8 2.8 9 29.75 1248 13520 152600 24 47.04 1624 13160 425600 54 59.18 3 80.1 8.8 11.0 7 20.43 925 21560 286700 24 47.04 1481 3479 6081 54 59.18 4 90.0 4.4 5.5 5.5 7.95 639 785 982 24 39.14 1446 3478 7449 32.5 44.59 2429 6706 19990 48 46.63 2782 9003 19370 54 47.08 3549 17260 186100 5 76.8 17.6 5.5 8 38.38 697 1121 1740 24 50.03 933 1980 3524 54 61.88 6 71.6 17.4 10.9 8.75 37.09 1 358 2112 3242 24 55.7 2256 4379 7564 34 59.83 1903 4085 7114 48.5 62.48 1912 5085 9960 54 63.67 1042 3623 9452 7 (Comparative) 85.0 15.0 12 6.76 709 985 1287 24 15.02 761 1218 1783 36 15.39 789 1334 2040 48 13.34 685 1138 1736 6 9.23 564 895 1300 72 9.66 525 822 1198 8 (Comparative) 100 10 14.30 863 1333 2001 24 32.72 1806 3508 5663 30 37.57 2115 4176 6645 2447 4510 6964 48 41.89 3007 7001 12250 54 39.68 3800 7986 13680 9 (Comparative) 91.1 8.8 9 27.23 1755 91370 1079000 24 46.51 1410 4159 17520 33.75 50.21 4539 24390 35200 48 50.91 1808 7074 73230 54 50.66 1682 3649 5809 The abbreviations used in the table indicate: 10 200829646 LLA= L_lactic acid btca== Dingling tetrazinc acid ISBa= Isosorbide

Tg == glass transition temperature 5 h = hour number average molecular weight Mw = weight average molecular weight Mz = z average molecular weight

Comp = comparative example, that is, not an embodiment of the invention. 10 Example 1 (Mg (a) Dry lactic acid. A rotary evaporator and a water-cooled heat sink were used to dry 88% L_lactic acid (tetra) P brain. Six known amounts of lactic acid were burned (4) and heated in an oil bath under atmospheric pressure. The oil bath was preheated to 155 its drying temperature. The drying 15 process is water distilled from the flask at short intervals after collection and concentration. When the concentrated water weight is about 12% of the initial weight of 88% lactic acid, the drying is stopped and the bottle is capped, weighed, and cooled to ambient temperature. (b) Polymerization The suspension was carried out in an oil bath and in a vacuum using a rotary evaporator and a water-cooled heat sink. The polymerization temperature was 18 CTC and the oil bath was preheated to this temperature. The system is filled with nitrogen before the start of the polymerization and before the sample is taken. At the beginning of the polymerization, the pressure of the vacuum pump was gradually set to 1 mbar for a period of 4 hours. The actual pressure after 4 hours was about 27 mbar. After 6 hours, when the pressure setting was reduced to 1 bar but just decreased to 3 mbar, 25 took the first sample. Similarly, after 22 hours, the second sample was taken after 3 mbar, but after 30, 46 and 54 hours, the pressure was slightly high, and between 6 and 15 mbar, the last 3 samples were taken. 11 200829646 When the pressure setting was reduced to 1 mbar, the polymerization was continued at 180 °C for 50 hours. The vacuum pump is stopped and the beaker is removed to take the sample after a specific time interval, after which the pressure is immediately reduced to a vacuum. The sample polymerization time was calculated from the polymerization at atmospheric pressure. 5 (c) Differential Scanning Calorimetry (DSC) Thermal conversion was measured using a differential scanning calorimetry (DSC) instrument as described in Examples 1-9 of the Examples. (d) Thermogravimetric Analysis (TGA) The TGA equipment used was Seiko Instruments TG/DTA 6200 Model No. 10 with an Exstar 6000 base unit. Analyze the sample with Program I (heated from 2 (TC to 500 °C) at 10 °C/min or isothermally, ie Program II (5 (TC/min heated from 20 °C to 300 °C)) And then kept at 300 ° C for 1 hour.) The results and polymer composition are shown in Table 2. Table 2 Example number LLA (%) Batch (%) ISB (%) Polymerization time (W IDT CC) Degradation Temperature ΓΟ Td5 CC) TdlO (°C) Td20 CC) Td50 CC) Residual amount at 500 ° C (TG%) 10 85.6 8.8 5.5 24 205 263 231 257 276 311 2.6 11 88.3 8.8 2.8 54 222 273 259 273 289 319 3.0 12 80.1 8.8 11.0 24 210 274 245 263 282 314 2.1 13 90.0 4.4 5.5 24 199 258 236 255 272 301 4.1 14 76.8 17.6 55 54 205 256 232 251 268 293 2.4 15 71.6 17.4 10.9 24 218 277 245 265 286 314 3.3 8.75 106 241 143 205 252 309 4.2 24 204 263 231 260 282 323 4.5 34 204 268 247 265 286 326 4. 48.5 206 267 244 264 285 326 4.3 54 219 268 246 267 289 327 4.9 16 (Comparative example) 85.0 15 48 168 230 180 211 233 260 1.5 17 (Comparative example) 100 54 211 257 228 251 268 296 0.5 18 (Comparative example) 91.1 8.8 24 217 283 250 270 287 311 0.9 54 232 289 257 276 293 313 0.4 12 200829646 Definition · IDT = initial decomposition temperature Td5 = 5% of the initial weight of the sample loss TdlO = sample has a loss of 1〇% of the initial weight of the temperature 5 Td20 = sample has a temperature of 2% by weight of the initial weight.

Td50 = residual amount of the sample having a temperature of 50% of the initial weight loss of 500 C =: % of the sample remaining at 500 ° C compared to the initial weight. From these results, the polymer of the present invention has a high glass transition temperature and can be Resistance to thermal degradation. 10 In the examples 19, the steps of Examples 10-18 were repeated with 71.6 w% LLA, 17.4 w% BTCA and 10.9 w%, but the polymerization was carried out for a longer period of time. The results are shown in Table 3. Polymerization time (h) Tgfc from the first heating cycle) Tgrc from the second heating cycle) 6 42.2 48.6 22 59.7 63.3 30 67.9 73.6 46 70.2 78.8 54 74.2 79.8 In the example of the application 20 15 18% by weight of L-lactic acid (as dried as described in Examples 10-18), 18.2% by weight of 1,2,3,4,5,6-cyclohexanehexacarboxylic acid (HCA) And 1 〇.9% by weight of isosorbide (HF_〇〇4_〇46) was polymerized. The total weight of the batch is 20g. When the ingredients are added to the flask, a thick layer of HCA is fixed to the funnel and the actual amount of the batch will be slightly less than estimated. However, this amount is very small' and its effect on the batch composition is considered to be negligible. The I compound is white cloud at the beginning of the polymerization. The polymerization 13 200829646 After 4 hours of action, the color dimmed slightly. After about 5 hours, the polymer appeared to be completely clear. However, when the polymerization started 6 hours after the start of the polymerization, it was noted that the polymer contained a small amount of white particles, and the particles were visible until the polymer 5 became more viscous and began to contain bubbles, so that the substance could not be seen clearly. colour. All samples were hard and fragile after cooling. Differential scanning calorimetry (DSC) The polymerization Tg values of 70.8 wt% LLA, 18.2 wt% HCA, and 10.9 wt% ISB are shown in Table 4. As shown in the table, the value obtained is higher than the value obtained when 10 is the same weight % 6 and BTCA is used as the polyacid. The Tg value increases to approximately 90 ° C at the end of the polymerization. Table 4 Polymerization time (h) Tg (°C) from the first heating cycle Tg (°C) from the second heating cycle 6 32.7 40.7 12 46.2 55.2 24 45.1 61.1 30 76.9 77.7 48 88.2 86.3

Tg value of 70.8 wt% LLA 18.2 wt% HCA and 10.9 wt% ISB polymerization polymerization obtained after about 30 hours was significantly higher than the typical Tg 15 value of PLA, and also higher than that obtained by earlier ISB and BTCA polymerization. By. I: Simple description of the figure 3 (none) [Explanation of main component symbols] (none) 14

Claims (1)

200829646 X. Patent Application Range: 1. A polymer comprising units derived from: lactic acid; isosorbide; and a polycarboxylic acid having at least a tricarboxylic acid group, the lactic acid unit comprising At least 50% by weight of the polymer. 2. The polymer of claim 1 wherein the lactic acid unit comprises at least 60% by weight of the polymer. 3. The polymer of claim 1, wherein the lactic acid unit comprises from 65 to 90% by weight of the polymer. 4. The polymer of claim 1, wherein the lactic acid unit comprises from 65 to 75% by weight of the polymer. 5. The polymer of any one of claims 1 to 4 wherein the isosorbide unit comprises no more than 20% by weight of the polymer. 6. The polymer of claim 5, wherein the isosorbide unit comprises from 2 to 20% by weight of the polymer. 7. The polymer of claim 6 wherein the isosorbide unit comprises from 2 to 15% by weight of the polymer. 8. The polymer of claim 6 wherein the isosorbide unit comprises from 5 to 11% by weight of the polymer. 9. The polymer of any one of claims 1 to 8 wherein the polycarboxylic acid or anhydride thereof is a compound having at least three (preferably from three to six) carboxylic acid groups. Or an anhydride of such a compound. 10. The polymer of claim 9, wherein the polycarboxylic acid or anhydride thereof is 1,2,3,4,5,6,-cyclohexanehexacarboxylic acid or 1,2,3,4- Butane tetracarboxylic acid, or an anhydride thereof. The polymer of any one of claims 1 to 10, wherein the polycarboxylic acid or anhydride unit comprises no more than 20% by weight of the polymer. 12. The polymer of claim 11, wherein the polycarboxylic acid or anhydride unit comprises from 3 to 20% by weight of units in the polymer. 13. The polymer of claim 12, wherein the polycarboxylic acid or anhydride unit comprises from 4 to 18% by weight of units in the polymer. 14. The polymer of claim 13 wherein the polycarboxylic acid or anhydride unit comprises from 5 to 11% by weight of units in the polymer. A method for producing a lactic acid polymer according to any one of claims 1 to 14, which comprises a mixture of lactide, isosorbide, and a group having at least a tricarboxylic acid group The carboxylic acid or anhydride thereof is polymerized in an amount sufficient to provide at least 50% by weight of the lactic acid unit in the lactic acid polymer. 16. The method of claim 15, wherein the polymerization is carried out at from 100 Torr to 250 °C. A composition comprising a mixture of a copolymer according to any one of claims 1 to 16 and at least one polyester. 18. For the composition of claim 17 of the patent scope, wherein the polyester is polylactic acid 0 16 200829646 VII. Designation of representative drawings: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: