Patent Publication Number: US-2021163709-A1

Title: Use of ethoxyamide polymer as delay combustion agent, low-odor combustion-delaying polyolefin composition and preparation method thereof

Description:
BACKGROUND 
     Technical Field 
     The present invention relates to the technical field of new polymer materials, and particularly relates to a use of an ethoxyamide polymer as a delay combustion agent, a low-odor combustion-delaying polyolefin composition and a preparation method thereof. 
     Description of Related Art 
     With the development of social informatization and intelligence, lightweighting of the automobile industry is undoubtedly an important development direction, which requires the thickness of auto parts to be thinned to achieve lightweight and fuel consumption reduction. At present, most automobile OEMs are developing towards this direction, reducing wall thickness from the original 3.0 mm to 2.0 mm, or even to 1.0 mm. The thinning of the wall thickness will inevitably bring to an increase in a combustion speed, but the industry or OEMs has not reduced the standard of the combustion speed (GB 8410 requires the combustion speed to be ≤100 mm/min, and some OEMs require the combustion speed to be ≤81 mm/min), which brings a relatively big problem to modified plastics. At present, to achieve the purpose of retarding combustion, it is necessary to add a flame retardant, especially a brominated flame retardant, which has direct negative impacts on automotive interior materials that are problems of odor and TVOC. 
     In the prior art applications, ethoxyamide polymers are mainly used as antistatic agents. 
     SUMMARY 
     An objective of the present invention is to overcome the above technical defects and provide a use of an ethoxyamide polymer as a delay combustion agent, which has advantages of a low additive amount, a good combustion-delaying effect and a low odor. 
     Another objective of the present invention is to provide a low-odor combustion-delaying polyolefin composition and a preparation method thereof, which includes the ethoxyamide polymer as the delay combustion agent and has the advantages of the good combustion-delaying effect and the low odor. 
     The present invention is realized through the following technical solutions. 
     A use of an ethoxyamide polymer as a delay combustion agent, wherein 0.3% to 2% of the ethoxyamide polymer is included in a polyolefin composition based on a weight percentage of the polyolefin composition. 
     The ethoxyamide polymer is selected from at least one of stearic acid ethoxyamide, lauric acid ethoxyamide, cocinic acid ethoxyamide and other ethoxyamide polymers. 
     Further, 0% to 2% of a combustion-delaying synergist is also included by weight percentage. The combustion-delaying synergist is selected from at least one of a phosphate. The phosphate is selected from at least one of aluminum hypophosphite, calcium hypophosphite, dimethyl aluminum hypophosphite, diethyl aluminum hypophosphite and methyl ethyl aluminum hypophosphite. 
     A low-odor combustion-delaying polyolefin composition includes the following components by weight percentage: 
     polyolefin 56% to 99.7%; 
     an ethoxyamide polymer 0.3% to 2%; 
     a combustion-delaying synergist 0% to 2%; and 
     a filler 0% to 40%. 
     The polyolefin is selected from at least one of polypropylene and polyethylene. 
     The ethoxyamide polymer is selected from at least one of ethoxyamide polymers such as stearic acid ethoxyamide, lauric acid ethoxyamide and cocinic acid ethoxyamide. 
     The filler is selected from at least one of talc powder, calcium carbonate, montmorillonite, clay and kaolin. 
     The combustion-delaying synergist is selected from at least one of a phosphate; the phosphate is selected from at least one of aluminum hypophosphite, calcium hypophosphite, dimethyl aluminum hypophosphite, diethyl aluminum hypophosphite and methyl ethyl aluminum hypophosphite. 
     0% to 5% of an auxiliary agent is further included by weight percentage, and the auxiliary agent is selected from at least one of a lubricant, an antioxidant and a light stabilizer. 
     A preparation method of the combustion-delaying polyolefin composition according to the present invention includes the following steps: 
     weighing each material according to weight percentages, then adding the polyolefin, the ethoxyamide polymer, the combustion-delaying synergist, the filler and the auxiliary agent into a high-speed mixer, mixing them evenly, and then adding the mixed materials into an extruder for extrusion and granulation, to obtain the low-odor combustion-delaying polyolefin composition, wherein a screw temperature is 180° C. to 220° C. 
     The present invention has the following beneficial effects. 
     The ethoxyamide polymer of the present invention is added to the polyolefin composition as the delay combustion agent, with an additive amount of only 0.2% to 3%, making the combustion-delaying polyolefin composition with the advantages of the good combustion-delaying effect and the low odor. Further, no more than 2% of the combustion-delaying synergist is also added to further enhance the combustion-delaying effect while maintaining the low odor. 
    
    
     DESCRIPTION OF THE EMBODIMENTS 
     The present invention will be illustrated below in combination with embodiments, but the present invention is not limited by the following embodiments. 
     Sources of raw materials used in the present invention are as follows: 
     stearic acid ethoxyamide: A4-88, purchased from Zhejiang Java; 
     lauric acid ethoxyamide: A-2000, purchased from Zhejiang Java; 
     polypropylene: PP N-Z30S, purchased from Sinopec; 
     talc powder: AH51210, purchased from Liaoning Aihai; 
     aluminum hypophosphite: OP1314, purchased from Clariant, Switzerland; 
     flame retardant A: decabromodiphenylethane (8010), purchased from Albemarle Corporation, USA; 
     flame retardant B: diantimony trioxide, purchased from Yiyang Hengchang Antimony White Factory; 
     flame retardant C: halogen-free nitrogen phosphorus flame retardant WR02, purchased from Suzhou Enhand; 
     lubricant: BS-2818, purchased from Shenzhen Huamingtai; 
     antioxidant 1010: SONOX 1010, purchased from Shandong Sanfeng; 
     antioxidant 168: SONOX 168, purchased from Shandong Sanfeng. 
     The remaining raw materials are purchased commercially. 
     A preparation method of a polyolefin composition in the embodiments and comparative examples: polyolefin, an ethoxyamide polymer (or a flame retardant), a combustion-delaying synergist, a filler and an auxiliary agent were weighed according to weight percentages, added into a high-speed mixer and mixed evenly, and then the mixed materials were added into an extruder for extrusion and granulation, to obtain the polyolefin composition. 
     Test Methods for Each Performance: 
     (1) Combustion test: test according to GB8410 standard, size of 365*100*1.0 mm, unit as mm/min; 
     (2) Odor level: test according to PV3900 standard of Volkswagen OEM, 20 g, at 80° C., for 2 hours, unit as level; 
     (3) TVOC: according to PV3341 standard of Volkswagen OEM, unit as μg C/g. 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 distribution ratios (weight percentages) of each component and test results 
               
               
                 of each performance for the embodiments and the comparative examples 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
               
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
               
               
                   
               
               
                 polypropylene 
                 99.4 
                 99.2 
                 98.7 
                 98.2 
                 97.7 
                 59.2 
               
               
                 stearic acid 
                 0.3 
                 0.5 
                 1 
                 1.5 
                 2 
                 — 
               
               
                 ethoxyamide 
               
               
                 lauric acid 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.5 
               
               
                 ethoxyamide 
               
               
                 aluminum 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 hypophosphite 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant A 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant B 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant C 
               
               
                 talc powder 
                 — 
                 — 
                 — 
                 — 
                 — 
                 40 
               
               
                 antioxidant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 1010 
               
               
                 antioxidant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 168 
               
               
                 lubricant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 combustion 
                 61 
                 58 
                 52 
                 47 
                 44 
                 56 
               
               
                 test, mm/min 
               
               
                 odor level 
                 3.5 
                 3.5 
                 3.6 
                 3.7 
                 4.0 
                 3.5 
               
               
                 TVOC, μg 
                 27 
                 28 
                 31 
                 35 
                 38 
                 30 
               
               
                 C/g 
               
               
                   
               
               
                   
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
                 Embodiment 
               
               
                   
                 7 
                 8 
                 9 
                 10 
                 11 
                 12 
               
               
                   
               
               
                 polypropylene 
                 99.5 
                 99.2 
                 99.1 
                 98.8 
                 98 
                 97.4 
               
               
                 stearic acid 
                 0.5 
                 — 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 ethoxyamide 
               
               
                 lauric acid 
                 — 
                 0.5 
                 — 
                 — 
                 — 
                 — 
               
               
                 ethoxyamide 
               
               
                 aluminum 
                 — 
                 — 
                 0.1 
                 0.4 
                 1.2 
                 1.8 
               
               
                 hypophosphite 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant A 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant B 
               
               
                 flame 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant C 
               
               
                 talc powder 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 antioxidant 
                 — 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 1010 
               
               
                 antioxidant 
                 — 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 168 
               
               
                 lubricant 
                 — 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 combustion 
                 60 
                 55 
                 53 
                 42 
                 36 
                 30 
               
               
                 test, mm/min 
               
               
                 odor level 
                 4.0 
                 3.6 
                 3.7 
                 3.8 
                 3.9 
                 4.0 
               
               
                 TVOC, μg 
                 36 
                 33 
                 29 
                 32 
                 35 
                 39 
               
               
                 C/g 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
               
               
                   
                 Example 1 
                 Example 2 
                 Example 3 
                 Example 4 
                 Example 5 
                 Example 6 
                 Example 7 
               
               
                   
               
               
                 polypropylene 
                 93.7 
                 83.7 
                 97.7 
                 83.7 
                 99.5 
                 97.2 
                 99.7 
               
               
                 stearic acid 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 2.5 
                 — 
               
               
                 ethoxy amide 
               
               
                 lauric acid 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 ethoxy amide 
               
               
                 aluminum 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 hypophosphite 
               
               
                 flame 
                 4.5 
                 12 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant A 
               
               
                 flame 
                 1.5 
                 4 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 retardant B 
               
               
                 flame 
                 — 
                 — 
                 2 
                 16 
                 — 
                 — 
                 — 
               
               
                 retardant C 
               
               
                 talc powder 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 antioxidant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 1010 
               
               
                 antioxidant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 168 
               
               
                 lubricant 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 combustion 
                 77 
                 55 
                 104 
                 60 
                 72 
                 37 
                 105 
               
               
                 test, mm/min 
               
               
                 odor level 
                 4.25 
                 4.5 
                 4.25 
                 5.5 
                 3.7 
                 4.5 
                 3.5 
               
               
                 TVOC, μg 
                 52 
                 68 
                 36 
                 82 
                 32 
                 99 
                 26 
               
               
                 C/g 
               
               
                   
               
            
           
         
       
     
     It can be seen from Embodiment 1 to Embodiment 5 that with an increased amount of the stearic acid ethoxyamide, a combustion-delaying performance increases. It can be seen from Embodiment 9 to Embodiment 12 that with an increased amount of the aluminum hypophosphite, the combustion-delaying performance increases. It can be seen from the embodiments and Comparative Example 1 to Comparative Example 4 that compared with traditional flame retardant formulations brominated flame retardants, antimony compound-containing compound flame retardants and halogen-free nitrogen phosphorus flame retardants, the ethoxyamide polymer as the delay combustion agent only needs to be added in a small amount to achieve the excellent combustion-delaying performance, and has a low odor level and low TVOC. It can be seen from Comparative Example 5 to Comparative Example 6 that when the amount of the stearic acid ethoxyamide is only 0.2%, the combustion-delaying performance is insufficient, and even the odor is worse compared with Embodiment 1; and when the amount of the stearic acid ethoxyamide is 2.5%, compared with Embodiment 5, the combustion-delaying performance only slightly improves while the odor level increases by 0.5 and TOVC greatly increases by 61 μg C/g.