Polyester polyol, thermoplastic polyurethane and article thereof
11396575 · 2022-07-26
Assignee
Inventors
- Chiu-Peng Tsou (Taichung, TW)
- Zhen-Wei Chen (Taichung, TW)
- Wen-Wei Cheng (Taichung, TW)
- Ting-Ti Huang (Taichung, CN)
- Sheng-Mao Tseng (Taichung, TW)
Cpc classification
C08G18/7671
CHEMISTRY; METALLURGY
C08G18/4238
CHEMISTRY; METALLURGY
C08G18/4211
CHEMISTRY; METALLURGY
C08G18/4018
CHEMISTRY; METALLURGY
C08G63/6926
CHEMISTRY; METALLURGY
C08G18/5078
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention provides a thermoplastic polyurethane (TPU) having a glass transition temperature between an ambient temperature and normal body temperature, wherein the TPU contains dicarboxyphenyl polyester structure represented by Formula 1 or 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide n(DOPO-ITA) polyester structure represented by Formula 2. The present invention also provides a polyester polyol containing DOPO-ITA polyester structure represented by Formula 2, a molar percentage of the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-oxide polyester structure in the whole polyester polyol ranges from 30% to 70%. The present invention further provides an article thereof. ##STR00001## in Formula 1, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; ##STR00002## in Formula 2, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2.
Claims
1. A thermoplastic polyurethane (TPU) having a glass transition temperature between an ambient temperature and normal body temperature, wherein the TPU contains a dicarboxyphenyl polyester structure represented by Formula 1 or a 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure represented by Formula 2; ##STR00007## in Formula 1, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the dicarboxyphenyl polyester structure in the thermoplastic polyurethane ranges from 6% to 25%; ##STR00008## in Formula 2, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polyester structure in the thermoplastic polyurethane ranges from 5% to 20%; wherein the dicarboxyphenyl polyester structure represented by Formula 1 and the DOPO-ITA polyester structure represented by Formula 2 each have an average molecular weight ranging from 700 to 2500 g/mole. wherein the TPU containing the dicarboxyphenyl polyester structure represented by Formula 1 has the glass transition temperature between 10° C. and 31.02° C.; and wherein the TPU containing the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide polyester structure represented by Formula 2 has the glass transition temperature between 10° C. and 40° C.
2. The thermoplastic polyurethane as claimed in claim 1, wherein a weight percentage of a soft segment in the thermoplastic polyurethane ranges from 60% to 80%.
3. The thermoplastic polyurethane as claimed in claim 1, wherein the glass transition temperature is between 15° C. and 28° C.
4. The thermoplastic polyurethane as claimed in claim 1, wherein the softening point of the TPU is between 50° C. and 100° C.
5. The thermoplastic polyurethane as claimed in claim 1, wherein the softening point of the TPU is between 60° C. and 85° C.
6. The thermoplastic polyurethane as claimed in claim 1, wherein the thermoplastic polyurethane has a function of hot melt adhesive.
7. A solvent-free hot melt adhesive, which is prepared by using the thermoplastic polyurethane as claimed in claim 1.
8. A nonwoven fabric, which is prepared by using the thermoplastic polyurethane as claimed in claim 1.
9. An article, which is prepared by using the thermoplastic polyurethane as claimed in claim 1.
10. The article as claimed in claim 9, wherein the article is textile, shoe material, decoration, toy, sporting goods or daily necessity.
11. A polyester polyol for producing the thermoplastic polyurethane (TPU) having a glass transition temperature between an ambient temperature and normal body temperature, wherein the TPU contains a dicarboxyphenyl polyester structure represented by Formula 1 or 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure represented by Formula 2; ##STR00009## in Formula 1, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the dicarboxyphenyl polyester structure in the thermoplastic polyurethane ranges from 6% to 25%; ##STR00010## in Formula 2, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10 -phosphaphenanthrene-10- oxide polyester structure in the thermoplastic polyurethane ranges from 5% to 20%; wherein the dicarboxyphenyl polyester structure represented by Formula 1 and the DOPO-ITA polyester structure represented by Formula 2 each have an average molecular weight ranging from 700 to 2500 g/mole; and wherein the TPU contains the 10(2,3 - dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polyester structure represented by Formula 2, and a molar percentage of the 10-(2,3 -dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polyester structure contained in the polyester polyol ranges from 30% to 70%.
12. The polyester polyol as claimed in claim 11, wherein the polyester polyol has an OH value between 160.3 and 44.8 mg of potassium hydroxide per gram.
13. The polyester polyol as claimed in claim 11, wherein a dicarboxylic acid contained in the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure is an addition of itaconic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), or an addition of itaconic acid, one selected from succinic acid or 1,6-adipic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
14. The polyester polyol as claimed in claim 11, wherein a diol monomer of the polyester polyol is a C2-C8 aliphatic polyol.
15. The polyester polyol as claimed in claim 14, wherein the C2-C8 aliphatic polyol is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butanediol, 2-methyl-1,3-propanediol, diethylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanediol, 2-ethylhexanediol, 1,8-octane diol or a combination thereof.
16. The polyester polyol as claimed in claim 11, wherein the polyester polyol is represented by any one of the following Formula 3 or any combinations thereof: ##STR00011## wherein n ranges from 1 to 10, x ranges from 1 to 10, and b ranges from 1 to 6.
17. The polyester polyol as claimed in claim 16, wherein the polyester polyol has an acid value less than 1.8 mg KOH/g.
18. A thermoplastic polyurethane (TPU) having a glass transition temperature between an ambient temperature and normal body temperature, wherein the TPU contains a dicarboxyphenyl polyester structure represented by Formula 1 or a 10-(2,3 -dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure represented by Formula 2; ##STR00012## in Formula 1, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the dicarboxyphenyl polyester structure in the thermoplastic polyurethane ranges from 6% to 25%; ##STR00013## in Formula 2, R is C2 to C8 alkylene group or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2; wherein a molar percentage of the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10 -phosphaphenanthrene-10- oxide polyester structure in the thermoplastic polyurethane ranges from 5% to 20%; wherein the dicarboxyphenyl polyester structure represented by Formula 1 and the DOPO-ITA polyester structure represented by Formula 2 each have an average molecular weight ranging from 700 to 2500 g/mole; and wherein a molar percentage of the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10 -phosphaphenanthrene-10- oxide polyester structure in the thermoplastic polyurethane ranges from 5% to 20%.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(19) Hereinafter, the preferred embodiments of the present invention will be described by the following examples, which are intended to illustrate and understand the invention and the invention is not limited to the embodiments. Various modifications and variations could be made in order to practice or apply the present invention without departing from the spirit and scope of the invention. In addition, all numerical ranges in the description include the upper limit and lower limit, and any integers thereof may be used as the minimum or maximum to form a narrower range.
(20) In the present invention, the following measuring methods are used:
(21) Fourier transform infrared spectrometer: the instrument was Thermo Nicolet 330FT-IR for surface analysis, particularly, the structural characteristics of the sample were tested by attenuation total reflection (ATR) test with a scanning range from 4000 cm.sup.−1 to 650 cm.sup.−1.
(22) Differential Scanning Calorimetry (DSC)
(23) A DSC821e differential scanning calorimeter produced by Mettler Toledo® was chosen, 5 to 10 mg samples were weighed by a microbalance scale with a sensitivity of ±0.01 mg and then put into an aluminum DSC crucible, and then the lid was firmly secured. The temperature inside the DSC chamber was set to 25° C. before use, the sample crucible and the control crucible (blank) were then placed into the DSC chamber, the nitrogen flow rate was set 80 ml per minute, the temperature was lowered at a rate of 10° C. per minute to −80° C. and maintained for 3 minutes, then increased to 220 to 250° C. at a heating rate of 10° C. per minute and maintained for 3 minutes, and then lowered at a rate of 10° C. per minute to −80° C. and maintained for 3 minutes. The peak in the process was its crystallization temperature (Tc); then increased to 220 to 250° C. secondly at a heating rate of 10° C. per minute and maintained for 3 minutes, the temperature of inflection point obtained from the process was its glass transition temperature (Tg), and the peak temperature was its melting point (Tm).
(24) The softening point test was carried out by American Standard Method (ASTM) D1525: preparing two overlapped sheets of 2 mm hot-press test pieces, placing a needle weighing 1 kg on the test piece, putting the test piece in an oven with temperature-controlled circulation for 25 minutes, and recording the temperature of the needle which could be inserted into the test piece.
(25) The OH value analysis was carried out in accordance with American Standard Method (ASTM) D4274-99.
(26) The acid value analysis was carried out in accordance with American Standard Method (ASTM) D4662-15.
(27) The Mn of Polyethylene polyol=(56100×2)/(OH value+acid value).
(28) Viscosity analysis was performed by the Brookfield model, laminar LVDV-I.
(29) The calculated value of phosphorus content (P wt %) in polyester polyol=[the number of raw DOPO moles×30.97)/the total weight of produced polyester polyol]×100%
(30) The calculated value of phosphorus content (P wt %) in TPU=[(the weight of polyester polyol×the calculated value of phosphorus content in polyester polyol)/the total weight of the TPU]×100%
(31) Gel Permeation Chromatography (GPC)
(32) Waters 2487 was chosen and the column type was HR1/HR3/HR4. The mobile phase was tetrahydrofuran (THF) at a flow rate of 1 ml per minute to measure the number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp) of the sample, based on external calibration performed by polystyrene standards.
(33) The raw materials used to produce the polyester polyol in the examples were explained below.
(34) The polyester polyol containing a dicarboxyphenyl polyester structure, wherein the polyester polyol of 1,2-phthalic acid/diethylene glycol (CAS 25916-41-0, chemical formula: (C.sub.8H.sub.6O.sub.4.C.sub.4H.sub.10O.sub.3).sub.x) was from Stepan Company, the trade name was PD-56; the polyester polyol of 1,2-phthalic acid/hexylene glycol (CAS 27516-71-8, chemical formula: (C.sub.8H.sub.6O.sub.4.C.sub.6H.sub.14O.sub.2).sub.x) was from Stepan Company, the trade name was PH-56; the polyester polyol of 1,4-phthalic acid/1,6-adipate/diethylene glycol (chemical formula: (C.sub.8H.sub.6O.sub.4.C.sub.6H.sub.10O.sub.4.C.sub.6H.sub.14O.sub.2)) was from JO-FON CHEMICAL INDUSTRY in Taiwan, the trade name was JF-022P.
(35) PBA700 (trade name: P-700), PBA1000 (trade name: PE-14), PBA2000 (trade name: PE-24) and PEBA2000 (trade name: PE-224) were all from Sunko Company.
(36) PTMEG1000 used in the present invention was from Mitsubishi Corporation of Japan.
(37) The polyester polyols containing DOPO-ITA polyester structure were prepared in accordance with Examples 1 to 6 herein.
Example 1
(38) The polyester polyol containing DOPO-ITA polyester structure was prepared by one-pot method at 140-220° C., followed by addition, condensation and dehydration. The embodiment was as follows: prepare a 3 L round bottomed flask with 4 necks which can be mechanically stirred, a fractionating tube (filled with glass beads) having a length of 30 cm, an inner diameter of 1.5 cm and an outer diameter of 4 cm, a distillation receiving flask and a thermometer; the diol was added in accordance with the raw material ratio as shown in Table 1, heated and stirred evenly, and then itaconic acid and DOPO were added in sequence, the internal temperature was raised to 140-180° C., and the distilled water was collected to more than 95% of its theoretical weight (it took 3-4 hours), heated under reduced pressure to an internal temperature of 210-215° C. for 10 hours. The reaction was monitored to have an acid value less than 1.8 mg KOH/g, and then heating was stopped and products were collected with nitrogen cooling, the finished product was weighed to calculate the yield and phosphorus content, and the appearance was recorded and the OH value, acid value and viscosity were detected. The results were shown in Table 1.
Examples 2 to 6
(39) Except that the raw materials ratio shown in Table 1 and Table 2 were used, the others were carried out in the same manner and test method as the first embodiment. The results were shown in Table 1 and Table 2.
(40) TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 DOPO 1114 g 1144 g 720.8 g (5.153 mole) (5.290 mole) (3.329 mole) Itaconic acid 677.1 g 694.7 g 437.4 g (5.205 mole) (5.340 mole) (3.359 mole) Adipic acid * * 491.2 g (3.359 mole) 1,6-hexaneglycol 913.9 g 865.1 g 1049.6 g (7.733 mole) (7.320 mole) (8.877 mole) Tin dichloride 33 mg 33 mg 0 Product formula (C.sub.17H.sub.15O.sub.6P•C.sub.6H.sub.14O.sub.2).sub.x (C.sub.17H.sub.15O.sub.6P•C.sub.6H.sub.14O.sub.2).sub.x (C.sub.17H.sub.15O.sub.6P•C.sub.6H.sub.10O.sub.4•C.sub.6H.sub.14O.sub.2).sub.x Product weight 2442 g 2423 g 2270 g (yield) (90.3%) (89.6%) (84.1%) Appearance Near colorless Light yellow Near colorless transparent liquid transparent liquid transparent liquid Chroma 75 85 45 (α value) OH value 85.4 58.4 79.9 (mg KOH/g) Acid value 1.49 0.87 1.49 (mg KOH/g) Molecular weight 1291 1921 1381 (Mn) Viscosity (cps) 9545 @85° C. 14900 @90° C. 1974 @75° C. Tg (DSC) 9.49° C. 15.75° C. −27.56° C. Phosphorus 6.54% 6.77% 4.55% content
(41) TABLE-US-00002 TABLE 2 Example 4 Example 5 Example 6 DOPO 985.7 g 1150 g 721.3 g (4.560 mole) (5.320 mole) (3.337 mole) Itaconic acid 593.3 g 700.0 g 438.5 g (4.560 mole) (5.380 mole) (3.370 mole) Adipic acid 222.3 g * * (1.520 mole) Succinic acid * * 398.0 g (3.370 mole) 1,6-hexanediol 901.1 g * * (7.621 mole) Diethylene * 847 g 1061 g glycol (7.982 mole) (9.998 mole) Tin dichloride 33 mg 33 mg 33 mg Product formula (C.sub.17H.sub.15O.sub.6P•C.sub.6H.sub.10O.sub.4•C.sub.6H.sub.14O.sub.2).sub.x (C.sub.17H.sub.15O.sub.6P•C.sub.4H.sub.10O.sub.3).sub.x (C.sub.17H.sub.15O.sub.6P•C.sub.4H.sub.6O.sub.4•C.sub.4H.sub.10O.sub.3).sub.x Product weight 2443 g 2395 g 2279 g (yield) (90.4%) (88.8%) (87.0%) Appearance Light yellow Light yellow Light yellow transparent liquid transparent liquid transparent liquid Chroma 50 90 95 (α value) OH value 51.0 72.7 124 (mg KOH/g) Acid value 1.06 1.60 1.50 (mg KOH/g) Molecular 2155 1510 894 weight (Mn) Viscosity (cps) 8687 @85° C. 11907 @90° C. 12926 @75° C. Tg (DSC) 0.56 16.69° C. −19.06° C. Phosphorus 5.79% 6.89% 4.54% content
(42) A small-volume laboratory preparing method of the TPU containing a dicarboxyphenyl polyester structure was described as below (Examples 7 to 12 and Comparative Example 1): a selective composition composed of the polyester polyol containing polycarboxyphenyl group and aliphatic polyol, diol and auxiliary agent were mixed into a 1 liter metal drum, stirred mechanically at the internal temperature of 110° C. controlled by a heating plate, and then added with the MDI liquid while stirring, which was kept for 3 minutes, and the melt flow index was analyzed. At the same time, the tray was placed in a circulating oven preheated at 70° C. for 24 hours and then taken out. Record the appearance of the TPU finished product and the softness change in contact with the palm temperature, test the TPU softening point and the Tg and carry out the hydrolysis resistance test. The relevant data and results of Examples 7 to 10 were shown in Table 3, the relevant data and results of Example 11, Example 12 and Comparative Example 1 were shown in Table 4. Further, the TPU finished products (containing the dicarboxyphenyl polyester structure) obtained in Examples 7 to 12 were subjected to attenuated total reflection (ATR) test by using a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330 FT-IR). The infrared spectrum of the obtained product was shown in
(43) TABLE-US-00003 TABLE 3 Example 7 Example 8 Example 9 Example 10 PD-56 225.9 g 114.7 g 275.3 g 280.5 g (0.117 mole) (0.059 mole) (0.142 mole) (0.145 mole) PTMEG1000 * 61.7 g * * (0.060 mole) 1,4-butanediol 24.1 g 23.6 g 24.7 g 19.5 g (0.268 mole) (0.262 mole) (0.275 mole) (0.217 mole) MDI 95.6 g 94.0 g 103.4 g 89.0 g (0.382 mole) (0.376 mole) (0.417 mole) (0.356 mole) Dicarboxyphenyl 15.2% 7.8% 17.0% 20.2% polyester/TPU (mole %) Weight percentage 65.4% 60.0% 68.2% 72.1% of soft segment The mole ratio of 0.993 0.986 0.991 0.984 MDI/(polyglycol + glycol)) MI(190° C., 8700 g, 11.0 12.0 15.9 20.2 10 min) Appearance Light yellow Light yellow Light yellow Light yellow transparent transparent transparent transparent elastomer elastomer elastomer elastomer The softness Obvious Change Obvious Obvious change in contact (elastic) (elastic) (elastic) (elastic) with the palm temperature The TPU softening 75~80° C. 80~85° C. 75~80° C. 75~80° C. point Tg (DSC) 31.02° C. 12.93° C. 24.38° C. The 4-hour No change No change No change No change accelerated hydrolysis test at 70° C., 10 wt % NaOH (aq)
(44) TABLE-US-00004 TABLE 4 Comparative Example 11 Example 12 Example 1 PH-56 274.7 g 225.4 g * (0.136 mole) (0.111 mole) JF-022P * * 225.6 g (0.113 mole) 1,4-butanediol 25.3 g 24.6 g 24.4 g (0.281 mole) (0.273 mole) (0.271 mole) MDI 103.9 g 95.9 g 96.9 g (0.415 mole) (0.383 mole) (0.388 mole) Dicarboxyphenyl 16.3% 14.5% 4.9% polyester/TPU (mole %) Weight percentage 68.0% 65.2% 65.0% of soft segment The mole ratio of 0.996 0.996 1.009 MDI/(polyglycol + glycol)) MI(190° C., 8700 g, 23.6 14.6 39.2 10 min) Appearance Light yellow Light yellow Light yellow transparent transparent transparent elastomer elastomer elastomer The softness change Obvious Obvious No change in contact with the (elastic) (elastic) (elastic) palm temperature The TPU softening 80~85° C. 80~85° C. 80~85° C. point Tg (DSC) 17.84° C. 15.39° C. −2.54° C. The 4-hour No change No change Change accelerated Severe hydrolysis test at blooming 70° C., 10 wt % NaOH (aq)
(45) A small-volume laboratory preparing method of the TPU containing a DOPO-ITA polyester structure was described below (Examples 13 to 18 and Comparative Example 2): a selective composition composed of the polyester diol containing DOPO-ITA polyester structure and aliphatic polyol, diol and auxiliary agent were mixed into a 1 liter metal drum, stirred mechanically at 110° C. of the internal temperature controlled by a heating plate, and then the MDI liquid was added while stirring, the stirring lasted for 3 minutes, the reaction mixture was poured into a tray, and the melt flow index was analyzed. At the same time, the tray was placed in a circulating oven preheated at 70° C. for 24 hours and then taken out. The appearance of the TPU finished product was recorded, the softness change thereof was measured in contact with the palm temperature, the TPU softening point and Tg were measured, and the hydrolysis resistance test was carried out. The relevant data and results of Examples 13 to 16 were shown in Table 5, and the relevant data and results of Example 17, Example 18 and Comparative Example 2 were shown in Table 6. Further, the TPU finished products (containing the DOPO-ITA polyester structure) obtained in Examples 13 to 18 were subjected to attenuated total reflection (ATR) test by using a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330 FT-IR). The infrared spectrum of the obtained product was shown in
(46) TABLE-US-00005 TABLE 5 Example 13 Example 14 Example 15 Example 16 The finished 114.1 g * * * product of (0.088 mole) Example 1 The finished * 90.2 g 115.6 g * product of (0.047 mole) (0.060 mole) Example 2 The finished * * * 230.4 g product of (0.167 mole) Example 3 PE-14 * * 115.6 g * (0.116 mole) PE-24 114.1 g 90.2 g * * (0.054 mole) (0.041 mole) 1,4-butanediol 21.9 g 19.7 g 18.8 g 16.0 g (0.243 mole) (0.219 mole) (0.209 mole) (0.178 mole) MDI 95.8 g 78.6 g 98.2 g 97.4 g (0.383 mole) (0.314 mole) (0.393 mole) (0.390 mole) DOPO-ITA 11.4% 7.6% 7.7% 11.4% polyester/TPU (mole %) Weight percentage 66.0% 64.7% 66.4% 67.0% of soft segment The mole ratio of 0.996 1.021 1.021 1.129 MDI/(polyol + diol)) MI(190° C., 2160 g, 52.3 10.0 30.0 52.0 10 min) Appearance Light yellow Light yellow Light yellow Light yellow transparent transparent transparent transparent The softness Change Change Change Change change in contact (elastic) (elastic) (elastic) (elastic) with the palm temperature The TPU softening 75~80° C. 75~80° C. 75~80° C. <80° C. point Tg (DSC) 14.99° C. 35.77° C. 15.36° C. 30.26° C. The 4-hour obviously obviously obviously obviously accelerated changed into changed into changed into changed into hydrolysis test at powder powder powder powder 70° C., 10 wt % NaOH (aq) Phosphorus content 2.16% 2.16% 2.36% 2.86%
(47) TABLE-US-00006 TABLE 6 Comparative Example 17 Example 18 Example 2 The finished product * * 173.4 g of Example 4 (0.080 mole) The finished product 113.5 g * * of Example 5 (0.075 mole) The finished product * 239.4 g * of Example 6 (0.268 mole) PE-24 113.5 g * * (0.053 mole) 1,4-butanediol 23.1 g 10.5 g 26.8 g (0.257 mole) (0.117 mole) (0.297 mole) MDI 100.2 g 101.5 g 99.2 g (0.383 mole) (0.406 mole) (0.397 mole) DOPO-ITA 9.8% 16.9% 7.8% polyester/TPU (mole %) Weight percentage 64.8% 68.1% 57.9% of soft segment The mole ratio of 1.041 1.06 1.05 MDI/(polyol + diol)) MI(190° C., 2160 32.2 16.2 25.4 g, 10 min) Appearance Yellow Yellow Near colorless transparent transparent transparent The softness change Change Obvious change No change in contact with the (elastic) (elastic) (rigid and brittle) palm temperature The TPU softening 85~90° C. 75~80° C. 90~100° C. point Tg (DSC) 33.06° C. 35.10° C. 52.49° C. The 4-hour obviously obviously obviously accelerated changed into changed into changed into hydrolysis test at powder powder powder 70° C., 10 wt % NaOH (aq) Phosphorus content 2.23% 3.09% 2.63%
(48) The present invention also provides a large-scale preparing method of the TPU having a dicarboxyphenyl polyester structure, which is applied to the production of a nonwoven fabric and evaluated for its performance as a hot melt adhesive. The embodiment will be described below.
(49) Example 19: 100 kg PD-56 was added with AO-1010 and T9 and then preheated to 105° C., 1,4-butanediol was preheated to 50° C. and MDI was preheated to 70° C., wherein the flow meter showed the molar ratio of MDI/(polyester polyol+diol) was 0.955, after being mixed into a synthetic perfusion machine for high-speed mixing, the material was continuously poured in a tray coated with a release agent and kept 24 hours after shaped at the ambient temperature, and colloidal blocks were removed and granulated. The finished product was analyzed for its melt flow index and Tg.
(50) In Example 20 and Example 21, the flow meter showed the molar ratios of the MDI/(polyester polyol+diol) were changed to 0.974 and 0.993, and the rest of the operations were the same as in Example 19.
(51) In Comparative Example 3, an aliphatic polyester polyol composition was selected, the flow meter showed the molar ratio of the MDI/(polyester polyol+diol) was changed to 0.980, and the rest of the operations were the same as in Example 19.
(52) The relevant data and results of Examples 19 to 21 and Comparative Example 3 were recorded in Table 7.
(53) The rigidity, tensile strength, elongation at break, hydrolysis resistance test, and softening point test recorded in Table 7 were tested by using shots, the TPU pallets prepared by Example 19, Example 20, Example 21, and Comparative Example 3 were sampled by the Injection molding, the injection temperature was 170° C. to 205° C., and the mold temperature was 25° C. to 30° C.
(54) The hardness was carried out in accordance with American Standard Method (ASTM) D1238.
(55) The tensile strength and elongation at break tests were carried out in accordance with Japanese Industrial Standard (JIS) K7311.
(56) In addition, attenuated total reflection (ATR) of the TPU product containing the dicarboxyphenyl polyester structure obtained in Examples 19 to 21 was carried out by using a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330 FT-IR). The infrared spectrums obtained by the test were shown in
(57) TABLE-US-00007 TABLE 7 Comparative Example 19 Example 20 Example 21 Example 3 PD-56 345.00 345.00 345.00 * (kg/hr) P700/P720(3/1) * * * 345.0 (kg/hr) 1,4-butanediol(kg/hr) 31.48 31.48 31.48 14.92 MDI (kg/hr) 125.20 127.80 130.30 137.8 Weight percentage of 68.8% 68.4% 68.1% 69.3% soft segment The mole ratio of 0.955 0.974 0.993 0.980 MDI/(polyol + diol)) Appearance Yellowish Yellowish Yellowish Near near colorless near colorless near colorless colorless pallets pallets pallets pallets MI(190° C., 2160 g, 98.0 48.8 9.6 24.3 10 min) Tg (DSC) 22.3° C. 23.1° C. 23.9° C. −22.6° C. Rigidity (23° C.) 65 D 70 D 70 D 78 A Rigidity (36° C.) 80 A 85 A 86 A 74 A Tensile 243 261 365 252 strength(kgf/cm.sup.2) (23° C., 100 mm/min) Tensile 147 187 198 223 strength(kgf/cm.sup.2) (36° C., 500 mm/min) Elongation at break 220 123 61 832 (23° C., 100 mm/min) Elongation at break 300 226 221 792 (36° C., 500 mm/min) The softening point 75~80° C. 75~80° C. 75~80° C. 70~75° C. The 4-hour accelerated No change No change No change Change hydrolysis test at 70° C., Severe 10 wt % NaOH (aq) blooming the number of days that 40 days 55 days 77 days 8 days cannot be hand-teared in 90° C. hot water long-term test Peel strength between 1.63 2.72 3.20 2.83 TPU melt-blown nonwoven and polyester woven (kgf/cm) Softness change of the The woven The woven The woven The woven joined woven at the palm was relatively was relatively was relatively was soft, and temperature stiff, and stiff, and stiff, and no change at became softer became softer became softer the palm at the palm at the palm at the palm temperature. temperature. temperature. temperature.
(58) According to Table 7, the hydrolysis time of the hot-melt adhesive containing the TPU of the present invention was at least 40 days in hot water of 90° C. By contrast, the hot-melt adhesive made of the thermoplastic polyurethane of Comparative Example 3 was hydrolyzed in 8 days. Therefore, it was concluded that the hot-melt adhesive made of the TPU having the dicarboxyphenyl polyester structure of the present invention had excellent high temperature hydrolysis resistance.
(59) Further, the TPU pallets obtained in Example 19, Example 20, Example 21, and Comparative Example 3 were subjected to a melt-blow test at a feed temperature of 110° C. to 120° C. and a nozzle temperature of 225° C. to 235° C. The melt-blow test was carried out at a spinning pressure of 2,500 psi to 3,000 psi, and then 0.5 mm non-wovens were taken at room temperature with a roller.
(60) According to the experiment results, the TPU pallets of Example 19, Example 20 and Example 21 were smoothly formed into silk, and could be directly collected at room temperature to obtain a TPU non-woven fabric having a smooth and stiff surface. The TPU pallets of Comparative Example 3 could be formed into silk, but the cooling and solidification speed was slow, so that the surface of the non-woven fabric had spheroidal granules, and the non-woven fabric itself was not easily separated when collected at room temperature.
(61) On the other hand, according to the Chinese National Standard GBT 2791 test method, the TPU non-woven fabrics obtained by melt-blown in Example 19, Example 20 and Example 21 were sandwiched in two pieces of polyester woven fabric for joining test by using the hot press. The temperature was set at 130° C. for 25 seconds and the pressure was set to 5 kg/cm.sup.2. The TPU non-woven fabric obtained by melt blown in Comparative Example 3 was operated as above, the temperature was set at 100° C. for 10 seconds, and the pressure was set to 5 kg/cm.sup.2; then the above-mentioned laminated fabric test piece was placed for 16 hours, then cut into 2.5 cm×12 cm strips and the peeling strength test was carried out by static hydraulic universal testing machine made by GOECH, model AI-70005, at the tensile speed of 100 mm/min. According to Table 7, the results were all above 1.6 kgf/cm, and had the function of hot melt adhesive. In particular, the woven fabric containing the thermoplastic polyurethane of the present invention as a hot melt adhesive has a relatively good appearance, and is softened when contacted with the palm or the skin, while the woven fabric containing the TPU of Comparative Example 3 as a hot melt adhesive was relatively easy to shrink and wrinkle.
(62) Further, the large-scale preparation of the TPU containing DOPO-ITA polyester structure was the same as the above large-scale preparation of the TPU containing dicarboxyphenyl polyester structure, and therefore will not be described herein.
(63) Further, as shown in Table 8, the TPU pallets obtained in Example 19, Example 20 and Example 21, and the TPU non-woven fabrics obtained by melt-blown were respectively analyzed by a differential scanning calorimeter (DSC) for crystallization temperature (Tc), glass transition temperature (Tg) and melting point (Tm), and analyzed by gel chromatography (GPC) for number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp). The molecular weight of the meltblown fabric produced by using the TPU pallets of Examples 19 to 21 was found to be higher than the TPU pallets. The detailed mechanism was not clearly understood, but the articles made of the meltblown fabric have the advantage of being strong and not easily damaged due to its large molecular weight.
(64) TABLE-US-00008 TABLE 8 GPC Tg ° C. Tc ° C. Tm ° C. Mw/Mn/Mp Example 19 TPU pallets 22.26 78.01 146.6 51598/30663/48020 0.5 melt-blown 23.70 79.3 145.1 82366/42761/75979 Example 20 TPU pallets 23.13 80.77 145.7 60790/36162/66705 0.5 melt-blown 21.63 78.35 143.3 98378/50616/92683 Example 21 TPU pallets 23.93 84.51 145.8 101896/60178/96348 0.5 melt-blown 25.05 85.53 146.7 120294/62495/125583
(65) The above embodiments can be implemented by combination as appropriate, as long as technically permitted. It should be understood by one skilled in the art that the various modifications and variations made without departing from the spirit are also included in the scope of the present invention.
(66) The thermoplastic polyurethane of the present invention has a Tg between the ambient temperature and normal body temperature, so that the articles thereof are easily-molded, less likely to wrinkle, visually stiff when displayed or placed, and provides soft and comfortable feel when in contact with the human body, so it is especially suitable for textiles (such as underwear, hats, label cloths, curtains, etc.), shoes, decorations (such as straps, wristbands, etc.), toys, sporting goods, daily necessities and so on, so the present invention is also industrially useful.
(67) Further, the aforementioned TPU can be prepared by the polyester polyol containing DOPO-ITA polyester structure represented by the Formula 2, so that the polyester polyol of the present invention is also industrially useful.