Continous process for producing polyol modified polyalkenylene terephthalate

Abstract

The present invention relates to a continuous process for the production of polyol modified polyalkenylene terephthalates and the application of such polyol modified polyalkylene therephtalate on wire enamels.

Claims

1. A continuous process for producing a polyol modified polyalkylene terephthalate, the continuous process comprising: introducing components in a continuous reactor comprising a reaction zone, the components including a polyalkylene terephthalate, a polyol, and a transesterification catalyst; reacting the components in the reaction zone of the reactor at a temperature in the range of 180° C. to 350° C. to produce a polyol modified polyalkylene terephthalate; wherein the polyol includes one or more of tris(2-hydroxyethyl)isocyanurate and glycerine, and wherein reacting the components is performed in a melt of the polyalkylene terephthalate.

2. The continuous process of claim 1, wherein the continuous process is performed in an extruder.

3. The continuous process of claim 1, wherein the melt of the polyalkylene terephthalate is substantially without a solvent.

4. The continuous process of claim 1, wherein reacting the components is performed in the absence of a solvent.

5. The continuous process of claim 1, wherein the polyalkylene terephthalate is polyethylene terephthalate or polybutylene terephthalate.

6. The continuous process of claim 1, wherein the amount of the polyol introduced in the continuous reactor includes at least 0.5 mol OH groups per 100 g of the polyalkylene terephthalate.

7. The continuous process of claim 1, wherein the Mn (number average) molecular weight of the polyol modified polyalkylene terephthalate is in the range of 800 to 3000 Daltons.

8. The continuous process of claim 1, wherein the amount of the transesterification catalyst introduced is in the range of 100 to 10000 ppm calculated on the sum of the polyalkylene terephthalate, the polyol, and the transesterification catalyst components.

9. The continuous process of claim 1, wherein the transesterification catalyst is a lewis acid.

10. The continuous process of claim 1, wherein the polyol further comprises one or more of trimetylolpropane and pentaerythritol.

11. The continuous process of claim 1, wherein the polyol is tris(2-hydroxyethyl)isocyanurate or glycerine.

12. The continuous process of claim 1, wherein the continuous process further comprises removing the polyol modified polyalkylene terephthalate from the reactor.

13. The continuous process of claim 1, further comprising dissolving the polyol modified polyalkylene terephthalate in a solvent to produce a dissolved polyol modified polyalkylene terephthalate.

14. The continuous process of claim 13, further comprising adding one or more of an additive and a diluent to the dissolved polyol modified polyalkylene terephthalate.

15. The continuous process of claim 1, further comprising applying the polyol modified polyalkylene terephthalate on a wire.

16. The continuous process of claim 15, further comprising adding one or more of an additive and a diluent to the dissolved polyol modified polyalkylene terephthalate.

Description

EXAMPLES

(1) All experiments were performed using a Brabender Co-Rotating Clamshell Twin Screw Extruder Model 20/40D. The extruder contained 4 heating zones, a die adapter heating zone and a die heating zone. If not otherwise specified, the first heating zone is the feeding zone and the remaining zones are reaction zones. The screw design contained forward and reverse conveying elements, forward and reverse kneading blocks, and teeth elements. Polyethylene terephthalate (PET) (SKC Films Inc.) was fed through a single spiral screw volumetric feeder. Tris (2-hydroxyethyl) isocyanurate (THEIC) as well as cyanuric acid were fed through either a twin concave screw volumetric feeder or a single auger screw volumetric feeder. Either zinc acetate or tetra-n-butyl titanate (TNBT) were used as catalysts and premixed with the THEIC or PET. When the amount of a catalyst is given in weight %, such amount is calculated based on the total weight of the components. All materials were dosed through a 3 L stainless steel hopper. No additional equipment was used unless otherwise specified.

Example 1 (Comparative)

(2) PET was fed with all temperature zones set to 270° C. The PET feed rate was 15 g/min and the extruder screw speed was set at 100 RPM. The PET exited the extruder as a meltand was collected into cans and cooled. The resulting product was solid at room temperature and insoluble in THF. Sample could not be measured by GPC in tetrahydrofuran (THF). Probably, the molecular weight of the resulting polymer is too high and therefore it could not be solved in THF.

Example 2 (Comparative)

(3) PET and THEIC were fed with no catalyst and with all zones set to 270° C. The rates of feed of the PET and THEIC were 15 g/min and 12 g/min respectively. The extruder screw speed was set at 100 RPM. The resulting plastic exited the extruder as a melt and was collected into cans and cooled. The resulting product was solid at room temperature and mostly insoluble in THF. Decomposition was observed by darkening of the material. Sample could not be measured by GPC in THF.

Example 3

(4) PET and THEIC/Zinc acetate catalyst premix were fed with all zones set to 270° C. The catalyst loading was 0.43% by weight. The rates of feed of the PET and THEIC premix were 15 g/min and 12 g/min respectively, corresponding to 0.92 mol OH per 100 g PET. The extruder screw speed was set at 100 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The clear product was soluble in THF and further characterized by GPC. The number and weight average molecular weight is comparable to batch produced THEIC polyester polymer used in wire enamel coatings. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

Example 4

(5) PET and THEIC/Zinc acetate catalyst premix were fed with all zones set to 300° C. The catalyst loading was 0.43% by weight. The rates of feed of the PET and THEIC premix were 15 g/min and 12 g/min respectively, corresponding to 0.92 mol OH per 100 g PET. The extruder screw speed was set at 100 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The clear product was soluble in THF and further characterized by GPC. The number and weight average molecular weight is comparable to batch produced THEIC polyester polymer used in wire enamel coatings. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

Example 5

(6) PET and THEIC/Zinc acetate catalyst premix were fed with all zones set to 270° C. The catalyst loading was 0.86% by weight. The rates of feed of the PET and THEIC premix were 15 g/min and 12 g/min respectively, corresponding to 0.92 mol OH per 100 g PET. The extruder screw speed was set at 100 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The clear product was soluble in THF and further characterized by GPC. The number and weight average molecular weight is comparable to batch produced THEIC polyester polymer used in wire enamel coatings. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

Example 6 (Batch Process)

(7) Terephthalic acid (190 g), THEIC (170 g), ethylene glycol (52 g) and tetrabutyltitanate catalyst (0.4 g) were added to flask with mechanical stirring, nitrogen purge and heating mantel. Cresylic acid solvent (30 g) was added. The components were heated to a temperature of 220° C. with removal of water to form a clear plastic resin after 12 hours. The clear product was soluble in THF and further characterized by GPC. Infrared spectrum, .sup.1H and .sup.13C NMR were taken after removal of the cresylic acid solvent.

(8) From examples 1-6 it is apparent that with use of a continuous reactor or extruder one can produce a THEIC polyester that is comparable to the batch process. It is also critical that PET, polyol and catalyst be present for the reaction to take place in a reasonable amount of time. Higher loading levels of catalyst also increase the rate of reaction.

(9) TABLE-US-00001 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 1 Not soluble Not soluble (comparative) 2 Not soluble Not soluble (comparative) 3 1129 2235 4 1752 7363 5 1230 2737 6 1391 4451 (batch)

Example 9

(10) PET and THEIC/Zinc acetate catalyst premix were fed with the feed zone set at 100° C., second zone set to 270° C., and the remaining two zones set to 315° C. respectively. The catalyst loading was 0.86% by weight. The rates of feed of the PET and THEIC premix were 47 g/min and 36 g/min respectively, corresponding to 0.87 mol OH per 100 g PET. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The residence time through the extruder was 45 seconds. The clear product was soluble in THF and further characterized by GPC. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

Example 10

(11) PET and THEIC/Zinc acetate catalyst premix were fed with the feed zone set at 100° C., second zone set to 270° C., and the remaining two zones set to 325° C. respectively. The catalyst loading was 0.86% by weight. The rates of feed of the PET and THEIC premix were 47 g/min and 36 g/min respectively, corresponding to 0.87 mol OH per 100 g PET. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The residence time through the extruder was 45 seconds. The clear product was soluble in THF and further characterized by GPC. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

(12) Examples 9 and 10 demonstrate that elevated temperatures of greater than 300° C. can be successfully used to produce modified polyester resin comparable to the batch process.

(13) TABLE-US-00002 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 9 1346 3306 10 1452 4542

Examples 15 and 17

(14) PET and THEIC/TNBT catalyst premix were fed with the feed zone set at 120° C., and the remaining zones set to 285° C. or 300° C. respectively. The catalyst loading was 0.20% by weight. The rates of feed of the PET and THEIC premix were 21 g/min and 15 g/min respectively, corresponding to 0.81 mol OH per 100 g PET. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The residence time through the extruder was 130 seconds. The clear product was soluble in THF and further characterized by GPC. Infrared spectrum is consistent with THEIC polyester polymer produced by the conventional batch process. .sup.1H and .sup.13C NMR are also consistent with material produced by batch process.

(15) Examples 15 and 17 demonstrate that alternate lewis acid catalysts can be used to produce a THEIC polyester with comparable properties to the batch process.

(16) TABLE-US-00003 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 15 1471 3854 17 1667 5301

Examples 23, 25 and 26

(17) PET and THEIC/TNBT catalyst premix were fed with the feed zone set at 130° C. and the remaining zones set to 290° C., 310° C., or 320° C., respectively. The catalyst loading was 0.20% by weight. The rates of feed of the PET and THEIC premix were 58 g/min and 42 g/min respectively, corresponding to 0.83 mol OH per 100 g PET. The extruder screw speed was set at 350 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled.

(18) Examples 23-26 show that temperature can be used to control the molecular weight of the resulting THEIC polyester resin. Higher temperatures gave material with higher molecular weight.

(19) TABLE-US-00004 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 23 1433 3551 25 1583 4584 26 1669 5651

Examples 31-32

(20) PET and a trimethylolpropane (TMP)/TNBT catalyst premix were fed with the feed zone set at 100° C. and the remaining zones set to 310° C. or 320° C. The catalyst loading was 0.20% by weight. The rates of feed of the PET and TMP premix were 29 g/min and 22 g/min respectively, corresponding to 1.67 mol OH per 100 g PET. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled in ambient conditions.

Example 36

(21) PET and a glycerin/TNBT catalyst premix were fed with the feed zone set at 100° C. and the remaining zones set to 320° C. The catalyst loading was 0.20% by weight. The rates of feed of the PET and glycerin premix were 30 g/min and 10 g/min respectively, corresponding to 1.1 mol OH per 100 g PET. This system contained excess glycerin. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled.

(22) Examples 31, 32 and 36 demonstrate that alternate polyols can be used in addition to THEIC to produce a modified polyester.

(23) TABLE-US-00005 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 31 862 1406 32 1076 1966 36 1449 3032

Examples 38-39

(24) Polybutylene terephthalate (PBT) and a THEIC/TNBT catalyst premix were fed with the feed zone set at 100° C. and the remaining zones set to 300° C., or 320° C. The catalyst loading was 0.20% by weight. The rates of feed of the PBT and THEIC premix were 20 g/min and 13 g/min respectively, corresponding to 0.75 mol OH per 100 g PET. The extruder screw speed was set at 250 RPM. The resulting polyol modified PET exited the extruder as a melt and was collected into cans and cooled. The clear product was soluble in THF and further characterized by GPC. The number and weight average molecular weight is comparable to batch produced THEIC polyester polymer used in wire enamel coatings. The infrared spectrum is consistent with THEIC polyester.

(25) TABLE-US-00006 Example M.sub.n (g mol.sup.−1) M.sub.w (g mol.sup.−1) 38 1403 3462 39 1977 7465

(26) Magnet Wire Coatings: The resin from example 17 and control sample 6 were used as the polymers for a magnet wire coating.

Example 40

(27) Resin from control Example 6 (300 g) was dissolved in 100 g of cresylic acid and 300 g of phenol. Solvent 100 (225 g) diluent was then added. Phenolic 877-R-50 (35 g) was then added along with Desmodur CT stable (25 g). Tetrabutyltitanate (16 g) crosslinker was finally added. The mixture was enameled on 1.0 mm copper wire monolithically and as base coat with a standard Polyamideimide top coat (75:25 thickness) using a conventional magnet wire oven (MAG).

Example 41

(28) Resin from control Example 17 (300 g) was dissolved in 100 g of cresylic acid and 300 g of phenol. Solvent 100 (225 g) diluent was then added. Phenolic 877-R-50 (35 g) was then added along with Desmodur CT stable (25 g). Tetrabutyltitanate (16 g) crosslinker was finally added. The mixture was enameled on 1.0 mm copper wire monolithically and as base coat with a standard Polyamideimide top coat (75:25 thickness) using a conventional magnet wire oven (MAG). The resin solutions were checked for viscosity and found to be equivalent at roughly 500 cP at 25° C. Each coating was then applied to a steel panel by a knife coater and cured in an oven at 260° C. for 30 minutes. A sample of the panel was then analyzed by TMA for glass transition (Tg). Examples 40 and 41 were found to have equivalent glass transition points.

(29) TABLE-US-00007 Sample μ [cP] Tg [° C.] Example 40 500 164 Example 41 474 162

(30) Mechanical Properties on wire are shown in the tables below. The batch process enamel (Example 40) was comparable in properties to the material synthesized by the continuous process (Example 41).

(31) Mandrel Test 1×Diameter with Pre-Stretching %

(32) TABLE-US-00008 Example 40/PAI Example Top coat Example 40 41/PAI % (control) (control) Top coat Example 41 0 3/3 3/3 3/3 3/3 5 3/3 3/3 3/3 3/3 10 3/3 3/3 3/3 3/3 15 3/3 3/3 3/3 3/3 20 3/3 3/3 3/3 3/3 25 3/3 3/3 3/3 3/3 30 3/3 3/3 3/3 3/3

(33) Peel Test

(34) TABLE-US-00009 Example 40/PAI Example Top coat Example 40 41/PAI (control) (control) Top coat Example 41 Twists 184 134 194 140

(35) Tan Delta

(36) TABLE-US-00010 Example 40/PAI Example Top coat Example 40 41/PAI (control) (control) Top coat Example 41 ° C. 166.6 166.3 162.9 167.2

(37) Cut-Through Large Plate

(38) TABLE-US-00011 Example 40/PAI Example Top coat Example 40 41/PAI (control) (control) Top coat Example 41 ° C. 420 430 410 420

(39) Measurements

(40) GPC measurement were performed using Agilent Infinity 1260 GPC. The Infinity GPC is equipped with an Infinity 1260 Degasser. The Infinity GPC is equipped with an isocratic pump that is also model number Infinity 1260. The serial number is DEAB902598. Next the Infinity GPC contains attachments for thermostating the GPC columns and autosampler features. The solvent is tetrahydrofuran (THF) and supplied by Honeywell. The purity is 99.9% with a peroxide level of less than 2 mg/L. Samples to be analyzed are first dissolved in THF with mild agitation. The sample is then filtered through a 5 mL syringe with a 0.5 micron filter filter housing. The solution is collected with a 5 mL vial suitable for the autosampler. A lid with a rubber septum is then crimped onto the vial using an Agilent supplied vial crimper. After all the samples have been loaded into the autosampler, the method is started. The method is set to a flow rate of 1 mL/min of THF through a mixed D column (2 in series) supplied by Phenomenex. The mixed D columns are thermostated at 40° C. and the refractive index detector is baseline zeroed. The effluent is collected in a suitable container with proper venting. Samples are injected on the column per the method with an injection volume of 0.5 microliters per injection. The refractive index detector is thermostated at 40° C. also to prevent signal drift. The signal polarity is positive. The maximum pressure allowed on the column set is 600 bar. Analysis was performed with Agilent Chemstation software. Reference samples of polystyrene purchased from Agilent are run in a similar fashion to develop a calibration curve. The standards range in molecular weight of 500 to 30,000 Daltons. The calibration curve can be a linear fit or first order or second order depending on the column set utilized. In this experiment we used a first order fit.

(41) Flexibility or Mandrel Test was performed according to the procedure IEC EN 60851-3. Therein it is described the Mandrel winding test. Coated wires were taken as such and pre-stretched at 5%, 10%, 15%, 20%, 25%, 30%. For each measurement point three probes were prepared. Each wire was wound around a polished mandrel, a piece of steel having the same diameter as the wire. Once the wire was on the mandrel, the presence of cracks was checked. The absence of cracks gives the flexibility of the coated wire.

(42) Peel Test was performed according to the procedure IEC EN 60851-3. Therein it is described the peel test applicable to enameled round wire with a nominal conductor diameter over 1000 mm.

(43) Tan delta was measured using Dansk tangent delta instrument.

(44) Cut Through Large Plate was measured using Nova 1005 Thermoplastic Cut-Through Tester that meets the NEMA-MW1000 and the JIS C3003 specifications.

(45) 1H and 13C NMR spectra were measured using 500 MHz Varian NMR in CDCl3.

(46) FT-IR was measured using Thermoscientific Nicolet FT-IR using ATR attachment. Viscosity was measured using Brookfield LV viscometer.

(47) Tg was measured using TA Instruments Thermomechanical Analyzer using a penetration probe. The heating rate was 10° C. per minute.