FLAME RETARDANT POLYBUTYLENE SUCCINATE COMPOUND

Abstract

Flame retardant polybutylene succinate (PBS) compounds using a non-halogenated intumescent flame retardant system are disclosed.

Claims

1. A flame retardant polymer compound, comprising: (a) polybutylene succinate; (b) ammonium polyphosphate; (c) melamine cyanurate; (d) mineral filler; and (e) optionally, polytetrafluoroethylene; wherein the mineral filler is a quaternary ammonium salt modified montmorillonite, talc, or a combination thereof.

2. The compound of claim 1, wherein the compound further comprises epoxy-functional styrene-acrylic oligomer as an optional additive.

3. The compound of claim 1, wherein the compound further comprises adhesion promoters; biocides; anti-fogging agents; anti-static agents; anti-oxidants; foaming agents; dispersants; fillers; smoke suppressants; impact modifiers; initiators; lubricants; colorants; plasticizers; processing aids; release agents; silanes; titanates; and zirconates; slip agents, anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; catalyst deactivators, and combinations of them.

4. The compound of claim 3, wherein ingredients of the compound have ranges of weight percents of the total compound as listed. TABLE-US-00009 Ingredient Wt. % Polybutylene succinate 59-70 Ammonium polyphosphate 24-30 Mineral filler 1-5 Melamine cyanurate 4-5 Optional polytetrafluoroethylene  0-0.1.

5. The compound of claim 3, wherein ingredients of the compound have ranges of weight percents of the total compound as listed. TABLE-US-00010 Ingredient Wt. % Polybutylene succinate 50-52 Ammonium polyphosphate 30 Mineral filler 1-5 Melamine cyanurate  5 Optional polytetrafluoroethylene .sup. 0-0.1 Other optional additives  0-7.

6. An article made from the flame retardant polymer compound of claim 1.

7. The article of claim 6 wherein the article is shaped by extrusion, molding, calendering, thermoforming, additive manufacturing for 3-D printing, or other means of shaping into a plastic article usable in an interior or confined space where fire can cause personal injury or property damage.

8. The article of claim 6, wherein the article is shaped by 3-D printing.

9. An article made from the flame retardant polymer compound of claim 2.

10. The article of claim 9 wherein the article is shaped by extrusion, molding, calendering, thermoforming, additive manufacturing for 3-D printing, or other means of shaping into a plastic article usable in an interior or confined space where fire can cause personal injury or property damage.

11. The article of claim 9, wherein the article is shaped by 3-D printing.

12. An article made from the flame retardant polymer compound of claim 3.

13. The article of claim 12 wherein the article is shaped by extrusion, molding, calendering, thermoforming, additive manufacturing for 3-D printing, or other means of shaping into a plastic article usable in an interior or confined space where fire can cause personal injury or property damage.

14. The article of claim 12, wherein the article is shaped by 3-D printing.

15. An article made from the flame retardant polymer compound of claim 4.

16. The article of claim 15 wherein the article is shaped by extrusion, molding, calendering, thermoforming, additive manufacturing for 3-D printing, or other means of shaping into a plastic article usable in an interior or confined space where fire can cause personal injury or property damage.

17. The article of claim 15, wherein the article is shaped by 3-D printing.

18. An article made from the flame retardant polymer compound of claim 5.

19. The article of claim 18 wherein the article is shaped by extrusion, molding, calendering, thermoforming, additive manufacturing for 3-D printing, or other means of shaping into a plastic article usable in an interior or confined space where fire can cause personal injury or property damage.

20. The article of claim 18, wherein the article is shaped by 3-D printing.

Description

EXAMPLES

[0047] Table 2 shows the list of ingredients. Table 3 shows the extrusion conditions. Table 4 shows the molding conditions. Table 5 shows the recipes and Tables 6A and 6B the test results. Properties of a typical flame retardant polymer compound of the invention are shown in Table 7.

TABLE-US-00002 TABLE 2 Brand Chemical Purpose Maker PBS ENP01 Polybutylene succinate Polymer Samsung Fine G4560m (CAS # 67423-06-7) matrix Chemicals Co., Ltd. PBS ENP01 Polybutylene succinate Polymer Samsung Fine G4560J (CAS # 67423-06-7) matrix Chemicals Co., Ltd. JLS-APP Ammonium Flame Hangzhou JLS polyphosphate retardant Flame Retardants Chemical Co., Ltd FP2200 Ammonium Flame Adeka polyphosphate retardant JLS-MC25 Melamine cyanurate Non-halogen Hangzhou JLS (CAS # 37640-57-6) flame Flame Retardants retardant Chemical Co., Ltd Melapur ® Melamine Cyanurate Non-halogen BASF MC15 (CAS # 37640-57-6) flame retardant Cloisite ™ Quaternary ammonium Co-additive Southern Clay 30B salt modified natural Products montmorillonite nanoclay TEFLON ® Polytetrafluoro- Anti- DuPont 6C ethylene dripping agent Jetfine ® Talc Co-additive Imerys Talc 3CA Irganox ® 50/50 blend of Heat Ciba B225 trisarylphosphite and processing sterically hindered stabilizers phenolic antioxidant Joncryl ® Epoxy-functional Chain BASF 4368 styrene-acrylic extender oligomer

TABLE-US-00003 TABLE 3 Extruder Conditions Extruder Type 18 mm Leistitz twin screw extruder Examples A-C, 1-2 3-4 Order of Addition All ingredients fed into the extruder hopper except APP, with APP added downstream. Zone 1 190° C. 190° C. Zone 2 190° C. 190° C. Zone 3 190° C. 190° C. Zone 4 190° C. 190° C. Zone 5 190° C. 190° C. Zone 6 190° C. 190° C. Zone 7 190° C. 190° C. Zone 8 190° C. 190° C. Main RPM 500 350 Side RPM 209 209 % load  58  58 Vacuum On On

TABLE-US-00004 TABLE 4 Molding Conditions Molding Machine: Nissei 88 Examples A-C, 1-2 3-4 Drying Conditions before Molding: Temperature (° C.) 70 70 Time (h) 16 4 Temperatures: Nozzle (° C.) 210 200 Zone 1 (° C.) 204 193 Zone 2 (° C.) 199 188 Zone 3 (° C.) 199 188 Mold (° C.) 49 27 Speeds: Screw RPM 131 65 Inj Vel Stg 1 20% 60% Inj Vel Stg 2 15% 40% Inj Vel Stg 3 10% 40% Inj Vel Stg 4  5% 30% Inj Vel Stg 5  5% 20% Pressures: Injection Pressure 8 8 Stg1 - Time (sec) Injection Pressure 1 0 90% Hold Pressure 2 90 25% Hold Pressure 3 40 0 Back Pressure 5  5% Timers: Injection Hold (sec) 8 7 Cooling Time (sec) 15 20 Operation Settings: Shot Size (mm) 43 40 Cushion (mm) 1.1 1.1

TABLE-US-00005 TABLE 5 Example A B C 1 2 3 4 Ingredients (by weight % of compound) Ultem ® 1000 100.0 Ultem ® 9085 100.0 PBS ENP01 G4560m 100.0 69.9 59.8 59.8 PBS ENP01 G4560J 69.9 Irganox ® B225 0.1 0.1 0.1 0.1 FP2200 24.2 JLS-APP 24.2 29.2 29.2 Melapur MC-15 4.8 JLS-MC25 4.8 4.8 4.8 Cloisite 30B 1.0 1.0 5.0 Jetfine ® 3CA 5.0 DuPont TEFLON 6C 0.1 0.1 Joncryl 4368 1.0 1.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[0048] Samples were tested according to the procedures and test standards described below.

[0049] HDT (ASTM D648): was measured on the Tinius Olsen HDT from Tinius Olsen Inc (PA, USA) at heating rate of 20° C./min. Two measurements were made for each sample.

[0050] Notched Izod Impact (ASTM D-256)

[0051] Cone calorimetry: The cone calorimeter was used to measure the heat release and smoke release of these formulations, according to ASTM E1354-13. A square sample of 100 cm×100 cm was placed horizontally 25 mm below the radiant heat source, the cone. The heat flux used was 65 kW/m.sup.2. Upon exposure to the cone, a spark igniter was placed above the surface of the sample and the time to ignition is recorded. The time to flameout was also manually recorded, while the instrumentation measures the consumption of oxygen from the sample stream as well as the production of carbon monoxide and carbon dioxide. A laser placed across the exhaust duct measured the obstruction of the beam by the combustion products to output smoke measurements.

[0052] PCFC: The samples were tested with the MCC at 1° C./sec heating rate under nitrogen from 150° C. to 800° C. using method A of ASTM D7309 (pyrolysis under nitrogen). Each sample was run in triplicate to evaluate reproducibility of the flammability measurements.

TABLE-US-00006 TABLE 6A Test Results Example 3 4 Flex Modulus (KSI @ 0.5 in/min)  234 ± 7.9   246 ± 10.8 Flex Strength (PSI @ 0.5 in/min) 5576.8 ± 248.4 5888.7 ± 55.6 Tensile Modulus (KSI) @ 2 in/min 192.7 ± 29.1 283.4 ± 3.6 Tensile Stength (PSI)@ 2 in/min 3166.1 ± 147.3 3369.4 ± 27.8 Tensile Strain at Break (%)@ 2 in/min 19.5 ± 3.sup.   17.6 ± 1.6 HDT @ 264 PSI 56.9 ± 1.1  58.8 ± 1.1 Notched IZOD (ft .Math. lb/in)  0.6 ± 0.03  0.47 ± 0.04 Density (g/cm3) 1.463 1.448 UL-94 @⅛″ V0 V0

TABLE-US-00007 TABLE 6B Additional Flammability Tests Example 1 A B C Cone Average HRR 160.7 N/A 101.7 119.1 calorimetry (KW/m2) Peak HRR 217.8 N/A 251.2 150 (KW/m2) Total Smoke 465.5 N/A 653.2 782.4 (m2/m2) Char Yield 14.6 ± 0.2  0.3 ± 0.1  51.2 ± 0.5 41.6 ± 0.4 (wt %) HRR    79 ± 56.6, 545.1 ± 6.3 Peak(s)Value 588 ± 49 312.4 ± 4.8 202.7 ± 3.9  (W/g) PCFC HRR 492.7 ± 1.2,  427.3 ± 0.6 Peak(s)Temp(s) 406 ± 1  567.6 ± 2.3 516.4 ± 3.4  (° C.) Total HR (kJ/g) 17.2 ± 0.9   20 ± 0.4  8.8 ± 0.1 10.9 ± 0.1

[0053] Properties of the flame retardant polymer compound of the present invention are shown in Table 7.

TABLE-US-00008 TABLE 7 Properties Units Test Methods Value Physical Density g/cm.sup.3 ASTM D-792 1.46 Tensile Modulus GPa ASTM D-638 1.3 (2 in/min) Tensile Strength Mpa ASTM D-638 22 (2 in/min) Tensile Elongation % ASTM D-638 19 (2 in/min) Flexural Modulus GPa ASTM D-790 1.6 (0.5 in/min) Flexural Strength (0.5 MPa ASTM D-790 38.5 in/min) Heat Deflection ° C. ASTM D-648 57 Temperature (264 psi) Notched Izod J/m ASTM D-256 32 Flammability (3 mm) UL-94 V0 Glass Transition ° C. ASTM D3418 74 Temperature via DSC Melting Temperature ° C. ASTM D3418 118 via DSC Melt Flow Index (g/10 min) ASTM D1238 29.3 230° C./2.16 kg Injection Molding - Processing DRYING CONDITIONS Drying temperature ° C. 80 Drying time hr 4 MOLDING CONDITIONS Melt temperature ° C. 185-200 Barrel temperature ° C. 185-200 Mold temperature ° C. 25-30 Maximum moisture % 0.05 content